(FCC) Symposium Volume 452) Mario L. Occelli (Eds.) - Fluid Catalytic Cracking II. Concepts in Catalyst Design-American Chemical Society (1991)

ACS SYMPOSIUM SERIES 452
Fluid Catalytic Cracking II

Concepts in Catalyst Design
Mario L. Occelli, EDITOR
Unocal Corporation
Developed from a symposium sponsored
by the Division of Petroleum Chemistry, Inc.
at the 200th National Meeting
of the American Chemical Society,
Washington, DC, August 26-31, 1990
American Chemical Society, Washington, DC 1991

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Library of Congress Cataloging-in-Publication Data
Fluid catalytic cracking II: concepts in catalyst design
Mario L. Occelli, editor.
p. cm.(ACS symposium series, ISSN 0097-6156; 452).
Developed from a symposium sponsored by the Division of
Petroleum Chemistry, Inc. at the 200th National Meeting of the
American Chemical Society, Washington, D.C., August 26-31, 1990."
Includes bibliographical references and index.
ISBN 0-8412-1908-7
1. Catalytic crackingCongresses.
I. Occelli, Mario L., 1942- .II. American Chemical Society.
Division of Petroleum Chemistry.III. Series.
TP690.4.F56 1991
665.5'33dc20 90-23463
CIP
The paper used in this publication meets the minimum requirements of American National
Standard for Information SciencesPermanence of Paper for Printed Library Materials, ANSI
Z39.48-1984. @
Copyright 1991
American Chemical Society
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PRINTED IN THE UNITED STATES OF AMERICA

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ACS Symposium Series
M. Joan Comstock, Series Editor
1991 ACS Books Advisory Board
V. Dean Adams
Tennessee Technological
University
Paul S. Anderson
Merck Sharp & Dohme
Research Laboratories
Alexis T. Bell
University of CaliforniaBerkeley
Malcolm H. Chisholm
Indiana University
Natalie Foster
Lehigh University
Dennis W. Hess
University of CaliforniaBerkeley
Mary A. Kaiser
E. I. du Pont de Nemours and
Company
Gretchen S. Kohl
Dow-Corning Corporation
Michael R. Ladisch
Purdue University
Bonnie Lawlor
Institute for Scientific Information
John L. Massingill
Dow Chemical Company
Robert McGorrin
Kraft General Foods
Julius J. Menn
Plant Sciences Institute,
U.S. Department of Agriculture
Marshall Phillips
Office of Agricultural Biotechnology,
U.S. Department of Agriculture
Daniel M. Quinn
University of Iowa
A. Truman Schwartz
Macalaster College
Stephen A. Szabo
Conoco Inc.
Robert A. Weiss
University of Connecticut

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Foreword
The ACS SYMPOSIUM S ERI ES was founded in 1974 to provide a
medium for publishing symposia quickly in book form. The
format of the Series parallels that of the continuing ADVANCES
I N CHEMISTRY S ERI ES except that, in order to save time, the
papers are not typeset but are reproduced as they are submitted
by the authors in camera-ready form. Papers are reviewed under
the supervision of the Editors with the assistance of the Series
Advisory Board and are selected to maintain the integrity of the
symposia; however, verbatim reproductions of previously pub-
lished papers are not accepted. Both reviews and reports of
research are acceptable, because symposia may embrace both
types of presentation.

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Preface
IN A PARENT VOLUME TO THIS ONE (ACS Symposium Series, Vol. No.
375), it was reported that refiners worldwide are meeting crude oil quality
problems as well as environmental issues and regulations by developing,in
cooperation with catalyst manufacturers, new fluid catalytic cracking
(FCC) formulations that will help improve air and water quality. The
focus of this volume has not changed. In fact, the reauthorization of the
U.S. Clean Air Act of 1970 will likely mandate the reformulation of gaso-
line and the implementation of even stricter sulfur emission tolerance lev-
els in the 1990s. Furthermore, the ever increasing dependence of western
nations on Middle Eastern crudes, together with recent developments in
Kuwait, have once more reaffirmed the need to process residual oil and,
most importantly, readily available but metal-contaminated crudes from
Central and South America. Thus, the demand for new, custom-designed
FCC will probably continue to increase in the years to come.
In this volume, theoretical as well as applied aspects of cracking have
been discussed in chapters dealing with the origin and effects of strong
acidity, modeling, catalyst testing, residue processing and additive usage
for gasoline octane enhancement. Novel concepts and catalyst design,
together with modern characterization techniques such as laser Raman
spectroscopy, solid-state NMR (MASNMR), X-ray photoelectron spec-
troscopy (XPS) and secondary ion mass spectrometry (SIMS), have been
used to provide guidance in the difficult problem of cracking metal-
contaminated feedstocks.
I would like to thank Professor S. L. Suib, Dr. A. Corma and Dr. A.
Peters for helping to chair the symposium from which this volume was
developed. The views and conclusions expressed in this book are those of
the authors and I thank them, too, for the effort they have made, both in
presenting their work at the symposium and in preparing the camera-
ready manuscripts used in this volume. I would like to express my grati-
tude to G. Smith for her inestimable secretarial help and to my colleagues
at Unocal and elsewhere for acting as technical referees.
MARIO L. OCCELLI
Unocal Science & Technology Division
P.O. Box 76
Brea, CA 92621
October 9, 1990
ix

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Chapter 1
Origin of Strong Acidity in Dealuminated
Zeolite-Y
Jack H. Lunsford
Department of Chemistry, Texas A&M University,
College Station, TX 77843
Dealumination processes which leave residual
extraframework aluminum in a Y-type zeolite result in a
decrease in the overall number of Brnsted acid sites but
an increase in the strength of the remaining acid sites.
The net effect is an increase in activity for acid-
-catalyzed reactions up to a maximum at ca. 32framework
A l atoms per unit cell. A model for strong Brnsted
acidity is proposed which includes (i) the presence of
framework A l atoms that have no other A l atoms in a 4-
membered ring and (ii) complex A l cations in the cages.
The essential role of extraframework aluminum is evident
from recent studies in which framework A l has been
completely removed from zeolite-Y and by experiments on
the related ZSM-20 zeolite.
The commercial utilization of dealuminated Y-type zeolites has
generated renewed interest in the origin of strong acidity in these
materials. It is now evident that a carefully prepared H-Y zeolite,
with its full complement of protons but with no extraf ramework A l,
exhibits very little activity for acid-catalyzed reactions such as
the dealkylation of cumene or the cracking of hexane (1.2) . If these
zeolites are dealuminated toca. 32framework aluminum atoms per unit
cell (A l
f
/u.c), either by steaming or by treatment with silicon
tetrachloride, their activities for these reactions increase
remarkably. This framework A l concentration corresponds to aSi/A l
ratio of 5.0 or a unit cell dimension, a
0
, of 24.54A. Even if
zeolites are not purposely dealuminated at the outset, they become
dealuminated to an equilibrium level during their regeneration in a
catalytic cracking unit (3).
Early theoretical arguments of Dempsey (4) and also of Mikovsky
and Marshall (5.) suggested that the acid strength was related to the
A l distribution in the framework and that only A l
f
atoms with no
second-neighbor A l
f
atoms in the 4-rings are responsible for strong
Bronsted acidity. The number of aluminum atoms with 0, 1, 2and 3
aluminum second neighbors in the 4-rings has been calculated by
Beagley et al. (6), and the results are shown in Figure 1. The
disordered unit cell, referred to in the figure caption, indicates
that a random distribution of Si and A l atoms was assumed, with the
only constraint being that an A l-O-A l linkage did not exist
(Loewenstein's Rule). In the unique structures model it was assumed
0097-6156y91/0452-0001$06.00/0
1991 American Chemical Society

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2 FLUID CATALYTIC CRACKING II: CONCEPTS IN CATALYST DESIGN
F i g u r e 1. D i s t r i b u t i o n o f t y p e s o f A l at o ms i n f a u j a s i t e s : ( - ) ,
u n i q u e s t r u c t u r e s o f Ca mb r i d g e g r o u p ; ( ) , d i s o r d e r e d u n i t
c e l l .

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1. LUNSFORD Strong Acidity in Dealuminated Zeolite-Y
3
t h a t A l - A l r e p u l s i o n a c r o s s 4 - r i n g s o r 6 - r i n g s r e s u l t e d i n
e n e r g e t i c a l l y p r e f e r r e d s t r u c t u r e s . T h u s , i f t h e h y p o t h e s i s o f
D e mp s e y a n d o f Mi k o v s k y a n d Ma r s h a l l ( h e r e i n r e f e r r e d t o a s t h e DMM
mo d e l ) i s c o r r e c t a n d i f o n e as s u me s t h e d i s t r i b u t i o n i n d i c a t e d b y
t h e u n i q u e s t r u c t u r e s mo d e l , o n e wo u l d e x p e c t t h a t t h e n u mb e r o f
s t r o n g l y a c i d i c p r o t o n s wo u l d i n c r e a s e t o a max i mu m l e v e l a t 3 2
A l
f
/ u . c . a n d wo u l d d e c r e a s e t o z e r o a t 6 4 A l
f
/ u . c .
T h e d e a l u mi n a t i o n p r o c e s s , wh e t h e r b y s t e a mi n g o r b y t r e a t me n t
wi t h S i C l
4
, n o t o n l y c h a n g e s t h e A l
f
d i s t r i b u t i o n b u t a l s o i n t r o d u c e s
e x t r a f r ame wo r k A l i n t o t h e z e o l i t e c a v i t i e s . T h i s e x t r a f r ame wo r k A l ,
wh i c h may b e p r e s e n t i n s e v e r a l f o r ms , a l s o h a s t h e p o t e n t i a l f o r
i n c r e a s i n g o r d e c r e a s i n g b o t h t h e n u mb e r a n d a c i d s t r e n g t h o f t h e
p r o t o n s . T h e p r o b l e m o f s e p a r a t i n g t h e e f f e c t s o f t h e A l
f
a n d t h e
v a r i o u s f o r ms o f e x t r a f r a me wo r k A l h a s b e e n f o r mi d a b l e ; h o we v e r ,
c o n s i d e r a b l e p r o g r e s s h a s b e e n made i n s e v e r a l l a b o r a t o r i e s . I t i s
t h e p u r p o s e o f t h i s r e v i e w t o s u mma r i z e t h e s e r e s u l t s a n d t o s u g g e s t
a mo d e l o f s t r o n g a c i d i t y t h a t a p p e a r s t o f i t mu c h o f t h e a v a i l a b l e
d a t a . T h e d a t a i n c l u d e c a t a l y t i c r e s u l t s o n f a u j a s i t e - t y p e z e o l i t e s
p r e p a r e d b y s e v e r a l me t h o d s , p o i s o n i n g s t u d i e s , a n d i n f r a r e d s t u d i e s
o f h y d r o x y 1 g r o u p s .
E f f e c t o f F r ame wo r k Al u mi n u m C o n c e n t r a t i o n
E a r l y s t u d i e s i n o u r l a b o r a t o r y ( 1. 2 ) f o c u s e d o n t h e e f f e c t o f
d e a l u mi n a t i o n , e f f e c t e d e i t h e r b y s t e a mi n g o r b y t r e a t me n t wi t h S i C l
4
,
o n t h e a c t i v i t y o f t h e z e o l i t e f o r t h r e e t e s t r e a c t i o n s : me t h a n o l
d e h y d r a t i o n , c u me n e d e a l k y l a t i o n a n d h e x a n e c r a c k i n g . T h e s e
r e a c t i o n s we r e c h o s e n b e c a u s e t h e y r e q u i r e i n c r e a s i n g a c i d s t r e n g t h ,
w i t h h e x a n e c r a c k i n g b e i n g t h e mo s t d e ma n d i n g . U n f o r t u n a t e l y , i t i s
n o t p o s s i b l e ( a t l e a s t i n o u r h a n d s ) t o p r e p a r e f r o m a n o r ma l
z e o l i t e - Y c r y s t a l l i n e ma t e r i a l s h a v i n g A l
f
v a l u e s o v e r t h e e n t i r e
r a n g e b e t we e n 0 a n d 5 4 A l
f
/ u . c . I n p a r t i c u l a r , t h e z e o l i t e s i n t h e
r a n g e f r o m a b o u t 3 2 t o 5 2 A l
f
/ u . c . a r e i n a c c e s s i b l e . N e v e r t h e l e s s ,
a s s h o wn b y t h e d a t a i n F i g u r e 2 o n c u me n e d e a l k y l a t i o n , t h e a c t i v i t y
i n c r e a s e d i n a n a l mo s t l i n e a r man n e r wi t h r e s p e c t t o t h e f r a me wo r k A l
c o n c e n t r a t i o n u p t o 3 2 A l
f
/ u . c . T h e D Y 5 5 0 s e r i e s a n d t h e D Y - ( S i / A l )
s e r i e s we r e p r e p a r e d b y d e a l u mi n a t i o n o f a NH
4
Na- Y Z e o l i t e w i t h S i C l
A
u n d e r d i f f e r e n t c o n d i t i o n s , f o l l o we d b y i o n e x c h a n g e w i t h N H
4
+
t o a
r e s i d u a l N a
+
i o n c o n t e n t <0 . 0 5 wt . %. T h e S DY z e o l i t e was p r e p a r e d b y
s t e a mi n g t h e z e o l i t e a t 6 0 0 C, f o l l o we d b y N H
4
+
i o n e x c h a n g e . A l l o f
t h e s e d e a l u mi n a t e d z e o l i t e s r e t a i n e d a h i g h d e g r e e o f c r y s t a l l i n i t y .
T h e n o r ma l H- Y z e o l i t e e x h i b i t e d a n a c t i v i t y t h a t was o n l y 6% o f t h e
S DY z e o l i t e a n d c o mp a r a b l e t o t h a t o f a DY z e o l i t e c o n t a i n i n g c a . 2
A l
f
/ u . c , wh i c h c o n f i r ms t h a t t h e a c i d s t r e n g t h o f t h e p r o t o n s i n
n o r ma l H- Y z e o l i t e i s n o t a d e q u a t e f o r p r o mo t i n g t h e r a p i d
d e a l k y l a t i o n o f c u me n e . Q u a l i t a t i v e l y s i mi l a r r e s u l t s we r e o b t a i n e d
d u r i n g t h e c r a c k i n g o f h e x a n e , a l t h o u g h h i g h e r t e mp e r a t u r e s we r e
r e q u i r e d t o o b t a i n c o mp a r a b l e r e a c t i o n r a t e s . I n t h e me t h a n o l
d e h y d r a t i o n r e a c t i o n , t h e c o n v e r s i o n o v e r t h e H- Y z e o l i t e was a b o u t
6 0 % o f t h a t o b t a i n e d o v e r t h e S DY z e o l i t e , wh i c h d e mo n s t r a t e s t h a t
d i f f e r e n c e s i n a c i d s t r e n g t h a r e i mp o r t a n t e v e n f o r l e s s d e ma n d i n g
r e a c t i o n s .
A l i n e a r r e l a t i o n s h i p b e t we e n t h e c a r b o n i u m i o n r a t e i n
i s o b u t a n e c o n v e r s i o n a n d t h e f r a me wo r k A l c o n c e n t r a t i o n u p t o 3 2
A l f / u . c . h a s b e e n mo r e r e c e n t l y r e p o r t e d b y B e y e r l e i n e t a l . ( 7 ) .
T h i s t y p e o f l i n e a r r e l a t i o n s h i p , wh i c h i s a n a l o g o u s t o t h a t o b s e r v e d
d u r i n g h e x a n e c r a c k i n g o v e r H- ZS M- 5 z e o l i t e s ( 8 ) , l e d u s t o s u g g e s t
t h a t i n t h e d e a l u mi n a t e d Y - t y p e z e o l i t e s e a c h A l
f
g a v e r i s e t o a n
e q u i v a l e n t B r o n s t e d a c i d s i t e h a v i n g a c o n s t a n t t u r n o v e r f r e q u e n c y
( 1 . 2 ) . T h e s e r e s u l t s a l s o s e e m t o s u p p o r t t h e DMM mo d e l . T h e s o l i d
l i n e i n F i g u r e 2 , wh i c h i s t h e N ( 0 ) d i s t r i b u t i o n f r o m F i g u r e 1, f i t s
t h e d a t a r e a s o n a b l y w e l l . Ot h e r r e s u l t s , h o we v e r , i n d i c a t e t h a t t h e
s i t u a t i o n i s mo r e c o mp l e x a n d t h a t o n l y a f r a c t i o n o f t h e A l
f
at o ms
a r e i n v o l v e d i n c r e a t i n g a c t i v e c e n t e r s . T h e a n a l o g y b e t we e n t h e s e
d e a l u mi n a t e d z e o l i t e - Y s a mp l e s a n d n o r ma l H- ZS M- 5 i s , i n f a c t , n o t

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c o r r e c t b e c a u s e t h e f o r me r c a t a l y s t h a s e x t r a f r a me wo r k a l u mi n u m,
wh e r e a s t h e l a t t e r d o e s n o t .
P o i s o n i n g S t u d i e s
P o i s o n i n g s t u d i e s c a r r i e d o u t b y s e v e r a l g r o u p s h a v e s h o wn t h a t t h e
e q u i v a l e n t s o f p o i s o n n e e d e d t o q u e n c h t h e c a t a l y t i c a c t i v i t y o f t h e
d e a l u mi n a t e d Y - t y p e z e o l i t e s a r e mu c h l e s s t h a n t h e n u mb e r o f A l
f
a t o ms . B e y e r l e i n e t a l . ( 9 ) r e p o r t e d t h a t r e s i d u a l s o d i u m c a t i o n s
e x t e n s i v e l y d e c r e a s e d t h e i s o b u t a n e c r a c k i n g a c t i v i t y o f s t e a m-
d e a l u mi n a t e d Y - t y p e z e o l i t e s . F r o m t h e i r r e s u l t s i t was c o n c l u d e d
t h a t o n l y o n e - t h i r d o f t h e A l
f
at o ms we r e a s s o c i a t e d w i t h s t r o n g
a c i d i t y t h r o u g h o u t t h e S i / A l > 5 c o mp o s i t i o n d o ma i n .
Mo r e r e c e n t l y , F r i t z a n d L u n s f o r d ( 10 ) s t u d i e d t h e e f f e c t t h a t
s o d i u m p o i s o n i n g h a d o n h e x a n e c r a c k i n g o v e r a s e r i e s o f Y - t y p e
z e o l i t e s t h a t h a d b e e n mo d i f i e d b y d e a l u mi n a t i o n w i t h S i C l
A
o r b y
s t e a mi n g . T h e r e s u l t s , d e p i c t e d i n F i g u r e 3 , i n d i c a t e t h a t e a c h
s o d i u m i o n a d d e d b a c k t o t h e z e o l i t e e f f e c t i v e l y n e u t r a l i z e s t h e
c a t a l y t i c a c t i v i t y p r e v i o u s l y t h o u g h t t o b e du e t o f i v e B r o n s t e d a c i d
s i t e s . T h e a b s c i s s a i n F i g u r e 1 r e p r e s e n t s t h e n u mb e r o f f r a me wo r k
A l at o ms wh i c h r e ma i n s u n p o i s o n e d a f t e r t h e a d d i t i o n o f s o d i u m. F o r
e x a mp l e , i f e a c h A l
f
at o m h a d a s t r o n g l y a c i d i c p r o t o n a s s o c i a t e d w i t h
i t , t h e A - s e r i e s s a mp l e , wh i c h i n t h e p u r e f o r m h a d 15 A l
f
/ u . c . , wo u l d
h a v e r e q u i r e d t h a t s ame n u mb e r N a
+
i o n s t o n e u t r a l i z e t h e a c i d i t y .
I n f a c t , o n l y a b o u t 3 N a
+
i o n s / u . c . ( A l
f
- Na - 12 ) d e s t r o y e d t h e
a c t i v i t y . B a s e d o n N H
4
+
p o i s o n i n g e x p e r i me n t s , L o mb ar d o e t a l . ( 11)
c o n c l u d e d t h a t a p p r o x i ma t e l y 10 % o f t h e p o t e n t i a l B r o n s t e d s i t e s ,
c o u n t e d a s A l
f
i o n s , we r e i n v o l v e d i n t h e c a t a l y t i c d e c o mp o s i t i o n o f
n e o p e n t a n e .
T h e e f f e c t o f s t e a mi n g a n d o f e x t e n s i v e p o i s o n i n g b y a l k a l i
me t a l i o n s i s n o t l i mi t e d t o Y - t y p e z e o l i t e s , a s L a g o e t a l . ( 12 )
h a v e o b s e r v e d s i mi l a r p h e n o me n a wi t h mi l d l y s t e a me d H- Z S M- 5 . T h e
a c t i v i t y f o r h e x a n e c r a c k i n g i n c r e a s e d b y a b o u t a f a c t o r o f f o u r u p o n
mi l d s t e a mi n g o f t h e c a t a l y s t . S e l e c t i v e Cs p o i s o n i n g i n d i c a t e d t h a t
t h e c o n c e n t r a t i o n o f a mo r e a c t i v e s i t e i n t h e s t e a me d s a mp l e was
o n l y a b o u t 6% o f t h e t e t r a h e d r a l f r a me wo r k a l u mi n u m. T h e s e s i t e s
e x h i b i t e d a s p e c i f i c a c t i v i t y 4 5 - 7 5 t i me s g r e a t e r t h a n t h a t o f a
n o r ma l s i t e i n H- ZS M- 5 .
Two p o s s i b l e me c h an i s ms f o r t h e e f f e c t i v e n e s s o f t h e p o i s o n s
h a v e b e e n p o s t u l a t e d . F i r s t , t h e p o i s o n may b e e f f e c t i v e t h r o u g h a
l o n g r a n g e i n t e r a c t i o n . E v i d e n c e f o r t h i s h y p o t h e s i s i s g i v e n b y
D y e r a n d S i n g h ( 1 3 ) , wh o f o u n d t h a t K
+
i o n s h a d a mu c h g r e a t e r e f f e c t
o n a c t i v i t y t h a n N a
+
i o n s . T h i s was a t t r i b u t e d t o d i f f e r e n c e s i n
c a t i o n i c r a d i i a n d e l e c t r o n e g a t i v i t i e s . A s e c o n d p o s s i b i l i t y i s t h a t
e v e n i n z e o l i t e s h a v i n g i s o l a t e d A l
f
a t o ms , o n l y a f r a c t i o n o f t h e
B r o n s t e d s i t e s a r e a s s o c i a t e d wi t h s t r o n g a c i d i t y . S t r o n g e v i d e n c e
f a v o r i n g t h e s e c o n d p o s s i b i l i t y i s f o u n d i n t h e i n f r a r e d s t u d i e s t o
b e d i s c u s s e d i n t h e n e x t s e c t i o n .
Hy d r o x y l I n f r a r e d B an d s
I n f r a r e d b a n d s o f d e a l u mi n a t e d z e o l i t e s i n t h e 0 - H s t r e t c h i n g r e g i o n
h a v e b e e n e x t e n s i v e l y s t u d i e d ( 1 4 - 1 7 ) : h o we v e r , e mp h a s i s w i l l b e
p l a c e d o n t h e s t u d y b y F r i t z a n d L u n s f o r d ( 1 0 ) , wh i c h d e s c r i b e s t h e
e f f e c t o f N a
+
o n t h e s e i n f r a r e d b a n d s . P e r h a p s t h e mo s t i n f o r ma t i v e
e x a mp l e i s t h e S i C l
A
- t r e a t e d z e o l i t e ( s e r i e s A o f F i g u r e 3 ) . T h e
S i C l
4
- t r e a t e d z e o l i t e s h a v e l e s s e x t r a f r ame wo r k a l u mi n u m t h a n do t h e
s t e a me d s a mp l e s ; t h e r e f o r e , t h e i n f r a r e d s p e c t r a i n t h e 0 - H
s t r e t c h i n g r e g i o n a r e l e s s c o mp l i c a t e d .
T h e e f f e c t o f a d d e d N a
+
o n t h e i n f r a r e d s p e c t r a o f t h e S i C l
A
-
t r e a t e d z e o l i t e i s s h o wn i n F i g u r e 4 . A t l e a s t f i v e ma j o r h y d r o x y l
b a n d s a r e a p p a r e n t i n t h e s p e c t r a . T h e r e a r e t wo s i l a n o l b a n d s : o n e
a t 3 7 4 5 c m , wh i c h r e s u l t s f r o m t e r mi n a l h y d r o x a l g r o u p s i n t h e
l a t t i c e ( 1 8 ) , a n d o n e a t 3 7 3 9 c m'
1
, wh i c h i s p o s s i b l y du e t o h y d r o x y l
n e s t s . T h e t wo b a n d s a t 3 6 3 5 a n d 3 5 6 0 c m"
1
a r e a s s o c i a t e d w i t h t h e

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LUNSFORD Strong Acidity in Dealuminated Zeolite-Y
F i g u r e 2 . D e p e n d e n c e o f c a t a l y t i c a c t i v i t y f o r c u me n e c o n v e r s i o n
a t 2 9 0 C o n f r a me wo r k a l u mi n u m c o n t e n t : ( O ) D Y 5 5 0 s e r i e s , ( )
D Y - ( S i / A l ) s e r i e s , ( ) S DY , ( ) HY .
120
100
~ i
c
o o 60
2
6 a
^ 40
c o
E
| ^ 20
0
0 10 20 30 40 50 60
Al
f
- No
F i g u r e 3 . T h e d e p e n d e n c e o f h e x a n e c r a c k i n g a c t i v i t y o n t h e
f r a me wo r k A l c o n t e n t f o r f o u r s e r i e s o f N a
+
- p o i s o n e d c a t a l y s t s .
E a c h Na* i s as s u me d t o p o i s o n o n e f r a me wo r k A l at o m. ( ) A
s e r i e s , ( ) B s e r i e s , ( ) C s e r i e s , ( ) D s e r i e s . T h e
s o l i d l i n e r e p r e s e n t s t h e t h e o r e t i c a l a c t i v i t y b a s e d o n i s o l a t e d
A l at o ms ( 6 ) . R e p r o d u c e d wi t h p e r mi s s i o n f r o m R e f . 10 .
Co pyr i gh t 1989 Ac ade mi c Pr es s .

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1
9
9
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1
0
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1
0
2
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b
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1
9
9
1
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0
4
5
2
.
c
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0
0
1
F i g u r e 4 . I n f r a r e d s p e c t r a o f t h e h y d r o x y l r e g i o n f o r a S i C l
A
-
t r e a t e d z e o l i t e ( s e r i e s A, wi t h A l
f
- 15 . 3 ) wi t h v a r i o u s amo u n t s
o f N a
+
a d d e d a s a p o i s o n : ( a ) 0 . 0 2 wt % N a
+
, ( b ) 0 . 2 3 wt % N a
+
, ( c )
0 . 4 9 wt % N a
+
. T h e o r d i n a t e i s a b s o r b a n c e i n a r b i t r a r y u n i t s .
R e p r o d u c e d w i t h p e r mi s s i o n f r o m R e f . 10 . Co pyr i gh t 1989 Ac ade mi c Pr es s .

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1
1. LUNSFORD Strong Acidity in Dealuminated Zeolite-Y 7
t r a d i t i o n a l B r o n s t e d s i t e s f o u n d i n a n o r ma l H- Y z e o l i t e . T h e f i f t h
b a n d , wh i c h i s t h e mo s t s e n s i t i v e t o N a
+
a d d i t i o n , i s f o u n d a t 3 6 0 2
c m" . T h i s b a n d d e c r e a s e d u p o n a d d i t i o n o f s ma l l amo u n t s o f N a
+
i n a
man n e r t h a t p a r a l l e l e d t h e d e c r e a s e i n c a t a l y t i c a c t i v i t y ( F i g u r e 3 ) ,
wh e r e a s t h e b a n d s a t 3 6 3 5 a n d 3 5 6 0 c m"
1
we r e n o t s i g n i f i c a n t l y
a f f e c t e d b y t h e i n t r o d u c t i o n o f s ma l l amo u n t s o f N a
+
. Mo r e c o mp l e t e
i o n e x c h a n g e w i t h N a
+
wo u l d h a v e r e s u l t e d i n a d e c r e a s e d a mp l i t u d e o f
t h e 3 6 3 5 a n d 3 5 6 0 c m'
1
b a n d s .
Wi t h r e s p e c t t o t h e me c h a n i s m b y wh i c h s o d i u m p o i s o n s t h e a c i d i c
z e o l i t e , i t i s i mp o r t a n t t o n o t e t h a t a t l e a s t t h r e e d i f f e r e n t t y p e s
o f a c i d i c p r o t o n s a r e p r e s e n t , a n d t h a t o n e f o r m i s a f f e c t e d mu c h
mo r e b y s o d i u m p o i s o n i n g t h a n a r e t h e o t h e r t wo . T h u s , o n l y a
f r a c t i o n o f t h e B r o n s t e d s i t e s i s s t r o n g l y a c i d i c , e v e n i n z e o l i t e s
h a v i n g o n l y t h e N ( 0 ) c o n f i g u r a t i o n i n t h e 4 - r i n g s ( F i g u r e 1 ) . T h e
q u e s t i o n a r i s e s a s t o wh a t , i n a d d i t i o n t o t h e A l
f
d i s t r i b u t i o n , i s
e s s e n t i a l f o r a s t r o n g l y a c i d i c s i t e . S i n c e d e a l u mi n a t i o n b y
s t e a mi n g o r b y t r e a t me n t w i t h S i C l
4
g e n e r a t e s e x t r a f r a me wo r k a l u mi n u m
i n v a r i o u s f o r ms , i t i s r e a s o n a b l e t o s u s p e c t t h a t o n e o f t h e s e t y p e s
o f e x t r a f r ame wo r k a l u mi n u m may b e i n v o l v e d i n t h e d e v e l o p me n t o f
s t r o n g a c i d i t y .
E v i d e n c e f o r t h e R o l e o f E x t r a f r a me wo r k Al u mi n u m
E v i d e n c e t h a t s o me t h i n g mo r e t h a n a p r o p e r A l
f
d i s t r i b u t i o n i s n e e d e d
t o c r e a t e s t r o n g a c i d i t y f i r s t c ame f r o m t h e e x p e r i me n t s o f B e y e r l e i n
e t a l . ( 7 ) . U s i n g t h e a c i d - c a t a l y z e d c o n v e r s i o n o f i s o b u t a n e as a
me a s u r e o f s t r o n g a c i d i t y , t h e y f o u n d t h a t a d e a l u mi n a t e d z e o l i t e
p r e p a r e d b y t r e a t me n t wi t h ammo n i u m h e x a f l u o r o s i l i c a t e ( AHF )
e x h i b i t e d mu c h l e s s c a r b o n i u m i o n a c t i v i t y t h a n mi g h t b e e x p e c t e d ,
b a s e d o n t h e n u mb e r o f A l
f
a t o ms . T h i s t r e a t me n t l e a v e s v e r y l i t t l e
e x t r a f r a me wo r k A l i n t h e z e o l i t e . Wh e n t h e s a mp l e was mi l d l y
s t e a me d , t h e a c t i v i t y b e c ame c o n s i d e r a b l y g r e a t e r . T h e a u t h o r s
c o n c l u d e d t h a t t h e e n h a n c e d a c i d i t y was a r e s u l t o f a s y n e r g i s m
b e t we e n t h e f r a me wo r k B r o n s t e d s i t e s a n d t h e L e wi s s i t e s a s s o c i a t e d
w i t h e x t r a f r a me wo r k a l u mi n u m.
E x p e r i me n t s t o f u r t h e r d e mo n s t r a t e t h e c r i t i c a l r o l e o f
e x t r a f r a me wo r k A l , o r a n o t h e r p o l y v a l e n t c a t i o n , h a v e r e c e n t l y b e e n
c a r r i e d o u t i n o u r l a b o r a t o r y ( 1 9 . 2 0 ) . A s e r i e s o f f a u j a s i t e - t y p e
z e o l i t e s was p r e p a r e d t h a t h a d A l
f
c o n c e n t r a t i o n s b e t we e n 2 1 a n d 5 4
p e r u . c . A t t h e l o w e n d o f t h e r a n g e , AHF was u s e d t o r e mo v e t h e
f r a me wo r k A l , a n d a n H- ZS M- 2 0 z e o l i t e wi t h 4 2 A l
f
/ u . c . was
s y n t h e s i z e d . Z S M- 2 0 i s a n i n t e r g r o wt h o f t h e c u b i c f a u j a s i t e
s t r u c t u r e a n d t h e h e x a g o n a l v a r i a n t k n o w a s B r e c k ' s s t r u c t u r e s i x
( B S S ) ( 2 1 ) . T h u s , i t i s a f a u j a s i t e - l i k e ma t e r i a l . T h e c a t a l y t i c
a c t i v i t i e s o f t h e s e z e o l i t e s f o r h e x a n e c r a c k i n g a r e c o mp a r e d i n
F i g u r e 5 ( l o we r d a t a s e t ) w i t h t h e a c t i v i t i e s o f z e o l i t e s p r e p a r e d b y
s t e a mi n g o r b y t r e a t me n t wi t h S i C l
A
( u p p e r d a t a s e t ) . T h e s o l i d l i n e s
r e p r e s e n t N ( 0 ) d i s t r i b u t i o n s . T h e s a mp l e s wi t h o u t e x t r a f r a me wo r k A l
e x h i b i t e d v e r y mo d e s t a c t i v i t y , e v e n t h o u g h s o me o f t h e m h a d a
f a v o r a b l e N ( 0 ) c o n c e n t r a t i o n .
T h e amo u n t o f e x t r a f r a me wo r k A l t h a t i s n e e d e d t o d e v e l o p a
s t r o n g l y a c i d i c H- ZS M- 2 0 z e o l i t e i s a c t u a l l y q u i t e s ma l l , as
i n d i c a t e d b y t h e r e s u l t s o f F i g u r e 6. D e a l u mi n a t i o n o f a n H- Z S M- 2 0
z e o l i t e f r o m a n o r i g i n a l c o n c e n t r a t i o n o f 4 1 A l f / u . c . t o 3 1 A l
f
/ u . c .
r e s u l t e d i n t h e max i mu m i n c r e a s e i n a c t i v i t y f o r h e x a n e c r a c k i n g .
T h i s i n c r e a s e i s a l mo s t t h e mi r r o r i mag e o f t h e d e c r e a s e s t h a t we r e
n o t e d p r e v i o u s l y f o r N a
+
p o i s o n i n g . T h e 10 A l at o ms t h a t h a v e b e e n
r e mo v e d f r o m t h e f r a me wo r k c o r r e s p o n d t o a b o u t 1. 3 A l p e r s ma l l
c a v i t y . As mo r e A l
f
at o ms a r e r e mo v e d , t h e a c t i v i t y d e c r e a s e d i n a
man n e r c o n s i s t e n t wi t h t h e N ( 0 ) d i s t r i b u t i o n t h a t i s i n d i c a t e d b y t h e
s o l i d l i n e i n F i g u r e 6.
F r i t z a n d L u n s f o r d ( 1 0 ) , a s w e l l a s L o mb ar d o e t a l . ( 1 1 ) , h a v e
s u g g e s t e d t h a t t h e e f f e c t i v e e x t r a f r a me wo r k A l i s p r e s e n t i n t h e @
c a g e s a s c a t i o n s t h a t a r e b r i d g e - b o n d e d t h r o u g h o x y g e n a t o ms . I n
o r d e r t o t e s t t h i s h y p o t h e s i s , o n e wo u l d l i k e t o i o n - e x c h a n g e A l
3 +

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Framework aluminum (Al /u.c.)
F i g u r e 5 . He x an e c r a c k i n g a c t i v i t y a s a f u n c t i o n o f f r a me wo r k
a l u mi n u m c o n t e n t : O , Y - t y p e z e o l i t e d e a l u mi n a t e d w i t h S i C l
4
;
, Y - t y p e z e o l i t e p r e p a r e d b y s t e a mi n g ; A , Y - t y p e z e o l i t e
d e a l u mi n a t e d wi t h ammo n i u m h e x a f l u o r o s i l i c a t e ; A , a f t e r L a
3 +
e x c h a n g e t o l e v e l o f max i mu m a c t i v i t y ; , Z S M- 2 0 ; g , a f t e r
L a
3 +
e x c h a n g e t o l e v e l o f max i mu m a c t i v i t y ; v , a s s y n t h e s i z e d
z e o l i t e Y ; , a f t e r e x c h a n g e t o l e v e l o f max i mu m a c t i v i t y ;
HL a- X. R e p r o d u c e d wi t h p e r mi s s i o n f r o m R e f . 2 0 .
Copyright 1990 Academic Press.
400C
0 10 20 30 40 50 60
Framework AI/U. C. by NMR
F i g u r e 6. D e p e n d e n c e o f h e x a n e c r a c k i n g a c t i v i t y o n f r a me wo r k
a l u mi n u m c o n t e n t f o r s t e a m- d e a l u mi n a t e d H- Z S M- 2 0 .

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1. LUNSFORD Strong Acidity in Dealuminated Zeolite-Y
9
i n t o a s e r i e s o f f a u j a s i t e - t y p e z e o l i t e s h a v i n g a r a n g e o f A l
f
v a l u e s ,
b u t t h i s i s p r o b a b l y n o t p o s s i b l e b e c a u s e A l
3 +
h y d r o l y z e s e x t e n s i v e l y .
As a n a l t e r n a t i v e , we h a v e i o n e x c h a n g e d L a
3 +
i o n s i n t o t h e s e r i e s o f
z e o l i t e s d e s c r i b e d p r e v i o u s l y f o r t h e d a t a o f F i g u r e 5 . L a n t h a n u m-
e x c h a n g e d z e o l i t e s a r e p a r t i c u l a r l y a t t r a c t i v e b e c a u s e o f t h e
s t r u c t u r a l i n f o r ma t i o n t h a t i s a v a i l a b l e o n t h e l o c a t i o n o f t h e
c a t i o n s . Wh e n L a - Y z e o l i t e s a r e h e a t e d t o a p p r o x i ma t e l y 3 0 0 C, t h e
h y d r a t i o n s p h e r e i s l o s t , a n d t h e l a n t h a n u m i o n s mi g r a t e i n t o t h e j3
c a g e s wh e r e t h e y a r e p r e f e r e n t i a l l y a t t a c h e d t o s i t e s I ' a n d t a k e o n
a n e f f e c t i v e c h a r g e o f +2 . 5 ( 2 2 ) . S p e c i e s s u c h a s [ L a C Q ^ L a ]
2 +
,
[ L a ^Q j j ^T L a ]
A +
, a n d L a ( 0 H)
2 +
h a v e b e e n p r o p o s e d . T h e r e i s n e u t r o n
d i f f r a c t i o n e v i d e n c e t o s u p p o r t b o t h t h e l o c a t i o n o f t h e L a i o n a n d
t h e p r e s e n c e o f e x t r a f r a me wo r k o x y g e n a n d h y d r o g e n i n t h e / ? c a g e s
( 2 3 ) .
Wh e n t h e s e r i e s o f NH
4
- Y o r NH
A
- Z S M- 2 0 z e o l i t e s h a v i n g 2 1 t o 5 4
A l
f
at o ms p e r u . c , a n d a l mo s t n o e x t r a f r a me wo r k A l , was e x c h a n g e d
w i t h L a
3 +
i o n s t o v a r i o u s e x t e n t s , t h e a c t i v i t y f o r h e x a n e c r a c k i n g
f i r s t i n c r e a s e d a n d t h e n d e c r e a s e d w i t h t h e e x t e n t o f i o n e x c h a n g e .
T h e max i ma i n a c t i v i t y f o r e a c h z e o l i t e a r e p l o t t e d a s t h e mi d d l e s e t
o f d a t a i n F i g u r e 5 . A g a i n , t h e r e s u l t s a r e r e a s o n a b l y w e l l
a p p r o x i ma t e d b y t h e N ( 0 ) d i s t r i b u t i o n , w i t h d a t a n o w b e i n g a v a i l a b l e
f o r t h e r a n g e o f 3 5 t o 5 4 A l
f
/ u . c . T h e HL a- X s a mp l e s we r e a l mo s t
c o mp l e t e l y i n a c t i v e , wh i c h i s c o n s i s t e n t w i t h t h e r e s u l t s e x p e c t e d
f r o m t h e N ( 0 ) d i s t r i b u t i o n . T h e s a mp l e s c o n t a i n i n g L a
3 +
we r e l e s s
a c t i v e t h a n t h e s a mp l e s d e a l u mi n a t e d w i t h S i C l
A
o r b y s t e a mi n g , b u t
t h i s i s e x p e c t e d b e c a u s e t h e p o l a r i z i n g o r i n d u c t i v e e f f e c t o f t h e
s ma l l e r A l i o n i s mu c h g r e a t e r t h a n t h a t o f t h e L a
3 +
i o n . T h e s e
r e s u l t s s u p p o r t a mo d e l o f s t r o n g a c i d i t y t h a t i n v o l v e s t h e
wi t h d r a wa l o f e l e c t r o n s f r o m s t r u c t u r a l 0 - H b o n d s b y p o l y v a l e n t
c a t i o n s t h a t a r e p r e s e n t i n t h e 0 c a g e s .
Mo d e l f o r S t r o n g A c i d i t y
T h e e v i d e n c e t o d a t e s u g g e s t s t h a t t h e d e v e l o p me n t o f s t r o n g B r o n s t e d
a c i d i t y i n Y - t y p e z e o l i t e s r e q u i r e s b o t h i s o l a t e d A l * at o ms a n d t h e
p r e s e n c e o f e x t r a f r a me wo r k a l u mi n u m. E x t r a f r a me wo r k a l u mi n u m may , o f
c o u r s e , e x i s t i n s e v e r a l f o r ms , i n c l u d i n g a b o e h mi t e - l i k e ma t e r i a l
( 2 4 ) a n d s e v e r a l i o n i c s p e c i e s , s u c h a s t h o s e d e s c r i b e d p r e v i o u s l y .
I t s e e ms u n l i k e l y t h a t p s e u d o - b o e h mi t e o r e v e n a l u mi n a i n t h e l a r g e
c a v i t i e s wo u l d b e c a p a b l e o f g e n e r a t i n g s t r o n g l y a c i d i c s i t e s i n t h e
z e o l i t e f r a me wo r k , wh e r e a s t h r o u g h i n d u c t i v e e f f e c t s t h e i o n i c f o r ms
o f A l i n t h e & c a g e s s h o u l d h a v e a p r o f o u n d e f f e c t o n t h e e l e c t r o n
d i s t r i b u t i o n i n t h e f r a me wo r k . T h e e x t e n t o f t h e s e i n t e r a c t i o n s
c o u l d p r o f i t a b l y b e e x p l o r e d b y t h e o r e t i c a l c a l c u l a t i o n s . Wh i l e t h e
c a t i o n i c f o r ms o f A l may p r o mo t e t h e a c i d s t r e n g t h , t h e y
s i mu l t a n e o u s l y d e c r e a s e t h e n u mb e r o f p r o t o n s n e e d e d t o ma i n t a i n
c h a r g e n e u t r a l i t y .
As a n u me r i c a l e x a mp l e , c o n s i d e r a p a r t i a l l y d e a l u mi n a t e d H- Y
z e o l i t e t h a t c o n t a i n s 3 2 A l
f
/ u . c , a l l o f wh i c h a r e i s o l a t e d , a n d 8
e x t r a f r a me wo r k A l c a t i o n s / u . c . T h i s e x a mp l e i s s i mi l a r t o t h e c a s e
o f t h e p a r t i a l l y d e a l u mi n a t e d H- Z S M- 2 0 z e o l i t e i n F i g u r e 6 i f o n e
as s u me s t h a t mo s t o f t h e e x t r a f r a me wo r k A l i s p r e s e n t i n t h e c a t i o n i c
f o r m. I f t h e e x t r a f r a me wo r k A l i s c o mp l e x e d s u c h t h a t e a c h A l h a s a n
e q u i v a l e n t c h a r g e o f +2 , 16 p r o t o n s wo u l d b e r e q u i r e d t o b a l a n c e t h e
f r a me wo r k c h a r g e . He r e i t i s a s s u me d t h a t t h e c a t i o n i c e x t r a f r a me wo r k
A l i s p r e s e n t a s [ A I ^QS^ A I ]
A +
. An e x a mi n a t i o n o f t wo r e p r e s e n t a t i v e
0 - c a g e s i n t h i s z e o l i t e r e v e a l s t h a t o n e c a g e c o n t a i n s t h e
[ A I C Q Â I ]
A +
c o mp l e x c a t i o n , wh e r e a s t h e o t h e r i s e mp t y . I f t h e
A l
f
at o ms a r e d i s t r i b u t e d s u c h t h a t t h e / ? - c ag e w i t h t h e c o mp l e x c a t i o n
h a s 6 A l f at o ms a n d t h e o t h e r - c ag e h a s 2 , t h e c a g e w i t h t h e c o mp l e x
c a t i o n wo u l d h a v e 2 h i g h l y a c i d i c p r o t o n s , a n d t h e r e ma i n i n g c a g e
wo u l d h a v e 2 we a k l y a c i d i c p r o t o n s . T h u s , f o r t h e 8 A l
f
at o ms t h e r e
wo u l d b e o n l y 2 h i g h l y a c i d i c p r o t o n s , wh i c h i s c o n s i s t e n t w i t h t h e

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10
FLUID CATALYTIC CRACKING II: CONCEPTS IN CATALYST DESIGN
Na
+
-poisoning experiments. The presence of a larger number of weakly
acidic protons is also consistent with the infrared results.
As the number of A l
f
/u.c. is increased, the probability of having
isolated A l
f
atoms decreases; thus, the activity would decrease. I t
is at the lower A l
f
concentrations, however, that a simple stati sti cal
treatment fails to predict the observed linear relationship between
catalytic activity and A l
f
concentration. For example, at 8 A lf/u.c.
i t is di ffi cul t to imagine how there would be a significant
concentration of strongly acidic centers. There must be fi-cages
that contain at least 3 A l
f
atoms and one A1(0H)
2+
cation in order for
there to be a strongly acidic proton. But this proton may be even
more acidic than in the case described previously.. Even within the
more acidic materials, theremay be subsets of strongly acidic sites.
The net effect may be the observed linear relationship between
catalytic activity and A l
f
content. Clearly, more theoretical and
experimental work is needed to test the validity of these models.
Acknowledgments
The author is indebted to several associates who carried out many of
the experiments described here and who were involved in the
development of the concepts. These include Steven DeCanio, Paul
Fri tz, S. J . Sohn, and Sun Yao. The research in our laboratory was
supported in part by the U. S. Army Research Office and by the
Regents of Texas A&M University through the AUF-sponsored Materials
Science and Engineering Program.
Literature Cited
1. DeCanio, S. J.; Sohn, J . R.; Fri tz, P. O.; Lunsford, J . H. J .
Catal. 1986, 101, 132.
2. Sohn, J . R.; DeCanio, S. J.; Fri tz, P. O.; Lunsford; J . H. J .
Phys. Chem. 1986, 90, 4847.
3. Pine, L. A .; Maher, P. J.; Wachter, W. A. J . Catal. 1984, 85,
466.
4. Dempsey, E. J . Catal. 1974, 33, 497; 1975, 39, 155.
5. Mikovsky, R. J.; Marshall, J. F. J . Catal. 1976, 44, 170.
6. Beagley, B.; Dwyer, J.; Fitch, F. R.; Mann, R.; Walters, J . J .
Phys. Chem. 1984, 88, 1744.
7. Beyerlein, R. A .; McVicker, G. B.; Y acullo, L. N.; Ziemiak, J .
J. J . Phys. Chem. 1988, 92, 1967.
8. Haag, W. O.; Lago, R. M.; Weisz, P. B. Nature (London) 1984,
309, 589.
9. Beyerlein, R. A .; McVicker, G. B.; Y acullo, L. N.; Ziemiak, J .
J. ACS Meeting, Div. Petrol. Chem., New Y ork, 1986; V ol. 31, p.
190.
10. Fri tz, P. O.; Lunsford, J. H. J. Catal. 1989, 118, 85.
11. Lombardo, E. A .; Sill, G. A .; Hall, W. K. J . Catal. 1989, 119.
426.
12. Lago, R. M.; Haag, W. O.; Mikovsky, R. J.; Olson, D. H.;
Hellring, S. D.; Schmitt, K. D.; Kerr, G. T. In Proceedings 7th
I ntl . Zeo. Conf.: Murakami, Y .; I ijima, A .; Ward, J. W., Ed.;
Kodansha Ltd.: Tokyo, 1986; p. 677.
13. Dyer, A .; Singh, A. P. Zeolites 1988, 8, 242.
14. J acobs, P. A .; Uytterhoeven, J . B. J . Chem. Soc. Faraday Trans.
1 1973, 2, 373.
15. Anderson, M. A .; Klinowski, J . Zeolites 1986, 6, 455.
16. Lohse, U.; Lffler, E.; Hunger, M.; Stchner, J., Patzelov, V.
Zeolites 1987, 7, 11.
17. Corma, A .; Forns, V .; Perez-Pariente, J.; Sastre, E.; Martens,
J. A .; Jacobs, P. A. ACS Symp. Ser. 1988, 368, 555.
18. J acobs, P. A. Carboniogenic A ctivity of Zeolites; Elsevier:
Amsterdam, 1977.
19. Sun, Y .; Lunsford, J . H. unpublished results.
20. Carvajal, R.; Chu, P.-J.; Lunsford, J. II. J . Catal., in press.

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1. LUNS FORD Strong Acidity in Dealuminated Zeolite-Y 11
21. Newsam, J. M .; Treacy, M. M. J.; Vaughan, D. E. W.; Strohmaier,
K. G.; Mortier, W. J. J . Chem. Soc., Chem. Commun. 1989, 493.
22. Marynen, P.; Maes, A.; Cremers, A. Zeolites 1984, 4, 287.
23. Cheetham, A. K.; Eddy, M. M.; Thomas, J. M. J. Chem. Soc.,
Chem. Commun. 1984, 1337.
24. Shannon, R. D.; Gardner, K. H.; Staley, R. H.; Bergeret, G.;
Gal l ezot, P.; Auroux, A. J. Phys. Chem. 1985, 89, 4778.
REC EI V ED September 17, 1990

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Chapter 2
Influence of Superaci d Sites i n Ul trastabl e
Y Zeolites on Gas Oi l Cracki ng
A. Corma, V. Forns, F. A. Mochol, J. B. Montn, and F. Rey
Instituto de Tecnologa Qumica, UPV-CSIC, Universidad Politcnica
de Valencia, Camino Vera S/N, 46071 Valencia, Spain
Gasoil Cracking has been carried out on two USY
samples with unit cel l sizes of 24.47 and 24.31 ,
which were steamed at 650 and 650 plus 725C,
respectively. The results were compared with those
obtained with the same series of samples after
removing most of the extraframework aluminum (EFA L )
by (NH
4
)
2
SiF
6
treatment. In the zeolite steamed at
lower temperature, the chemical treatment produces
a strong decrease on the cracking activity. This
decrease is not due to surface framework
dealumination, as shown by XPS analysis and n-
-heptane cracking, but to the absence of EFAL. The
removal of EFAL also produces an increase in gas
and coke formation. Much less marked effects are
observed on the high temperature steamed zeolites
after being chemically treated. Gasoil cracking,
activity and selectivity of the 24.47 USY sample
after removing EFAL and being subject to an
ulterior high temperature steaming gives slightly
less gases and coke and more gasoline than a USY
sample with the same unit cel l size but containing
all the EFAL.
Most of the actual refineries are using high octane
catalysts based on ultrastable Y zeolite (USY).
Ultrastabilization is achieved by increasing the
framework Si /Al ratio of the zeolite by either steam
(1,2), chemical treatments (3-5) or a combination of both
(6) . If a partial dealumination of the Y zeolite is
carried out during the manufacturing of the catalyst, the
ulterior dealumination in the FCC unit becomes slower,
and more crystal l i ni ty is retained. If partially NH
4
+
exchanged NH
4
NaY zeolite is steam calcined, a slow
0097-6156/91/0452-0012$06.00/0

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2. CORMA ET AL. Influence of Superacid Sites in USY Zeolites 13
framework d eal u mi n at i on oc c u rs wh i l e s i l i c o n m i g r a t i o n t o
s t a b i l i z e t h e d e f e c t s s i t e s t akes p l a c e ( 1 ) . Fo l l o w i n g
t h i s p roc ed u re, t h e ext raframework aluminum (EFAL)
remai n s i n t h e z e o l i t e and i t s ex ac t n at u re and t h e r e f o r e
i t s c a t a l y t i c r o l e depends on t h e method and c o n d i t i o n s
u s ed f o r i t s format i on ( 7 , 8 ) . The c a t a l y t i c r o l e of EFAL
d u r i n g g a s o i l c r a c k i n g i s a mat t er of d i s c u s s i o n . T h ere
are s t u d i e s wh i c h c l a i m a n eg at i v e r o l e f o r t h e EFAL
component (9) as r e s p o n s i b l e f o r a non s e l e c t i v e
c r a c k i n g . Ot h ers (8,10) c l a i m t h a t some EFAL p l a y s a
p o s i t i v e r o l e b y en h an c i n g t h e B ron s t ed a c i d i t y of t h e HF
and LF h y d rox y l g rou p s . T h i s r o l e i s s p e c i a l l y e f f e c t i v e
i n s amp l es steamed a t mod erat ed t emp erat u res ( 1 1 ) . The
EFAL p res en t i n an e q u i l i b r i u m c a t a l y s t i s i n t h e form of
c on d en s ed t y p es of al u mi n a, and i t i s b e l i e v e d (11) t h a t
i t i s a c t i v e f o r b ot t oms c on v ers i on and Li g h t C y c l e O i l
(LCO) p rod u c t i on , b u t on t h e ot h er hand g i v e s c oke and
d ry g as . I n ord er t o e l i m i n a t e t h e n eg at i v e e f f e c t s , a
p roc ed u re b as ed on an ( NH
4
)
2
S i F
6
t reat men t (4) h as b een
c ommerc i al l y d ev el op ed wh i c h i s ab l e t o e x t r a c t aluminum
wh i l e r e p l a c i n g b y s i l i c o n and remov i n g t h e EFAL from t h e
z e o l i t e . However, and b y f o l l o w i n g t h i s t reat men t , no
more t h an 40% of t h e A l c on t ai n ed i n a Y z e o l i t e c an b e
removed u n d er ec on omi c al l y c omp et i n g p roc ed u res (12) .
Nev ert h el es s , when t h e p red eal u mi n at i on i s c a r r i e d ou t b y
t h i s p roc ed u re, t h e e q u i l i b r i u m c a t a l y s t h as s t i l l EFAL
p res en t when t h e z e o l i t e b ecomes f u r t h e r d eal u mi n at ed i n
t h e u n i t . I t i s p o s s i b l e t o e l i m i n a t e t h e EFAL formed
d u r i n g t h e u l t r a s t a b i l i z a t i o n b y s t eam t reat men t , b y a c i d
l e a c h i n g ( 6 , 1 3 ) . However, t h e p roc ed u re w i l l a l s o remove
A l from t h e framework, and p rob ab l y w i l l g en erat e a
framework S i / A l g r a d i e n t al on g t h e c r y s t a l .
I n a p rev i ou s p ap er (14) we h av e shown t h a t b y an
ad eq u at e t reat men t of steam d eal u mi n at ed Y z e o l i t e s wi t h
( NH
4
)
2
S i F
6
i t i s p o s s i b l e t o remove s e l e c t i v e l y t h e EFAL.
The p h y s i c oc h emi c al c h a r a c t e r i z a t i o n of t h es e s amp l es
shows t h a t t h e p res en c e of EFAL i s t h e r e s p o n s i b l e f o r
t h e format i on of s u p erac i d s i t e s , as w e l l as f o r t h e
n e u t r a l i z a t i o n of a p a r t of framework h y d rox y l s .
I n t h i s work we have s t u d i e d t h e e f f e c t of t h e
e l i m i n a t i o n of t h e EFAL on t h e g a s o i l c r a c k i n g b eh av i ou r
of t h e z e o l i t e s .
E x p eri men t al
Samples USY-1, USY-2 and U1F-25, U2F-15, U2F-35 were
ob t ai n ed f o l l o w i n g t h e p roc ed u re d e s c r i b e d i n t h e
p rev i ou s p ap er ( 1 4 ) . Moreov er, a new USY sample (U1F-
25S) was ob t ai n ed b y s t eami n g sample U1F-25 a t 7 50
a
C and
100% steam d u r i n g 5 h ou rs . A c i d i t y measurements were
c a r r i e d ou t on wafers of 10 mg.cm"
2
p r e v i o u s l y d eg as s ed i n
a I.R. c e l l a t 4 00
Q
C and 10"
3
Pa, ov ern i g h t . 6.66.10
2
Pa
of p y r i d i n e were i n t rod u c ed i n t o t h e c e l l a t room
t emp erat u re. A f t e r e q u i l i b r i u m , t h e s amp l es were

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ou t g as s ed at t emp erat u res of 250, 350 and 4 00
a
C u n d er
vacuum, and t h e s p e c t r a i n t h e 1800-1300 cm" r e g i o n
rec ord ed a t room t emp erat u re. I n t e n s i t i e s of t h e b ands
at 1540 cm"
1
( B ron s t ed s i t e s ) and 1450 cm" ( Lewi s s i t e s )
and ap p aren t e x t i n c t i o n c o e f f i c i e n t s r e p o r t e d b y Hughes
and Wh i t e (15) were u s ed t o d et ermi n e t h e amount of a c i d
c e n t e r s .
XPS measurements were p erformed f o l l o w i n g t h e
ex p eri men t al c o n d i t i o n s p r e v i o u s l y p u b l i s h e d ( 1 6 ) .
C rac ki n g c a t a l y s t s were p rep ared b y d i l u t i n g t h e
z e o l i t e s i n a h i g h s u r f a c e s i l i c a mat ri x . A vacuum
g a s o i l was c rac ked at 4 8 2
C
C i n a t u b u l a r f i x e d b ed
r e a c t o r . The c a t a l y s t t o o i l r a t i o ( g . z e o l i t e / g . g a s o i l )
was v a r i e d b etween 0.1 and 1.1 g.g"
1
, i n ord er t o o b t a i n
d i f f e r e n t l e v e l s of c on v ers i on , t h e t i me on s t ream was
al way s kep t a t 60 s ec on d s . In t h i s way i t i s p o s s i b l e t o
o b t a i n t h e y i e l d s of g a s o l i n e , d i e s e l , g as es and c oke, a t
d i f f e r e n t l e v e l s of c on v ers i on , and t h e r e f o r e t o compare
t h e s e l e c t i v i t i e s of t h e d i f f e r e n t c a t a l y s t s a t t h e same
l e v e l of c on v ers i on . The c a t a l y s t s were reg en erat ed "i n
s i t u " a f t e r eac h exp eri men t b y p as s i n g 6 ml.h"
1
fl ow of
a i r at 530C f o r 5 h ou rs . Gas es were an al y z ed b y GC and
s ep arat ed wi t h a Poropak-Q p l u s s i l i c a c ol u mn . Li q u i d s
were an al y z ed b y S i mu l at ed D i s t i l l a t i o n .
C rac ki n g of n -h ep t an e was c a r r i e d ou t on c a t a l y s t s
USY-1 and U1F-25 i n a c on t i n u ou s fl ow, f i x e d b ed r e a c t o r
( 1 5) , at 4 50
a
C and at mos p h eri c p res s u re. I n a l l
exp eri men t s , 0.223 g of z e o l i t e c a t a l y s t , and 8.625 g of
n -h ep t an e were u s ed . Wi t h eac h c a t a l y s t t h e r e a c t i o n was
p erformed at 75, 150 and 375 s ec on d s of t i me on s t ream.
The c a t a l y s t was reg en erat ed "i n s i t u " a f t e r eac h
exp eri men t b y p as s i n g fl ow of a i r at 52 0
a
C d u r i n g 4
h ou rs , and l i q u i d s were an al y z ed b y GC b y means of a
Porapak-Q s i l i c a and a S-30 c ol u mn s r e s p e c t i v e l y .
Re s u l t s and Di s c u s s i o n
The c h a r a c t e r i s t i c s of a l l s amp l es are g i v en i n T ab l e 1,
wh i l e a c i d i t y measurements at d i f f e r e n t d eg as s i n g
t emp erat u res are summariz ed i n T ab l e 2.
C rac ki n g a c t i v i t y
Fi g u r e l a shows t h e a c t i v i t y of s amp l es USY-1 and UF1-25
f o r g a s o i l c r a c k i n g . I t b ecomes ap p earen t t h a t t h e
e x t r a c t i o n of EFAL b y t h e ( NH
4
)
2
S i F
6
t reat men t h as
d ec reas ed t h e a c t i v i t y of t h e z e o l i t e c a t a l y s t ,
ev en t h ou g h t h e b u l k framework S i / A l r a t i o h as remai n ed
p r a c t i c a l l y unchanged a f t e r t h e c h emi c al t reat men t ( T ab l e
1) . I f one t r i e s t o e x p l a i n t h i s b eh av i ou r on l y on t h e
b as es of t h e framework A l , and s i n c e t h e g a s o i l c r a c k i n g
t akes p l a c e mai n l y a t t h e e x t e r n a l s u r f a c e of t h e z e o l i t e
c r y s t a l l i t e s , one c o u l d t h i n k t h a t ev en t h ou g h t h e b u l k
framework S i / A l h as n ot b een c h an g ed b y t h e c h emi c al

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16 FLUID CATALYTIC CRACKING H: CONCEPTS IN CATALYST DESIGN
t reat men t , t h e ( NH
4
)
2
S i F
6
, b es i d es remov i n g t h e EFAL h as
d eal u mi n at ed p r e f e r e n t i a l l y t h e framework of t h e s u r f a c e
of t h e c r y s t a l l i t e s . I n ord er t o c h ec k t h a t p o s s i b i l i t y
t h e s u r f a c e S i / A l r a t i o of s amp l es USY-1 and U1F-25 h av e
b een measured b y XPS and t h e r e s u l t s are g i v e n i n T ab l e
1. T h ey show t h a t , as h as b een p r e v i o u s l y p res en t ed
( 1 7 , 1 8 ) , i n t h e c as e of steam d eal u mi n at ed s amp l es , a
s e n s i b l e amount of EFAL mi g rat es t o t h e s u r f a c e of
c r y s t a l l i t e s d ec reas i n g t h e s u r f a c e S i / A l r a t i o wi t h
r e s p e c t t o t h a t of t h e b u l k. The XPS a n a l y s i s of t h e
T ab l e 2. B ron s t ed and Lewi s a c i d i t y , meas u red as
mmols of p y r i d i n e ad s orb ed at d i f f e r e n t
t emp erat u res
B ron s t ed Lewi s
SAMPLE 250C 3 50
a
C 4 00
a
C 250C 350
f l
C 400
f i
C
USY-1 167 109 60 52 40 35
U1F-25 302 169 101 23 19 19
U1F-25S 10 5 4 4 2 2
USY-2 26 16 8 23 15 9
U2F-15 134 80 30 83 75 68
U2F-35 145 74 23 27 25 25
USY-3 14 7 4 15 6 4
z e o l i t e a f t e r t h e ( NH
4
)
2
S i F
6
t reat men t of t h e steamed
sample, d oes n ot i n d i c a t e u n eq u i v oc al y a p r e f e r e n t i a l
d eal u mi n at i on of t h e framework at t h e s u r f a c e . I n f a c t ,
t h e s u r f a c e S i / A l r a t i o i s c l o s e , b u t s l i g h t l y l ower,
t h an t h a t of t h e b u l k, s omet h i n g wh i c h c an b e e x p l a i n e d
b y t h e remai n i n g 2 EFAL p er u n i t c e l l wh i c h h av e n ot b een
e x t r a c t e d . The XPS r e s u l t s are i n f a v o r of t h e
h y p ot h es i s t h a t t h e ( NH
4
)
2
S i F
6
h as b een u s ed t o e x t r a c t
EFAL and v ery l i t t l e , i f any , i n e x t r a c t i n g framework A l
from t h e c r y s t a l l i t e s s u r f a c e . However, on t h e b as es of
t h e XPS r e s u l t s we c an n ot c omp l et el y r u l e d ou t t h e
p o s s i b i l i t y of a framework d eal u mi n at i on a t t h e s u r f a c e
and t h e r e f o r e t o r e j e c t c omp l et el y t h e h y p ot h es i s made
ab ov e. What b ecomes c l e a r , however i s t h a t , ev en i f a
c e r t a i n d e p l e t i o n of t h e FAL h as oc c u rred a t t h e s u r f a c e
of t h e c r y s t a l l i t e s , most of t h e b u l k framework S i / A l
r a t i o h as remai n ed p r a c t i c a l l y u n c h an g ed . Then, i f we
p erform a c r a c k i n g r e a c t i o n wi t h a r e a c t a n t , n -h ep t an e,
wh i c h c an e a s i l y p en et rat e i n s i d e of t h e z e o l i t e , i f t h e
s i t e s a s s o c i a t e d t o framework A l are t h e on l y r e s p o n s i b l e
f o r t h e c r a c k i n g we s h ou l d n ot exp ec t d i f f e r e n c e s i n
a c t i v i t y b etween s amp l es USY-1 and U1F-25. I n any c as e,
i t i s c l e a r t h a t i n t h i s c as e t h e s u r f a c e e f f e c t c l ai med
f o r t h e g a s o i l wou l d b e n e g l i g i b l e .

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CORMA ET AL. Influence of Superacid Sites in USY Zeolites
Conversion (%)
Conversion (%)
Conversion (%)
Fi g u r e 1. G a s -o i l c r a c k i n g a c t i v i t y of s amp l es
USY-1 () and U1F-25 ( ) ; b ) USY-2 ( ) , U2F-
( ) and U2F-35 ( A ) ; c) USY-3 ( ) and U1F-25S

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Re s u l t s from Fi g u re 2, show t h a t sample U1F-25 i s
ab ou t 30% l e s s a c t i v e t h an sample USY-1 f o r n -h ep t an e
c r a c k i n g . T h i s r e s u l t c l e a r l y shows t h a t t h e s i t e s
a s s o c i a t e d t o framework A l are n ot t h e on l y ones
r e s p o n s i b l e f o r t h e c r a c k i n g a c t i v i t y , and a l s o t h a t t h e
d i f f e r e n c e s i n g a s o i l a c t i v i t y g i v en i n Fi g u r e l a are
r e l a t e d wi t h t h e p res en c e of t h e EFAL.
I n t h e p rev i ou s p ap er (14) we have shown t h a t t h e
( NH
4
)
2
S i F
6
t reat men t of r e l a t i v e l y low t emp erat u re steamed
s amp l es p rod u c es an i n c r e a s e i n t h e i n t e n s i t y of t h e HF
and LF h y d rox y l s due t o exchange of c a t i o n i c s p e c i e s
(A10
+
, A1(0H) , e t c . . ) b y p rot on s , as w e l l as an
i n c r e a s e i n t h e B ron s t ed a c i d i t y measured b y p y r i d i n e
a d s o r p t i o n -d e s o r p t i o n ( T ab l e 2 ) . On t h e ot h er hand, t h e
( NH . )
2
S i F
6
t reat men t , removes n ot on l y t h e EFAL s p e c i e s
g i v i n g non a c i d i c OH g rou p s at 3670 and 3610 cm b u t a l s o
t h os e s p e c i e s d i r e c t l y or i n d i r e c t l y r e s p o n s i b l e f o r t h e
v ery s t ron g a c i d h y d rox y l g rou p s a t 3600 and 3525 cm"
1
( 1 4 , 1 9 ) . A f t e r t h e a c i d i t y measurements ( p y r i d i n e
a d s o r p t i o n -d e s o r p t i o n i n T ab l e 2 ) , i t b ecomes ap p aren t
t h a t i f on l y t h e a c i d s i t e s a s s o c i a t e d t o t h e HF and LF
h y d rox y l s were a c t i v e f o r c r a c k i n g , t h e a c t i v i t y of
sample U1F-25 s h ou l d b e h i g h er t h an t h a t of sample USY-
1. S i n c e t h e c o n t r a r y i s o c c u r r i n g , we h av e t o c l a i m an
i mp ort an t r o l e of t h os e v ery s t r o n g B ron s t ed a c i d s i t e s
a s s o c i a t e d t o h y d rox y l s ap p eari n g a t 3600 and 3525 cm"
1
,
whose t u rn ov er numb er w i l l b e h i g h er t h an t h a t of t h e
c l a s s i c a l HF and LF h y d rox y l b ands a s s o c i a t e d t o a c i d
s i t e s . The p res en c e of t h os e s u p erac i d s i t e s h as b een
r e l a t e d wi t h t h e p res en c e of EFAL s p e c i e s e i t h e r as i n
t h e form of amorphous s i l i c a -a l u m i n a , an d / or b y
i n t e r a c t i o n of c a t i o n i c EFAL s p e c i e s and B ron s t ed (HF and
LF) a c i d s i t e s ( 1 4 , 1 9 ) .
I n any c as e, i f a USY c r a c k i n g c a t a l y s t i s p rep ared
b y s t e a m -c a l c i n a t i o n fol l owed b y an ( NH
4
)
2
S i F
6
t reat men t
t o remove EFAL, t h e a c t i v i t y of t h e t r e a t e d c a t a l y s t w i l l
b e l ower t h an t h a t of t h e c h e m i c a l l y u n t reat ed one.
When t h e c h emi c al t reat men t i s a p p l i e d t o a sample
p r e v i o u s l y steamed at a h i g h er t emp erat u re (725C) ,
wh i c h wou l d s i mu l at e t h e z e o l i t e i n an e q u i l i b r i u m
c a t a l y s t , on l y a v ery s mal l , i f any , d ec reas e i n a c t i v i t y
i s ob s erv ed ( Fi g . l b ) . The f a c t t h a t when t h e s t eami n g
t emp erat u re i s h i g h (> 7 00
Q
C ) , t h e B ron s t ed s i t e s of
en h an c ed a c i d i t y (b ands a t 3600 and 3525 cm"
1
) are n ot
ob s erv ed ( 8 ) , and on l y t h e HF and LF b ands are p res en t
(8) , w i l l e x p l a i n t h e a c t i v i t y b eh av i ou r ob s erv ed f o r
s amp l es USY-2 and U2F-35.
I t remai n s one s e t of s amp l es t o b e d i s c u s s e d , and
t h i s i s t h e sample U1F-25 a f t e r s t eami n g a t 7 50
a
C (U1F-
25S) and an USY sample of s i m i l a r u n i t c e l l s i z e (USY-3) .
T h i s t reat men t wou l d s i mu l at e t h e b eh av i ou r of a

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2
Conversi on (%)
10
r
T. O. S. (s)
Fi g u r e 2. N-heptane c r a c k i n g a c t i v i t y of s amp l es
USY-1 ( O) and U1F-25 ( ) .

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20
FLUID CATALYTIC CRACKING H: CONCEPTS IN CATALYST DESIGN
c l a s s i c a l USY z e o l i t e a f t e r c h emi c al t reat men t t o remove
a l l EFAL and u l t e r i o r e q u i l i b r i u m i n t h e u n i t . Re s u l t s
from Fi g u r e l c , show t h a t sample U1F-25S p res en t a
s i m i l a r a c t i v i t y t h a t USY-3.
C rac ki n g S e l e c t i v i t y
I n Fi g u r e 3 t h e y i e l d s f o r g as es , g a s o l i n e , d i e s e l and
c oke a t d i f f e r e n t l e v e l s of c on v ers i on are g i v en f o r
s amp l es USY-1 and U1F-25. I t c an b e s een t h ere t h a t when
e x t r a c t i n g t h e EFAL of t h e l ower t emp erat u re steam
d eal u mi n at ed sample (U1F-25), t h e s e l e c t i v i t y t o g as es
and c oke i n c r e a s e s wh i l e t h a t t o g a s o l i n e and d i e s e l
d ec reas es . S i n c e t h e ( NH
4
)
2
S i F
6
t reat men t of sample USY-
1 p rod u c es t h e d i s ap p earan c e of t h e s t r o n g B ron s t ed a c i d
s i t e s , and t h e i n c r e a s e of t h e i n t e n s i t y of t h e HF and LF
h y d rox y l b an d s , t h e n et r e s u l t of t h e c h emi c al t reat men t
i s an i n c r e a s e i n t h e d e n s i t y of c l a s s i c a l framework a c i d
s i t e s . T h i s , i n t u r n , w i l l make t h e sample more s i m i l a r
t o one steamed a t a l ower t emp erat u re and t h e r e f o r e more
s i m i l a r t o a sample wi t h a u n i t c e l l s i z e h i g h e r t h an
24.47 A. Re s u l t s from Fi g u r e 4 shows t h a t when g a s o i l
c r a c k i n g i s c a r r i e d ou t on s amp l es wi t h h i g h u n i t c e l l
s i z e s (> 24.47 A) t h e s e l e c t i v i t y t o g as es and c oke
i n c r e a s e s when i n c r e a s i n g u n i t c e l l s i z e , wh i l e t h a t t o
g a s o l i n e and d i e s e l d ec reas es . T h es e r e s u l t s wou l d
s u g g es t t h a t Y z e o l i t e c a t a l y s t s wi t h low a c i d s t r e n g t h ,
i . e . z e o l i t e Y wi t h h i g h d e n s i t y of a c i d s i t e s and low
d e n s i t y of s u p erac i d s i t e s (3600 and 3525 cm"
1
) , n ot on l y
are l e s s a c t i v e f o r c r a c k i n g , b u t t h e c r a c k i n g
s e l e c t i v i t y b eh av i ou r w i l l ap p roxi mat e more t o t h a t of
s amp l es steamed a t low t emp erat u res .
Then, we do n ot s ee any a c t i v i t y and s e l e c t i v i t y
b e n e f i t , from t h e p o i n t of v i ew of t h e f r e s h c a t a l y s t b y
i n t r o d u c i n g , i n f r e s h USY c r a c k i n g c a t a l y s t a z e o l i t e
i n wh i c h most of t h e EFAL h as b een removed.
I n t h e c as e of t h e h i g h er t emp erat u re steamed sample
USY-2, t h e ( NH
4
)
2
S i F
6
t reat men t d oes n ot p rod u c es b i g
c h an g es i n s e l e c t i v i t y b u t a s mal l d ec reas e i n d ry g as es
and d i e s e l ( Fi g . 5) . T h i s i n d i c a t e s t h a t t h e al u mi n a
t y p e EFAL formed a t h i g h t emp erat u res p l a y s a p o s i t i v e
r o l e f o r c r a c k i n g b ot t oms , b u t a l s o p rod u c es more d ry
g as es .
I n t h e c as e of z e o l i t e U1F-25S, t h e r e s u l t s from
Fi g u r e 6 show t h a t t h i s sample p rod u c es l e s s g as es and
c oke and more g a s o l i n e t h an sample USY-3. T h es e r e s u l t s
wou l d b e i n agreement wi t h t h e h y p ot h es i s made ab ove,
t h a t al u mi n a t y p e EFAL, wh i l e b ei n g a c t i v e f o r b ot t oms
c on v ers i on i s l e s s s e l e c t i v e f o r g a s o l i n e and more
s e l e c t i v e f o r g as es and c oke.

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Fi g u r e 3. S e l e c t i v i t y t o g as es , CI + C2, G as ol i n e,
Di e s e l , Coke and B u t en e/ B u t an e r a t i o of s amp l es
USY-1 () and U1F-25 () i n g a s - o i l c r a c k i n g .

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.

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Fi g u r e 5. S e l e c t i v i t y t o Gas es , CI + C2, G as ol i n e,
Di e s e l , Coke and B u t en e/ B u t an e r a t i o of s amp l es
USY-2 ( ) , U2F-15 ( ) and U2F-35 ( ) i n g a s - o i l
c r a c k i n g .

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Fi g u r e 6. S e l e c t i v i t y t o Gas es , CI + C2, G as ol i n e,
Di e s e l and Coke f o r s amp l es USY-3 ( ) and U1F-25S
( ) i n g a s - o i l c r a c k i n g .

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Acknowledgments
Fi nanci al support by the CICYT (project MAT 88-0147) is
gratefully acknowledged.
L i t e r a t u r e Ci t e d
1.McDa ni e l, C.V.; Maher, P.K. Z e o l i t e Che mi st r y and
Ca t a l y s i s , Rabo, J.A., CS Monograph 171, Washingto n
DC, 1976, p.285.
2.Ward, J.W. J. Ca t a l . 1970 18, 348.
3.Be ye r , H.K.; Be le nka ja , I. Ca t a l y s i s by Z e o l i t e s ,
Ime li k ., Ed., St u d . Su r f . Sc i . Ca t a l . , Amsterdam,
1980, 5, p. 203.
4.Ske e ls, G.W.; Br e ck, D.W. Pr o c. 6t h In t e r . Z e o l.
Co nf., Reno, Nevada, 1983.
5.Ke r r , G.T. J. Phys. Chem. 1968, 72, 2594.
6.Sche r ze r , J. Ca t a l . Rev. Sci. Eng. 1989, 31, 215.
7.Corma, A.; Forns, V.; Mart nez .; Sanz, J. F l u i d
Ca t a l y t i c Cr a cki ng. Ro le in Modern Re f i n i n g, Oc c e l l i ,
M., Ed., ACS Symp. Se r ., 375, Chap. 2, 1988, p. 17.
8.Corma, .; Forns, V.; Mart nez , .; Orchills, A.V.
P ers p ec t i v es i n Molecular Sieve Science, Flank, W.H.;
Whyte Jr., T.E., Eds., ACS Symp. Ser. 368, Chap. 35,
1988, p. 542.
9.Rel l ed , R.J.; B l ac kwel l , C.S.; Rabo, J.A. J. C at al . ,
1988, 114, 71.
10.B ey erl ei n , R.A.; McV icker, G.B.; Y ac u l l o, L.N.;
Ziemiak, J. J. J. Phys. Chem., 1988, 92, 1967.
11.Corma, ., 8 IZ C, Z e o l i t e s : F a ct s, F i gu r e s, F u t u r e ,
Ja co bs, P.A.; va n Sa nt e n, R.A., Eds., St u d . Su r f . Sci.
Ca t a l . , 1989, 49, p.49.
12.Ga r r a ln, G.; Forns, V.; Corma, A. Z eol i t es , 1988,
8, 268.
13.Macedo, .; Ra a t z, F.; Bo u le t , R.; Ja ni n, .;
L a va l l e y , J.C. Inno va t i o n i n Z e o l i t e Ma t e r i a l s
Sci e nce , Gr o be t , P.J.; Mo r t i e r , .J.; Va nsa nt , E.F .;
Sc hu l z - Ek l o f f , G., Eds., St u d . Su r f . Sc i . Ca t a l . ,
E l s e vi e r , Amsterdam, 1988, 37, p.375.
14.Corma, .; Forns, V.; Rey, F. Ap p l i ed C at al y s i s 1990,
59, 267.
15.Hughes, T.R.; While, H.M. J. Phy s. Chem. 1967, 71,
2191.
16.Corma, .; Forns, V.; Mart nez , .; Melo , F.;
Pa l l o t a , . Inno va t i o n i n Z e o l i t e Ma t e r i a l Sci e nce ,
Gr o be t , P.J., Ed., St u d . Su r f . Sc i . Ca t a l . , 1988,
37, 495.
17.Dwyer, J.; F i t c h, F.R.; Machado, F .; Qu i n, G.; Smyth,
S.M.; Vi cke r ma n, J.C. J. Chem. So c. Chem. Commun.,
1981, 422.
18.Andrea, V.; Kub elkov, L.; Novkov, J.; Vichterlov
.; Bednarv, S. Z eol i t es 1985, 5, 67.
19.Garral n, G. ; Cor ma, .; Forns, V.; Z eol i t es 1988,
9, 84.

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20. Fichtner-Schmittler, H. ; Lohse, U. ; Engelhard, G. ;
Patzelov, V. Cri st. Res. Technol. 1984, 19, K1-K3,
1.
21.Sohn, J. R. ; De Canio, S.J.; Lunsford, J.H.; O'Donnell,
D. J. Zeolites, 1986, 6, 225.
REC EI V ED June 8, 1990

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Chapter 3
Characterization of Zeolite-Cracking Catalysts
G. T. Kokotailo, C. A. Fyfe, Y. Feng, and H. Grondey
Department of Chemistry, University of British Columbia,
Vancouver, British Columbia V6T 1Y6, Canada
The revolutionary zeol i te cracking catalyst (syn-
thetic Linde X and Y) was introduced commercially over
28 years ago, but considerable effort i s still being
expended on the improvement of its stability and cat-
alytic properties. Decreasing the aluminumcontent of
the zeol i te framework and the replacing the rare-
-earth with thehydrogen formhave greatly increased
activity at the expense of stability. Thethermal
stability of the faujasites i s fairly wel l under-
stood, while the reasons for the increased catal yti c
activitity are still not fully known.
The use of tradi ti onal and new techniques to
elucidate the structure of synthetic faujasites with
different silica alumina rati os, dealuminated by
steaming and chemical treatment, and with and without
faulting will bedescribed. Themigration and fixa-
tion of cations and the role of aluminum in the
dealumination of the zeol i te will be discussed.
Very clean and highly dealuminated samples have
been prepared that have removed some of the variables
i n determining the state of the framework and extra-
-framework aluminum.
T h e r e p l a c e me n t o f amo r p h o u s s i l i c a a l u mi n a c r a c k i n g c a t a l y s t s w i t h
s y n t h e t i c f a u j a s i t e s was a t r e me n d o u s s t e p f o r wa r d a n d r a p i d l y c ame
t o d o mi n a t e t h e p e t r o l e u m r e f i n i n g i n d u s t r y . T h e u s e o f t h e r a r e -
e a r t h - e x c h a n g e d f o r m o f s y n t h e t i c f a u j a s i t e ( L i n d e X) i n c r a c k i n g
c a t a l y s i s r e s u l t e d i n a l a r g e i n c r e a s e i n c r a c k i n g a c t i v i t y a n d
g a s o l i n e " mak e " wh i l e r e d u c i n g g a s a n d c o k e f o r ma t i o n . I n c r e a s e s
o f u p t o 4 0 % i n y i e l d we r e a t t a i n e d b y 19 6 2 . Mo b i l ' s z e o l i t e - b a s e d
c r a c k i n g c a t a l y s t , D u r a b e a d 5 (1) , was i n c o mme r c i a l u s e a n d p r o -
v i d e d t h e i mp e t u s f o r f u r t h e r r e s e a r c h . T h e r a r e - e a r t h f o r m o f
0097-6156/91/0452-0027$06.00/0

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28
z e o l i t e Y ( RE Y ) r a p i d l y r e p l a c e d t h e X f o r m b e c a u s e Y o f f e r e d
i mp r o v e d c h e mi c a l a s w e l l a s h y d r o t h e r ma l s t a b i l i t y . RE Y h a s s i n c e
b e e n r e p l a c e d b y u l t r a s t a b l e HY ( U S Y ) . To c o mp e n s a t e f o r s o me l o s s
i n h y d r o t h e r ma l s t a b i l i t y , s o me RE HY may b e a d d e d .
R e c e n t l y t h e e f f e c t o f s t e a mi n g o n t h e p r e s e n c e o f f r a me wo r k
a n d e x t r a - f r a me wo r k a l u mi n i u m a n d i t s e f f e c t o n c a t a l y t i c a c t i v i t y
h a s b e e n t h e s u b j e c t o f a c o n s i d e r a b l e r e s e a r c h e f f o r t .
T h e F a u j a s i t e / Z S M- 2 0 F a mi l y
F a u j a s i t e i s a r a r e a l u mi n o s i l i c a t e mi n e r a l . I t s s y n t h e t i c h i g h -
a l u mi n i a c o u n t e r p a r t , L i n d e X, was s y n t h e s i z e d b y M i l t o n ( 2 ) , a n d
L i n d e Y , a h i g h - s i l i c a / a l u mi n a s y n t h e t i c f a u j a s i t e , was s y n t h e s i z e d
b y B r e c k ( 3 ) . T h e f r a me wo r k o f f a u j a s i t e - t y p e z e o l i t e s h a s b e e n
w e l l e s t a b l i s h e d b y B e r g e r h o f f e t a l . ( A) a n d B r o u s s a r d a n d
S h o e mak e r ( 5 ) .
T h e f r a me wo r k s t r u c t u r e i s s h o wn i n F i g . l a . T h e b a s i c b u i l d -
i n g b l o c k i s a s o d a l i t e c a g e . L a y e r s f o r me d b y l i n k i n g s o d a l i t e
c a g e s t h r o u g h d o u b l e s i x - me mb e r e d r i n g s ( D6 MR) a r e l i n k e d a l s o
t h r o u g h D6 MR t o g i v e a d i a mo n d - t y p e s t r u c t u r e , s p a c e g r o u p F d3 m,
wi t h f o u r 12 MR o p e n i n g s t o e a c h l a r g e c a g e . Th e l a y e r s a r e s t a c k e d
i n an AB S s e q u e n c e . I f e v e r y s e c o n d l a y e r i s r o t a t e d s o t h a t t h e
s t a c k i n g o f s u p e r c a g e s a l o n g [ 111] c u b i c o r [ 0 0 1] h e x a g o n a l i s
AB AB , a h e x a g o n a l f r a me wo r k r e s u l t s , wi t h f i v e 12 MR o p e n i n g s t o
e a c h s u p e r c a g e . T h e t wo o p e n i n g s t o t h e c a g e s i n t h e 0 0 1 d i r e c -
t i o n s a r e p l a n a r , wh i l e t h o s e p e r p e n d i c u l a r t o [ 0 0 1] a r e n o n p l a n a r
a n d e l l i p t i c a l ( F i g . l b ) . T h e s e t wo f r a me wo r k s a r e t h e e n d me mb e r s
o f a f a mi l y o f s t r u c t u r e s wi t h o t h e r s v a r y i n g o n l y i n t h e s t a c k i n g
s e q u e n c e . T h e r e l a t i o n s h i p o f t h e l a t t i c e p a r a me t e r s o f t h e t wo
s t r u c t u r e s i s g i v e n b y
a 2 a
a
H
= ^ a n d c
H
= ^ ( 1)
T h e s y mme t r y o f t h e h e x a g o n a l f o r m, Z S M- 2 0 , i s P 6
3
/ mmc .
Wh e n s t a c k i n g f a u l t s a r e i n t r o d u c e d i n t h e c u b i c f a u j a s i t e
s t r u c t u r e , t h e r e f l e c t i o n s wi t h H - K = 3 N a n d L = 3 N' ( wh e r e N a n d
N' a r e i n t e g e r s ) r e ma i n s h a r p , b u t t h e o t h e r r e f l e c t i o n s b r o a d e n
an d t h e i r max i ma s h i f t i n o p p o s i t e d i r e c t i o n s . Man y o f t h e l i n e
p r o f i l e s i n t h e f a u l t e d s t r u c t u r e s a r e a s y mme t r i c , wi t h l i n e b r o a d -
e n i n g du e t o t h e s i z e o f t h e c r y s t a l s a n d t h e d o ma i n s . C i r i c s y n -
t h e s i z e d t h r e e me mb e r s o f t h i s f a mi l y : Z S M- 2 0 ( 6 ) , wh i c h i s t h e
h e x a g o n a l f o r m wi t h s o me s t a c k i n g f a u l t s ( 7 , 8 ) , i s s y n t h e s i z e d f r o m
a l u mi n o s i l i c a t e g e l s c o n t a i n i n g t e t r a e t h y l a mmo n i u m ( TE A) c a t i o n s ;
ZS M- 3 ( 9 ) , wh i c h h a s a n i n e - l a y e r s e q u e n c e a n d c o n s i d e r a b l y mo r e
s t a c k i n g f a u l t s ( 1 0 ) , i s s y n t h e s i z e d i n t h e L i
2
0 - N a
2
0 - A l
2
0
3
- S i 0
2
-
H
2
0 s y s t e m; ZS M- 2 ( j j . ) h a s a r an d o m s t a c k i n g s e q u e n c e , p r o b a b l y
c l o s e r t o f a u j a s i t e a n d i s a l s o c r y s t a l l i z e d i n a L i
2
0 - N a
2
0 b a s e .
CS Z - 1 i s a d i s t o r t e d f a u j a s i t e f r a me wo r k wi t h r h o mb o h e d r a l r a t h e r
t h a n c u b i c s y mme t r y ( 12 ) a n d i s c r y s t a l l i z e d f r o m a l u mi n o s i l i c a t e
g e l s c o n t a i n i n g c e s i u m.
I n t e r g r o wt h s a n d s t a c k i n g f a u l t s i n z e o l i t e Y a n d Z S M- 2 0 h a v e
b e e n o b s e r v e d b y l a t t i c e i ma g i n g u s i n g h i g h - r e s o l u t i o n e l e c t r o n -
mi c r o s c o p y t e c h n i q u e s . T h e s u p e r c a g e s a n d t h e i r l i n k a g e s a r e r e a d -
i l y o b s e r v e d , p r o v i d i n g d i r e c t i n f o r ma t i o n r e g a r d i n g l o c a l a n d

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3. KOKOTAILO ET AL. Characterization of Zeolite-Cracking Catalysts 29
l o n g - r a n g e o r d e r i n g o f b u i l d i n g b l o c k s o r l a y e r s i n z e o l i t e s .
R e c u r r i n g o r r an do m t wi n n i n g may h a v e a n e f f e c t o n i o n e x c h a n g e ,
t h e S i / A l r a t i o , a n d a l s o e a s e o f d e a l u mi n a t i o n .
T h e o c c u r r e n c e o f i n t e r g r o wt h s o f z e o l i t e Y an d Z S M- 2 0 , t h e
c u b i c a n d h e x a g o n a l f o r ms , i s a n a l o g o u s t o s i mi l a r i n t e r g r o wt h s i n
S i C a n d Z n S c r y s t a l s . I n t e r g r o wt h s i n z e o l i t e Y a n d Z S M- 2 0 do n o t
b l o c k c h a n n e l s , a s i s t h e c a s e i n t h e e r i o n i t e - o f f r e t i t e f a mi l y ,
wh e r e r o t a t i o n o f c a n c r i n i t e l a y e r s b l o c k s t h e 12 MR c h a n n e l s , b u t
a r e mo r e l i k e i n t e r g r o wt h s i n t h e Z S M- 5 / Z S M- 11 f a mi l y , wh i c h mo d i f y
t h e c h a n n e l s y s t e m.
R e c e n t r e s u l t s h a v e s h o wn t h a t HZ S M- 2 0 i s a p r o mi s i n g c r a c k i n g
c a t a l y s t wi t h h i g h e r i n i t i a l a c t i v i t y a n d t h e r ma l s t a b i l i t y t h a n HY
( _13) . Wi t h Ce H Z S M- 2 0 , t h e c r a c k i n g a c t i v i t y i n c r e a s e d wi t h c e r i u m
e x c h a n g e . T h i s i n c r e a s e i n a c t i v i t y i s a t t r i b u t e d t o t h e f o r ma t i o n
o f h y d r o x i d e b r i d g e s t r u c t u r e s i n v o l v i n g c e r i u m c a t i o n s ( _ 13) . T h e
d i f f e r e n c e i s a t t r i b u t e d t o s t r u c t u r a l d i f f e r e n c e s b e t we e n z e o l i t e
Y a n d Z S M- 2 0 , wi t h g r e a t e r a c c e s s i b i l i t y o f t h e p o r e s t r u c t u r e i n
Z S M- 2 0 du e t o t h e l i n e a r a l i g n me n t o f t h e s u p e r c a g e s .
P i - an d T r i v a l e n t E x c h a n g e o f S y n t h e t i c F a u j a s i t e
Ce r i u m a n d l a n t h a n u m e x c h a n g e o f z e o l i t e X r e s u l t e d i n s o me c h a n g e s
i n t h e p o wd e r - X - r a y - d i f f r a c t i o n p a t t e r n . C a l c i n a t i o n r e s u l t e d i n
f u r t h e r c h a n g e s t h a t we r e n o t r e v e r s i b l e o n r e h y d r a t i o n , i n d i c a t i n g
c h a n g e s i n t h e s t r u c t u r e t h a t we r e s t a b i l i z e d . S i n g l e - c r y s t a l
a n a l y s i s o f c e r i u m- e x c h a n g e d f a u j a s i t e ( c o n t a c t e d wi t h c o n c e n t r a t e d
c e r i u m n i t r a t e f o r s i x mo n t h s ) a n d p o wd e r - d i f f r a c t i o n a n a l y s i s o f
l a n t h a n u m- e x c h a n g e d L i n d e X ( b a t c h e x c h a n g e d a t 10 0 C f o r 13 d a y s )
i n d i c a t e d t h a t r o o m t e mp e r a t u r e e x c h a n g e h a d l i t t l e e f f e c t o n t h e
f a u j a s i t e o r L i n d e - X f r a me wo r k . T h e c a t i o n p o s i t i o n s we r e e s t a b -
l i s h e d a n d t h e s i t e d e s i g n a t i o n s u s e d h e r e a r e t h o s e i n t r o d u c e d b y
P i c k e r t e t a l . ( J L 4 ) . S I i s i n t h e c e n t e r o f t h e h e x a g o n a l p r i s m;
S I
1
i s a d j a c e n t t o S I i n t h e s o d a l i t e c a g e ; S I I
1
i s i n t h e s o d a l i t e
c a g e a n d i s a d j a c e n t t o t h e s u p e r c a g e 6 MR; S I I i s i n t h e s u p e r c a g e
a d j a c e n t t o S I I
1
( F i g . 1 ) . F u l l y h y d r a t e d L a a n d Ce c a t i o n s we r e
l o c a t e d i n t h e c e n t e r o f t h e 12 MR s i t e d e s i g n a t e d S I I I ( L 5 , 1 5 ) . On
c a l c i n a t i o n , t h e f r a me wo r k c h a n g e d v e r y l i t t l e , b u t t h e e x t r a -
f r a me wo r k at o ms u n d e r we n t a c o mp l e t e c h a n g e i n p o s i t i o n s . T h e
C e ( I I I ) i o n s mi g r a t e d t o S I ' a n d f o r me d a t i g h t Ce - 0 L a - 0 c o mp l e x
( F i g . 2 ) . T h e l o c a t i o n o f a l l Re i o n s i n S I * i s o f p a r t i c u l a r
i n t e r e s t , a s a l l t h e c a t i o n s a r e i n t h e s o d a l i t e c a g e , l e a v i n g t h e
s u p e r c a g e v o i d o f me t a l i o n s . T h e 3 o r 4 L a o r Ce i o n s , 4 wa t e r
o x y g e n s , an d 12 l a t t i c e o x y g e n s f o r m an e x t r e me l y s t a b l e c o mp l e x i n
t h e s o d a l i t e c a g e a n d c a n n o t b e b a c k e x c h a n g e d . T h i s g r e a t l y c o n -
t r i b u t e d t o t h e t h e r ma l a n d h y d r o t h e r ma l s t a b i l i t y o f t h e r a r e -
e a r t h s y n t h e t i c f a u j a s i t e c a t a l y s t s .
D i v a l e n t c a t i o n ( N i , Ca , S r ) e x c h a n g e a n d s u b s e q u e n t v ac u u m
c a l c i n a t i o n o f f a u j a s i t e p r o d u c e s a l o s s o f r e g u l a r i t y i n t h e z e o -
l i t e f r a me wo r k ( 17 , _ J L 8 ) . T h i s l o s s i s e v i d e n t o n c o mp a r i s o n o f
b o n d l e n g t h s an d a n g l e s o f t h e d i v a l e n t - c a t i o n - e x c h a n g e d n a t u r a l
f a u j a s i t e a n d t h e h y d r a t e d n a t u r a l f a u j a s i t e . T h e r e i s a 10 . 5
a v e r a g e d e v i a t i o n f r o m t h e me an v a l u e o f t h e S i - O - S i a n g l e f o r
n i c k e l f a u j a s i t e c o mp a r e d t o a 1. 7 a v e r a g e d e v i a t i o n f o r h y d r a t e d
f a u j a s i t e . A s i mi l a r l o s s i n r e g u l a r i t y i s o b s e r v e d i n d e h y d r a t e d

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F i g u r e s
F i g . 1: ( a) F a u j a s i t e f r a me wo r k
( b ) S o d a l i t e c a g e
( c ) He x a g o n a l f a u j a s i t e Z S M- 2 0
REX SODALITE CAGE REX SODALITE CAGE
COMPLEX COMPLEX
F i g . 2 : S t e r e o s c o p i c d r a wi n g o f RE X s o d a l i t e c a g e c o mp l e x .
Re p r o d u c e d wi t h p e r mi s s i o n f r o m r e f e r e n c e 15 . ( C o p y r i g h t
19 6 7 Ma c mi l l a n )

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CaX a n d S r X, b u t i t i s mu c h mo r e p r o n o u n c e d f o r n i c k e l f a u j a s i t e .
T h e N i ( I I ) o c c u p i e s t wo - t h i r d s o f t h e S I s i t e s a n d a t t a i n s n e a r -
p e r f e c t o c t a h e d r a l c o o r d i n a t i o n wi t h s i x f r a me wo r k o x y g e n s , wi t h
a l l s i x o x y g e n at o ms s h i f t i n g . 5 A t o wa r d s N i ( F i g . 3 ) . T h e
r e ma i n i n g N i ( I I ) i o n s a r e d i s t r i b u t e d i n f o u r u n i q u e p o s i t i o n s , t wo
i n S I ' s i t e s a n d t h e o t h e r t wo i n S I I a n d S I I
1
s i t e s ( F i g . 4 ) .
C a t i o n M o b i l i t y
S i mi l a r e f f e c t s we r e n o t i c e d i n c a l c i n e d Ca - e x c h a n g e d e r i o n i t e
wh e r e Ca f o r c e d K o u t o f t h e c a n c r i n i t e c a g e s an d mo d i f i e d t h e c a g e
s t r u c t u r e (19 ). T h e r e i s a l s o e v i d e n c e o f r e d u c e d wa t e r a b s o r p -
t i o n i n c a l c i n e d Re - e x c h a n g e d f a u j a s i t e .
Th e mo b i l i t y o f c a t i o n s i n z e o l i t e s a n d t h e i r mi g r a t i o n a c r o s s
c o n t a c t b o u n d a r i e s b e t we e n a d j a c e n t c r y s t a l s may b e s t u d i e d u s i n g
X- r a y d i f f r a c t i o n b y me a s u r i n g t h e r a t e o f c h a n g e o f t h e l a t t i c e
p a r a me t e r s . I f t h e l a t t i c e p a r a me t e r s o f t wo c a t i o n i c f o r ms s u c h
a s L i a n d Na a r e c o n s i d e r a b l y d i f f e r e n t , t h e i n t e r - an d i n t r a -
c r y s t a l l i n e i n t e r c h a n g e s o f c a t i o n s c a n b e r e a d i l y t r a c k e d . A
c o mp l e t e e x c h a n g e du e t o mi x i n g L i A a n d NaA was a c c o mp l i s h e d b y
mi x i n g t h e p o wd e r s f o r l e s s t h a n t wo mi n u t e s ( 2 0 ) . A
2 9
S i - MAS - N MR
s p e c t r u m o f a mi x t u r e o f L i A an d NaA, p r e p a r e d s e p a r a t e l y a n d mi x e d
f o r l e s s t h a n 10 s e c o n d s w i t h t h e s p e c t r u m r e c o r d e d i mme d i a t e l y
a f t e r mi x i n g , s h o ws a s i n g l e l i n e s p e c t r u m f o r t h e mi x e d s a mp l e a n d
t wo s h a r p r e s o n a n c e s f o r L i A a n d NaA a t 6 = - 8 5 . 1 a n d - 8 8 . 9 du e t o
t h e t wo l o c a l s i l i c o n e n v i r o n me n t s ( 2 1 a ) . T h i s i n d i c a t e s t h e r a p i d
d i f f u s i o n o f L i
+
a n d N a
+
c a t i o n s o n p h y s i c a l l y mi x i n g L i A a n d NaA
p o wd e r s . T h e r a t e o f i n t e r c h a n g e i s d e p e n d e n t o n t h e amo u n t o f
me c h a n i c a l mi x i n g , t h e c r y s t a l l i t e s i z e , a n d t h e d e g r e e o f h y d r a -
t i o n . X - r a y - d i f f r a c t i o n p a t t e r n s o f L i X a n d NaX s u p e r i mp o s e d s h o w
a d o u b l e t p a t t e r n i n d i c a t i v e o f a t wo - p h a s e s y s t e m ( 2 0 ) . Wh e n
e q u a l we i g h t s o f L i X a n d NaX a r e mi x e d f o r l e s s t h a n t wo mi n u t e s ,
t h e X- r a y d i f f r a c t i o n i n d i c a t e s a s i n g l e s p e c i e s wi t h an i n t e r me -
d i a t e l a t t i c e p a r a me t e r . P r e c a l c i n i n g a n d mi x i n g t h e c o mp o n e n t s
wh i l e h o t , t h e n ma i n t a i n i n g t h e mi x t u r e a t 5 0 0 C f o r 14 h o u r s ,
s h o ws a t r e n d t o wa r d s a s i n g l e s p e c i e s , i n d i c a t i n g c a t i o n e x c h a n g e
e v e n i n a h i g h l y d e h y d r a t e d s y s t e m.
D e a l u mi n a t e d S y n t h e t i c F a u j a s i t e
Wi t h t h e p h a s i n g o u t o f l e a d c o mp o u n ds a s o c t a n e p r o mo t e r s , t h e RE Y
c r a c k i n g c a t a l y s t h a s b e e n r e p l a c e d b y h i g h - s i l i c a o r u l t r a s t a b l e
HY , wh i c h i s a t t r a c t i v e b e c a u s e o f i mp r o v e d o c t a n e r a t i n g s . T h e
me c h a n i s m o f o c t a n e e n h an c e me n t b y US Y p r o p o s e d b y P i n e ( 2 1b ) was
b e l i e v e d t o i n v o l v e a r e d u c t i o n i n t h e h y d r o g e n - t r a n s f e r r e a c t i o n
a n d a n e n h an c e me n t o f t h e c r a c k i n g r e a c t i o n du e t o mo d i f i c a t i o n o f
a c i d - s i t e c h a r a c t e r i s t i c s . T h e h i g h - s i l i c a HY i s o b t a i n e d b y
d e a l u mi n a t i o n t e c h n i q u e s . V a r i o u s me t h o d s f o r d e a l u mi n a t i o n l e a d
t o ma t e r i a l s wi t h a r a n g e o f d i f f e r e n t s t r u c t u r a l a n d c h e mi c a l
f e a t u r e s t h a t a f f e c t t h e a c t i v i t y a n d s e l e c t i v i t y o f t h e c r a c k i n g
c a t a l y s t . T h e s i l i c a / a l u mi n a r a t i o i s l i n e a r l y r e l a t e d t o t h e u n i t
c e l l d i me n s i o n ( 2 2 a ) . D i s c o n t i n u i t i e s i n t h e l i n e a r r e l a t i o n s h i p
o c c u r a t 8 0 , 6 4 , an d 5 2 A l at o ms p e r u n i t c e l l ( 2 2 b ) . T h e s e

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34
S u p e r i mp o s e d p a t t e r n ;
* * d e n o t e L i X r e f l e c t i o n s
Two mi n u t e Wi g g l e B u g mi x t u r e
o f 1: 1 h y d r a t e d c o mp o n e n t s
P r e c a l c i n e d 6 h r s a t 5 0 0 C,
mi x e d h o t
P r e c a l c i n e d 6 h r s a t 5 0 0 C,
mi x e d h o t an d c a l c i n e d 14 h r s
a t 5 0 0 C
Two t h e t a i n d e g r e e s
F i g . 5 : X- r a y d i f f r a c t i o n p a t t e r n s o f t h e L i X- N a X s y s t e m. Re p r o -
d u c e d wi t h p e r mi s s i o n f r o m r e f e r e n c e 2 0 . ( C o p y r i g h t 19 7 7 Ame r i c a n
C h e mi c a l S o c i e t y )

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3. KOKOTAILO ET AL. Characterization ofZeolite-Cracking Catalysts 35
r e s u l t s a r e s u p p o r t e d b y s i mi l a r r e s u l t s f o r g a l l i u m- s u b s t i t u t e d
z e o l i t e Y ( 2 3 ) , wh i c h s h o ws d i s c o n t i n u i t i e s a t 4 9 a n d 8 0 g a l l i u m
i o n s p e r u n i t c e l l . B e y e r e t a l . ( 2 4 ) s h o we d t h a t e x t r a p o l a t i o n
t o l o w- A l c o n t e n t s y i e l d s t h e r e l a t i o n s h i p
a = 8 . 6 8 x 1 0 " V - i
+ 2
-
4
2 5
o A l
I n g e n e r a l t h e S i / A l r a t i o c a n b e i n c r e a s e d o r t h e A l c o n t e n t
d e c r e a s e d u s i n g u s i n g t wo t r e a t me n t s .
C h e mi c a l E x t r a c t i o n o f A l . B a r r e r a n d Mi k k i ( 2 5 ) f i r s t r e p o r t e d
t h e e x t r a c t i o n o f t e t r a h e d r a l l y c o o r d i n a t e d A l f r o m z e o l i t e s b y
a c i d s ; K e r r ( 2 5 ) u s e d e t h y l e n e d i a mi n e t e t r a c e t i c a c i d ( E D T A) , a
c h e l a t i n g a g e n t ; Gar wo o d e t a l . ( 2 6 ) u s e d h y d r a t e d c h r o mi u m( I I I )
c h l o r i d e ; S k e e l s a n d B r e c k u s e d ammo n i u m h e x a f l u o r o s i l i c a t e ( AHF ) ;
an d B e y e r ( 2 4 ) u s e d s i l i c o n t e t r a c h l o r i d e .
T h e l a t t e r i s t h e p r e f e r r e d c h e mi c a l d e a l u mi n a t i o n t e c h n i q u e
f o r z e o l i t e Y , a s i t i s a s i n g l e - s t e p me t h o d . An i n e r t g as s a t u r -
a t e d wi t h s i l i c o n t e t r a c h l o r i d e i s p a s s e d t h r o u g h a b e d o f d e h y -
d r a t e d z e o l i t e ma i n t a i n e d a t a n e l e v a t e d t e mp e r a t u r e ( 5 2 0 K ) . T h e
S i / A l r a t i o c a n b e v a r i e d b y a l t e r i n g t h e t e mp e r a t u r e an d d u r a t i o n
o f t r e a t me n t . P a r t o f t h e A l r e ma i n s i n t h e z e o l i t e as N a +Al C l ^,
wh i c h i s r e mo v e d b y wa t e r t r e a t me n t , l e a v i n g a c l e a n z e o l i t e .
Hy d r o t h e r ma l T r e a t me n t . He a t t r e a t i n g ammo n i u m- e x c h an g e d z e o l i t e Y
p r o d u c e s an u l t r a s t a b l e HY ( 2 6 , 2 9 ) .
2 9
S i - MAS - N MR s p e c t r a o f h y d r o -
t h e r ma l l y d e a l u mi n a t e d N H
A
Y i n d i c a t e t h e p r e s e n c e o f " NMR-
i n v i s i b l e " A l ( 3 0 ) . T h e f r a me wo r k A l c a n b e d e t e r mi n e d f o r z e o -
l i t e Y f r o m t h e r e l a t i o n s h i p
4 4
( S i / A 1 )
N MR
= l
n
1
S i ( n A l )
/
* 4
I
S i ( n A l )
n =0 n =0
a s a p p l i e d t o t h e f i v e - p e a k
2 9
S I - MAS - NMR s p e c t r u m o f d e a l u mi n a t e d
NH, Y .
T h e
2 9
S i - MAS - N MR s p e c t r a o f a s e r i e s o f d e a l u mi n a t e d s a mp l e s
A1- A8 a r e g i v e n i n F i g . 6. T h e NaNH^Y s a mp l e was s t e a me d f o r
2 h o u r s a t t h e i n d i c a t e d t e mp e r a t u r e s , ammo n i u m e x c h a n g e d a f t e r
e v e r y s t e a mi n g f o r 3 0 mi n a t 8 0 C i n a ( N H
A
)
2
S 0
4
s o l u t i o n , f i l -
t e r e d , an d wa s h e d . S amp l e A8 was s t e a me d f o r 3 h o u r s a t 5 5 0 C,
c o o l e d , ammo n i u m e x c h a n g e d 3 t i me s , t h e n s t e a me d f o r 3 h o u r s a t
8 0 0 C. A l l s a mp l e s we r e d r i e d a t 10 0 C o v e r n i g h t . T h e s p e c t r a
s h o w a p r o g r e s s i v e d e c r e a s e i n t h e i n t e n s i t i e s o f t h e S i ( 3 A l ) ,
S i ( 2 A l ) a n d S i ( l A l ) p e a k s wi t h r e s p e c t t o S i ( O A l ) , wh i c h i n c r e a s e s
i n i n t e n s i t y . T h e f r a me wo r k A l c a n a l s o b e d e t e r mi n e d f r o m t h e
2 7
A1- MAS - NMR s p e c t r u m a s a r a t i o o f t h e o c t a h e d r a l s i g n a l t o t h e
t o t a l s i g n a l , a l t h o u g h i t i s d i f f i c u l t t o d e c o n v o l u t e t h e s i g n a l s
a n d t h e s p i n n i n g s i d e b a n d s . T h e
2 7
A1- MAS - NMR s p e c t r a A1- A8 o f t h e
s a mp l e s a r e g i v e n i n F i g . 7 . T h u s t h e r e a r e t h r e e g e n e r a l t y p e s o f
A l i n h y d r o t h e r ma l l y d e a l u mi n a t e d NH
A
Y : t e t r a h e d r a l l y c o o r d i n a t e d
f r a me wo r k A l ; o c t a h e d r a l l y c o o r d i n a t e d e x t r a - f r a me wo r k A l ; a n d NMR-
i n v i s i b l e A l . T h i s l a t t e r A l c o u l d b e p r e s e n t as A 1 ( 0 H)
3
,
A 1 ( 0 H)
2
+
, A 1
2
0
3
, o r s o me p o l y me r i c f o r m o f A l . E x a mi n a t i o n o f t h e
s e r i e s o f s a mp l e s d e r i v e d b y h y d r o t h e r ma l l y d e a l u mi n a t i n g a s t a r t -
i n g NaY s a mp l e wi t h S i / A l = 2 . 6 r e s u l t s i n o n l y a s ma l l amo u n t o f

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80 -100 -120 -80 100 -120
ppm from TMS
F i g . 6:
2
9 s i - MAS - N MR s p e c t r a o f h y d r o t h e r ma l l y d e a l u mi n a t e d s a mp l e s .
T e mp e r a t u r e s i n C. Re p r o d u c e d wi t h p e r mi s s i o n f r o m r e f e r e n c e 3 0 a .
( C o p y r i g h t 19 8 5 R o y a l S o c i e t y o f C h e mi s t r y )

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F i g . 7: 2 7 AI _ MAS -NMR s p e c t r a o f s a mp l e s o f h y d r o t h e r ma l l y d e a l u -
mi n a t e d z e o l i t e Y . T e mp e r a t u r e i n C. Re p r o d u c e d wi t h p e r mi s s i o n
f r o m r e f e r e n c e 3 0 a . ( C o p y r i g h t 19 8 5 R o y a l S o c i e t y o f C h e mi s t r y )

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3
A l b e i n g r e mo v e d f r o m t h e s a mp l e s . D e s p i t e r e p e a t e d ammo n i u m
e x c h a n g e f o l l o we d b y h y d r o t h e r ma l t r e a t me n t s , t h e b u l k o f t h e A l ,
as mu c h a s 5 8 . 8 % f o r A8 , i s s t i l l i n t h e z e o l i t e i n t e r s t i c e s . F o r
a l l t h e s a mp l e s t h e f r a me wo r k - S i / Al r a t i o a s d e t e r mi n e d b y NMR i s
c o n s i d e r a b l y h i g h e r t h a n t h e S i / A l r a t i o me a s u r e d b y e l e me n t a l
a n a l y s i s , i n a g r e e me n t wi t h t h e p r e s e n c e o f e x t r a - f r a me wo r k A l .
T h e
2 7
A1- MAS - NMR s p e c t r a o f t h e h y d r o t h e r ma l l y t r e a t e d s a mp l e s
c o n s i s t o f a s h a r p p e a k a t c a . 6 1 ppm du e t o t e t r a h e d r a l l y c o o r d i -
n a t e d A l i n t h e z e o l i t e f r a me wo r k a n d t wo s i g n a l s du e t o o c t a h e -
d r a l l y c o o r d i n a t e d e x t r a - f r a me wo r k A l , a v e r y b r o a d p e a k o f c a .
10 0 ppm i n h a l f wi d t h , a n d i n s o me s a mp l e s a s h a r p p e a k a t 0 . 3 5 -
3 . 5 ppm.
2 9
S i - MAS - N MR s p e c t r a o f t h e s y n t h e t i c f a u j a s i t e s i n d i c a t e a
mu c h l o we r c o n c e n t r a t i o n o f n o n - f r a me wo r k A l wh e n d e a l u mi n a t e d w i t h
S i C l
4
t h a n i n t h e c a s e o f t h e h y d r o t h e r ma l l y t r e a t e d s a mp l e s . T h e
d i f f e r e n c e b e t we e n t h e S i / A l r a t i o a s o b t a i n e d b y
2 9
S i - MAS - N MR a n d
e l e me n t a l a n a l y s i s i s mu c h s ma l l e r , i n d i c a t i n g t h a t mu c h o f t h e A l
i s c o mp l e t e l y r e mo v e d f r o m t h e l a t t i c e .
P a r i s e a n d c o wo r k e r s ( 3 0 b ) d e a l u mi n a t e d s a mp l e s o f z e o l i t e Y
( L Z - Y 8 2 ) u s i n g N H
3
/ s t e a m a t 8 2 3 ( 10 ) K f o r 6 h o u r s t o a S i / A l p =
10 . 5 a n d S i / A l = 2 . 6 7 ( wh e r e A l p i s f r a me wo r k al u mi n u m) wi t h 16 . 7
f r a me wo r k a n d 3 5 . 6 e x t r a - f r a me wo r k A l at o ms p e r u n i t c e l l . I f t h e
s a mp l e i s t r e a t e d w i t h a S i C l
4
/ A r mi x t u r e a t t h e s ame t e mp e r a t u r e
a n d f o r t h e s ame t i me , t h e f r a me wo r k A l i s e s s e n t i a l l y t h e s ame ,
10 . 8 A l a t o ms / u c , b u t t h e e x t r a - f r a me wo r k A l i s c o n s i d e r a b l y
r e d u c e d , t o 8 . 1. U s i n g n e u t r o n - d i f f r a c t i o n d a t a a n d a c o mb i n a t i o n
o f R e e t v e l d r e f i n e me n t a n d d i f f e r e n c e - F o u r i e r t e c h n i q u e s , t h e y
( 3 0 b ) d e t e r mi n e d t h e p r e s e n c e o f t e t r a h e d r a l l y c o o r d i n a t e d A l i n
t h e c e n t e r o f t h e s o d a l i t e c a g e s i n b o t h d e a l u mi n a t e d s a mp l e s , b u t
t o a l e s s e r e x t e n t i n t h e S i C l
4
/ A r - t r e a t e d s a mp l e . No o t h e r t y p e s
o f a' l u mi n at e s p e c i e s we r e d e t e c t e d , s o t h a t t h e o c t a h e d r a l s p e c i e s
d e t e c t e d b y K l e n o ws k i , F y f e a n d Go b b i ( 3 0 a) a r e d i s o r d e r e d o v e r t h e
c h a n n e l s y s t e m o f Y . T h e s t r u c t u r a l d i f f e r e n c e s b e t we e n t h e t wo
s a mp l e s a r e ma n i f e s t e d i n t h e T- O- T a n g l e . T h e s i l i c o n at o ms
r e ma i n r e l a t i v e l y f i x e d , b u t t h e o x y g e n at o ms t e n d t o mo v e .
Me r a d o t o s a n d B a r t h o me u f ( 3_ 1) f o u n d e n h a n c e d a c t i v i t y i n
h y d r o t h e r ma l l y t r e a t e d mo r d e n i t e s , wh i c h t h e y a c c r e d i t e d t o b r i d g -
i n g h y d r o x y l g r o u p s i n t e r a c t i n g wi t h e x t r a - f r a me wo r k A l . L ag o e t
a l . ( 3 2 ) f o u n d a l a r g e i n c r e a s e i n t h e a c t i v i t y o f HZS M- 5 a f t e r
mi l d s t e a mi n g a t 5 A0 C, wh i c h t h e y a t t r i b u t e d t o p a i r e d A l a t o ms .
B e y e r l e i n e t a l . ( 3 3 ) s t u d i e d t h e c a t a l y t i c p r o p e r t i e s o f a
s e r i e s o f u l t r a s t a b l e s y n t h e t i c f a u j a s i t e s d e a l u mi n a t e d b y s t e a mi n g
a n d b y a c i d e x t r a c t i o n t o d e t e r mi n e c a t a l y t i c a c i d i t y a s a f u n c t i o n
o f f r a me wo r k c h a r a c t e r i s t i c s . T h e y f o u n d t h a t c a r b o n i u m- i o n a c t i v -
i t y i n i s o b u t a n e c o n v e r s i o n i s p r o p o r t i o n a l t o f r a me wo r k - Al c o n -
t e n t , a n d c o mp a r i n g r e s u l t s o b t a i n e d b y u s i n g h y d r o t h e r ma l l y a n d
AHF - d e a l u mi n a t e d s y n t h e t i c f a u j a s i t e , t h e y f o u n d t h a t t h e s t e a me d
ma t e r i a l , wh i c h c o n t a i n s e x t r a - f r a me wo r k A l , g av e a l a r g e i n c r e a s e
i n c a r b o n i u m- i o n a c t i v i t y c o mp a r e d w i t h t h e A HF - t r e a t e d ma t e r i a l ,
wh i c h h a d a r e l a t i v e l y c l e a n f r a me wo r k . T h i s i n d i c a t e s t h a t s t r o n g
a c i d i t y e x h i b i t e d b y mi l d l y s t e a me d s y n t h e t i c f a u j a s i t e , wh i l e
d i r e c t l y r e l a t e d t o f r a me wo r k - Al c o n t e n t , d e p e n d s o n a b a l a n c e
b e t we e n f r a me wo r k a n d e x t r a - f r a me wo r k A l , a n d t h a t t h i s e x t r a -
f r a me wo r k A l c o n t r i b u t e s g r e a t l y t o wa r d s c a t a l y t i c p e r f o r ma n c e .

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Co t t e r ma n e t a l . ( 3 4 ) s h o we d t h a t h e x a d e c a n e - c r a c k i n g a c t i v i t y
o f AF S a n d US Y z e o l i t e s a p p e a r e d t o b e a f u n c t i o n o f t o t a l A l
c o n t e n t , i n d e p e n d e n t o f me t h o d o f d e a l u mi n a t i o n , i mp l y i n g t h a t
h e x a d e c a n e c r a c k i n g o c c u r s o v e r b o t h f r a me wo r k - a n d e x t r a - f r a me -
wo r k - a c i d s i t e s . He n c e , e x t r a - f r a me wo r k ma t e r i a l i n mi l d l y s t e a me d
s y n t h e t i c f a u j a s i t e , US Y , mak e s a s i g n i f i c a n t c o n t r i b u t i o n t o c a t a -
l y s t a c t i v i t y , a s p r e v i o u s l y r e p o r t e d ( 33. ) . Ga s o l i n e s e l e c t i v i t y
i s i n f l u e n c e d b y b o t h t h e me t h o d o f d e a l u mi n a t i o n a n d s t e a m t r e a t -
me n t , a n d d e p e n d s o n b o t h f r a me wo r k - a c i d s i t e s a n d t h e p r e s e n c e o f
e x t r a - f r a me wo r k ma t e r i a l .
V a n B r o e k h o v e n e t a l . ( 3 5 ) me a s u r e d t h e e f f e c t o f d e a l u mi n a -
t i o n o f Y z e o l i t e s b y s t e a m AF S a n d S i C l
4
a n d s h o we d t h a t t h e N a
2
0
l e v e l d u r i n g s t e a mi n g h a s a s t r o n g e f f e c t o n t h e l e v e l o f f r a me wo r k
d e a l u mi n a t i o n . At 1. 6 % N a
2
0 , u p t o 18 % o f e x t r a - f r a me wo r k A l i s
f o r me d , wh i l e a t 3 . 9 % N a
2
0 o n l y u p t o 11% i s f o r me d . S o me o f t h e
e x t r a - f r a me wo r k A l i s r e mo v e d a l o n g wi t h N a
2
0 o n wa s h i n g . I n t h e
S i C l
A
a n d AF S t r e a t me n t s , o n l y s ma l l amo u n t s o f e x t r a - f r a me wo r k A l
a r e p r e s e n t , a n d ma i n l y o f t h e N MR - v i s i b l e t y p e . XP S a n a l y s i s
s h o ws t h a t t h e s u r f a c e c o n c e n t r a t i o n o f e x t r a - f r a me wo r k A l i s h i g h ;
a l s o , s t e a mi n g o f t h e A F S - t r e a t e d s a mp l e r e s u l t e d i n a s t r o n g
f r a me wo r k d e a l u mi n a t i o n .
Cr u z e t a l . ( 3 6 ) a l s o f o u n d t h a t AF S p r e f e r e n t i a l l y d e a l u mi -
n a t e s t h e s u r f a c e o f z e o l i t e Y c r y s t a l s t o a d e p t h o f a b o u t 10 0 A
an d p r o d u c e s a n e x t r a - f r a me wo r k - A l - f r e e z e o l i t e . T h e y f o u n d t h a t
t h e a c t i v i t y f o r n - h e p t a n e c r a c k i n g i s t h e s ame a s f o r a s t e a me d
d e a l u mi n a t e d s a mp l e , wh i l e t h e g as o i l c r a c k i n g was l o we r , b e i n g
c o n t r o l l e d b y t h e o u t e r s h e l l .
A me t h o d h a s b e e n d e v e l o p e d t o c h a r a c t e r i z e t h e N MR - i n v i s i b l e
A l ( 3 7 ) , wh i c h e n t a i l s t h e c o mp l e x i n g o f n o n - f r a me wo r k A l wi t h
a c e t y l a c e t o n e ( a c a c ) t o f o r m A l ( a c a c )
3
c o mp l e x e s . B e c a u s e o f t h e i r
n e a r - s p h e r i c a l A l s y mme t r y , t h e s e c o mp l e x e s y i e l d
2 7
A1- MAS - NMR
s p e c t r a t h a t c a n b e u s e d f o r mo r e q u a n t i t a t i v e i n t e r p r e t a t i o n .
T h i s me t h o d c a n b e a p p l i e d t o z e o l i t e s d e a l u mi n a t e d b y v a r i o u s
t e c h n i q u e s . I n s t e a me d f a u j a s i t e s d i f f e r e n t e x t r a - f r a me wo r k A l a n d
S i s p e c i e s a r e o b s e r v e d . T h e d e a l u mi n a t e d s a mp l e s a r e s o a k e d i n a
3 8 % a c a c - me t h a n o l s o l u t i o n a t r o o m t e mp e r a t u r e u n d e r a f l o w o f d r y
a i r . A f t e r o n e h o u r t h e e t h a n o l a n d e x c e s s a c a c a r e e v a p o r a t e d .
I n h y d r o t h e r ma l l y d e a l u mi n a t e d f a u j a s i t e s a d d i t i o n a l
2 7
A 1 l i n e s i n
t h e 5 0 - 3 0 ppm r a n g e a p p e a r , i n a d d i t i o n t o t h e t e t r a h e d r a l a n d
o c t a h e d r a l l i n e s a t 6 0 a n d 0 ppm. Gi l s o n f o u n d a l i n e a t 3 4 ppmi n
z e o l i t e Y wi t h f r a me wo r k S i / A l = 2 0 b y s t e a mi n g a t 7 6 0 C i n 10 0 %
s t e a m. F r e u d e a n d c o wo r k e r s ( 3 9 , 4 0 ) h a v e d e s c r i b e d t h e u s e o f
1
H-
a n d
2 7
A1- MAS - NMR t e c h n i q u e s t o d e t e r mi n e t h e d e a l u mi n a t i o n me c h a-
n i s m i n t h e h y d r o t h e r ma l a n d a c i d t r e a t me n t o f z e o l i t e Y . T h e y
d e t e r mi n e d t h e f r a me wo r k a l u mi n u m f r o m t h e e q u i v a l e n c e o f A1 0
2
"
a n i o n s i n t h e f r a me wo r k a n d N H
4
+
c a t i o n s u s i n g t h e K j e l d a h l me t h o d
t o d e t e r mi n e t h e amo u n t o f N H
3
i n t h e z e o l i t e .
T h e
2 7
A1- MAS - NMR s p e c t r a o f d e a l u mi n a t e d z e o l i t e Y g e n e r a l l y
c o n s i s t o f t h r e e s i g n a l s i n d i c a t i v e o f t h r e e t y p e s o f a l u mi n u m,
b u t t h e i n t e n s i t y d o e s n o t a c c o u n t f o r a l l t h e a l u mi n u m i n t h e
s a mp l e . T h e a u t h o r s a s c r i b e t h e d i f f e r e n c e t o N MR - i n v i s i b l e A l
p r e v i o u s l y d e t e r mi n e d ( 3 0 ) f r o m an a n a l y s i s o f t h e
2 9
S i - MAS - N MR
d a t a f o r d e a l u mi n a t e d HY s a mp l e s . T h e NMR r e s o n a n c e a t 6 0 ppm f o r
f r a me wo r k A l i s r e l a t i v e l y s h a r p . O c t a h e d r a l l y c o o r d i n a t e d n o n -

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3
f r a me wo r k A l a l s o y i e l d s a s h a r p l i n e a t 0 ppm. T h e t h i r d s p e c i e s ,
a t e t r a h e d r a l l y c o o r d i n a t e d e x t r a - f r a me wo r k A l , g i v e s a b r o a d l i n e
a t a b o u t 5 0 ppm a n d i s c l e a r l y v i s i b l e i n z e o l i t e h y d r o t h e r ma l l y
d e a l u mi n a t e d a t 7 7 0 C t o a f r a me wo r k A l o f 7 a t o ms / u c . Th e
a u t h o r s ( AO) a s c r i b e t h e t wo l i n e s a t 0 a n d 5 0 as du e t o
e x t r a - f r a me wo r k - A l c o mp l e x e s , A 1 ( H
2
0 )
6
3 +
a n d Al ( OOH) . T h e y p r o p o s e
t h a t t h e Al ( OOH) mo l e c u l e i s a s s o c i a t e d wi t h t wo f r a me wo r k o x y g e n s
t o g i v e a t e t r a h e d r a l l y c o o r d i n a t e d A l at o m wi t h a we a k l y
i n t e r a c t i n g p r o t o n wi t h a f r a me wo r k o x y g e n f u r t h e r away . T h e y
c l a i m t h a t t h e ma j o r i t y o f e x t r a - f r a me wo r k A l i s a c o n d e n s a t i o n o f
t h i s s p e c i e s a n d h a s n o n c u b i c s y mme t r y . T h e s e s p e c i e s a r e as s u me d
t o b e NMR i n v i s i b l e a n d t h e i r c o n c e n t r a t i o n i s d e t e r mi n e d b y
s u b t r a c t i o n .
T h e t o t a l c o n c e n t r a t i o n o f OH g r o u p s i n d e a l u mi n a t e d z e o l i t e Y
s a mp l e s was d e t e r mi n e d u s i n g
1
H- NMR t e c h n i q u e s d e s c r i b e d ( 4 0 ) a n d
i s i n r e a s o n a b l e a g r e e me n t wi t h t h e c o n c e n t r a t i o n o f t e t r a h e d r a l l y
c o o r d i n a t e d e x t r a - f r a me wo r k A l . T h e c o n c e n t r a t i o n o f S i OH g r o u p s
d o e s n o t c h an g e i n h y d r o t h e r ma l d e a l u mi n a t i o n , b u t i n c r e a s e s o n
a c i d l e a c h i n g du e t o r e mo v a l o f f r a me wo r k A l .
T h e n u mb e r o f b r i d g i n g OH g r o u p s i s e q u a l t o t h e n u mb e r o f
f r a me wo r k - Al a t o ms .
S amo s an ( 4 J J o b s e r v e d
2 7
A 1 s i g n a l s a t 5 0 an d 3 0 ppm i n z e o l i t e
Y d e a l u mi n a t e d wi t h 0 . 1 M P a s t e a m s u c c e s s i v e l y a t 6 0 0 C an d 8 5 0 C
t o g i v e a f r a me wo r k S i / A l = 2 0 . We ak p e a k s we r e a l s o o b s e r v e d a t
6 0 a n d 0 ppm. Gi l s o n a t t r i b u t e d t h e l i n e a t 3 0 ppm t o p e n t a -
c o o r d i n a t e d e x t r a - f r a me o wr k A l . Mo b i l e , o c t a h e d r a l A 1 ( H
2
0 )
6
3 +
c o m-
p l e x e s l o c a t e d i n t h e z e o l i t e c h a n n e l s g i v e r i s e t o 0 - ppm s i g n a l s
( 3 0 ) . T h e s h a r p l i n e a t 0 ppm i s c a u s e d b y e x c h a n g e a b l e c a t i o n s
( 3 7 ) . T h e 5 0 - ppm s i g n a l d e c r e a s e s a n d t h e 3 0 - ppm s i g n a l i n c r e a s e s
wi t h i n c r e a s e d s t e a mi n g s e v e r i t y . T h e
2 7
A 1 s p e c t r a o f a c a c - t r e a t e d
s a mp l e s i n d i c a t e t h a t t h e N MR - i n v i s i b l e A l i s c o r n p l e x e d , r e s u l t i n g
i n an i n c r e a s e i n t h e 0 - ppm s i g n a l du e t o o c t a h e d r a l A l ( 3 7 ) . T h e
a u t h o r s n o t e t h a t c a r e s h o u l d b e e x e r c i s e d i n t h e u s e o f t h i s p r o -
c e d u r e f o r q u a n t i f i c a t i o n o f e x t r a - f r a me wo r k A l ( 3 7 ) , a s s o me may
s t i l l n o t b e o b s e r v a b l e .
A l t h o u g h man y s t e a mi n g p r o c e d u r e s l e a v e c o n s i d e r a b l e q u a n t i -
t i e s o f e x t r a - f r a me wo r k A l i n t h e i n t e r s t i c e s , as d e s c r i b e d a b o v e ,
i t s h o u l d b e p o s s i b l e t o p r o d u c e h i g h l y d e a l u mi n a t e d , c l e a n ma t e r i -
a l s wi t h o u t d e f e c t s o r amo r p h o u s S i an d A l c o mp l e x e s . S o me p r o -
g r e s s h a s b e e n made i n t h i s d i r e c t i o n . F i g u r e s 8 a n d 9 s h o w t h e
c o r r e s p o n d i n g S i a n d A l s p e c t r a o f d e a l u mi n a t e d f a u j a s i t e wi t h
S i / A l r a t i o s a s i n d i c a t e d . T h e
2 9
S i s p e c t r a , o b t a i n e d a t 7 9 . 5 MHz
o n a B r u k e r MS L 4 0 0 s p e c t r o me t e r , i n d i c a t e t h a t a l l t h e ma t e r i a l i s
h i g h l y c r y s t a l l i n e wi t h n o amo r p h o u s s i l i c a p r e s e n t . T h e
2 7
A 1
s p e c t r a , o b t a i n e d a t 10 4 . 2 MHz o n t h e s ame s p e c t r o me t e r , s h o w o n l y
s h a r p p e a k s a t 5 0 a n d 0 ppm, c o r r e s p o n d i n g t o t e t r a h e d r a l - f r a me wo r k
A l a n d o c t a h e d r a l A l . T h e r e i s n o e v i d e n c e o f b r o a d r e s o n a n c e
p e a k s du e t o amo r p h o u s a l u mi n a . T h e a d d i t i o n o f a c a c d o e s n o t
i n c r e a s e t h e i n t e n s i t y o f t h e o c t a h e d r a l p e a k .
C o n c l u s i o n s
S e l e c t i v i t i e s a n d a c t i v i t i e s o f d e a l u mi n a t e d z e o l i t e Y a r e d e p e n -
d e n t o n t h e me t h o d o f d e a l u mi n a t i o n a n d t h e " s t a t e " o f t h e a l u mi n u m

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F i g . 8 :
2 9
S i - MAS - N MR s p e c t r a o f h i g h l y d e a l u mi n a t e d z e o l i t e Y
s a mp l e s . S i / A l r a t i o s i n d i c a t e d .
-90 -100 -110
PPM
F i g . 9:
2 7
A1- MAS - NMR s p e c t r a o f h i g h l y d e a l u mi n a t e d z e o l i t e Y
s a mp l e s . S i / A l r a t i o s i n d i c a t e d .

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s p e c i e s i n t h e f r a me wo r k , t h e c h a n n e l s , o r t h e s u r f a c e o f t h e z e o -
l i t e c o mp o n e n t o f t h e c a t a l y s t .
I mp r o v e d NMR, XRD, n e u t r o n - d i f f r a c t i o n , I R, a n d a d s o r p t i o n
t e c h n i q u e s a r e h e l p i n g t o s o r t o u t t h e p h y s i c a l p r o p e r t i e s o f t h e s e
v a r i o u s A l s p e c i e s i n t h e d e a l u mi n a t e d z e o l i t e Y s a mp l e s , a n d t h e i r
r e l a t i o n s h i p t o c a t a l y t i c a c t i v i t y .
Go o d c r y s t a l l i n e s a mp l e s a r e n e c e s s a r y , as w e l l a s t h e a b i l i t y
t o p r e p a r e s a mp l e s t h a t i s o l a t e o r c o n c e n t r a t e t h e A l s p e c i e s g e n e -
r a t e d b y t h e v a r i o u s d e a l u mi n a t i o n t e c h n i q u e s i n o r d e r t h a t mo r e
s t r u c t u r a l i n f o r ma t i o n may b e d e r i v e d , wh i c h w i l l g i v e u s f u r t h e r
u n d e r s t a n d i n g o f t h e c a t a l y t i c a c t i v i t y du e t o t h e s e t r e a t me n t s a n d
i t s r e l a t i o n s h i p t o s t r u c t u r a l f e a t u r e s .
T h e f o r ma t i o n o f t h e A l - 0 c o mp l e x e s i n t h e s o d a l i t e c a g e s o f
z e o l i t e Y i s a n a l a g o u s t o s i mi l a r L a - 0 c o mp l e x e s p r e v i o u s l y d e s -
c r i b e d ( 1 5 , 1 6 ) . T h e s e p h e n o me n a a r e u n d e r s t u d y wi t h n e u t r o n - a n d
s y n c h r o t r o n - X - r a y d i f f r a c t i o n .
T h e NMR d a t a o n c l e a n d e a l u mi n a t e d s a mp l e s o f z e o l i t e Y i n d i -
c a t e t h a t wi t h g o o d s a mp l e p r e p a r a t i o n a n d t h e a d v a n c e d t e c h n i q u e s
f o r s t r u c t u r a l s t u d i e s , i t w i l l b e p o s s i b l e t o e l u c i d a t e f u r t h e r
t h e r e l a t i o n s h i p b e t we e n s t r u c t u r a l f e a t u r e s an d c a t a l y t i c p r o p e r -
t i e s .
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J . Chem. Soc., Chem. Commun. 1987, 91.
39. Freude, D.; Hunger, M.; Pfeiffer, H. Z. Phys. Chem. NF,
1987, 152, 171.

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40. Freude, D.; Brunner, H.; Pfeiffer, H.; Prager, D.;
J erschkiwitz, H. G.; Lohse, U.; Oehlmaun, G. Chem. Phys.
Letters 1987, 139, 325.
41. Samosan, A .; Lippmaa, E.; Engelhardt, G.; Lohse, U.;
J erschkewitc, H. C. Chem. Phys. Letters 1987, 134, 589.
REC EI V ED July 20, 1990

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Chapter 4
Increasing Motor Octanes by Using ZSM5
in Catalytic Cracking
Riser Pilot Plant Gasoline Composition Analyses
D. A. Pappal
1
and P. H. Schipper
2
1Paulsboro Research Laboratory, Mobil Research and Development
Corporation, Paulsboro, NJ 08066
2
Engineering Department, Mobil Research and Development Corporation,
Princeton, NJ 08543
This paper documents compositional analyses obtained for FCC
gasolines produced over two commercially produced and available
faujasite catalysts with and without the addition of ZSM-5additive.
These data indicate that ZSM-5is effective at increasing the motor
octane of the FCC gasolines produced. This is accomplished by
increasing the iso to normal ratio of the aliphatic portion of the FCC
gasoline.
ZSM-5, Mobil's propriety shape-selective zeolite, has been used commercially in
synthetic fuels (methanol-to-gasoline), petrochemicals (xylene isomerization, toluene
disproportionation, benzene alkyiatton) and in petroleum refining (lube and distillate
dewaxing). Using these examples, Chen and Garwood(1) have demonstrated the shape
selective behavior of this catalyst. In the dewaxing process, for example, ZSM-5
preferentially cracks the straight chain paraffins, substantially reducing the pour and
cloud points while retaining high distillate yields.
Since 1983, ZSM-5has been used in catalytic cracking to increase both the
research and motor octanes and the production of light olefins. These olefins can then
increase the yields of alkylate, MTBE and TAME. ZSM-5accomplishes this by upgrading
low octane components in the gasoline boiling range (C
7
- C
1 0
hydrocarbons) into light
olefins (C
3
, C
4
, C
5
). It also increases the concentration of C
4
and C
5
branched olefins,
which are feed to MTBE and TAME units (2,3,4). Since its introduction in 1983, ZSM-5
has been in use in over 10% of the free world's cracking capacity.
In catalytic cracking applications, the ZSM-5content in the unit has ranged up to
three weight percent, the variations due primarily to variations in base octane, gasoline
cut-point, catalyst make-up rate and regenerator temperature. It has been used primarily
in the form of high concentration, separate particle additives since this method affords
maximum flexibility to achieve the target octane increase in as little as one day of
addition by accelerating the initial catalyst make-up rate. In contrast, octane catalysts
containing Y zeolites with reduced unit cell size can generally take several months to
boost octane, since they require significant turnover of the catalyst inventory.
Although the commercial benefits of ZSM-5in catalytic cracking have frequently
been discussed, there has not been significant discussion of the shape selective
behavior of ZSM-5in catalytic cracking. Rajagopalan et. al. (5) claim based on gas oil
studies in a fixed bed reactor, that both the straight chain and mono-methyl branched
paraffins have equivalent reactivity. Biswas et. al. (6) also report a large reduction in
0097-6156/91/0452-0045$06.00/0

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branched paraffins with ZSM-5 blended with a USY zeolite catalyst. This work was done
at very low oil partial pressures (less than 7 psia.). In both cases only small quantities of
gasoline were produced, such that the all the liquids were evaluated by gas
chromatography (GC) and the octanes calculated by correlations. Schipper et. al. (4)
show that the compositional shifts which occur with ZSM-5 depend on the initial gasoline
composition without ZSM-5; the olefin to paraffin ratio of the base gasoline was found to
be a strong parameter in determining the compositional shifts. Pappal et. al. (7)
reported, based on fixed fluidized bed data, that the iso to normal paraffin ratio increases
with ZSM-5, and the olefin to paraffin ratio of the base gasoline determined the
compositional shifts with ZSM-5. The authors suggested that these shifts could be
responsible for the significant increase in FCC gasoline motor octane observed in riser
pilot plant data.
In this paper we will discuss the detailed compositional analyses generated in riser
pilot plant studies with and without ZSM-5. In particular, we note the relative yields of
both the branched and normal paraffins and the iso and normal olefins as a function of
carbon number and relate these to the increase in motor octane. Two different base
catalysts were used in this study to provide a wide range in the base gasoline
composition.
Experimental Procedure
Two conventional faujasite catalysts commercially produced and available were used in
this study, catalyst A, which contains about three percent rare earth and catalyst B which
contains almost zero rare earth and significantly more zeolite (as measured by X-ray
crystallinity) than catalyst A.
The conventional faujasite catalysts were steamed at 1400' F in 2 atmospheres
steam at varying times in order to achieve the same activity as measured by our
standard Fluid Activity Index (FAI). Table I summarizes the steaming conditions
employed.
Table I.
Summary of Catalyst Steaming Conditions
Catalyst A B ZSM-5
Additive
Time, Hours 20 4.5 10
Temperature, F 1400 1400 1450
Steam Partial
Pressure, Atrn. 2 2 0.45
Relative Catalyst Make-up
to Achieve Constant Activity Base 5xB a 36
Despite the increase in zeolite content, catalyst B deactivated faster than A
requiring only four and a half hours to reach 66 FAI activity. Using our catalyst
deactivation model which allows us to accurately translate laboratory catalyst
deactivation to commercial make-up predictions (10), we estimate a much higher
makeup rate is required for catalyst B to achieve the same activity as catalyst A (see
Table I).
Physical and chemical properties of the two steamed catalysts are summarized in
Table II.

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4. PAPPAL AND SCHIPPER Increasing Motor Octanes by Using ZSM-S
47
Because of the low rare earth content and initially higher zeolitic silica/alumina
ratio of catalyst B, its unit cell size after steaming is lower than that for catalyst A.
The ZSM-5 additive used in the study was commercially available and contains
25% ZSM-5 zeolite in an inert matrix. The ZSM-5 additive was steamed at conditions (8)
chosen to simulate the activity of a commercially equilibrated REX cracking catalyst
(Table I). Eight weight percent of the additive was then blended with each faujasite
catalyst (two weight percent ZSM-5 zeolite).
These catalysts were evaluated in an isothermal, bench-scale, riser pilot plant at
1000 F average riser temperature, 5 seconds oil residence time (ORT) and at least four
different catalyst to oil ratios varying from 4 to 10. The feedstock used was a Nigerian
gas oil with properties as shown in Table III. Gases were analyzed by GC. The liquids
were analyzed by a GC to give the carbon number isomer breakdown. In addition there
was enough sample to analyze for mini-micro Motor octane which has a reported
reproducibility of 0.75 octane for a single determination.
Results
Table IV shows the impact of ZSM-5 with respect to the overall yields/octanes for both
catalysts A and at 70 volume percent conversion.
The results on both catalysts A and show the previously reported yield and
octane shifts with ZSM-5 (2,3,4): an increase in gasoline motor octane, a reduction in the
gasoline yield, an increase in C
3
and C
4
olefins, and isobutane, and no change in coke,
C
2
-, LCO or MCB yields. For both catalysts, the motor octane gain and also the motor
octane gain per gasoline yield loss are essentially the same within experimental error.
Note, that several motor octanes were determined to lend significance to the results.
The PONA composition of the gasoline as a percent of fresh feed (Table V) shows
that the ZSM-5 is acting primarily on the C
7
+ olefins and paraffins in the gasoline boiling
range.
There is no increase in the naphthene or aromatic yields. Catalyst A which has a
higher unit cell size and rare earth content, has increased hydrogen transfer reactivity
resulting in a higher initial concentration of paraffins. Contrary to previous fixed fluidized
bed data (7), adding ZSM-5 to catalyst A results in a decrease in the C
7
+ olefin yield in a
short contact time riser pilot plant. Catalyst which has a much higher initial olefin
concentration, because of lower hydrogen transfer reactivity, also shows a decrease in
Cj+ olefins when ZSM-5 is added. The C
7
+ paraffins decrease somewhat for both
catalysts but for Catalyst A this decrease is much less than in the previous fixed fluidized
bed data (7). The total paraffin yield is unchanged when ZSM-5 is used.
Table VI shows the detailed gasoline composition (as a per cent of fresh feed),
particularly the breakdown of the straight chain and branched paraffins. The results
show an increase in the ratio of the branched to straight chain paraffins for each carbon
number when ZSM-5 is used. This is particularly striking in that the total paraffin yield is
unchanged when ZSM-5 is added. Thus, although the total paraffin yield remains
essentially unchanged, the iso/normal paraffin ratio increases for all carbon numbers.
There is also a change in the paraffin carbon number distribution in that the C
8
and Cg
paraffin yields decrease and the C
5
and C
6
paraffin yield increases. The normal
paraffins are decreasing at a faster rate than the isoparaffins despite the fact that their
initial concentration is 5 to 10 times lower. In the C
7
carbon number, catalyst A shows
an increase in the isoparaff ins while catalyst shows a decrease. The normal C
7
decreases for both catalysts.
The olefins (Tables VI and VII) show very similar shifts depending on the base
catalyst.

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Table II.
Summary of Catalyst Properties
Catalyst
Steamed Catalyst Properties
Surface Area, m*/gram
X-Ray Crystallinity, wt %
Total Rare Earth, wt %
Unit Cell Size, A
FAI Activity, %
Fresh Catalyst Properties
Unit Cell Size, A
Surface Area, rr^/gram
A B
75
162
8 28
3
0.2
24.36 24.28
66 66
24.51 24.43
221 202
Table III.
Summary of Feedstock Properties
Distillation Yields, Total 650-
Wt% 100 9.7
Physical Properties
API Gravity
Density at 70 *C 0.8920 0.8452
Distillation, D1160
IBP, " F 460
5% 608
10% 676
20% 735
30% 778
40% 810
50% 832
60% 857
70% 882
80% 923
90% 993
Aniline Point, *F 177
Bromine Number 3.3
Molecular Weight 390 239
CCR,Wt % 0.92
Pour Point,
-
F 120
Refractive index, 70
-
C 1.4946 1.4680
Chemical Analysis
Hydrogen, Wt% 12.6
Sulfur, Wt% 0.24 0.18
Nitrogen, ppm 1400
Basic Nitrogen, ppm 748 115
Nickel, ppm 2.2
Vanadium, ppm 0.1
Iron, ppm 2.3
Molecular Composition, Wt %
Paraffins 28.0
Naphthenes 41.2
Aromatics 30.8
17.0

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4. PAPPAL AND SCHIPPER Increasing Motor Octanes by Using ZSM-5 49
Table IV.
Summary of Yields at 70 Vol % Conversion
Catalyst A A + B B +
ZSM-5 ZSM-5
Conversion, vol % 70 70 70 70
Yields, wt %
Gasoline 46.2 45.5 47.4 46.8
LCO 27 27 27 27
MCB 6 6 6 6
C
3
= + C
4
= 7.4 8.2 8.7 9.3
Co + nC
4
2.1 2.0 1.6 1.6
i C
4
3.0 3.1 2.0 2.3
Co- 3.5 3.5 3.3 3.3
Coke 4.8 4.7 4.0 3.7
Gasoline M+0 81.5 82.0 81.2 81.6
Delta M+0/
Delta C
5
+ yield 0.7 0.6
Table V.
PONA Composition of Gasolines at 70 Vol% Conversion
ZSM-5 ZSM-5
PONA.wt %FF
P
6.4 6.8 3.3 3.6
o
C 7 +
4.3 4.1 2.6 2.2
C
6-
5.2 5.1 8.3 8.7
C r
7.0 6.4 11.7 10.6
N 3.8 4.0 3.1 3.0
A 19.5 19.1 18.4 18.5
Total 46.2 45.5 47.4 46.8
Olefin/Paraffin 1.1 1.1 3.4 3.3

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Table VI.
FCC Gasoline Composition
ZSM-5 ZSM-5
Paraffins, wt % FF
nC
5 0.40 0.40 0.29 0.29
3.02 3.33 1.76 1.95
l/N 7.55 8.33 6.07 6.72
nC
6
0.29 0.27 0.16 0.14
mmC
6 2.40 2.45 0.90 1.00
dmCg 0.30 0.35 0.15 0.17
l/N 9.31 10.37 6.56 8.36
nCj 0.22 0.19 0.17 0.13
mmCy 1.44 1.48 0.70 0.60
dmCy 0.29 0.31 0.18 0.20
l/N 7.86 9.42 5.18 6.15
nC
8
0.20 0.18 0.10 0.08
mmCg 0.95 0.90 0.60 0.50
dmCg 0.10 0.12 0.08 0.07
l/N 5.25 5.67 6.80 7.13
nC
9
0.10 0.09 0.09 0.07
mmCg 0.60 0.55 0.35 0.25
dmCg 0.38 0.30 0.38 0.35
l/N 9.80 9.40 8.11 8.57
Olefins. wt %FF
2.70 2.80 4.14 4.42
2.50 2.35 4.13 4.43
2.50 2.20 3.90 3.70
c
8
= 3.40 2.90 5.00 4.60
Cg= 1.10 1.30 2.80 2.30
Aromatics. wt % FF
c
6
0.85 0.85 0.90 0.90
1.78 1.83 1.70 1.85
c
8
4.20 3.95 3.80 3.80
C10
+
4.5 4.20 4.00 4.00
C10
+
8.20 8.20 8.00 8.00

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4. PAPPAL AND SCHIPPER Increasing Motor Octanes by Using ZSM-5
51
Table VII.
Detailed C5and C
6
Olefin Composition
Catalyst A
g5' s,wt%
C
5
= 2.70
C
5
Linear- 1.25
C
5
l s o 1.45
C
5
I/L= 1.15
Cg's, wt %
C
6
= 2.5
C
6
Linear = 0.80
C
6
MM= 1.45
C
6
DM = 0.25
C
6
I/L= 2.12
A+ B B+
ZSM-5 ZSM-5
2.80 4.14 4.42
1.10 1.72 1.47
1.70 2.42 2.95
1.53 1.41 2.00
2.35 4.13 4.43
0.67 1.35 1.3
1.40 2.40 2.75
0.28 0.38 0.38
2.51 2.06 2.41
Catalyst A shows a decrease in the C$ through C
8
olefins while catalyst B shows
a decrease in the C
7
through C
9
olefins. The respective lighter olefins increase for both
catalysts. For both catalysts the iso to linear olefin ratio increases. In the C5carbon
number range, the iso olefins increase and the linear olefins decrease for both catalysts.
The increase in iso olefins results in increased TAME feedstock. In the C
6
carbon
number range, both the linear and iso olefins decrease for catalyst A with the linear
olefins decreasing faster. For catalyst B, the linear olefins decrease and the iso olefins
increase.
Discussion
The componential yield shifts on a fresh feed basis provide an indication of the type of
chemistry which occurs when ZSM-5 is used in catalytic cracking. Figure 1 indicates that
ZSM-5 alters the distribution of olefin yields in the gasoline boiling range by decreasing
the higher carbon number olefins (C
7
+) and increasing the lower carbon number olefins
(C
6
-). In addition, the increase in the lower carbon number olefins is all in the branched
olefins as illustrated below using Catalyst B as an example.
Olefin Shifts with ZSM-5 (wt % FF)
C
6
- Olefins C
6
- Iso-Olefins
+0.58 +0.88
This example shows that ZSM-5 is still reacting the lower carbon number linear
olefins and also is significantly increasing the formation of C
5
and C
6
iso-olefins.
Figure 1 also illustrates that a larger C
7
+ olefin yield decrease occurs when ZSM-5
is blended with Catalyst B which produced the higher olefin content in the base gasoline.
However, the C
7
+ olefin conversion rate resulting from ZSM-5 is essentially the same for
both catalysts, 8.5% for Catalyst A and 9.4% for Catalyst B. This result suggests that
gasolines which initially contain a higher concentration of olefins will show a larger
decrease in C
7
+ olefin yields when ZSM-5 is added.
Figure 2 shows that the distribution of isoparaffins (on a fresh feed basis) is also
altered with ZSM-5; the C
7
+ isoparaffin yields are decreased and the C
6
- isoparaffin
yields are increased when ZSM-5 is added to either Catalyst A or B. The increase in the

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a
t- 3 . 5
1
CATALYST B -I- ZSM-5
1
-
CATALYST B
~~ CATALYST A
~~ CATALYST
1
A -- ZSM-5
1 1
5 6 7
CARBON NUMBER
8 9
Figure 1. Olefin yields for the C
5
through C
9
cartx>n numbers for Catalysts A and B with
and without ZSM-5.
5 6 7 8
CARBON NUMBER
Figure 2. Iso-paraffin yields for the C
5
through C
9
cartx>n numbers for Catalysts A and B
with and without ZSM-5.

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4. PAPPAL AND SCHIPPER Increasing Motor Octanes by Using ZSM-5 53
lower cartoon number isoparaffin is consistent with the increase in isobutane yield shown
in Table IV and reported by others (2,4). Table VI shows that the addition of ZSM-5 also
lowers the normal paraffin concentrations throughout the gasoline boiling range and
increases the iso/normal paraffin ratio. Figure 3 shows that, in all cases, the iso/normal
paraffin ratio is higher than that expected from equilibrium calculations.
Figure 3 also indicates that Catalyst B which has a lower unit cell size than
Catalyst A also has a lower iso/normal paraffin ratio over the entire carbon number
range. These lower unit cell size catalysts, which have been introduced into FCC units
over the last 5 years have generally given higher research octane but very little (if any)
increase in motor octane. Table IV and Figure 2 confirm this trend, showing that the
motor octane of gasoline produced from Catalyst B is actually lower than that produced
from Catalyst A, correlating with the lower iso/normal paraffin ratios. The iso/normal
paraffin ratio for Catalyst B with ZSM-5 is close to that of Catalyst A, as is its motor
octane.
The two previous papers which discussed the chemistry of ZSM-5 (5,6) have
stated that ZSM-5 increases octane by mainly concentrating the aromatics in the
gasoline due to non-selective cracking of the olefins and paraffins in the gasoline boiling
range. However, the data presented here indicate that ZSM-5 is doing far more than just
concentrating the gasoline aromatics. Table VIII illustrates the component shift on a
gasoline yield basis. The gasoline aromatic content has increased similar to previous
reports. However, ZSM-5 also increases the iso-olefins and isoparaffins (high octane
components) and decreases the n-paraffins and the C
5
and C
6
straight chain olefins
(low octane components). This data clearly illustrates the unique gasoline compositional
shifts when ZSM-5 is used to increase the octane in catalytic cracking.
5 6 7 8
CARBON NUMBER
Figure 3. Iso to normal paraffin ratios for the C
5
through C
9
carbon numbers for
Catalysts A and B with and without ZSM-5.

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54
Table VIII.
Gasoline Composition Analysis
Catalyst Type B B+ZSM-5
Wt %, Gasoline
Aromatics 38.8 39.5
Naphthenes 6.5 6.4
Olefins 42.2 41.2
i C
5
i = 5.1 6.3
C
5
Linear = 3.6 3.1
C
6
= 5.9 6.6
C
7
8.3 7.8
C
8
10.6 97
C
9
5.9 4.9
Paraffins 12.4 12.4
i C
5
3.7 4.2
nC
5
0.6 0.6
i C
6
2.2 2.5
nC
6
0.3 0.3
i C
7
1.9 17
nC
7
0.4 0.3
IC
8
1.4 1.2
nC
8
0.2 0.2
i C
9
1.5 13
nC
9
0.2 0.1

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4. PAPPAL AND SCHIPPER Increasing Motor Octanes by Using ZSM-5
55
Acknowledgments
The authors would like to thank the many scientists and technicians within the laboratory
whose efforts made this paper possible. Specifically, Rob Absil, Art Chester and Joe
Herbst were particularly helpful.
Literature Cited
1. Chen, N. Y., Garwood, W. E., Catalysis Reviews, 28, (2+3), 185.
2. Dwyer, F. G., Schipper, P. H., Gorra, F., NPRA Annual Meeting,
March 29-31, 1987, San Antonio, Texas (AM-87-63)
3. Yanik, S. J. , Campagna, R. J. , Demmel, E. J. ; Humphries, A. P., NPRA Annual
Meeting, March 24-26, 1985, San Antonio, Texas, (AM-85-48)
4. Schipper, P. H., Dwyer, F. G., Donnelly, S. P.,Huss, A. Jr., Sparrell, P. T.,
Mizrahi S., Herbst, J. A., ACS Meeting, Division of Petroleum
Chemistry, August 30 - September 4, 1987.
5. Rajagopalan, K., and Young, G. W., ACS Preprints, Symposium on
Advances in FCC, pg. 627.
6. Biswas, J. , Maxwell, I. E., Applied Catalysis, 58, pg. 1, 1990
7. Pappal, D. A., and Schipper, P. H., ACS Meeting, Division of Petroleum
Chemistry, Chemistry of FCC Naphtha Formation, September 10-15, 1989,
Miami Beach, Florida.
8. Sparrell, P. T., Donnelly, S. P. and Schipper, P. H., Tenth N. American Meeting
of the Catalysis Society, March 1987, San Diego, California
9. Chester, A. W. and Stover, W. A., Ind. Eng. Chem. Prod. Res. Dev.,
16 #4, pg. 285, 1977.
10. Schipper, P. H., Sarli, M. S., Almgren, B. S., Krambeck, F. J. , and Tanzio, M.,
Ninth N. American Meeting of the Catalysis Society, March 19, 1985,
Houston, Texas.
REC EI V ED June 8, 1990

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Chapter 5
Modification of Fluid Catalytic Cracking
Catalysis by the Addition of ZSM-5
Gasoline Over-Cracking Studies
D. J. Rawlence
1
and J. Dwyer
2
1
Crosfield Catalysts, Warrington WA5 1AB, Cheshire, United Kingdom
2
Department of Chemistry, University of Manchester Institute of Science
and Technology, Sackville Street, Manchester, United Kingdom
Over-cracking of FCC gasoline with either ZSM-5 or
REHY results, in both cases, in a preferential loss of
heavier olefin components. The major differences
between the two zeolites is the increased C3/C4 ratio
with ZSM-5 which has been assigned to pore size
effects, and enhanced bimolecular hydrogen transfer
reactions with REHY, resulting in a higher
paraffin/olefin ratio.
Typical carbenium ion reaction mechanisms are
used to explain the general differences in yields
obtained for the two zeolite structures.
Ad d i t i on of ZSM-5 t o the FCC c i rc u l at i n g inventory res u l t s i n a
s l i g h t reduction i n gasoline y i el d b ut an enhancement of gasoline
q u al i t y i n terms of octane rat i n g [ 1]. In addition, increased
y i el d s of L.P.G. components are ob served, notab ly propene and
b utenes which, sub sequently , can b e fed t o al ky l at i on reactors.
T y p i c al l y , the ZSM-5 i s contained i n a separate micro-
spheroidal p art i c l e which i s p h y s i c al l y b lended with conventional
z eol i t e Y b ased cracking c at al y s t s p ri or t o ad d i t i on t o the FCC
u n i t . Concentration of the ZSM-5 c ry s t al i n the FCC u n i t can b e
regulated conveniently b y t h i s approach and i s , generally , i n the
range 0.5-3.0 weight % of the t ot al c at al y s t inventory .
The pore opening i n ZSM-5 i s smaller than for z eol i t e Y and
access of the complex gas o i l molecules i n t o the pores w i l l b e
res t ri c t ed . As a res u l t , ZSM-5 has l i t t l e effec t on the primary
cracking of gas o i l and, when allowance i s made for the s l i g h t
l os s i n conversion ari s i n g from d i l u t i on of the ac t i v e z eol i t e Y
concentration, there i s no s i g n i fi c an t change i n coke, b ottoms,
or l i g h t gas y i el d s .
0097-6156y9iy0452-0056$06.75/0

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5. RAWLENCE AND DWYER Modification of FCC Catalysis 57
The major rol e of ZSM-5 i s t o reac t with converted products
and, i n p art i c u l ar, c ert ai n gasoline components. The shape
s el ec t i v i t y of the z eol i t e allows only l i n ear and mono-methyl
p araffi n s and ol efi n s ready access t o ac t i v e s i t es wh i l s t other
structures, such as aromatics and multi-b ranched p araffi n s , w i l l
b e res t ri c t ed [ 2]. Octane enhancement with ZSM-5 ari s es from
t h i s shape s el ec t i v i t y as the most ac c es s i b l e hy drocarb ons are
al s o octane depressants, wh i l s t those structures precluded from
the z eol i t e structure e.g. aromatics have high octane rat i n g s .
The gain i n octane therefore res u l t s from the combined effec t of
reducing the concentration of low octane compounds together with
the rel at i v e increase i n concentration of d es i rab l e hy oxocarb ons
as a res u l t of the ov eral l l os s i n gasoline y i el d . In addition,
isomerisation of l i g h t l i n ear ol efi n s can occur, leading t o
fu rt h er octane enhancement [ 3].
T h i s paper examines the ov eral l reac t i on between ZSM-5 and
gasoline i n more d et ai l b y comparing the compositional changes
t h at ari s e aft er cracking of gasoline over a deactivated ZSM-5
c at al y s t . In addition, gasoline wer-cracking over a REHY
c at al y s t i s studied i n p aral l el t es t s , allowing comparisons t o b e
made between the shape s el ec t i v i t y and hy drogen t ran s fer
properties of the respective z eol i t e structures.
EXPERIMENTAL
A conventional mi c ro-ac t i v i t y (MAT) reactor was employed i n these
studies [ 4]. Reactor temperature was 516C and operating
conditions were s et at 4.08 c at al y s t / feed rat i o, 11.8 WHSV.
The feed used was an FOC gasoline sample ob tained from a
European refi n ery and was sub sequently d i s t i l l e d t o g i v e an
approximate b oi l i n g range of 35-190C.
The gasoline feed was cracked over a fi xed b ed (4.69g) of
the relevant c at al y s t and l i q u i d and gaseous products were
c ol l ec t ed i n conventional MAT rec ei v ers . Gaseous products were
analy sed on a dual-column Hewlett Packard 5890 gas dircmatograph
where hy drogen and nitrogen were q u an t i fi ed on a 13X column
l i n ked t o the TCD detector. Individual hy drocarb ons i n the
number range CI - CJ were q u an t i fi ed on a 50m alumina-PIOT column
carb on l i n ked t o an FID detector. The l i q u i d frac t i on from each
t es t was analy sed d i rec t l y on a PIONA analy ser supplied b y
An al y t i c al Control BV.
Results from b oth analy ses were combined t o g i v e carb on
d i s t ri b u t i on i n the range 0-10 b y several hy drocarb on ty pes
namely i s o, normal and c y c l o p araffi n s , i s o, normal, and c y c l o
ol efi n s , and mono-ring aromatics. For convenience these groups
are ab b reviated t o IP, NP, CP, 10, NO, CO, and AR res p ec t i v el y ,
and s u ffi xed b y the relevant carb on number i . e. IP-5 equates t o
t ot al C5 i s o-p araffi n s .

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58
Coke on c at al y s t was measured b y a IECO 244 Carb on/ Sulphur
analy ser.
Cracking reactions were duplicated and the res u l t s were
averaged. In a l l cases, mass b alances were i n the range
98.0-100.5% and res u l t s were normalised t o 100% using a feed
weight c orrec t i on .
The REHY c at al y s t employed was a commercial Quantum 2000
sample with a rare earth content of 1.27 wt%. The ZSM-5 c at al y s t
was prepared on a p i l o t p l an t spray dry er from 25% wt% z eol i t e,
25% wt% s i l i c a s ol , and 50 wt% kaol i n c l ay . The ZSM-5 sample
used i n t h i s study analy sed at 30:1 s i l i c a-al u mi n a rat i o.
Both c at al y s t s were el u t ri at ed , pre-heated at 538C i n a i r
for 3 hours, and f l u i d b ed steam deactivated at 816C for 5 hours
i n 100% steam. Aft er t h i s treatment, the u n i t c e l l s i z e of the
REHY component i n Quantum 2000 reduced from 2.453 nm t o 2.427 nm.
EFFECT OF ZSM-5 ADDITION
Lab oratory s c al e FCC evaluation studies are u s u al l y conducted i n
fi xed b ed reactors such as MAT, the res u l t s from which can
provide a rel i ab l e and rap i d means of ranking c at al y s t
performance [ 4]. Depending upon the conditions employed, the
effec t of added ZSM-5 can al s o b e predicted [5] and can give the
same trends as those experienced i n ccsnmercial reactors. For
example, the effec t of 2.5 wt% ad d i t i on of ZSM-5 on gas o i l
cracking y i el d s with Quantum 2000 i s describ ed i n Tab le 1. In
t h i s example, a 4% reduction i n gasoline y i el d occurs,
predominantly from 105C+ material. The L.P.G. composition
i n d i c at es an enhancement of propene, b utenes, and iso-b utane, i n
agreement with commercial res u l t s and, furthermore, the rel at i v e
increase i n the i n d i v i d u al b utenes are s i mi l ar t o those reported
b y Schipper et a l [ 1].
From d et ai l ed PIGNA analy ses of the gasoline frac t i on s [5]
i t was apparent t h at i s o-p araffi n s , p art i c u l arl y i n the C7-C9
range, were the most reac t i v e towards ZSM-5. However the
gasoline composition produced from such reactors tends t o b e
p araffi n ri c h , and ol efi n d efi c i en t when compared t o commercial
samples.
Commercial FCC gasolines have, for example, a low
concentration of n-paraffins which, although they can b e eas i l y
cracked b y ZSM-5, are u n l i kel y t o b e the major source of propene
and b utenes as has b een claimed [ 6]. However, such gasolines
have much higher l ev el s of n -ol efi n s which al s o react read i l y
with ZSM-5 [7] and could therefore contrib ute s i g n i fi c an t l y t o
the ov eral l effec t on L.P.G./ gasoline composition induced b y ZSM-
5. In order t o investigate more f u l l y the ori g i n s of the L.P.G.
components and the changes i n gasoline composition, a s eri es of
ever-cracking studies were conducted using a commercial FCC
gasoline as feed. By comparing the res u l t s ob tained with ZSM-5

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RAWLENCE AND DWYER Modification of FCC Catalysis
TABLE 1
EFFECT OF ZSM-5 ON GAS-OIL CRACKING
YIELD (Wt% Feed) Q-2000 Q-2000/ZSM-5
Conversion ( to 221C) 68.00 68.00
Coke 2.10 2.13
350C Bottoms 9.25 9.70
35-221C Gasoline 49.45 45.40
105-221C Gasoline 26.91 23.71
35-105C Gasoline 22.54 20.69
L.P.G. 14.74 18.66
Dry Gas 1.73 1.84
H2-C4 GAS YIELDS (Wt% Feed)
Hydrogen 0.053 0.048
Methane 0.52 0.53
Ethane 0.52 0.54
Ethene 0.62 0.68
Propane 0.82 0.88
Propene 4.34 5.92
Iso-Butane 3.56 4.12
N-Butane 0.73 0.81
1-Butene 1.23 1.54
C-Butene-2 1.14 1.44
T-Butene-2 1.63 2.06
Iso-Butene 1.29 1.81
MAT CONDITIONS
Feed : Kuwait Waxy Di s t i l l at e
Catalyst/Feed : 3.50
WHSV : 13.7
Reactor Temperature : 516C
Cataly st Deactivation : 5 hours, 816C, 100% Steam

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with those using REHY the rel at i v e effec t s of hy drogen t ran s fer
compared t o shape s el ec t i v i t y could al s o b e studied.
PARENT GASOLINE (IMPOSITION
FIONA an al y s i s b y weight % of the parent gasoline i s reported i n
Tab le 2A and includes the low l ev el of C11+ material not
completely analy sed b y PICNA. I t i s more convenient t o eliminate
t h i s frac t i on and express the remainder as moles per 100 moles
CIO- feed (Tab le 2B) and, on t h i s b as i s , the average molecular
weight of the parent gasoline feed i s computed at 101.8, with a
c al c u l at ed density of 0.7542 g/ml and a U/C atomic rat i o of 1.88.
OVER-VIEW OF GASOLENE CRACKING
Results from the ov er-c oc ki n g of the parent gasoline over
z eol i t es ZSM-5 and Y are summarised i n Tab le 3.
I t i s evident that ZSM-5 i s more ac t i v e for gasoline
cracking as 23.7 wt% L.P.G. + dry gas was produced compared with
18.2 wt% for REHY. As i s commonly ob served, a lower coke y i el d
was al s o produced with ZSM-5.
The REHY c at al y s t produced more saturated l i g h t gas, most
l i k e l y due t o the s l i g h t l y ac t i v e matrix components, present i n
the cxxnmercial sample b ut ab sent from the experimental ZSM-5
c at al y s t . However, t ot al dry gas y i el d s were s i mi l ar for b oth
z eol i t es due t o the enhanced ethene y i el d s ob served with ZSM-5.
S i mi l arl y , REHY produced more saturated L.P.G., notab ly i s o-
b utane, p os s i b l y as a res u l t of hy drogen t ran s fer reactions
i n v ol v i n g ol efi n s . Propene and t ot al b utenes al s o increase, b ut
there i s a rel at i v el y low gain i n iso-b utene. A considerab le
amount of propene i s formed with ZSM-5, accounting for 40% of
converted product, and wh i l s t t ot al b utenes are n i c ker than for
REHY, the enhanced production of iso-b utene i s the major
c on t ri b u t i n g fac t or. Again, with ZSM-5, the rel at i v e gains i n
the i n d i v i d u al b utenes i s s i mi l ar t o those reported b y Schipper
et a l [ 1].
The an al y s i s of product gasoline i n d i c at es an increased
aromatic content with the ZSM-5 b ut t h i s ari s es s ol el y from a
concentration effec t fl .6 1 . The gain i n aromatics with REHY,
however, i s greater than can b e explained b y concentration alone
and suggests ad d i t i on al aromatic formation from more extensive
hy drogen t ran s fer reactions.
In b oth cases, there i s l i t t l e reac t i on with c y c l o-p araffi n s
b ut c y c l o-ol efi n s v i rt u al l y disappear with REHY. ZSM-5 al s o
reacts with c y c l o-ol efi n s , and a s i mi l ar res u l t has b een ob served
with g as -oi l cracking [ 6].

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TABLE 2
PARENT GASOLINE ANALYSIS
TABLE 2A - WEIGHT % OF HYDROCARBON TYPES
PARAFFINS OLEFINS AROMATICS TOTAL
c# i s o n c y c l o i s o n c y c l o
0 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
1 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
2 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
3 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
4 0.22 0.34 0.00 0.33 1.37 0.00 0.00 2.26
5 4.01 0.81 0.13 3.23 3.72 0.00 0.00 11.01
6 3.87 1.00 1.86 4.26 3.35 2.13 0.42 17.78
7 2.78 0.57 2.32 4.82 1.18 2.79 4.46 18.93
8 2.03 0.39 1.81 3.72 0.43 2.14 6.75 17.26
9 1.71 0.30 1.08 2.74 0.33 0.84 6.57 13.58
10 1.42 0.25 0.52 2.08 0.34 0.28 10.91 15.80
TOT 16.04 3.66 7.72 21.18 10.72 8.18 29.11 96.62
Coke 0.00
Un-analy sed C11+ 3.38
100.00
TABLE 2B - MT>TFS PRE? mn MDT FS FRFT>
c#
AROMATICS TOTAL
0 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
1 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
2 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
3 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
4 0.39 0.60 0.00 0.60 2.48 0.00 0.00 4.06
5 5.65 1.14 0.18 4.68 5.39 0.00 0.00 17.06
6 4.57 1.18 2.20 5.15 4.05 2.57 0.55 20.26
7 2.82 0.58 2.35 4.99 1.22 2.89 4.92 19.78
8 1.81 0.35 1.61 3.37 0.39 1.94 6.46 15.93
9 1.36 0.24 0.86 2.21 0.27 0.68 5.56 11.16
10 1.01 0.18 0.37 1.51 0.25 0.20 8.26 11.79
TOT 17.61 4.26 7.57 22.51 14.05 8.28 25.75 100.03

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TABLE 3
SUMMARY OF GASOLINE OVER-CRACKING
YIELD (Wt% Feed)
C5-10 Gasoline
L.P.G.
Dry Gas
Coke
PARENT
94.36
2.26
0.00
0.00
ZSM-5
73.36
22.45
23
58
ZEOLITE Y
78.32
16.92
1.37
1.46
H2-C4 GAS COMPOSITION (Wt% Feed)
Hydrogen
Methane
Ethane
Ethene
Propane
Propene
Iso-Butane
N-Butane
1-Butene
C-Butene-2
T-Butene-2
Iso-Butene
0.00
0.00
0.00
0.00
00
,00
22
,34
,42
39
56
33
0.028
0.18
0.13
0.89
43
23
19
64
82
70
42
0.051
0.44
0.38
0.58
0.70
4.83
4.01
16
04
41
32
70
66
C5-C10 GASOLINE ANALYSIS (Wt% Gasoline)
Average Mol.Wt 101.8
T ot al IP
T ot al NP
T ot al CP
T ot al IO
T ot al NO
T ot al CO
T ot al AR
16.8
3.5
8.2
22.1
9.9
8.7
30.9
94.6
26.
4.
9.
9.
8.
2.
38.
94.4
36.
4.
8.
6.
4.9
0.6
39.3
.3
.7
.2
.0

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RESULTS AND DISCUSSION
More d et ai l ed res u l t s of gasoline ever-cracking with ZSM-5 or Y
are given i n Tab les 4 and 5 where, for each hy drocarb on ty pe and
carb on number, the d i fferen c e i n moles i . e. moles product - moles
(parent) are presented. From these, d el t a mole d i s t ri b u t i on s for
t ot al hy drocarb on and for p araffi n s and ol efi n s can b e compared
(Figures 1-5).
The impression from the t ot al hy drocarb on d i s t ri b u t i on
(Figure 1) i s t h at b oth z eol i t es b ehave i n a s i mi l ar manner b y
producing C3-C5 products from C6+ hy drocarb ons, the most
s i g n i fi c an t d i fferen c e b eing the rat i o of C3/C4 y i el d s . However,
as i s apparent from Figures 2-5, there are marked d i fferen c es i n
p araffi n s and ol efi n s for each z eol i t e.
Cl earl y the losses and gains of a p art i c u l ar species present
i n the product gasoline as compared t o the parent feed gasoline
can represent the b alance of complex reactions. However, under
the reac t i on conditions employed, i t i s not l i k e l y that there
w i l l b e appreciab le generation of C6+ hy drocarb ons other than as
intermediates, so that an examination of reactant losses i n t h i s
region provides a reasonab le comparison of reactant conversion
over the two z eol i t es .
Figure 2 shows that there i s a l i mi t ed conversion of higher
p araffi n s on ei t h er z eol i t e. There i s some evidence t o suggest
t h at C7/C8 p araffi n conversion i s higher with ZSM-5 and C9/C10
with REHY. However, i t would appear t h at ZSM-5 i s not, under the
present conditions, p art i c u l arl y effec t i v e i n p araffi n
modification i n the presence of a rel at i v el y high concentration
of ol efi n s .
REACTIONS OF OIEFINS
For b oth z eol i t es , the major reactants are the b ranched and
l i n ear C6+ ol efi n s . The i s o-ol efi n s present i n the FCC gasoline
are considered t o b e predominantly mono-branched which, using C8
i s o-ol efi n (IO-8) as an example, react t y p i c al l y as i n Scheme 1.
A previous report indicates that the conversion of 10-8 at 450C
gives mainly C4 products with l i t t l e C3 + C5 [ 8]. T h i s suggests
t h at the increased rat e of b eta s c i s s i on associated with the
c oc ki n g of the C8 c at i on isomer (III, Scheme 1) i s the preferred
route t o cracked products. This i s i n keeping with the accepted
order of reac t i v i t y for cracking (A > B > C), and s i mi l ar
c oc ki n g schemes can b e postulated for the other C6+ ol efi n s .
[ 8,9].
The major products, for b oth z eol i t es are C2-C5 ol efi n s
(Figures 3-5) and C1-C6 p araffi n s . Results show c l earl y the
enhanced b imolecular hy drogen t ran s fer with REHY as compared t o
ZSM-5 since i n d i v i d u al C1-C7 p araffi n s are c on s i s t en t l y higher

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TABLE 4
GASOLINE OVER-CRACKING WITH ZSM-5
DELTA MDTKS PER 1QQ MDTiES FRRD
c#
PARAFFINS OLEFINS
AROMATICS TOTAL
AROMATICS TOTAL
0 +0.00 +1.62 +0.00 -KD.00 + 0.00 +0.00 +0.00 + 1.62
1 +0.00 +1.14 +0.00 +0.00 + 0.00 +0.00 +0.00 + 1.14
2 +0.00 +0.44 +0.00 +0.00 + 3.23 +0.00 +0.00 + 3.67
3 +0.00 +0.99 +0.00 +0.00 +22.31 +0.00 +0.00 +23.30
4 +3.45 +0.53 +0.00 +6.67 + 8.28 +0.00 +0.00 +18.93
5 +3.54 +0.17 -0.01 -0.14 + 2.25 +0.00 +0.00 + 5.80
6 +2.25 +0.13 -0.20 -1.40 - 3.05 -1.43 -0.21 - 3.90
7 +0.10 -0.07 +0.14 -4.63 - 1.15 -2.12 +1.11 - 6.62
8 -0.12 -0.05 -0.09 -3.24 - 0.32 -1.60 +0.87 - 4.54
9 -0.20 -0.04 -0.17 -2.21 - 0.23 -0.68 +0.03 - 3.49
10 -0.24 -0.04 -0.11 -1.51 -0.25 -0.20 -2.08 - 4.44
TOT +8.78 +4.28 -0.44 -6.46 +31.08 -6.03 -0.28 31.47
TABLE 5
GASOLINE OVER-CRACKING WITH REHY
DELTA MOLES PER 100 MOLES FEED
c#
AROMATICS TOTAL
0 +0.00 +2.44 +0.00 -KD.00 + 0.00 +0.00 +0.00 + 2.44
1 +0.00 +2.79 +0.00 +0.00 + 0.00 +0.00 +0.00 + 2.79
2 +0.00 +1.01 +0.00 +0.00 + 2.10 +0.00 +0.00 + 3.12
3 +0.00 +1.61 +0.00 +0.00 +11.67 +0.00 +0.00 +13.29
4 +6.72 +1.23 +0.00 +2.41 + 5.89 +0.00 +0.00 +16.25
5 +9.30 +0.51 +0.01 -1.33 - 0.94 +0.00 +0.00 + 7.55
6 +5.88 +0.19 +0.11 -2.95 - 3.29 -2.25 -0.22 - 2.53
7 +1.37 +0.01 -0.08 -4.52 - 1.11 -2.76 +1.40 - 5.68
8 +0.32 -0.03 -0.41 -3.27 - 0.36 -1.91 +2.53 - 3.13
9 -0.17 -0.04 -0.41 -2.21 - 0.24 -0.68 +1.04 - 2.71
10 -0.35 -0.04 -0.24 -1.51 - 0.25 -0.20 -2.52 - 5.11
TOT --23.07 +9.68 -1.02 -13.3' '+13.48 -7.79 +2.23 +26.26

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B- Isom
(D
C- Cracking
H*
( 2) (3)
B- Cracking A- Cracking
Scheme (1)

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5. RAWLENCE AND DWYER Modification of FCC Catalysis
71
for reactions over REHY, with the converse b eing t ru e for ol efi n s .
The product d i s t ri b u t i on for ZSM-5 favours C3 hy drocarb ons (23
moles) compared t o 13 moles with REHY. This trend has al s o b een
ob served i n the cracking of several p araffi n s [10] and t h i s i s
assigned t o cage effec t s . This explanation may al s o apply here
as the rat i o of C3/C4 (1.00 for ZSM-5 and 0.65 for REHY) w i l l
rat i o t o 1.54, a value s i mi l ar t o t h at derived from the cracking
of Cn hy drocarb ons [ 10]. A s t ru c t u ral as opposed t o a
compositional effec t for the enhanced C3/C4 rat i o i n ZSM-5 i s
supported b y res u l t s from a p aral l el s eri es of t es t s on gasoline
cracking using a US-Y of s i mi l ar s i l i c a-al u mi n a rat i o t o t h at of
ZSM-5 describ ed here [ 11]. The C3/C4 rat i o from t h i s study was
i d en t i c al t o t h at ob served for REHY.
Results for C4 products (Tab le 6) i n d i c at e that, wh i l s t the
t ot al C4 y i el d i s s l i g h t l y higher with ZSM-5 (due t o the greater
conversion compared t o REHY), the rat i o of p>araffins t o ol efi n s
i s s i g n i fi c an t l y lower, and i s p art i c u l arl y so with the i s o
cx3mpounds. T h i s refl ec t s the greater f a c i l i t y for hy drogen
t ran s fer i n REHY, as opposed t o ZSM-5, which can b e explained i n
terms of the influence of s i t e proximity [ 12], or the effec t s of
sorption preference [13] b oth of which favour hy drogen t ran s fer
i n more alumina-rich z eol i t es .
TABLE 6
YIELDS OF C4 products ( A MOLES)
REHY
i s o normal i s o normal
3.45 0.53 6.72 1.23
6.67 8.28 2.41 5.89
10.12 8.81 9.13 7.12
PARAFFINS
OLEFINS
TOTALS
TOTAL C4 18.93 16.25
PARAFFIN/OIEFIN 0.27 0.96
i-BCJTANE/i BOTENE 0.52 2.79
Si z e res t ri c t i on s i n ZSM-5 are expected t o i n h i b i t hy drogen
t ran s fer processes [ 14]. However, the y i el d of iso-b utane shows
that t h i s process i s not en t i rel y excluded i n ZSM-5 since
al t ern at i v e explanations for s u b s t an t i al y i el d s of t h i s product,
for example d i rec t attack of alkane chains b y protonic hy drogen or
b y carb enium ions, seem l es s l i k e l y i n view of the l i mi t ed
reac t i on of higher alkanes (Figure 2) under the present
conditions. Si z e res t ri c t i on s on b imolecular hy drogen t ran s fer
i n v ol v i n g l arg er b ranched ol efi n i c carb enium ions such as those
generated from c y c l o-ol efi n s are expected t o b e more s i g n i fi c an t
with ZSM-5, however, and w i l l b e discussed l at er.

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72
Both normal and iso-b utenes are formed l arg el y from higher
ol efi n s b ut are not i n i t i a l l y i n thermodynamic eq uilib rium. In
ZSM-5, eq uilib rium between the b utenes i s approximated b ut there
i s excess iso-b utane over n-b utane. S i mi l arl y for REHY, i s o-
b utane i s al s o i n excess of eq uilib rium b ut there i s a c l ear
d efi c i en c y i n iso-b utene. Y i el d s of iso-b utene are very
susceptib le t o the hy drogen t ran s fer function of z eol i t e Y [11]
and the present ob servation may b e explained i f i t i s assumed
t h at hy drogen t ran s fer i n v ol v i n g the iso-C4 c at i on i s rel at i v el y
rap i d compared t o isomerisation. In t h i s case iso-b utene w i l l b e
depleted with REHY b ut much l es s hy drogen t ran s fer reac t i on w i l l
occur with ZSM-5. Excess iso-b utane over eq uilib rium i s ob served
for b oth z eol i t es and suggests t h at b imolecular hy drogen t ran s fer
i n v ol v i n g nC4 cations i s l es s rap i d than for the iso-C4 c at i on .
We are not aware
of any d et ai l ed studies for these reactions b ut suggest,
t en t at i v el y , t h at the greater s t ab i l i t y of the iso-C4 c at i on may
enhance i t s concentration and increase the rat e of (b imolecular)
hy drogen t ran s fer as compared t o the n-C4 c at i on which
p referen t i al l y desorb s t o ol efi n s .
Reference t o Figure 6 shows that, i n ad d i t i on t o the greater
y i el d of i s o-p araffi n s over REHY, the d i s t ri b u t i on s are d i fferen t
for the two z eol i t es . The l arg er C5-C7 iso-alkanes are
rel at i v el y more abundant with REHY suggesting t h at hy drogen
t ran s fer i n the l arg er pore z eol i t e can take place more read i l y
with l arg er carb enium ions. In the smaller pore ZSM-5, the
reduced rat e of hy drogen t ran s fer, discussed above, along with
reduced space, for b imolecular reactions i n v ol v i n g l arg er ions
favours more s c i s s i on of these l arg er ions t o smaller ions where
a l i mi t ed amount of hy drogen t ran s fer can then occur t o produce
l i g h t alkanes.
REACTIONS OF CYCLIC STRUCTURES
Cy clo-paraffins react more read i l y with REHY, presumab ly as a
res u l t of pore s i z e d i fferen c es between the 10 ri n g ZSM-5 and the
12 ri n g fau j as i t e, res u l t i n g i n s i z e d i s c ri mi n at i on (reactant
shape s el ec t i v i t y ) . Over b oth z eol i t es , C9-C10 c y c l o-ol efi n s are
completely converted so t h at s i z e d i s c ri mi n at i on i s not ob served.
However, where conversion of c y c l o-ol efi n s i s not complete ( i . e.
C6-C8) there i s c l ear evidence for cUscximination between the two
z eol i t es (Figure 7). Presumab ly t h i s high reac t i v i t y of C9/C10
c y c l o-ol efi n s over ei t h er z eol i t e can b e explained b y i n i t i a l
fac i l e attack at outer surfaces.
Reactions of c y c l o-ol efi n s within the z eol i t es can generate
aromatics b y b i-molecular hy drogen t ran s fer reactions. Such
reactions are expected t o b e more favourab le with REHY b ecause of
i t s greater framework aluminium content and b ecause of res t ri c t ed
access t o the i n t er-c ry s t al l i n e pores i n ZSM-5. T h i s i s

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REHY
ZSM- 5
0 1 2 3 4 5 6 7 8 9 10
CRRBON NUMBER >
Figure 7 : Rel at i v e l os s of c y c l o-ol efi n s .

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supported b y the increased t ot al aromatics ob served with REHY.
There are changes i n composition of the aromatics frac t i on i n
ZSM-5 b ut t h i s i s l arg el y accounted for b y the d eal ky l at i on of
CIO aromatics t o C7/C8 aromatics i . e.
AR-10 > AR-8 + NO-2
AR-10 > AR-7 + NO-3
As t ot al number of aromatic ri n g s remains constant for
ZSM-5, the converted cy cle-hy drocarb ons must l arg el y b e cracked
t o non-cy clic smaller molecules. To an extent, t h i s must al s o b e
t ru e for REHY since l es s aromatics are formed than t ot al c y c l o-
hy drocarb ons are l os t .
Cracking patterns for c y c l o-p araffi n s over US-Y have
rec en t l y b een reported [9] where products from the conversion of
methy cy clchexane include C2-C6 exxrpounds with C3 + C4
hy drocarb ons as the major y i el d s . The authors of t h i s study have
assumed that iscmerisation of the i n i t i a l carb enium i on i s
rel at i v el y fac i l e and that a comb ination of hy drogen t ran s fer,
iscmerisation, and b eta s c i s s i on generates the products. T h i s i s
envisaged i n Scheme 2 which uses the c l as s i fi c at i on A, B, C for
cracking, A, B for iscmerisation [8.9] and which presumes t h at
intramolecular hy drogen t ran s fer i s rap i d [ 8].
S i mi l ar fates can b e postulated for isomers II and III
(Scheme 2A) and al s o for C8 - CIO c y c l o-ol efi n s which would
generate C4+ ol efi n s . C5 and C6 ol efi n s are al s o presumed t o
ari s e from cracking of methy lcy clopentane [8] b y the i n t erac t i on
of small carb enium ions with ol efi n s t o form l arg er carb enium
ions which can sub sequently undergo b eta s c i s s i on . Such
reactions can c l earl y modify product d i s t ri b u t i on s i n the present
more complicated system.
Scheme 2 suggests that the rel at i v el y large ol efi n i c
carb enium ions are involved i n b imolecular hy drogen t ran s fer
reactions generating ol efi n s which can then reac t further. T h i s
process i s l i k e l y t o b e i n h i b i t ed i n the smaller pore ZSM-5 which
could res u l t i n more conversion v i a intramolecular reac t i on paths
t o g i v e a l l y l i c or d i -ol efi n i c intermediates, as i n Scheme 3.
Under the present conditions, i n v ol v i n g long contact times and
high conversion, dienes are not ob served with ei t h er c at al y s t .
Low y i el d s of b utadiene are ob served during ri s er cracking with
z eol i t e Y b ased c at al y s t s ; t o date, however, there i s no
evidence for increased diene formation with ZSM-5.
CONCLUSIONS
From a study of gasoline over-cracking with ei t h er ZSM-5 or REHY,
the res u l t i n g t ot al hy drocarb on d i s t ri b u t i on s b y carb on number
are g ros s l y s i mi l ar. In b oth cases, predominantly C2 - C5
products are formed from C6+ components. However, there are
s i g n i fi c an t d i fferen c es i n d et ai l , notab ly i n hy drocarb on-ty pe
d i s t ri b u t i on s .

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(Isomers)
<*y (2)
(1)
(3)
C- Cracking
(nC
7
Carbenium ion)
RH + R*
B- Isom
C-Cracking ^ +
Scheme (2)

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Scheme (3)

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The major effec t of ZSM-5 i s t o convert higher molecular
weight i s o-ol efi n s i n t o C3/C4 ol efi n s with no d i s c ern i b l e change
i n aromatics other than some d eal ky l at i on of the C9+ frac t i on .
Most of the enhanced LPG ol efi n i c i t y ari s es from cracking of C7+
ol efi n s and a pore s i z e effec t i s thought t o b e responsib le for
the high C3/C4 rat i o compared t o REHY.
A major d i fferen c e between the two z eol i t es concerns the
extent of b imolecular hy drogen t ran s fer. Whilst REHY i s al s o
very reac t i v e with C7+ ol efi n s , l es s t ot al b utenes are formed due
t o hy drogen t ran s fer involving, i n p art i c u l ar, iso-b utene >
iso-b utane. The more effec t i v e hy drogen t ran s fer i n REHY i s al s o
evident from the hici p araffi n / ol efi n rat i o and from increased
coke production.
ACKNOWLEDGMENTS
The authors wish t o acknowledge Dr. G.J. Earl ,
Mr. A. Howard Monks, Mr. M.R. Butler, Miss C. de Prez , and
Mr. M. Woodhouse of Cros fi el d Cataly sts for the preparation and
analy ses of the c at al y s t s and Dr. B. Booth of U.M.I.S.T. for
h el p fu l discussion.
LITERATURE CITED
1. Schipper P. H. ; Dwyer F. G. ; Sparrell P. T. ; Mizrahi S;
Herbst J. A. In Fluid Catalytic Cracking : Role in Modern
Refining : American Chemical Society, 1988, P.65.
2. Chen N. Y. ; Garwood W. E. , J. Catal. 1978, 58, p.453.
3. Scherzer J. Catal.Rev.-Sci.Eng., 1989, 31(3), p.215
4. Rawlence D. J. ; Gosling K. Appl. Catal. , 1988, 43, p.213
5. Rawlence D. J. ; Dwyer J., In preparation.
6. Biswas J.; Maxwell I. E. In Zeolites : Facts, Figures, Future;
Elsevier 1989, p.1263.
7. Wojciechowski B. J.; Corma A. Catalytic Cracking;
Marcel Dekker Inc. , 1986, p.154.
8. Lin L.; Gnep N. S. ; Guisnet M.R. Symposium on the
Hydrocarbon Chemistry of Naphtha Formation, ACS Div. Pet.
Chem.Inc, American Chemical Society Miami, Sept. 1989, p.687.
9. Weitkamp J.; Jacobs P. ; Martens P.A. Appl. Catal. , 1983, 8,
p.123.
10. Barthomuef D. ; Merodatos C. Reference 8, p.714.
11. Rawlence D. J. Unpublished results.
12. Pine L.; Mather P.J.; Wachter W.A. J. Catal. 1984, 85,
p.466.
13. Corma A. ; Faraldos M. ; Mifsud A. Appl. Catal. 1989, 47,
p.125.
14. Haag W.O.; Weiss P.B. Chem. Soc. Faraday Disc. 1981, p.317
RECEIVED October 5, 1990

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Chapter 6
Hydrothermal Stability and Cracking Behavior
of Silicoaluminophosphate Molecular Sieve-37
with Different Silicon Contents
A. Corma, V. Forns, M. J. Franco, F. A. Mochol, and J. Prez-Pariente
Instituto de Tecnologa Qumica, UPV-CSIC, Universidad Politcnica
de Valencia, Camino de Vera S/N, 46071 Valencia, Spain
The decomposition of organic templates i n
SAPO-37 and the evolution of the hydroxyl
groups upon cal ci nati on as well as the
stability of the framework have been followed
by IR spectroscopy. Moreover, acti vi ty and
selectivity to n-heptane and gas-oil cracking
allow us to discuss the acidity character of
SAPO-37 as compared to USY zeolites.
The main objective i n FCC catal yst design i s to prepare
cracki ng catal yst compositions which are acti ve and
selective for the conversion of gas-oi l into high octane
gasol i ne f r act i on. From the poi nt of view of the
zeol i ti c component, most of the present advances i n
octane enhancement have been achieved by introducing low
unit cel l size ul trastabl e zeol i tes ( 1) and by i ncl usi on
of about 1-2$ of ZSM-5 zeol i te i n the fi nal catal yst
formulation (2). With these formulations, i t i s possible
to i ncrease the Research Octane Number (RON) of the
gasol i ne, while only a minor i ncrease i n the Motor
Octane Number (MON) has been obtained. Other materials
such as mixed oxides and PILCS (3,4) have been studied
as possi bl e components, but there are sel ect i vi t y
l i mi tati ons which must be overcome.
The actual research i s focused on finding new types
of zeol i tes or modifying al ready known ones (5), to
sel ecti vel y catal yze branching isomerization and sel f
al kyl ati on reactions i n the gasol i ne f ract i on, while
minimizing overcracking. Efforts have also been devoted
to development of new active and selective matrices.
In the f i r st l i ne of research, l arge pore high
si l i ca to alumina rati o zeol i tes obtained by synthesis,
0097-6156/91/0452-0079$06.00/0

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80
such as Beta and ZSM-20, have been studied for catal yti c
cracking (6-9). Beta zeol i tes produce gasol i ne with a
higher RON than USY, but at the same time give more
gases and less gasoline. ZSM-20 zeol i te shows a si mi l ar
cracki ng behavi or to faujasi te (10), whi ch i s not
surpri si ng taking into account that i t i s a faujasi te
type structure cryst al l i zed with cubi c and hexagonal
symmetry (11).
The synthesi s of a new type of mol ecul ar sieves
contai ni ng si l i con, aluminum and phosphorous i n the
framework (SAPOS) (12), has opened new possi bi l i ti es for
increasing the RON and MON of the gasoline obtained i n
FCC. The possi bi l i ty of using di fferent SAPO structures
as components i n FCC cat al yst s has al so recent l y
appeared i n the patent l i terature (12-20). SAPO-37, with
a faujasi te structure, looks especi al l y promi si ng and
deserves further studies. SAPO-37 has low stabi l i ty i n
the presence of water at room temperature after hi gh
temperature acti vati on (12,22). This complicates the use
of structural reasons to give a chemical i nterpretati on
of SAPO-37 cracking behavior.
In the present work, samples of SAPO-37 wi th
di fferent si l i con content have been synthesized, and
studi ed from the poi nt of view of thei r st abi l i t y,
physi cochemi cal and texture characteri sti cs. Fi nal l y
thei r behavior as cracking catalysts has allowed us to
formulate a hypothesis on the parameters which control
acti vi ty and sel ecti vi ty i n SAPOS.
Experimental Materials
The SAPO-37 samples were synthesized following a proce-
dure si mi l ar to that descri bed by Sal darri aga et
al . ( 21) . H 3 P O 4 (85#), A I 0 O 3 ( pseudobohemi te),
tetrapropylammonium hydroxide {40% TPAOH, Al fa products
with K+Na= 340 ppm), tetramethyl ammonium hydroxide
pentahydrate (TMAOH.5H2O, from Al dri ch) and Aerosil-200
were used as starti ng materials.
Gel s of the fol l owi ng oxide molar composi ti on:
0. 025( TMA)
2
0:( TPA)
2
0:A1
2
0
3
:P
2
0
5
:xSi 0
2
. 52H
2
0 (x being
0. 5, 1.0 and 1.5 for samples S5/-1, S37-2 and S37-3)
were prepared by adding a solution B into a solution A
with vigorous sti rri ng, and kept at 293 K for 24 hours
i n a cl osed system. Solution A was prepared by adding
the pseudobohemite i nto the phosphoric aci d sol uti on
with vigorous sti rri ng; the viscous mixture was sti rred
for 8 hours i n order to obtai n complete homogeneity.
Solution B was prepared by adding, while sti rri ng, the
TMAOH to the TPAOH unti l i t was di sol ved. The si l i ca was
then added and sti rred for one hour unti l the solution
was homogeneous. The cr ys t al l i zat i on react i on was
carri ed out at 473 K duri ng 22-26 hours i n a stati c
system by usi ng stai nl ess steel autoclaves of 60 cm3
provided with tefl on l i ners. After crystal l i zati on the
SAPO was washed, centrifuged and, fi nal l y, dried at 353

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6. CORMA ETAL. Stability and Cracking Behavior of SAPO-37 81
K. Chemical composition of the fi nal products are given
i n Table I. Minor amounts of unreacted pseudobohemite
were detected by XRD i n al l samples.
Table I. Chemical composition of samples
SAMPLE Molar oxide composition (TO2 formula) Si / u. c.
S37-1
S37-2
S37-3
(Alo.60
p
0.2lSio.19)2
Al
0
.55
p
0.22Si0.23>2
(Alo.51
p
0.20Sio.28)2
36
44
54
Procedures
X-ray powder di f f ract i on was performed on a Phi l l i ps
diffractometer usi ng CuK
a
radi ati on. IR spectroscopy
measurements were car r i ed out i n a conventi onal
greasel ess c el l . Wafers of 10 mg.cm~"2 were pretreated
under di fferent conditions of temperature and vacuum;
the spectra i n the 4000-1300 cm"
1
region were recorded
at room temperature.
The cracking catal ysts were prepared by di l uti ng
SAPO-37 samples i n a s i l i c a mat ri x. The cracki ng
experiments were carri ed out i n a quartz fi xed bed
tubul ar react or af t er "i n si t u" act i vat i on. The
acti vati on was performed by increasing the temperature
up to 823 K at 2K. rai n-
1
, under N
2
flow (240 raLmin"
1
).
These conditions were maintained for 4 hours, and then
N
2
was changed to dry ai r (240 ral.min"
1
) for 1 hour. At
thi s point, the temperature was raised (2K. min"
1
) up to
923 K and maintained overnight. After thi s treatment al l
the organic template was removed from SAPO crystal s.
Table II. Characteri sti cs of vacuum gas-oi l
Density (g/ c) 0.873 Conradson carbon (wt.#) 0.03
API gravity 30. 6" MeABP (
2
C) 366
Nitrogen (ppm) 370 K-UOP 12. 00
Sulfur (%) 1.65 Vi scosi ty (c. s. at 50
2
C) 8.249
Di sti l l ati on Curve (
2
C)
IBP 5 10 20 30 40 50 60 70 80 90 FBP
167 245 281 304 328 345 363 380 401 425 450 551
A vacuum gas-oi l (characteri sti cs given i n Table
II) was cracked at 755 K. The catal yst to oi l rati o
(g. SAPO/g. gas-oi l ) was vari ed between 0.20 and 0.84
g. g"
1
i n order to obtain di fferent l evel s of conversion,

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while the time on stream was always 60 seconds. In thi s
way i t i s possible to obtain the yi el ds of gasol i ne,
di esel , gases and coke at di f f er ent conversi ons.
Conversion i s defined here as the sum of gases, coke,
gasoline (483 K") and di esel (593 K~). The catal yst was
regenerated "in si tu" after each experiment, by passing
100 ml. min-1 of ai r through the reactor at 803 K for 5
hours.
Gases were anal yzed by GC and separated by a
Porapak-Q plus si l i ca column. Liquids were analyzed by
simulated di st i l l at i on.
Results and Discussion
Thermal and hydrothermal stabi l i ty
It has been shown (13,22) that SAPO-37 i s a hi ghl y
t hermal and hydrothermal stabl e mat er i al . More
speci f i cal l y, SAPO-37 free of organi c templ ates i s
stabl e i n the presence of water vapor at temperatures
above 345 K. The crystal l i ni ty i n the presence of water
decreases only i f the contact occurs at temperatures
below 34515 K (22). One hypothesis which would explain
thi s observati on i s the formati on of P-O-P bonds i n
SAPO-37 during treatments, which would hydrolyze at room
temperature i n the presence of water causi ng the
breaking of the P-O-P bonds, while producing the aci d
attack of the Si -O-Al bonds. If this is the reason, i t
becomes apparent that the formation of P-O-P bonds would
occur as a consequence of the acti vati on procedure,
si nce i n our or i g i n a l mat er i al s , 31p MAS NMR
spectroscopy only shows the signal correspondi ng to P
coordi nated with four Al . In order to produce P-O-P
bonds duri ng acti vati on, some deal umi nati on and/ or
breaki ng of some parts of the structure should occur.
Treati ng the SAPO-37 i n a Gui ni er-L enne camera (22)
i ndi cates a smal l deal umi nati on, since the unit cel l
size decreases from 2.469 to 2.465 nm.
When the sample S37-1 i s treated at 923 K i n ai r,
and then cooled down at room temperature into a sealed
jar, the zeol i te is s t i l l highly crystal l i ne i f the X-
ray di ffracti on i s carri ed out rightaway when taking the
sample from the sealed jar (22). However, most of the
crystal l i ni ty i s l ost after 40 minutes i n contact with
moisture. This i s a clear i ndi cati on that the structure
i s not destroyed by the thermal treatment, but takes
place during exposure to moisture at room temperature.
Nevertheless, when the sample was f i rst heated i n the
presence of N
2
at 753 K, for 4 hours and then calcined
at 803 K i n dry ai r (100 mL mi n"
1
) overni ght, i t
retains 75$ of the crystal l i ni ty after exposure to the
moisture at room temperature for several hours. After
thi s treatment al l the TPA
+
has been removed, but most
of the TMA
+
remai ned i n the st r uct ur e. If the
cal ci nati on temperature i s i ncreased to 823 K, the

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6. CORMA ETAL. Stability and Cracking Behavior of SAPO37
83
crystal l i ni ty (after exposure to moisture) i s only 55%
of the ori gi nal value. After the corresponding treatment
at 873 K, crystal l i ni ty retention i s only 20%. Since
al l the TMA
+
has also been removed (see below) at 873 K,
one i s tempted to relate the fi nal effect observed to a
modification of the SAPO-37 structure produced when the
TMA
+
(which i s the countercation i n the sodalite cages)
i s decomposed. This can be due either to a modification
of bond angles (22) or to the formation of P-O-P bonds
due to l ocal breaking of the structure.
In order to better di scuss the i nfl uence of the
decomposition of the organi c templates, the changes
observed i n the zeol i te (and the nature of the remaining
products when heated) were fol l owed "i n si tu" by IR
spectroscopy using a quartz cel l .
In the IR spectra of Figure 1, i t can be seen that
vacuum treatment at 373 K and 1. 33 10"
2
Pa of S37-1
removes most of the water present i n the sol i d (see 1640
cm"
1
band). The bands corresponding to the stretching
vi brati ons of CH
3
- and CH
2
- groups of the templates
appear i n the 2800-2900 cm"
1
region. The study i n the
bending region allows more preci si on on the ori gi n of
the bands, and fol l owi ng Bellamy (23). a tentati ve
assignment could be made:
1491 cm"
1
CH
3
(TMA+)
1484 " -CH
3
(TPA+)
1474-1462 " -CH
2
- (TPA+)
1386,1377
11
-CH
3
(TMA
+
,TPA
+
)
When the sample i s heated i n vacuum at i ncreasi ng
temperatures, the following changes are observed i n the
spectra (Fi g. 1). Fi rst, at 523 K, the 1484 cm"
1
band
decreases while a new band at 1600-1610 cm"
1
appears
which can be assigned to the RNH
3
+
group of a protonated
amine. This indicates that the TPA
+
i s the f i rst organic
decomposing, and that decomposition takes place through
a mechanism involving al i phati c amine intermediates, as
has been proposed i n the l i terature (24). At 573 K, the
IR spectrum shows the presence of, at l east, six types
of hydroxyl groups, whose assi gnment coul d be as
follows:
3745 cm"
1
SiO-H external
3675 " PO-H external
3
632 " Si -O-Al directed to the
supercavity, high
frequency hydroxyls (HF)
3
57
3
it Si -O-Al directed to sodalite
cages, low frequency
hydroxyls (LF)
3612 & 3530 " Assigned, i n pri nci pl e, to HF
& LF hydroxyls shifted by
i nteracti on with organics.

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6. CORMA ETAL. Stability and Cracking Behavior of SAPO-37 85
At 623 K. the rati o of the HF to LF hydroxyls i s
very high, while the 1482, 1462 and 1386 cm"' bands, al l
assigned to TPA
+
, have practi cal l y disappeared. On the
other hand, the 1491 cm"
1
band associated with TMA
+
has
sl i ghtl y decreased. When the sample i s heated at 673 K,
the 1491 cm"
1
band decreases, while the OH population
sl i ght l y i ncreases. If the treatment at 673 K i s
maintained for 16 hours, a strong increase i n both HF
and LF hydroxyl groups i s observed, the increase of the
LF being proporti onal l y bigger. This treatment strongly
decreases the i ntensi ty of the 1491 cm"
1
band. This
resul t i ndi cat es that the el i mi nati on of the TMA
+
located i n the sodalite cages i s strongly control l ed by
di ffusi on.
In order to completely eliminate the organics, the
temperature was raised to 873 K (Fi g. 1) and maintained
for 1 hour. Under these conditions, no bands associated
with organic materials were detected, while a strong
i ncrease i n the i ntensi ty of the HF and LF hydroxyl
bands was observed. From thi s spectrum two points have
to be remarked:
- A decrease i n the i ntensi ty of the bands at 3745
(SiO-H) and 3678 cm"
1
(PO-H).
- The disappearance of the 3612 and 3530 cm"
1
bands.
The f i rst observation could be explained by assuming
that at 873 K there i s a condensation of some M-OH, M
being ei ther Si or P, forming Si -O-Si or P-O-P bonds. The
second observati on agrees wi th the hypothesi s made
above, considering that these two bands correspond to
the HF and LF hydroxyls, shifted to lower frequencies
due to thei r i nteracti on with the organic molecules i n
the cryst al s. When organic molecules are removed, the
i nt eract i on di sappears and, correspondi ngl y, the
hydroxyl band associ ated with thi s i nteracti on also
disappears.
In order to study the influence of the decomposition
of the TPA+ and TMA+ on the st abi l i t y of the f i nal
materi al , a sample heated at 673 K and 1.33 10"
2
Pa (i n
which TMA
+
was s t i l l present) was exposed to moisture at
room temperature for two hours. After thi s treatment,
the IR spectrum shows the presence of a strong band at
1640 cm"
1
charact eri st i c of mol ecul ar water, which
i nteracts with the hydroxyl groups of the SAPO (Fi g. 2).
The presence of species [H2O5]
+
(2500 cm"
1
) which have
also been observed i n HY zeol i tes should be noted (25).
When the sample was dehydrated at 673 K i n vacuum, the
ori gi nal spectrum was restored, i ndi cati ng that the
s t r u ct u r e was mai ntai ned. However, i f the same
experiment i s carri ed out at 873 K ( Fi g. 3), the
subsequent exposure to moisture at room temperature
resul ts i n the disappearance of the structural hydroxyl
groups. The disappearance of these bands can be due

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WAVENUMBER (cm"
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Fi gure 2. IR spectra of sample S37-1 treated at
several conditions: a) vacuum at 673 K. b) after
expos i t i on to at mospheri c moi st ure at room
temperature, c) Sample b) heated again at 673 K.

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CORMA ET AL. Stability and Cracking Behavior of SAPO-37
I i I i i
4000 3500 1700 1500
WAVENUMBER (cm-1)
Fi g u r e 3. IR s p e c t r a of s amp l e S37-1 t r e a t e d at
s ev eral c o n d i t i o n s : a) vacuum at 673 K. b ) vacuum at
873 K. c ) a f t e r e x p o s i t i o n o f s amp l e b ) t o
at mos p h eri c moi s t u re an d h eat ed a g a i n a t 673 K i n
vacuum.

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ei ther to a collapse of the structure or to a breaking
of Si - O- Al bonds and to the compensati on of the
remai ni ng negati ve framework charge by posi ti vel y
charged extra-framework aluminum species. These species
could be formed by parti al dealumination of the zeol i te.
From al l these experiments we can propose one
hypothesi s to expl ai n the s t abi l i t y of H-SAPO-37
mol ecul ar si eve. The el i mi nati on of TMA
+
from the
sodalite units by thermal treatment and the exi t of the
decomposi ti on products through the si x member ri ng
windows produces the breaking of some T-O-T bonds and
the formation of T-OH groups. If the temperature i s high
enough, some of these groups can condensate forming Si -
O-Si or P-O-P bonds. The faci l i ty of hydrolysis of the
P-O-P bonds i n the presence of l i qui d water and the
formati on of very strong aci di c species (which would
attack the structure, preferenti al l y Si -O-Al bonds)
would be responsible for the breakdown of the structure,
and, at l east, for the l oss of the bri dged hydroxyl
groups. Thi s ef f ect coul d be stronger with hi gher
acti vati on temperatures, and could al so be influenced by
the atmosphere i n contact with the sample during the
acti vati on treatment. In Figure 4a i t can be seen that
for samples treated previously i n N
2
and then i n ai r,
the higher the acti vati on temperature i n ai r, the lower
the cr yst al l i ni t y after exposure to moisture at room
temperature. Neverthel ess, al l the organi c has been
removed after cal ci nati on at T>823 K (Fi g. 4b), which
might suggest that the concentrati on of P-O-P bonds
i ncreases with the acti vati on temperature. In contrast
with the behavior of samples acti vated i n vacuum, no
hydroxyl groups are vi si bl e after the N
2
-ai r acti vati on,
(and subsequent exposure to moi st ure at room
temperature) despite the fact that the crystal l i ni ty i s
more than 55#. This observation would be i n favor of
the breaki ng of Si -O-Al bonds by the strongly aci di c
species formed during hydrolysis of P-O-P bonds.
Cracking acti vi ty
It can be seen i n Fi gure 5 that when the amount of
s i l i c on i n SAPO-37 i s i ncreased, the conversi on
increases up to 44 Si /uni t cel l and then decreases. In
order to avoid the possi bl e contri buti on of the free
alumina (Table I), present i n minor amounts in these
samples, the f i rst order ki neti c rate constant per unit
of BET surface area (calculated at cat/ oi l = 0.4) has
been pl otted as a functi on of the si l i con content,
Figure 6. The same behavior i s observed. This behavior
can be explained i n an analogous way as i n the case of
zeol i tes, but considering that the acid si tes i n SAPO
are related to the introduction of si l i con. Therefore,
i n SAPO, the number and density of acid si tes wi l l be
related to the number of si l i con atoms. Consequentl y,

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6. CORMA ETAL. Stability and Cracking Behavior of SAPO37
89
100
Cryst (%)
900
4000
3500 1700 1500
WAVENUMBER (cm-1)
Fi gure 4. a) Var i at i on of c r ys t al l i ni t y with
ac t i vat i on t emperat ure i n n i t r og e n / d r y - a i r
atmosphere. b) IR spectrum of sample S37-1
activated i n ni trogen/dry-ai r atmosphere.

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the densi ty of aci d si tes and, therefore, the aci d
strength of these si tes wi l l depend on the number of
si l i con atoms i n the next nearest neighbors of a given
si l i con atom. This concept could be di rectl y applied to
those samples i n which most of the Si substi tuti on takes
place through a mechanism 2 (26), i . e. si l i con replacing
phosphorus. In the cases where Si substi tuti on takes
place by a mechanism 2, and also by a mechanism 3 ( i . e.
two Si replace one Al -P pai r), the behavior would be the
same but with the maximum probably shi fted to samples
wi th l ower s i l i c on content. It has recentl y been
proposed (27) that i n SAPO-37, si l i con i nserti on takes
pl ace by both mechanisms 2 and 3. The contribution of
mechanism 3 i ncreases when the s i l i c on cont ent
increases. In any case, the contribution of mechanism 3
to the total si l i con substi tuti on i n samples with an
overal l Si/Si+Al+P rati o 0.16 i s below 10#, being i n the
order of 20% for samples with a rati o of 0. 21. Thi s
result indicates that one can assume rel ati vel y safely,
that a maximum i n acti vi ty for carbonium ion reactions
needing strong aci d si tes, wi l l be found i n SAPO-37
containing 20-30 Si per uni t cel l . So far, our gas oi l
cracki ng resul ts i ndi cate that maximum act i vi t y i s
achieved with samples contai ni ng between 40 and 50
Si / u. c. which should correspond, following our model, to
acid si tes of medium strength. Moreover, thi s behavior
coul d suggest that the di fference i n aci d strength
between the several types of aci d si tes would not be
very hi gh.
When the cracking acti vi ty of SAPO-37 i s compared
with that of an USY with uni t cel l si ze of 2. 447 nm
( Fi g. 5), which would be equivalent to the stabi l i zed
zeol i te compared i n the patent l i terature (13,14), the
acti vi ty of the SAPO 37-2 i s higher.
The lower aci d strength of SAPO compared to USY has
been checked by n-heptane cracking at 743 K, and the
acti vi ty of S37-2 has been found to be ten times lower
than that of USY. Thi s resul t seems to indicate (in
contrast to what i s currentl y bel i eved), that strong
acid si tes are not necessarily required to obtain high
acti vi ty during gas-oi l cracki ng. Materials l i ke SAPO-
37, having very high concentrations of acid si tes of
medium strength, can also be very effecti ve i n cracking
l ong-chai n hydrocarbons. Moreover, the lower aci d
strength shown by SAPO-37 with respect to zeol i te Y
cannot be rel ated to Sanderson's el ectronegati vi ty,
since SAPO-37 has equal or higher X than Y zeol i tes
(28).
In order to properly compare the catal yti c acti vi ty
of these two types of materi al s, a sample of SAPO-37
free of amorphous alumina (S37-4) with 35 Si / u . c , has
been prepared. Its cat al yt i c act i vi t y i s compared i n
Figure 7 with that of a USY zeol i te with unit cel l of
2.442 nm described i n previous studies (29). The sample

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CORMA ET AL. Stability and Cracking Behavior of SAPO-37
Conversion (%)
90i
Figure 5. Gas-oi l cracking acti vi ty of samples S37-1
( ), S37-2 ( O ), S37-3 ( * ) and USY (a=2. 447 nm)
(*).
Fi gure 6. Vari ati on of act i vi t y per uni t of BET
surface with Si content i n SAPO-37 samples.
.Conversi on (%)
0.1 0.2 0.3 0.4 0.5
cat/oi l
Figure 7. Gas-oi l cracking acti vi ty of samples S37-4
( ) and USY (a=2.442 nm) (x).

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of SAPO-37 i s shown to be more active than the one with
a si mi l ar si l i con content because of the hi gher cr i s-
t al l i ni t y of the former. Meanwhile, i t i s al so more
acti ve than the USY zeol i t e. From the viewpoint of
sel ecti vi ty, i t can be seen i n Figure 8 that the SAPO-37
gives less gases and coke and more gasoline and di esel
than the USY zeol i t e. The di fferences observed i n
Butene/Butane rati o are remarkable, being much higher i n
SAPO-37 than i n USY. This indicates that the extent of
hydrogen transfer reacti ons are lower i n the former.
This effect can hardly be explained by considering the
density of aci d si tes, or the framework Al content, as
the only factor control l i ng hydrogen transfer. Indeed,
i f the densi ty of aci d si tes were the only factor,
hydrogen transfer should be higher i n the case of SAPO-
37 with -40 Si / u. c. than on a USY with -20 Al / u. c.
It has been presented that i n Y zeol i tes, the
rel ati ve rate of cracking versus hydrogen transfer i s
rel at ed to di f f erences i n adsorpti on capaci ty and
adsorption sel ecti vi ti es. Changes i n zeol i te composition
modi fy the e l e c t r os t a t i c f i e l d s , changi ng the
hydrophilic-hydrophobic character and, consequently, the
adsorpti on properti es of the zeol i tes. If thi s i s so,
the higher cracking to hydrogen transfer rati o shown by
SAPO-37 with respect to Y zeol i tes, could be related to
i ts less polar character (less pronounced el ectrostati c
fi el ds i n the pore system) with respect to Y zeol i tes
(30). Thi s would imply a rel ati ve l ower ol ef i n to
par af f i n adsor pt i on r at i o on the SAPO-37, and,
consequently, a lower hydrogen transfer.
Conclusions
It has been shown that st abi l i t y of SAPO-37 can be
improved i f cal ci nati on i s made i n the presence of N
2
.
However, the exi t of TMA+ makes the cri st al l i ni t y of the
sample f al l to <2Q%.
IR spectroscopy allow us to conclude that TPA
+
are
removed f i rst , through the formation of amines. At 623
K, TMA
+
starts to desorb, and at 873 K, al l organic
materials are removed.
Besides from the non-aci di c SiOH and POH and the
aci di c HF and LF hydroxyls, the presence of two bands at
3612 and 3530 cm"
1
has been related to the presence of
organic templates i nteracti ng with HF and LF framework
hydroxyls respecti vel y.
An hypothesi s to expl ai n the col l apse of SAPO-37
after high temperature cal ci nati on followed by exposure
to moisture at room temperature, i s the breaking of T-0-
T bonds due to the exi t of TMA
+
. This i s followed by the
formation of T-OH that, at rel ati vel y high temperature
condenses, forming Si -O-Si and P-O-P bonds. The presence
of l i qui d water hi drol yzes the P-O-P bonds forming
P(0H)
n
speci es, aci di c enough to attack the Si -O-Al

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6. CORMA ETAL. Stability and Cracking Behavior of SAPO37 93
25
20
15
10
Yield (%)
Gases
/
/
/
a
Coke
a
3.0
2.5
2.0
1.5
1.0
Yield (%)
0.5
C1+C2
/
X 6 y
/
/ a
0 /
65 70 76 80 85
Conversion(%)
90 96 76 80 86
Conversion(%)
Fi gure 8. Sel ect i vi t y to diverse products from
gas-oi l cracking using samples S37-4 ( ) and USY
(a=2.442 nm) (x).

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bonds.
It appears from short chain alkane cracking experi -
ments that SAPO-37 shows a weaker aci di ty than USY
zeol i t es , regardl ess of the hi gher Sanderson's
el ectronegati vi ty of the former st ruct ure (28). A
maximum i n gas-oi l cracking acti vi ty i s found for SAPO-
37 with 40-50 Si per unit cel l . Gas-oi l cracking acti -
vi ty i s higher for SAPO-37 than for USY zeol i tes, and
therefore strong aci d si tes as well as si tes with medium
strength seems to be active for gas oi l cracki ng.
SAPO-37 produces more l i qui d di st i l l at es and l ess
gases and coke than USY zeol i tes with 20 Al / u. c. (2.442
nm). Meanwhile the hydrogen transfer i s lower i n SAPO-
37, than i n USY samples with lower densi ty of aci d
si tes. The high rati o of cracking to hydrogen transfer
i s related to the less polar character (less pronounced
el ectrostati c fi el ds) of SAPO-37 with respect to USY
zeol i tes.
Acknowledgments
Fi nanci al support by the CICYT (project MAT 88-0147) i s
grateful l y acknowledged.
L i terature Cited
1. Pine, L.A.; Maher, P.J.; Wachter, W.A. J. Catal.
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2. Yanik, S.J.; Demmel, F.J.; Hummthries, A.C.;
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3. Esterte, J.; J. Prep. Div. Petr. Chem. 1989, 34,
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4. McCouley, J. R. ; PCT Int. Appl. WO 8806, 488, 1988.
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Eds. , A. C. S. Symp. Ser. , 1984, 248, 157.
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Corp.) 1977.
9. Dessau, R. M. , U. S. Patent 4 384 153 (to Mobil Oil
Corp.) 1983.
10. Dwyer, J.; Millward, D. ; J. O'Malley, P. ; Araya, A. ;
Corma, A. ; Forns, V; Martnez, A. J. Chem. Soc.
Far. Trans. I, 1990 86, 1001.
11. Vaughan, D. E. W. ; Tracey, M. M. J. ; Newsam, J.H.;
Strohmaier, K. G. ; Mortier, W. J. A. C. S. Symp. Ser.
1989, 398, 546.
12. Lok, B. M. ; Messina, C. A. ; Patton, R. L . ; Gajek, R. T. ;
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6. CORMA ETAL. Stability and Cracking Behavior of SAPO37 95
13. Edwards, G. C. ; Gilson, J. P. ; McDaniel, C. V. , U.S.
Patent 4 681 864, 1987.
14. Edwards, G. C. ; Gilson, J. P. ; McDaniel, C. V. , U. S.
Patent 4 764 269, 1988.
15. Pellet, R. J. ; Coughlin, P. K. ; Staniulis, M. T. ; Long,
G. N. ; Rabo, J.A., U. S. Patent 4 734 185, 1988.
16. Herbst, J.A.; Dwyer, F. G. ; Huss, A. Jr. , Eur Pat.
AppI. 0 208 409, 1987.
19. Edwards, G. C. ; Gilson, J. P. ; McDaniel, C. V. , Eur.
Pat. Appl. 0 209 793, 1987.
20. Masel l i , J. M. ; Gilson, J.P.; Edwards, G. C. , Eur.
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21. Sierra de Saldarriaga, L . ; Saldarriaga, C. ; Davis,
M. E. J. Am. Chem. Soc. 1987, 109, 2686.
22. Bri end, M. ; Shi khol esl ami , A. ; Pel tre, M.J.;
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23. Bellamy, L.J. Infrared Spectra of Complex Molecules,
Chapman and Hall, London (1975).
24. Parker, L . M. ; Bibby, D. M. ; Patterson, J. E. Zeolites
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25. Corma, A. ; Lopez-Agudo, A. ; Forns, V. J. Chem. Soc.
Chem. Commun. 1983, 942.
26. Flanigen, E. M. ; Patton, R. L . ; Wilson, S. T. Innova-
tions in zeolites materials science, Grobet, P. J. ;
Jacobs, P. A. , Eds. , Stud. Surf. Sci . Catal . 1988,
37, 13.
27. Martens, J.; Janssens, C. ; Grobet, P.J.; Beyer,
H. K. ; Jacobs, P. A. Zeolites: Facts, Figures, Future,
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RECEIV ED October 5, 1990

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Chapter 7
Octane Enhancement in Catalytic Cracking
by Using High-Silica Zeolites
S. J. Miller and C. R. Hsieh
Chevron Research and Technology Company, P.O. Box 1627,
Richmond, CA 94802-0627
The effec t of ZSM-5 as an octane additive to a cracking
c at al y s t was studied i n b oth a small fixed-b ed reactor and a
fluidiz ed-b ed p i l ot plant. Analy ses of the products of these
t es t s were used to determine the reaction chemistry . It was
found that by maximiz ing the rat i o of isomeriz ation ac t i v i t y
to hydrogen transfer ac t i v i t y , gasoline octane was increased
with a minimum of y i el d l os s . This could be accomplished by
increasing the silica-to-alumina rat i o of the additive
z eol i t e.
Approximately 40% of the gasoline produced i n the United States i s
made by f l u i d c at al y t i c cracking. Because of the need for higher
gasoline octane, refi n ers are looking for economical ways of
improving octane i n t h ei r FCC units, either by changing operating
conditions or cracking c at al y s t . The l at t er has p ri mari l y involved
the use of c at al y s t s containing low unit c e l l s i z e ultrastab le-Y
z eol i t e (USY) which produces fewer p araffi n s and more ol efi n s than
conventional rare earth cataly sts (1). A second c at al y t i c option,
which may be used i n conj unction with USY, i s the introduction of a
minor amount of a c at al y s t designed to improve gasoline octane.
Anderson et a l . (2) and Donnelly et a l . (3) have reported on
the use of the z eol i t e ZSM-5 as an additive c at al y s t for increasing
the octane of FCC gasoline. This z eol i t e has been reported by
workers at Mob il (4) to increase octane by cracking out low octane
straight-chain p araffi n s and ol efi n s i n the heavy gasoline product
and by ol efi n isomeriz ation. Rajagopalan and Young (5.) have
proposed that the ZSM-5 prevents p araffi n formation by cracking
carb onium ions or ol efi n intermediates to l i g h t products. In ei t h er
case, C
3
and C
4
ol efi n s increase while gasoline y i el d decreases.
Chevron researchers (6,7) have shown that gasoline loss can be
reduced by using a ZSM-5 ty pe additive of high s i l i c a to alumina
rat i o, i n p art i c u l ar one of Si0
2
/ Al
2
0
3
molar rat i o greater than 500.
In t h i s report we examine the effec t of Si 0
2
/ Al
2
0
3
rat i o on the
s el ec t i v i t y of ZSM-5 ty pe additives and discuss the chemistry
involved.
EXPERIMENTAL
CATALYST PREPARATION ZSM-5 was prepared according to procedures
discussed i n the l i t erat u re (8.9 ) and i d en t i fi ed as such by X-ray
d i ffrac t i on analy sis. Ultrastab le Y z eol i t e was ob tained from the
0097-6156/91/0452-0096$06.00/0

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7. MILLER AND HSIEH Octane Enhancement in Catalytic Cracking 97
Union Carb ide Corporation. Dealuminated H-mordenite was prepared by
ac i d extraction of H-mordenite ob tained from the Norton Company.
Octane additives were composed of 25 wt % z eol i t e i n a s i l i c a -
alumina b inder, spray -dried to conventional FCC c at al y s t s i z e, and
treated at 1450F i n 100% steam at 1 atm for fi v e hours b efore
t es t i n g .
An eq uilib rium cracking cataly st containing approximately
25 wt % z eol i t e was used as the base cataly st for a l l ad d i t i v es .
FIXED-BED AND FLUIDIZED-BED TESTS In the fixed-b ed t es t , a sample
of cracking c at al y s t was contacted with an FCC feed i n a manner
s i mi l ar to the standard microactivity t es t (MAT) prescrib ed by ASTM
(10). One major difference was that the reactor temperature was
increased from 900F to 960F to b etter simulate current commercial
operations.
The fluidiz ed-b ed tests were conducted i n a 0.5 BPD
c i rc u l at i n g p i l ot plant equipped with a 50-ft ri s er reactor and an
on-line deb utaniz er. The t ot al l i q u i d product from each t es t period
was d i s t i l l e d externally , and the i n d i v i d u al cuts were sub mitted for
inspections.
In b oth ty pes of t es t s , additives were admixed with the
eq uilib rium c at al y s t p ri or to t es t i n g .
HYDROGEN TRANSFER INDEX (HTI) TEST In t h i s t es t , 0.5 /*L pulses of
1-hexene feed were c arri ed from a heated sampling valve into a
fi xed -c at al y s t bed i n a s t ai n l es s s t eel reactor by a nitrogen
c arri er stream at 800 mL/min. (at STP). The c at al y s t was -250 mesh
and d i l u t ed with alumina of the same mesh siz e plus 80-100 mesh
acid-washed Alundum. Reactor pressure was c on t rol l ed by an Annin
valve. The effl u en t stream went to the i n j ec t or s p l i t t er of a gas
chromatograph. The reactor conditions included a c at al y s t
temperature of 221C and 3.45 MPa t ot al pressure.
The HTI was calculated from the product rat i o of
3-methylpentenes to 3-methylpentane at a l i n ear hexene conversion of
30-70%.
RESULTS
MICROACTIVITY TESTING
S el ec t i v i t y to C
5
-Plus
Versus Si 0
2
/ Al
2
0
3
Ratio
An additive containing a sieve of 40 S/A (Si0
2
/ Al
2
0
3
) was compared
with one of 525 S/A. Figure 1 shows the C
5
-plus gasoline y i el d
using the 525 S/A sieve was less than with the b ase c at al y s t alone,
b ut s u b s t an t i al l y higher than when using the 40 S/A sieve at equal
conversion. Furthermore, the C
4
ol efi n i c i t y (Figure 2), generally
an i n d i c at or of l i g h t gasoline research octane, showed about the
same improvement rel at i v e to the base for b oth ad d i t i v es .
Using another b inder which was higher i n s i l i c a , the 525 S/A
was compared with a sieve of 1000 S/A. Figure 3 shows a continued
increase i n C
5
-plus y i el d up to 1000 S/A. Again, a l l additives
produced about the same C
4
ol efi n i c i t y (Figure 4), above that for
the b ase c at al y s t as well as the base plus additive with no z eol i t e.
Effec t of Additives on
Selected Hydrocarb on Types
The effec t of the 40 S/A and 525 S/A additives on c ert ai n
hy drocarb on ty pes was examined by adding to the t es t feed ei t h er an
n-paraffin (n-nonane) i n the higher b oi l i n g range of gasoline or a
1 -ol efi n (1-pentene) i n the lower b oi l i n g range. A high amount of
ad d i t i v e (10%) was used.

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7
$
1
8
s 2
co
O
_ 51
B
49
48
O Base
+40 S/A
+525 S/A
73
Conversion Wt%
Figure 1. Effec t of z eol i t e Si0
2
/ Al
2
0
3
rat i o on gasoline
s el ec t i v i t y i n MAT.
0
c
1
O
3
0.520
0.515
0.510
0.505
0.500
0.495
0.490
0.485
0.480 [-
0.475 -
0.470 -
0.465 -
0.460 H
0.455
0.450
70
Figure 2.
MAT.
O Base
+40 S/A
+525 S/A
72 73 74
Conversion, Wt.%
Effec t of z eol i t e Si0
2
/ Al
2
0
3
rat i o on C
4
ol efi n i c i t y i n

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7
7. MILLER AND HSIEH Octane Enhancement in Catalytic Cracking
99
55 -
48 I
68 69 70 71 72 73 74
Conversion Wt%
Figure 3. Effec t of z eol i t e Si 0
2
/ Al
2
0
3
rat i o on gasoline
s el ec t i v i t y i n MAT.
O510
&505
0.500
0.495
^ 0.490
O 0.485
C
g 0.480
O 0.475
^ 0.470
0.465
0.460
&4S5
OBase
+525 S/A
A+1000 S/A
+Matrix
70 71
Conversion Wt%
73
Figure 4. Effec t of z eol i t e Si0
2
/ Al
2
0
3
rat i o on C
4
o l e f i n i c i t y i n
MAT.

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With 5% nC
9
i n feed, conversion of the nonane was less than 5%
with ei t h er the 40 S/A or 525 S/A additives. If l es s than 10%
ad d i t i v e had been used, the conversion of nC
9
due to the additive
would have been almost undetectab le. Since the rate of cracking of
lower b oi l i n g p araffi n s i s l i kel y to be lower than that of nC
9
,
those components should also be unaffected. This suggests that any
octane enhancement ob served with the additives has l i t t l e to do with
cracking of n-paraffins.
With 1% 1-pentene i n feed, and using the 525 S/A additive,
there was an increase i n C
5
b ranched ol efi n s and p araffi n s , as well
as an increase i n C
5
normal ol efi n s and p araffi n s . Other carb on
numbers remained unaffected (Tab le I ) .
Tab le I. Relative Yields of C
5
-C
6
Paraffins and Ol efi n s
Upon Addition of 1% 1-Pentene to Feed i n MAT
i C
5
1.2
nC
5
1.2
1.1
t and C-2-C
5
= 1.1
iso-C
5
= 1.1
i c
6
1.0
nC
6
1.0
n-C
6
= 1.0
iso-C
6
= 1.0
Effec t of Additives on
Iso/Normal P araffi n Composition
The effec t of 40 S/A and 525 S/A additives on the iso/ normal
p araffi n rat i os of the product gasoline was studied using b oth fresh
and steam-deactivated samples.
Iso/ normal C
4
-C
7
p araffi n rat i os versus carb on number are
shown i n Figure 5. If a major function of the additive i s to crack
away n-paraffins, then one would expect the iso/ normal rat i o to be
higher with additive than i n the base case. While t h i s i s found for
C
4
and C
5
, with fresh additive the opposite was ob served with C
6
and
C
7
. Since C
6
and C
7
p araffi n s are more prone to crack than C
4
and C
5
,
i t i s u n l i kel y that an n-paraffin mechanism i s involved i n
increasing iso/ normal rat i os .
HYDROGEN TRANSFER INDEX TEST
Relative hydrogen transfer ac t i v i t y can be determined using an HTI
t es t (11), where the index i s a measure of the degree of saturation
i n the reaction product. The t es t determines the product rat i o of
3-methylpentenes to 3-methylpentane derived from a 1-hexene feed.
While the b ranched products come mainly from oligomeriz ation
followed by cracking, the res u l t s should be relevant here as wel l .
The higher the index, the lower the rel at i v e hydrogen t ran s fer
ac t i v i t y .
Figure 6 shows the HTI values for a number of c at al y s t s as a
function of l i n ear hexene conversion. Ultrastab le Y was very ac t i v e
for H-transfer, with dealuminated H-mordenite somewhat l es s .
Although i t s Si 0
2
/ Al
2
0
3
rat i o was near that of the mordenite, ZSM-5
of 78 S/A cataly z ed even less H-transfer, possib ly res u l t i n g from
the l i mi t ed space i n the ZSM-5 c av i t i es for forming the b imolecular

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7
7. MILLER AND HSIEH Octane Enhancement in Catalytic Cracking 101
0.6 LJ 1 1 L
4 5 6 7
Ca r b o n Numb e r
Figure 5. Iso/ normal rat i o of paraffins rel at i v e to b ase.

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Figure 6. Hydrogen transfer index t es t res u l t s .

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103
H-transfer reaction complex (12). ZSM-5 of 2200 S/A had the highest
index with very l i t t l e H-transfer even at high conversion.
PILOT PLANT TEST
Comparisons were made using a c i rc u l at i n g p i l ot plant for the
following cases:
a. Base case (eq uilib rium cracking c at al y s t ) .
b . Base plus 40 S/A.
c. Base plus 525 S/A.
Reactor conditions were 950F and 5 c at al y s t / oi l . The conversion
below 430F was 60 wt %. Before use, the additives were steam
deactivated for fi v e hours at 1450F i n 100% steam.
The incremental differences i n y i el d and measured octanes
produced by the additives are shown graphically i n Figures 7 and 8,
res p ec t i v el y . These show that b oth additives reduced gasoline
y i el d , mainly 265-430F, with 525 S/A giving the l eas t reduction.
Most of the y i el d loss i n b oth cases was accompanied by gains i n
C
3
-C
4
ol efi n s . These also show an octane gain/wt % y i el d loss i n
the C
5
-430F gasoline of 0.6 (1.0/1.7) for 40 S/A and 1.0 (0.9/0.9)
for 525 S/A.
Compositional information on the product C
3
-C
7
frac t i on s and
c al c u l at ed research octanes are given i n Tab le II. The C
4
-C
7
frac t i on s a l l show higher iso/ normal p araffi n rat i os with the
additives than i n the b ase case. The additives also give higher
ol efi n i c i t y , p art i c u l arl y i n the C
3
-C
5
range, and higher iso/ normal
ol efi n rat i os with reduction es p ec i al l y i n the rel at i v e amounts of
normal 1-olefins. These factors a l l res u l t i n higher octanes.
Tab le II. Product Inspections at 60% Conversion and 950F
Base +40 S/A +525 S/A
C
3
=/C
3
P 4.18 5.05 4.89
C
4
=/C
4
P 1.56 1.92 1.83
1-C
4
=/C
4
= 0.23 0.21 0.22
I-C
4
=/C
4
= 0.24 0.28 0.27
I-C
4
/nC
4
3.83 4.06 4.08
C
5
=/ C
5
P 1.44 1.72 1.59
i - c
5
=/ c
5
= 0.11 0.085 0.089
i c
5
=/ c
5
= 0.54 0.62 0.60
IC
5
/ nC
5
6.97 7.39 7.78
C
5
P RON 88.4 88.6 88.8
C
5
= RON 98.8 98.9 98.9
C
6
=/ C
6
P 1.01 1.07 1.11
i - c
6
=/ c
6
= 0.067 0.049 0.050
i c
6
=/ c
6
= 0.49 0.58 0.57
IC
6
/ nC
6
6.06 6.41 6.72
C
6
P RON 70.0 70.1 70.4
C
6
= RON 93.9 94.5 94.5
C
7
=/C
7
P 0.90 0.92 0.91
1-C
7
=/C
7
= 0.074 0.073 0.069
i c
7
=/ c
7
= 0.597 0.685 0.680
IC
7
/ nC
7
9.6 10.8 12.0
C
7
A/C
7
0.225 0.232 0.223
C
7
P RON 53.1 54.0 54.7
C
7
= RON 84.6 85.1 85.6

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C5-265T
EUD 40 S/A
525 S/A
265-430F
Figure 7. Incremental p i l ot plant y i el d s at 950 F and 60%
conversion.
Dmn 40 S/A
525 S/A
Figure 8.
conversion
C5-265RON C5-265 MON 265-430 RON 265-430 MON
Incremental p i l ot plant octanes at 950F and 60%

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105
Looking at what happens within each carb on number group, one
finds that for 40 S/A, the main contrib utor to octane enhancement i n
the C
5
's i s increased ol efi n i c i t y . While the ol efi n i c i t y also
increases with 525 S/A, nearly half the C
5
octane increase with that
ad d i t i v e comes from a higher iso/ normal p araffi n rat i o. The
ol efi n i c i t y enhancement i s of a lesser degree i n the C
6
's and
es s en t i al l y n i l i n the C
7
's. Nevertheless, higher iso/ normal rat i os
contrib ute to octane improvement i n b oth carb on number frac t i on s .
Relative y i el d s per volume of feed versus the b ase case are
shown for each carb on number i n the C
5
-265F gasoline i n Figure 9.
This shows that the 40 S/A additive increases C
5
while reducing
C
6
-C
8
. With 525 S/A, the C
5
-C
7
stay s about the same, with some
reduction i n C
8
.
Because the octane rat i n g i n the C
5
-265F gasoline decreases
with an increase i n carb on number, increasing C
5
*s at the expense of
higher b oi l i n g components increases octane even without a change i n
the octane within an i n d i v i d u al carb on number group. For the 40 S/A
additive, i n fac t , about half the octane increase comes from t h i s
effec t . Producing t h i s s h i ft , however, also involves a y i el d l os s .
Most of the t ot al gasoline y i el d loss, b oth for 40 S/A and 525
S/A, i s found i n the heavy gasoline (265-430F). Tab le III shows
t h i s loss to be spread throughout the carb on number range of t h i s
frac t i on , due i n large part to a reduction i n p araffi n s as indicated
by a higher rat i o of aromatics to p araffi n s . This increased
aromaticity contrib utes to higher octane.
Tab le III. 265-430F Gasoline Composition
Additive 40 S/A 525 S/A
Carb on No. Relative to Base
C
8
0.950 0.966
C
9
0.956 0.965
C
10
+ 0.930 0.946
Wt Aromatics/ Paraffins Relative to Base
C
8
* 1.12 1.04
C
9
1.14 1.06
C
1 0
1.22 1.18
Includes C
8
i n C
5
-265F frac t i on .
DISCUSSION
Based on the findings that the ZSM-5 additives do not cataly z e much
conversion of gasoline range p araffi n s , we conclude that they
p ri mari l y work on ol efi n s produced by the large-pore cracking
c at al y s t . We can divide these ol efi n s into two main groups, those
that are so small, e.g., C
4
-C
5
=, that further cracking can be
neglected, and larger ol efi n s where further cracking i s s i g n i fi c an t .
In looking at the f i r s t case for a C
5
ol efi n , for example, we
consider the main reactions that can occur to the normal ol efi n once
i t has been protonated at a Bronsted s i t e to form a normal carb enium
ion.
As shown i n Figure 10, one reaction i s the isomeriz ation of
the normal carb enium ion. We can neglect the reverse reaction since
the iso/ normal ol efi n rat i o produced over the cracking c at al y s t i s
usually well below the thermodynamic eq uilib rium value, due i n part
to depletion of the i s ool efi n s by hydrogen t ran s fer.
A second reaction i s oligomeriz ation with another ol efi n to
produce a larger b ranched carbenium ion. Earl i er work on normal

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7
al p h aol efi n oligomeriz ation over ZSM-5 ty pe c at al y s t at lower
temperature showed very l i t t l e s kel et al isomeriz ation of the
unconverted feed ol efi n , b ut sub stantial production of isomeriz ed
species through oligomeriz ation and cracking (11). If the carb enium
ion formed by oligomeriz ation i s larger than C
5
+, i t can then crack
to form a d i fferen t ol efi n and a b ranched carb enium ion, e.g.:
+H
+
+H"
c
4
= + c
7
= > i i V > c
5
= + ic
6
+
-> ic
6
If
i c
L
The MAT t es t with 1-pentene spiked feed did not show an
increase i n carb on numbers other than C
5
, leading to the conclusion
that isomeriz ation predominates over oligomeriz ation at high
temperatures, so that i s ool efi n s come mainly from isomeriz ation, and
from cracking of larger ol efi n s which are not products of
o1igomeriz at ion.
The main competing reaction to isomeriz ation of the
n-carb enium ion i s i t s hydrogen transfer to the n-paraffin which
should then be rel at i v el y unreactive. By maximiz ing the rel at i v e
rates of isomeriz ation to hydrogen transfer (k,/ k
H
), the y i el d of
b ranched products, es p ec i al l y b ranched ol efi n s , should also be
maximiz ed.
The s i t u at i on i s more complex with a larger carb enium ion, for
example, a C
7
+
(Figure 11). In t h i s case, we consider not only
isomeriz ation and hydrogen transfer, b ut cracking as wel l ,
p art i c u l arl y of the iso carbenium ion to form a smaller carb enium
ion and an ol efi n . Where the rat i o of cracking rate to hydrogen
t ran s fer rate i s high, the y i el d of b ranched C
7
products w i l l be
reduced, rather than enhanced, due to conversion of i C
7
+
to lower
molecular weight species.
The low iso/ normal C
6
-C
7
p araffi n rat i os ob served i n the MAT
t es t i n g with fresh additive i s then the res u l t of iso-C
6
and -C
7
carb enium ion cracking, reducing the amount of these species
av ai l ab l e for conversion to i s op araffi n s by H-transfer. C
4
and C
5
carb enium ions are too small to crack, req uiring the formation of a
primary ion, so that C
4
and C
5
isoparaff ins increase due to cracking
of C
7
-plus ions. For deactivated additive, the C
6
-C
7
iso/ normal
rat i os are higher than for the base c at al y s t , since the cracking
ac t i v i t y of the additive i s reduced, and since H-transfer ac t i v i t y
for, e.g., nC
7
+
> nC
7
i s lower than for the b ase, the 525 S/A
additive having less H-transfer ac t i v i t y than the 40 S/A.
Minimiz ing hydrogen transfer minimiz es the formation of low
octane n-paraffins. For optimum s el ec t i v i t y , therefore, an additive
c at al y s t should have a high rat i o of isomeriz ation ac t i v i t y compared
to hydrogen transfer ac t i v i t y . The high HTI of ZSM-5 ty pe z eol i t es
compared to larger pore z eol i t es confirms the usefulness of these
z eol i t es as octane additives. Assuming that isomeriz ation of the
normal carb enium ion i s a unimolecular reaction while H-transfer i s
b imolecular (13) would explain why the HTI increases with the
Si 0
2
/ Al
2
0
3
rat i o of the ZSM-5 ty pe sieve.
In improving gasoline octane, cracking such as:
iC
8
= > C
3
= + iC
5
=
can improve octane, mostly by producing higher octane, lower
molecular weight i s ool efi n s , and by concentrating more refrac t ory
high octane components ( i . e. , aromatics) i n the C
7
-plus frac t i on .
This mechanism has the drawback, however, of reducing the l i q u i d
C
5
-plus y i el d . As the additive ages, t h i s effec t should diminish,
p art i c u l arl y involving the cracking of smaller species such as C
7
+
.

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MI LLE R A ND H S I EH Octane Enhancement in Catalytic Cracking 107
2
>-
>
I
DC
1.15
1.10
1.05
1.00
0.95
0.90
0.85
0.80
40 S/A
: 525 S/A
Figure
versus
Ca r b o n Numbe r
9. Relative carb on number y i el d s i n C
5
-265F gasoline
b ase case i n p i l ot plant t es t .
n C 5
+
i C 5
+
nCs nC5
=
1C5 i C s
=
Figure 10. Normal C
5
carbenium ion reactions.
n C 7
+
k i
i C 7
+
/ \
i C
7
=
C3= + i C 4
+
i C y
Figure 11. Normal C
7
carbenium ion reactions.

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The octane upgrade w i l l not be as great as with fresh c at al y s t ,
since a sub stantial frac t i on of the i C
7
carbenium ions w i l l undergo
H-transfer to form C
7
i s op araffi n s which have octane numbers lower
than the rest of the gasoline. Isomeriz ation ac t i v i t y w i l l also
decline during aging, but not as fast as cracking, so that there
w i l l s t i l l be formation of b ranched products. Since t h i s involves
no y i el d l os s , and since the isoparaffins and i s ool efi n s have higher
octanes than t h ei r respective normals, the delta octane/ % y i el d loss
w i l l be greater than with fresh additive.
Since the rat i o of isomeriz ation ac t i v i t y to H-transfer
ac t i v i t y increases with Si0
2
/ Al
2
0
3
rat i o, the s el ec t i v i t y for octane
enhancement w i l l improve at higher rat i os . The t ot al octane gain
per u n i t of additive w i l l drop at very high Si0
2
/ Al
2
0
3
, however, due
to reduced cracking of lower octane C
7
-plus species. This factor
may be offs et by increasing additive concentration.
SUMMARY
FCC additives of the ZSM-5 ty pe are effec t i v e for increasing
gasoline octane due to t h ei r low ac t i v i t y for hydrogen t ran s fer.
Octane i s increased by the cracking and isomeriz ation of ol efi n s
produced by the b ase cracking c at al y s t . Cracking converts low
octane components i n the C
7
-plus gasoline p art l y to higher octane
components of lower molecular weight, and to C
4
-minus, reducing
gasoline y i el d . Isomeriz ation increases the concentration of
i s ool efi n s and i s op araffi n s , increasing octane without y i el d l os s .
Isomeriz ation i s maximized and, therefore, y i el d loss minimiz ed, as
the z eol i t e Si 0
2
/ Al
2
0
3
rat i o increases. While c at al y s t deactivation
also improves s el ec t i v i t y , the advantage for a high Si 0
2
/ Al
2
0
3
rat i o
i s retained.
Li t erat u re Cited
1. Pine, L. A., Maher, P. J., and Wachter, W. A., J. Catal., 85,
466 (1984).
2. Anderson, C. D., Dwyer, F. G., Koch, G., and Niiranen, P.,
Proc. Ninth Iberoam. Symp. Catal., 247 (1984).
3. Donnelly , S. P., Miz rahi, S., S p arrel l , P. T., Huss, Jr. , A.,
Schipper, P. H., and Herb st, J. A., PREPRINTS, Div. of P et rol .
Chem., ACS, 32 (3), 621 (1987).
4. Dwyer, F. G., Schipper, P. H., and Gorra, F., NPRA Ann. Mtg.,
March (1987).
5. Raj agopalan, K., and Young, G. W., PREPRINTS, Div. of P et rol .
Chem., ACS, 32 (3), 627 (1987).
6. Mi l l er, S. J. , and Bishop, K. C. III, U.S. Patent 4,340,465
(1982).
7. Mi l l er, S. J. , U.S. Patent 4,309,276 (1982).
8. Argauer, R. J., and Landolt, G. R., U.S. Patent 3,702,886
(1972).
9. Grose, R. W., and Flanigan, E. M., U.S. Patent 4,061,724
(1977).
10. ASTM, D 3907-87, Annual Book of ASTM Standards, 503, 733
(1989).
11. Mi l l er, S. J., Stud. Surf. S c i . Catal., 38, 187 (1987).
12. Haag, W. O., Lago, R. M., and Weisz, P. B., Faraday Disc., 72,
317 (1982).
13. Chen, N. Y., and Haag, W. O., i n Hydrogen Effec t s i n Cat al y s i s
Fundamentals and Practices; Paal, Z., and Menon, P. G., Eds;
Dekker: New York, p 695 (1988).
RECEIVED June 8, 1990

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Chapter 8
Monitoring Fluid Cracking Catalyst Deactivation
Profile by Equilibrium Catalyst Separation
R. A. Beyerlein, G. A. Tamborski, C. L. Marshall, B. L. Meyers, J. B. Hall,
and B. J. Huggins
Amoco Corporation, Naperville, IL 60566
Successful separation of aprecoked, equilibriumUSY
cracking catalyst into fractions of increasing age
reveals adeactivation profile that is largely
controlled by zeolite dealumination. Precoking is
found to aid thedensity/age separation only for the
youngest fractions. Theobserved change inNi/V
ratio with increasing "Ni age" is indicative of
vanadiummigration.
Catalytic activity, assessed by cumene cracking
on separated fractions and also by analysis of
residual coke on catalyst fractions, shows a sharp
decline with increasing density (age). This rapid
loss of initial activity coincides with zeolite
dealumination which is largely completed as aslow
rate of zeolite destruction is established. Subsequent
loss of crystallinity has little additional effect on
activity. Theassociated loss of microporosity leads
to an apparent increase in skeletal density with
increasing age.
Lattice imaging studies by TEM on a"young"
fraction showed extensive regions of crystallinity
with minimal evidence of crystallite fracturing. By
contrast, similar investigations of an "old" fraction,
combined with in situ compositional analysis, revealed
small "islands" of crystallinity within a "sea" of
disordered material that was once crystalline. Fracture
lines at crystallite boundaries are absent. Instead,
the small USY crystallites within the"old" fraction are
in intimate mixture with thecollapsed zeolite.
L a b o r a t o r y e v a l u a t i o n o f f l u i d i z e d - b e d c a t a l y t i c c r a c k i n g
( F CC) c a t a l y s t s i s c r i t i c a l l y d e p e n d e n t u p o n t h e me t h o d c h o s e n t o
s i mu l a t e c a t a l y s t d e a c t i v a t i o n i n t h e c o mme r c i a l F CU .
C o n v e n t i o n a l l a b o r a t o r y d e a c t i v a t i o n s ( h i g h - t e mp e r a t u r e s t e a m
0097-6156/91/0452-0109$09.75/0

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treatment) are t y p i c al l y designed to simulate only the
i rrev ers i b l e loss of ac t i v i t y that res u l t s from hy drothermal
deactivation of the z eol i t i c component i n the FCC regenerator.
The comb ination of high temperature and steam i n the regenerator
causes framework dealumination (rapid) and c ry s t al l i n e z eol i t e
destruction (slower). Dealumination b oth lowers ac t i v i t y and
produces important changes i n s el ec t i v i t y , while z eol i t e
destruction leads p ri mari l y to a loss i n ac t i v i t y .
Zeol i t e destruction i s slower for dealuminated z eol i t es which
have increased hy drothermal s t ab i l i t y , b ut i s accelerated b y
deposition of metals, p art i c u l arl y vanadium and sodium from the
feed. In addition, these metals are powerful poisons which
n eu t ral i z e ac i d s i t es , thereb y reducing ac t i v i t y and compromising
s el ec t i v i t y . Nickel species, which accompany vanadium as feed
contaminants, are powerful dehy drogenation c at al y s t s and lead to
increased production of hy drogen and coke with reduced gasoline
y i el d s . A l l of t h i s i s complicated by the fac t that the
c i rc u l at i n g eq uilib rium c at al y s t inventory i n the FCU contains a
wide spectrum of ages and l ev el s of deactivation, owing to the 1%
to 3% d ai l y fresh c at al y s t make-up rate.
Lab oratory steam deactivations represent a s i g n i fi c an t
compromise i n the effort to simulate eq uilib rium c at al y s t . Since
hy drothermal deactivation of FCC c at al y s t s i s not rap i d i n
commercial p rac t i c e, deactivation of the fresh c at al y s t i n the
lab oratory req uires accelerated techniques. The associated
temperatures and steam p art i al pressures are often i n sub stantial
excess of those encountered i n commercial u n i t s . In some
instances, the effec t of contaminant metals i s measured by an
independent t es t not a f f i l i a t e d with steam deactivation. In
sub sequent y i el d s t es t i n g , interactions between d i fferen t modes of
deactivation may be overlooked. Fi n al l y , single mode deactivation
procedures can not reproduce the complex p rofi l e of ages and
l ev el s of deactivation present i n eq uilib rium c at al y s t .
Density Separation of Precoked Cataly st. In order to monitor and
understand c at al y s t deactivation i n the commercial u n i t and to
supply guidance for developing improved lab oratory deactivation
procedures, we have c arri ed out a separation by density of
eq uilib rium cracking c at al y s t from an Amoco FCU. The density
separation i s b ased, i n part, on the ac t i v i t y of the eq uilib rium
c at al y s t for coke deposition from isob utene. Each c at al y s t
p art i c l e develops a coke l ev el proportional to i t s i n t ri n s i c
ac t i v i t y l ev el . The coked c at al y s t p art i c l es are then separated
into frac t i on s b y immersion i n progressively more dense mixtures
of carb on t et rac h l ori d e and tetrab romoethane. Since coked
p art i c l es exh i b i t lower s kel et al density , the higher ac t i v i t y and
presumab ly younger c at al y s t p art i c l es are sequestered into the
l i g h t er frac t i on s . A recent report (1) indicates that t h i s
separation method produces frac t i on s of increasing age, the
heaviest frac t i on s b eing the oldest. In the present work, i t i s
found that the separation b y density i s b ased only i n part on
differences i n coking ac t i v i t y .

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8. BEYERLEIN ETAL. Monitoring FCC Deactivation Profile 111
Measured Ni l ev el s on c at al y s t are expected to supply an
independent age marker, as i t has b een shown that Ni tends not to
migrate following deposition on the c at al y s t (2). In fac t , metals
(Ni and V) deposition from the feed onto the c at al y s t i s expected
to as s i s t the separation by density / age/ activity as older c at al y s t
p art i c l es exh i b i t higher metals l ev el s which contrib ute to an
increase i n density . Except for the oldest frac t i on s , which
contain the highest metals l ev el s , the older portion of c at al y s t
tends to make less coke as the increase i n ac t i v i t y due to
increasing metals content i s overwhelmed by the loss of ac t i v i t y
due to c ry s t al l i n e z eol i t e destruction (1).
The present study shows that only the y oungest, most active
frac t i on s are density -separated on the b asis of ac t i v i t y for
coking from isob utene. For the maj ority of the separated
frac t i on s , the gradual increase i n s kel et al density with
increasing age (Ni l ev el ) appears to be associated with the
gradual loss of z eol i t e c ry s t al l i n i t y that occurs with increasing
time i n the u n i t .
Cataly st History
Cataly st Changeover. Metals Content. The eq uilib rium sample of a
USY octane c at al y s t , Cataly st A, was withdrawn from an Amoco FCU.
Results of metals analy ses on the eq uilib rium c at al y s t and on i t s
parent are given i n Tab le I. Cataly st A was introduced to the
u n i t during a five-month period over Cataly st B, which was
i d en t i c al to Cataly st A i n a l l respects, except for a low l ev el of
contaminant rare earth. Cataly st B had, i n turn, b een introduced
over a rare earth-containing c at al y s t , Cataly st C, eight months
p ri or to withdrawal of the eq uilib rium sample. Cataly st h i s t ory
and rare earth contents are summarized i n Tab le II.
Tab le I. Eq uilib rium and Fresh USY Cataly st Inspections*
Elemental
Fresh
Cataly st A
Eq uilib rium
Cataly st A
Ni, ppm (XRF) 30 570
Fe (XRF) 2140 3110
V (XRF) <200 440
Sb (XRF) <30 80
Nd (XRF) <300 310
Ce (XRF) <100 360
La (XRF) <100 740
Rare Earth (XRF) <500 1410
T i (XRF) 4900 5600
Na, ppm (AA) 1360 1430
S i , wt% 29.8 30.4
A l , wt% 15.3 20.4
*A11 c at al y s t s calcined at 538C for fi v e hours.
The u n i t c e l l dimension of fresh Cataly st A i s 24.40 A.

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112
Tab le II. Rare Earth Material Balance and Feedstock Contaminant
Metals Material Balance on Eq uilib rium Cataly st
From To Rare Earth on Eq u i l . , Wt%
Cataly st B Cataly st A 0.55
Cataly st C Cataly st B 0.85
Cataly st A--USY octane c at al y s t .
Cataly st B--USY octane c at al y s t with low l ev el s of rare earth
contamination (0.5 wt%).
Cataly st C--Rare-earth-containing (REY) c at al y s t .
Estimated changeover b ased on rare earth material b alance - 88%
Fresh Cataly st Addition Rate (see t ext ) : 2% of inventory / day
Contaminant Metals on Feedstock:
Metals i n Feedstock, ppm: Ni 0.7
V - 0.5
Fe - 1.2
Metals Laydown, lb / day : Ni - 5.57
V - 3.98
Fe - 8.76
Metals on Cataly st/ Day , ppm: Ni 11.1
V - 8.0
Fe - 17.4
During the fi v e months of operation with the z ero rare earth
octane c at al y s t , the effec t i v e fresh c at al y s t addition rate, aft er
c orrec t i on for c at al y s t loss from the u n i t as fi n es , was ab out 5
tons/ day . Based on a rare earth material b alance (Tab le II) that
was used to give the b est estimate of pedigree, the eq uilib rium
sample consists of 88% USY octane c at al y s t . The remaining 12%
should be a mixture of the p ri or two c at al y s t s , the f i r s t of which
contains a contaminant rare earth l ev el of 0.5 wt% versus 0.1 wt%
for the octane c at al y s t . The b alance of t h i s mixture i s the rare
earth-Y c at al y s t from the previous changeover which exhib its a
rare earth l ev el of 0.85 wt% (Tab le I I ) .
Feedstock Metals. Cataly st Age. Monthly FCU operating reports for
the FCU indicate that average u n i t throughput during Cataly st A
usage was f a i r l y constant. Feedstock metals l ev el s averaged 1.2
ppm Fe, 0.7 ppm Ni, and 0.5 ppm V during the two months preceding
withdrawal of the eq uilib rium sample. From these data a metals
b alance can be constructed, as shown i n Tab le II.
The u t i l i z at i on of n i c kel l ev el on c at al y s t as an age marker
i s b ased on previous evidence that n i c kel deposits uniformly on
the c i rc u l at i n g c at al y s t inventory , independent of c at al y s t
ac t i v i t y (1.2). In contrast to the case for n i c kel , vanadium

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8. BEYERLEIN ET AL. MonitoringFCC Deactivation Profile 113
migration i s known to occur at regenerator conditions (1.2).
Therefore, the vanadium l ev el cannot be used as an age marker.
Nickel deposition rate was, on average, 5.57 lb / day or
11.1 ppm on cataly st/ day . Ob serving that the ov eral l n i c kel l ev el
on c at al y s t i s 570 ppm (Tab le I) , the average inventory age i s
ab out 50 days.
Experimental Method
Coking of Eq uilib rium Cataly st. A 200 g portion of eq uilib rium
USY octane c at al y s t (Cataly st A) was precoked i n a fl u i d i z ed b ed
using a stream of isob utene d i l u t ed with nitrogen gas
(400 ml/min) at 510C. The c at al y s t was held i n a 2-inch diameter
quartz tube while 27.8 g of isob utene gas was passed upflow
through i t at atmospheric pressure over a period of 25 minutes.
The net amount of carb on deposited on c at al y s t was determined to
be 0.55 wt%.
Separation Method. T ri al experiments with small portions of the
coked c at al y s t i n progressively more dense mixtures of carb on
t et rac h l ori d e (d - 1.594 g/cc) and 1,1,2,2- tetrab romoethane
(d - 2.967 g/cc) showed that the l i g h t es t c at al y s t frac t i on s
exhib ited a density of ab out 2.3 g/ cc. A solvent mixture with
d - 2.33 g/cc was prepared from a mixture of 46.4 ml of carb on
t et rac h l ori d e and 53.6 ml of tetrab romoethane. A 20 g portion of
coked c at al y s t was placed i n a 120 ml q uantity of t h i s solvent
mixture i n a 250 ml Teflon centrifuge b ot t l e. The mixture was
thoroughly agitated for several minutes and then placed i n a
centrifuge at 3,600 rpm for 30 minutes. Upon removal from the
centrifuge, the mixture was allowed to stand for several hours i n
order to ob tain well-defined fl oat and sink frac t i on s .
Apparently , the c at al y s t was redispersed to some extent by the
slowing and b raking of the centrifuge. In these procedures, the
centrifuge i s viewed merely as an ad d i t i on al means to ob tain
eq uilib rium of the c at al y s t with the solvent. Each fl oat frac t i on
was removed i n several installments using a vacuum p i p et t e.
Introduction of the vacuum pipette dispersed some of the fl oat
frac t i on into the solvent. Complete removal of a fl oat frac t i on
req uired two to four installments separated by 30 to 60 minutes to
allow gravity separation. Following removal of a fl oat frac t i on ,
a 10 ml q uantity of solvent was withdrawn by sy ringe i n order to
determine the solvent density by pycnometer. At l eas t two
pycnometer measurements were made i n each case. Net solvent loss
was determined b y comparing centrifuge b ot t l e mass b efore and
aft er fl oat frac t i on withdrawal. Using a 10 ml sy ringe and a
p rec i s i on b alance, an eq uivalent mass solvent mixture was prepared
at a density chosen so that, upon addition to the cataly st/ solvent
s l u rry , a net increase i n solvent density of Ad0.02 g/ml was
ob tained. (The incremental change i n density was increased for the
l at er (heavier) frac t i on s , which exhib ited less pronounced density
gradients.) The centrifuge b ot t l e remained capped except for
fl oat frac t i on withdrawal and solvent addition i n order to avoid

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p referen t i al loss of carb on t et rac h l ori d e by evaporation. The
above procedures were repeated to ob tain a t ot al of seven fl oat
frac t i on s and a fi n al sink frac t i on within an ov eral l density
range of 2.3 to 2.6 g/ml.
Residual solvent was washed from each fl oat frac t i on b y
soxhlet extraction with methanol for a period of one to two hours.
Each c at al y s t frac t i on was then dried i n a 50C vacuum oven for at
l eas t three hours. Except for the smallest fl oat frac t i on s , fresh
methanol was used for each frac t i on to avoid contamination of the
rinse with high l ev el s of the tetrab romoethane/ carb on
t et rac h l ori d e mixture. The separation procedures j u s t describ ed
were also applied to fresh Cataly st A and to a portion of t h i s
c at al y s t which had b een steam deactivated at 815C. ^No precoking
was c arri ed out for these materials.
Analy sis of Fractions. Surface areas and pore s i z e d i s t ri b u t i on s
for b oth coked and regenerated c at al y s t frac t i on s were determined
by low temperature (Digisorb ) N
2
adsorption isotherms. Relative
z eol i t e (micropore volume) and matrix (external surface area)
contrib utions to the BET surface area were determined b y t -p l ot
analy ses (3). Carb on and hy drogen on c at al y s t were determined
using a Perkin Elmer 240 C instrument. Unit c e l l s i z e and
c ry s t al l i n i t y for the molecular z eol i t e component were determined
for coked and for regenerated c at al y s t frac t i on s by x-ray
d i ffrac t i on . Elemental compositions for Ni, Fe, and V on each
frac t i on were determined by ICP. Regeneration of coked c at al y s t
frac t i on s was accomplished i n an ai r muffle furnace heated to
538C at 2.8C/min and held at that temperature for 6 hr.
Cumene Cracking Reactions on Separated Fractions. Cumene cracking
reactions were tested on a gravimetric setup; the b asic flow
diagram for the reactor system i s shown i n Figure 1. The reactor
determines b oth the ac t i v i t y of the c at al y s t (cracking of cumene
to benzene and propy lene) and the instantaneous rate at which coke
i s deposited on the c at al y s t (poly meriz ation of the propy lene).
Conversion of the cumene i s adj usted to exclude the amount of
cumene disproportionation which y i el d s benzene and d i i s op rop y l
b enz ene.
Correl at i on of Eq uilib rium Cataly st Fraction Properties with
Frac t i on Density / Age
Coke Deposition. The properties of c at al y s t frac t i on s separated
i n coked condition from spent eq uilib rium c at al y s t are summarized
i n Tab les III and IV. The d i s t ri b u t i on of c at al y s t frac t i on s
along with the percent carb on found on each coked frac t i on i s
given i n Figure 2. The ac t i v i t y for coke deposition f a l l s off
sharply with increase i n density . Only the three l i g h t es t
frac t i on s show a coke make that i s s i g n i fi c an t l y above the minimum
coke make exhib ited by the heavier frac t i on s . The fac t that the
l i g h t es t frac t i on s are the most active i s consistent with the
notion that they are the y oungest. The d i s t ri b u t i on of c at al y s t

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BEYERLEIN ET AL . Monitoring FCC Deactivation Profile 115
Top He
Bottom He [ X h
Cahn 2000
microbalance
Air C X -
Coking gas I X] 1
Cumene |
bubblers \j \j
Cahn/ Ventron
control station
Cahn/ Ventron
control station

Strip chart
recorder
a
Reactor
C H 3 CHCH 3
60 *
CH
3
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2
"Coke"
Figure 1. Gravimetric reactor used i n cumene cracking studies.
60
IB
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=
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CL
n 1 1 1 1 1 1 l l
2.32 2.36 2.40 2.44 2.48 2.52 2.66 2.60
Skeletal density (g/cc)
Figure 2. Di s t ri b u t i on of c at al y s t fractions--carb on content on
coked frac t i on s .

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116 FLUID CATALYTIC CRACKING JTJ: CONCEPTS IN CATALYST DESIGN
Tab le III. Properties of Eq uilib rium Cataly st Fractions
Cataly st Density Median % of % C ppm Ni ppm V ppm Fe
Frac t i on Limit,
g/cc
Density ,
g/cc
Total
Float A <2.340 2.330 2.6 2, .00 161 206 3070
Float B <2.371 2.355 10.3 1. .06 188 234 2680
Float C <2.393 2.382 50.0 0, .62 330 339 2340
Float D <2.415 2.404 20.2 0, .49 670 434 2950
Float E <2.457 2.436 4.8 0, .43 992 612 3560
Float F <2.514 2.486 3.8 0, .41 905 612 5520
Float G <2.588 2.551 0.7 0, .42
Sink H >2.588 2.604 8.1 0, .44 1910 1180 7000
Unit
ppm ppm ppm BET S.A. BET S.A. C el l % Cry st. % Cry s
T i RE Na (coked) (regen) A micropore XRD
volume
Fi t . A 5060 1710 181 213 24, .31 28. .0 24
Fi t . B 3850 232 1680 207 219 24. .27 27. .0 26
Fi t . C 5200 455 1320 206 208 24. .26 25. .0 25
Fi t . D 4750 975 1530 190 192 24. .24 22. .0 23
Fi t . E 6580 232 1710 162 160 24. .26 18, .0 16
Fi t . F 6050 1551 1730 117 118 24. .28 13. .0 13
Fi t . G 95 92 24. .33 10, .0 7
Sink H 11380 6790 1040 83 82 2, .6 5
frac t i on s i s sharply peaked about a density d - 2.38 g/cc, with
80% of the c at al y s t occupy ing a density range 2.34 to 2.42 g/ cc.
Cumene Cracking A c t i v i t y . Portions of each of the f i r s t fi v e
separated frac t i on s were regenerated and sub j ected to cumene
cracking investigations i n order to determine rel at i v e ac i d i t y and
coke s el ec t i v i t y trends. The c at al y s t within the
thermogravimetric reactor was exposed to a constant flow of cumene
vapor at 400C. Coke b uildup on c at al y s t was continuously
monitored by gravimetry , while converted products i n the effl u en t
stream were analy z ed at regular i n t erv al s by gas chromatography
(Figure 1). The res u l t s for net coke on c at al y s t at constant
conversion (25%) given i n Tab le V-A show a steady decrease i n coke
on c at al y s t for increasingly dense frac t i on s . These res u l t s are
consistent with those for residual carb on on c at al y s t j u s t
discussed. The l i g h t er frac t i on s prove to be the most active
ones, while the heavier, less active frac t i on s make p rop ort i on al l y
l es s coke. "Coke s el ec t i v i t y ", defined as the rat i o
conversion/ coking, increases with increasing density i n agreement
with the expected trend for USY c at al y s t frac t i on s of increasing
age.

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Tab le V. Cumene Cracking Results on Eq uilib rium Cataly st
Fractions*
A. Net Coke Content and Coke S el ec t i v i t v at Constant Conversion
(25*)
Corrected* "Coke
c
Cataly st Wt% Coke S el ec t i v i t y "
Frac t i on (wt%) (conv/coke)
Float A 1.50 17
Float B 1.15 22
Float C 0.26 96
Float D 0.25 100
Float E 0.0
B. Conversion at Constant Coke (0.25 wt%)
Catalvst Fraction Conversion (%)
Float A 45
Float B 43
Float C 25
Float D 25
Float E 7
a
Conditions 400C, 50 mg c at al y s t .
b
Corrected wt% coke on c at al y s t - (wt% coke at time t)
(wt% coke at t - 15 minutes)
c
An increase i n "coke s el ec t i v i t y " implies a reduced tendency for
coking.
The difference i n ac t i v i t y among the separated frac t i on s i s
demonstrated by the steady drop i n coke make at constant
conversion with increasing density / age (Tab le V-A). The
an t i c i p at ed drop i n ac t i v i t y with age i s demonstrated from a
complementary way of presenting the cumene cracking data,
s p ec i fi c al l y , the res u l t s for conversion at constant coke make
(0.25 wt%) given i n Tab le V-B. The conversion l ev el shows a
steady decrease from a maximum of 45% for the f i r s t (y oungest)
frac t i on (A) to only 7% for the f i f t h frac t i on (E).
Metals Deposition/ Cataly st Age. The metals on c at al y s t res u l t s
given i n Figure 3a indicate that the separation by density i s
eq uivalent to a separation by age. The n i c kel l ev el on each
c at al y s t frac t i on exhib its a monotonic increase with increasing
density . The dramatic decrease exhib ited b y the rat i o V/ Ni with
increasing c at al y s t density / age (Figure 3b) comprises i n d i rec t
evidence for i n t erp art i c l e vanadium migration. The rat i o V/ Ni
(ppm on c at al y s t ) i s highest for the younger ( l i g h t er) p art i c l es
due to a net migration of vanadium from the older p art i c l es with

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8. BEYERLEIN ETAL. MonitoringFCC Deactivation Profile 119
h i g h me t a l s l e v e l s . T h e o l d e s t p a r t i c l e s e x h i b i t a me t a l s r a t i o
V / N i - 0 . 6 5 , wh i c h i s c o mp a r a b l e t o b u t s l i g h t l y l o we r t h a n t h a t
c h a r a c t e r i s t i c o f t h e f e e d , V / N i - 0 . 7 1 ( T a b l e I I ) . I n d i r e c t
e v i d e n c e f o r i n t e r p a r t i c l e v a n a d i u m mi g r a t i o n i n t h e s t e a m
r e g e n e r a t o r h a s b e e n c i t e d p r e v i o u s l y ( 1 . 2 ) .
I n s p e c t i o n o f t h e f e e d r e c o r d s f o r t h e F CU f r o m wh i c h
C a t a l y s t A was r e mo v e d s h o ws n o s i g n i f i c a n t v a r i a t i o n o f t h e
n i c k e l c o n t e n t i n t h e f e e d d u r i n g t h e p e r i o d o f c a t a l y s t
r e s i d e n c e . T h e r e f o r e , t h e n i c k e l c o n t e n t o n e a c h c a t a l y s t
f r a c t i o n c a n b e u s e d t o e s t i ma t e a f r a c t i o n a g e . A p p l i c a t i o n o f a
l i n e a r r e g r e s s i o n a n a l y s i s t o t h e N i c o n t e n t d a t a g i v e n i n F i g u r e
3 a ( F r a c t i o n s A- F ) s h o ws t h a t t h e t r e n d f o r i n c r e a s i n g n i c k e l
c o n t e n t w i t h i n c r e a s i n g d e n s i t y i s g i v e n b y :
wh e r e dn, i s t h e me d i a n d e n s i t y ( g / c c ) f o r e a c h f r a c t i o n
( T a b l e s I I I a n d I V ) . S i n c e t h e l o w d e n s i t y l i mi t o f t h e f i r s t
f r a c t i o n , A, i s 2 . 3 2 g / c c , a n d t h e N i c o n t e n t o f f r e s h c a t a l y s t i s
3 0 ppm ( T a b l e I ) , t h e l i n e a r r e g r e s s i o n a n a l y s i s was c o n s t r a i n e d
t o p a s s t h r o u g h N i ( ppm) - 3 0 a t = 2 . 3 2 g / c c . T h e q u a n t i t y
( N i ( p p m) - 3 0 ppm) d e t e r mi n e d f r o m E q u a t i o n 1 r e p r e s e n t s t h e
a c c u mu l a t e d N i l e v e l o n c a t a l y s t du e t o d e p o s i t i o n f r o m t h e f e e d .
T h e e s t i ma t e d ag e d i s t r i b u t i o n wh i c h r e s u l t s u p o n d i v i s i o n o f t h i s
q u a n t i t y b y t h e r a t e o f N i d e p o s i t i o n o n c a t a l y s t , 11. 1 p p m/ day
( T a b l e I I ) , i s a s f o l l o w s :
F r a c t i o n B 2 6 d a y s
F r a c t i o n C - - 3 6 d a y s
F r a c t i o n D 4 9 d a y s
F r a c t i o n E - - 6 8 d a y s
F r a c t i o n F - - 9 7 d a y s
( S i n k ) F r a c t i o n H - - 16 9 d a y s
S u r f a c e A r e a / Mi c r o p o r e V o l u me L o s s f o r E q u i l i b r i u m C a t a l y s t :
Co mp a r i s o n w i t h R e s u l t s o f S u r f a c e Ar e a . Mi c r o p o r e V o l u me L o s s
D u r i n g C a t a l y s t D e a c t i v a t i o n . T h e t o t a l B E T s u r f a c e a r e a s a n d t h e
mi c r o p o r e a r e a s a r e g i v e n f o r c o k e d a n d f o r r e g e n e r a t e d c a t a l y s t
f r a c t i o n s i n F i g u r e 4 a n d T a b l e I V ( t o t a l B E T s u r f a c e a r e a e q u a l s
mi c r o p o r e s u r f a c e a r e a p l u s ma t r i x s u r f a c e a r e a ) . T h e s u r f a c e
a r e a v a l u e s f o r c o k e d f r a c t i o n s d i f f e r s i g n i f i c a n t l y f r o m t h o s e
f o r r e g e n e r a t e d f r a c t i o n s o n l y f o r t h e f i r s t t wo f r a c t i o n s ,
c o n s i s t e n t w i t h t h e c a r b o n o n c a t a l y s t r e s u l t s g i v e n i n F i g u r e 2 .
F o r t h e s e c o n d a n d s u c c e e d i n g f r a c t i o n s , t h e r e i s a s y s t e ma t i c
d e c r e a s e i n mi c r o p o r e a r e a w i t h i n c r e a s i n g d e n s i t y . I n
c o n s i d e r a t i o n o f t h e e v i d e n c e j u s t d i s c u s s e d f o r a n a s s o c i a t i o n o f
i n c r e a s i n g d e n s i t y wi t h i n c r e a s i n g f r a c t i o n a g e , t h i s r e s u l t
r e f l e c t s t h e o c c u r r e n c e o f i n c r e a s i n g d e s t r u c t i o n o f t h e
c r y s t a l l i n e z e o l i t e w i t h i n c r e a s i n g t i me i n t h e u n i t . F o r
c o mp a r i s o n , r e s u l t s o f XRD, p o r o s i t y , a n d s u r f a c e a r e a a n a l y s e s
f o r t h e f r e s h p a r e n t o f C a t a l y s t A, a n d f o r p o r t i o n s o f t h i s
N i ( ppm) - ( d ^ - 2 . 3 2 ) x 6 4 7 0 + 3 0
( 1)
F r a c t i o n A 6 d a y s

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120 FLUID CATALYTIC CRACKING IL CONCEPTS IN CATALYST DESIGN
a.
b.
| 1000
a.
800
600
400
2
Z
o
200
/
Nickel
/
/ ^
-
/ "
-
00^^ Vanadium
...... -.,1 ,. ,_.J 1
2.32 2.36 2.40 2.44 2.48
1.3
1.2
1.1
1.0
0.9
0.8
0.7
2.36 2.40 2.44 2.48
o
z
<
Figure 3 . (a) Nickel and vanadium concentrations on separated
c at al y s t frac t i on s , and (b) V/ Ni rat i o for separated
c at al y s t frac t i on s .
2.32 2.36 2.40 2.44 2.48 2.52 2.56 2.60
Figure 4. BET and micropore surface areas for coked and
regenerated c at al y s t frac t i on s shown together with
d i s t ri b u t i on of c at al y s t frac t i on s versus density .

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8. B EY ERLEI N E T A L. Monitoring FCC Deactivation Profile
121
c a t a l y s t t h a t h a v e b e e n s t e a m d e a c t i v a t e d f o r d i f f e r e n t t i me s a t
t e mp e r a t u r e s i n t h e r a n g e 7 0 0 C- 8 15 C a r e g i v e n i n T a b l e V I . T h e
ma t e r i a l s s t e a me d a t t e mp e r a t u r e s i n t h e r a n g e 7 6 0 C t o 8 15 C s h o w
a c h a n g e i n p h y s i c a l p r o p e r t i e s s i mi l a r t o t h o s e e x h i b i t e d b y
F r a c t i o n s A- D o f t h e e q u i l i b r i u m c a t a l y s t ( T a b l e V I I ) . XRD u n i t
c e l l s i z e s , mi c r o p o r e a n d ma t r i x s u r f a c e a r e a s , a n d t o t a l p o r e
v o l u me s a r e c o mp a r a b l e , a n d a d e c r e a s e i n mi c r o p o r e v o l u me / a r e a o f
a b o u t 2 0 % i s o b s e r v e d f o r e a c h s e t o f ma t e r i a l s . T h e s e r e s u l t s
i n d i c a t e t h a t s i n g l e mo de d e a c t i v a t i o n p r o v i d e s a p o o r s i mu l a t i o n
o f c a t a l y s t a g i n g i n t h e F CU.
T h e f a c t t h a t t h e mi c r o p o r e a r e a f o r r e g e n e r a t e d c a t a l y s t
f r a c t i o n s d e c r e a s e s mo n o t o n i c a l l y w i t h i n c r e a s e i n d e n s i t y
s u p p l i e s a n a d d i t i o n a l c l u e a b o u t t h e n a t u r e o f t h i s s e p a r a t i o n .
E x c e p t f o r e q u i l i b r i u m c a t a l y s t f r a c t i o n s A, B , a n d C, f o r wh i c h
r e s i d u a l c o k e o n c a t a l y s t c h a n g e s wi t h d e n s i t y ( F i g u r e 2 ) , t h e
s e p a r a t i o n b y d e n s i t y c a n n o t b e a s s o c i a t e d w i t h a c t i v i t y f o r c o k e
f o r ma t i o n f r o m i s o b u t e n e . F o r F r a c t i o n C a n d s u c c e e d i n g
f r a c t i o n s , t h e i n c r e a s e i n c a t a l y s t d e n s i t y i s s t r o n g l y c o r r e l a t e d
w i t h a d e c r e a s e i n t h e c r y s t a l l i n e , mi c r o p o r o u s z e o l i t e c o mp o n e n t
( F i g u r e 4 , T a b l e I V ) . T h e l o s s o f mi c r o p o r e v o l u me d o mi n a t e s t h e
d e c r e a s e i n t o t a l s u r f a c e a r e a w i t h i n c r e a s i n g t i me i n t h e u n i t .
T h e e x t e r n a l o r ma t r i x s u r f a c e a r e a s h o ws n o s i g n i f i c a n t d e c r e a s e
u n t i l a f t e r t h e f o u r t h f r a c t i o n a n d t h e n e x h i b i t s o n l y a s l o w
d e c r e a s e i n c o mp a r i s o n t o t h e r a t e o f l o s s o f mi c r o p o r e
a r e a / v o l u me ( F i g u r e 4 a n d T a b l e I V ) .
D e n s i t y o f S t e am D e a c t i v a t e d v s . F r e s h C a t a l y s t . T h e r e s u l t s o f
d e n s i t y me a s u r e me n t s o n t h e f r e s h p a r e n t o f C a t a l y s t A a n d o n a
p o r t i o n o f t h i s c a t a l y s t t h a t h a s b e e n s t e a m d e a c t i v a t e d a t 8 15 C
f o r f i v e h o u r s ( T a b l e V I I I ) i n d i c a t e a d i r e c t c o n n e c t i o n b e t we e n
t h e l o s s o f c r y s t a l l i n e mi c r o p o r o u s z e o l i t e a n d i n c r e a s e i n
c a t a l y s t d e n s i t y . T h e ma j o r p o r t i o n ( 6 7 %) o f t h e f r e s h c a t a l y s t
i s f o u n d i n t h e d e n s i t y r a n g e 2 . 3 3 0 < d < 2 . 3 5 5 g / c c . B y
c o n t r a s t , t h e ma j o r p o r t i o n ( 8 7 %) o f t h e s t e a m d e a c t i v a t e d
c a t a l y s t i s f o u n d i n t h e d e n s i t y r a n g e 2 . 3 7 2 t o 2 . 3 9 4 g / c c .
T a b l e V I . P r o p e r t i e s o f F r e s h a n d S t e am D e a c t i v a t e d C a t a l y s t A
U n i t
S t e am C e l l % C r y s t % C r y s t B E T S A Cum P o r e
T r e a t me n t A XRD mi c r o p o r e
m
2
/ g
V o l u me
v o l u me c c / g
F r e s h 2 4 . 4 0 3 5 3 4 2 8 1 0 . 15
7 0 4 C, 2 - h r 2 4 . 3 3 3 1 3 0 2 4 9 0 . 15
7 6 0 C, 2 - h r 2 4 . 3 0 3 1 3 0 2 3 6 0 . 14
7 8 8 C, 5 - h r 2 4 . 2 6 2 8 2 8 2 2 4 0 . 15
8 15 C, 5 - h r 2 4 . 2 1 2 5 2 4 19 9 0 . 14
8 15 C, 2 4 - h r 2 4 . 2 4 2 0 2 1 16 9 0 . 15
S t e am Av g . P o r e Mi c r o p o r e Mi c r o p o r e Ma t r i x
T r e a t me n t R a d i u s , A V o l u me A r e a A r e a
c c / g m
2
/ e m
2
/ e
F r e s h 3 3 0 . 0 9 1 18 8 9 3
7 0 4 C, 2 - h r 4 4 0 . 0 8 2 17 0 7 9
7 6 0 C, 2 - h r 5 1 0 . 0 8 0 16 4 7 1
7 8 8 C, 5 - h r 5 8 0 . 0 7 6 15 7 6 7
8 15 C, 5 - h r 7 1 0 . 0 6 6 13 8 6 1
8 15 C, 2 4 - h r 5 1 0 . 0 5 7 117 5 2

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122
T a b l e V I I . Co mp a r i s o n o f L a b - S t e a me d C a t a l y s t w i t h E q u i l i b r i u m
F r a c t i o n s
L a b - S t e a me d C r y s t *
C a t a l y s t ; U n i t Mi c r o p o r e Ma t r i x R e l a t i v e
S t e a m- T r e a t C e l l a r e a a r e a t o
C o n d i t i o n s A m
2
/ e m
2
/ e F r e s h
7 6 0 C, 2 - h r 2 4 . 3 0 16 4 7 1 8 7
7 8 8 C, 5 - h r 2 4 . 2 6 15 7 6 7 8 4
8 15 C, 5 - h r 2 4 . 2 1 13 8 6 1 7 3
8 15 C, 1 2 - h r 2 4 . 2 4 13 0 6 0 6 9
8 15 C, 2 4 - h r 2 4 . 2 4 117 5 2 6 2
% C r y s t *
E q u i l i b r i u m U n i t Mi c r o p o r e Ma t r i x R e l a t i v e
C a t a l y s t C e l l a r e a a r e a t o
F r a c t i o n A m
2
/ e
m
2
/ e F r e s h
A 2 4 . 3 1 15 6 5 6 8 3
B 2 4 . 2 7 15 1 6 8 8 0
C 2 4 . 2 6 13 8 6 9 7 3
D 2 4 . 2 4 12 4 6 8 6 6
E 2 4 . 2 6 9 9 6 2 5 3
F 2 4 . 2 8 7 2 4 6 3 8
* 0 n t h e b a s i s o f mi c r o p o r e v o l u me s

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BEYERLEIN ET AL. MonitoringFCC Deactivation Profile 123
T a b l e V I I I . D e n s i t y S e p a r a t i o n o f F r e s h ( F ) a n d 8 15 C
S t e a me d ( S ) C a t a l y s t A: P r o p e r t i e s o f
S e p a r a t e d C a t a l y s t F r a c t i o n s
D e n s i t y Me d i a n U n i t
C a t a l y s t L i mi t , D e n s i t y , % o f C e l l % C r y s t
F r a c t i o n g / c c g / c c T o t a l A XRD
F , F l o a t A <2 . 3 2 0 2 . 3 3 0 3 3 . 0 2 4 . 4 1 3 7
F , F l o a t B <2 . 3 5 5 2 . 3 4 2 6 7 . 0 2 4 . 4 0 3 5
S , F l o a t A <2 . 3 7 2 2 . 3 6 2 8 . 1 2 4 . 2 3 2 6
S , F l o a t B <2 . 3 9 4 2 . 3 8 3 8 7 . 0 2 4 . 2 3 2 2
C a t a l y s t B E T Cum P o r e Av g P o r e Mi c r o p o r e Mi c r o p o r e Ma t r i x
F r a c t i o n S A, V o l u me R a d i u s V o l u me , A r e a , A r e a ,
m
2
/ g c c / g A c c / g m
2
/ g m
2
/ e
F , F i t A 2 7 0 0 . 14 3 2 0 . 0 8 7 17 9 9 1
F , F i t B 2 6 8 0 . 14 3 0 0 . 0 8 2 16 9 9 9
S , F i t A 2 0 4 0 . 13 7 6 0 . 0 7 1 14 6 5 8
S , F i t B 2 0 4 0 . 18 5 9 0 . 0 5 8 119 8 5
I t i s o b s e r v e d ( T a b l e V I ) t h a t a r e d u c t i o n i n mi c r o p o r e v o l u me o f
mo r e t h a n 2 7 % o c c u r s a s a r e s u l t o f s t e a m d e a c t i v a t i o n a t 8 15 C
f o r f i v e h o u r s . I n t h e d i s c u s s i o n wh i c h f o l l o w s , i t i s s h o wn h o w
d e s t r u c t i o n o f c r y s t a l l i n e z e o l i t e w i t h t h e c o n c o mi t a n t l o s s i n
mi c r o p o r e v o l u me l e a d s t o i n c r e a s e d a c c e s s i b i l i t y b y t h e s o l v e n t ,
wh i c h ma n i f e s t s i t s e l f a s a n e f f e c t i v e i n c r e a s e i n s k e l e t a l
d e n s i t y .
T h e h e a v i e r p o r t i o n o f t h e f r e s h a n d l a b o r a t o r y s t e a me d
c a t a l y s t ( F l o a t B ) e x h i b i t s a d e c r e a s e d mi c r o p o r e v o l u me w i t h
r e s p e c t t o t h e l i g h t e r p o r t i o n ( F l o a t A ) , s u g g e s t i n g t h a t t h e
d e n s i t y f r a c t i o n a t i o n w i t h i n e a c h c a t a l y s t r e f l e c t s t h e p r e s e n c e
o f a f i n i t e r a n g e o f z e o l i t e c r y s t a l l i n i t i e s . P a r t i c u l a r l y f o r
t h e f r e s h c a t a l y s t , t h i s i n h o mo g e n e i t y i s s ma l l ( T a b l e V I I I ) .
S o l v e n t A c c e s s i b i l i t y i n Z e o l i t i c P o r t i o n - I n f l u e n c e o f E x c l u d e d
V o l u me
Mi c r o p o r e S t r u c t u r e a n d S o l v e n t A c c e s s i b i l i t y . L o s s o f mi c r o p o r e
v o l u me i s e x p e c t e d t o l e a d t o a n i n c r e a s e i n me a s u r e d c a t a l y s t
d e n s i t y o wi n g t o e x c l u d e d v o l u me e f f e c t s a n d t o i mp e r f e c t p a c k i n g
o f t h e t wo s o l v e n t mo l e c u l e s , p a r t i c u l a r l y t e t r a b r o mo e t h a n e ,
i n s i d e t h e z e o l i t e c a g e s . T h e mi c r o p o r e v o l u me a s s o c i a t e d w i t h
t h e f a u j a s i t i c z e o l i t e c o mp o n e n t o f t h e c a t a l y s t i s c o mp o s e d o f a
t h r e e - d i me n s i o n a l l y c o n n e c t e d s y s t e m o f l a r g e c a g e s ( s u p e r c a g e s )
a n d s ma l l c a g e s ( s o d a l i t e u n i t s a n d d o u b l e s i x - r i n g p r i s ms ) , a s
s h o wn i n F i g u r e 5 a .
T h e l a r g e c a g e s ( s u p e r c a g e s ) a r e a c c e s s e d t h r o u g h 12 - me mb e r e d
o x y g e n r i n g s wh i c h d e f i n e a p o r e o p e n i n g o f a b o u t 7 . 6 A. Ca r b o n
t e t r a c h l o r i d e wi t h a n e f f e c t i v e d i a me t e r o f a b o u t 5 . 8 A ( 4 ) i s
r e a d i l y a d mi t t e d . U s i n g mo l e c u l a r mo d e l i n g ( 5. ) , t h e e f f e c t i v e

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F i g u r e 5b. Mo l e c u l a r g r a p h i c s r e p r e s e n t a t i o n o f c a r b o n
t e t r a c h l o r i d e a n d o f 1 , 1 , 2 , 2 -t e t r ab r o mo e t h an e .

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8. BEYERLEIN ETAL. MonitoringFCC Deactivation Profile US
diameter of 1,1,2,2-tetrabromoethane was estimated to be ab out 7.5
A (see Figure 5b ), roughly eq uivalent to the s i z e of the window
opening. Any c on s t ri c t i on of these apertures associated with
occluded alumina or with metals deposition might lead to a p art i al
or t ot al exclusion of tetrab romoethane. More pronounced pore
plugging could lead to exclusion of carb on t et rac h l ori d e as wel l .
The small cages are accessed through six-membered rings with
an effec t i v e pore opening of only about 2.8 A and are
inaccessib le, not only to b oth solvent molecules, b ut also to N
2
molecules (4) during c ol l ec t i on of the low temperature nitrogen
isotherm data that i s used to determine micropore volume. These
small cages do admit small polar molecules such as H
2
0 and NH
3
.
Comparison of water uptake with uptake of nitrogen or normal
p araffi n s shows that these small cages comprise ab out 12% of the
t ot al micropore volume (6).
Factors Leading to Density V ari at i on . Summarizing, the factors
which lead to an increase i n measured c at al y s t density with
increasing age are categoriz ed as follows: 1) decreased ac t i v i t y
for coke deposition, 2) increasing metals deposition, 3) excluded
volume associated with the small z eol i t e cages, 4) excluded volume
associated with imperfect packing of tetrab romoethane and of
carb on t et rac h l ori d e i n the supercages, 5) p referen t i al adsorption
of carb on t et rac h l ori d e associated with imperfect packing of the
b ulky tetrab romoethane molecule inside the supercages, and 6) pore
mouth c on s t ri c t i on s that lead to p art i al or complete pore mouth
plugging. The s i z e of Factors 1 and 2 may be read i l y estimated
from the an al y t i c al data given i n Tab les III and IV. The
contrib ution from the excluded volume associated with the small
cages, Factor 3, i s also read i l y estimated. An effec t i v e
contrib ution from Factors 4 and 5, modeled as an excluded volume
effec t , can be estimated on the b asis of the ob served density
difference between fresh and steamed c at al y s t (Tab le V III) .
Quantitative Estimates of Density V ariations. Quantitative
estimates of the rel at i v e contrib ution of Factors 1-5 to changes
i n c at al y s t density are given i n Tab le IX. In carry ing out these
c al c u l at i on s , the average s kel et al density of coke on c at al y s t was
taken to be 1.2 g/cc (Appendix A). Nickel, vanadium, and rare
earth were assumed to be present as the oxides NiO, V
2
0
4
, and RE
2
0
3
with densities of 6.7, 4.3, and 6.9, respectively . Similar
assumptions were made for i ron and titanium (Appendix A), b ut the
effec t of Fe and T i was included only for the heavier Fractions E,
F, and H, which exhib ited increased l ev el s of these two metals
(Tab le I I I ) . For the fl oat Fractions A-F, t h i s approach, b ased on
b ulk oxide densities, i s expected to overestimate the density
increase due to metals that are present as well-dispersed species.

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126
Ho we v e r , t h e c o n t r i b u t i o n t o d e n s i t y i n c r e a s e f r o m me t a l s
t e n d s t o b e s ma l l f o r t h e s e f r a c t i o n s ( T a b l e I X ) . F o r t h e s i n k
F r a c t i o n H, wh i c h h a s l o w s u r f a c e a r e a , l o w z e o l i t e c o n t e n t , a n d
h i g h me t a l s l e v e l s ( T a b l e s I I I a n d I X ) , h i g h me t a l s d i s p e r s i o n ,
p a r t i c u l a r l y f o r F e , T i , a n d RE , i s u n l i k e l y .
T a b l e I X. E s t i ma t e o f R e l a t i v e C o n t r i b u t i o n o f F a c t o r s
A f f e c t i n g D e n s i t y Ch an g e
C a t a l y s t Mi c r o p o r e A( Mp o r e A ( N i +V ) A RE A Ca r b o n
F r a c t i o n V o l u me V o l u me ) ppm ppm wt %
c c / g c c / g
Re g e n A 0 . 0 7 5
Re g e n B 0 . 0 7 3 - 0 . 0 0 2 5 5 - 0 . 9 4
Re g e n C 0 . 0 6 7 - 0 . 0 0 6 2 4 7 2 2 3 - 0 . 4 4
Re g e n D 0 . 0 6 0 - 0 . 0 0 7 4 3 5 5 2 0 - 0 . 13
Re g e n E 0 . 0 4 8 - 0 . 0 12 5 0 0 - 0 . 0 6
Re g e n F 0 . 0 3 5 - 0 . 0 13 - 8 7 5 7 6
Re g e n G 0 . 0 2 6 - 0 . 0 11
S i n k H 0 . 0 0 7 - 0 . 0 19 15 3 0 5 2 3 9
Ad C o n t r i b u t i o n x 10 0
C a t a l y s t AMp o r e A ( N i +V ) A RE A C N e t Ad
F r a c t i o n e x c l v o l g / c c
Re g e n A . .
Re g e n B 0, . 3 0 0. . 0 1 2. . 24 0 . 0 2 6
Re g e n C 0, . 90 0. . 0 5 0. , 04 1, , 0 5 0 . 0 2 0
Re g e n D 1. . 0 5 0. . 08 0. , 10 0. , 3 1 0 . 0 15
Re g e n E 1. . 79 0. . 10 0. , 14 0 . 0 2 4 ( a )
Re g e n F 1. . 94 0. , 11 0 . 0 2 4 ( b )
Re g e n G 1. . 64
.
S i n k H 2. . 84 0. 2 9 0. , 96 0 . 0 5 1 ( c )
F r o m t h e d a t a g i v e n i n T a b l e I I I ,
( a ) F l o a t E, e x h i b i t s a n F e c o n c e n t r a t i o n t h a t i s 8 0 0 ppm g r e a t e r
t h a n t h e a v e r a g e f o r A- D. T h e r e s u l t a n t c o n t r i b u t i o n s t o
d e n s i t y a r e Ad ( F e ) + A d ( T i ) - 0 . 0 0 15 + 0 . 0 0 2 4 - 0 . 0 0 3 9 g / c c .
F o r F r a c t i o n E , t h e n e t Ad ( E ) - 0 . 0 17 9 + 0 . 0 0 1 + 0 . 0 0 14 +
0 . 0 0 3 9 - 0 . 0 2 4 g / c c .
( b ) S i mi l a r l y , f o r F l o a t F , Ad ( F e ) + A d ( T i ) - 0 . 0 0 3 7 +0 , a n d
Ad ( F ) - 0 . 0 2 0 5 + 0 . 0 0 3 7 - 0 . 0 2 4 g / c c .
( c ) S i mi l a r l y , f o r S i n k H, Ad ( F e ) + A ( T i ) - 0 . 0 0 2 8 + 0 . 0 0 6 9 , a n d
Ad ( H) - 0 . 0 4 1 + 0 . 0 12 - 0 . 0 5 1 g / c c .
I n o r d e r t o e s t i ma t e t h e d e n s i t y i n c r e a s e a s s o c i a t e d w i t h
l o s s o f mi c r o p o r e v o l u me , t h e c o n t r i b u t i o n f r o m t h e l a r g e c a g e s
was " c a l i b r a t e d " u s i n g t h e c o mp a r a t i v e d a t a o n f r e s h a n d s t e a me d
c a t a l y s t g i v e n i n T a b l e s V I a n d V I I I . S t e am t r e a t me n t o f t h e
f r e s h c a t a l y s t a t 8 15 C f o r f i v e h o u r s r e s u l t e d i n a n i n c r e a s e i n

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a v e r a g e d e n s i t y o f Ad0 . 0 4 g / c c a n d a n a s s o c i a t e d d e c r e a s e i n
( l a r g e c a g e ) mi c r o p o r e v o l u me f r o m 0 . 0 9 1 t o 0 . 0 6 6 c c / g .
C a l c u l a t i o n s g i v e n i n Ap p e n d i x A s h o w t h a t a b o u t 3 0 % o f t h e
me a s u r e d d e n s i t y i n c r e a s e i s c o n t r i b u t e d b y F a c t o r 3 , t h e e x c l u d e d
v o l u me a s s o c i a t e d w i t h t h e s ma l l c a g e s . T h e l a r g e c a g e p a c k i n g
f r a c t i o n t h a t i s r e q u i r e d t o a c c o u n t f o r t h e b a l a n c e o f t h e
d e n s i t y i n c r e a s e i s f o u n d t o b e 6 7 %, o r e q u i v a l e n t l y , a 3 3 %
e x c l u d e d v o l u me . I t i s s h o wn i n Ap p e n d i x A t h a t , f o r a g i v e n
p a c k i n g f r a c t i o n , s e l e c t i v e a d s o r p t i o n o f t h e l i g h t e r c o mp o n e n t ,
c a r b o n t e t r a c h l o r i d e , wo u l d l e a d t o a d e c r e a s e i n t h i s e s t i ma t e d
p a c k i n g f r a c t i o n wi t h a p a r a l l e l i n c r e a s e i n t h e s i z e o f t h e
e x c l u d e d v o l u me .
F o r t h e f i r s t s i x c a t a l y s t f r a c t i o n s ( A - F ) , t h e e s t i ma t e d n e t
c h a n g e i n d e n s i t y ( n e t Ad ( e s t ) 0 . 11 g / c c , T a b l e I X) i s 7 0 % o f
t h a t a c t u a l l y o b s e r v e d ( Ad0 . 16 g / c c , T a b l e I I I a n d F i g u r e 1 ) .
T h e e s t i ma t e d Ad ' s g i v e n i n T a b l e I X i n d i c a t e t h a t c o k e o n
c a t a l y s t d o mi n a t e s t h e d e n s i t y s e p a r a t i o n o n l y i n t h e c a s e o f t h e
s e p a r a t i o n o f F r a c t i o n A f r o m F r a c t i o n B. F o r s e p a r a t i o n o f
F r a c t i o n B f r o m F r a c t i o n C, t h e e f f e c t o f l o s s o f mi c r o p o r e v o l u me
i s c o mp a r a b l e t o t h a t o f d e c r e a s e d c o k e mak e , wh i l e f o r s u c c e e d i n g
f r a c t i o n s , d e n s i t y i n c r e a s e i s du e p r i ma r i l y t o t h e c o mb i n e d
e f f e c t s o f l o s s o f mi c r o p o r e v o l u me a n d i n c r e a s i n g me t a l s l e v e l s .
T h e e s t i ma t e s i n T a b l e I X r e p r e s e n t t h e mi n i mu m e f f e c t o f t h e
l o s s o f mi c r o p o r e v o l u me . P o r e - mo u t h c o n s t r i c t i o n s wh i c h l e a d t o
p a r t i a l o r c o mp l e t e mi c r o p o r e p l u g g i n g wo u l d s e r v e t o i n c r e a s e t h e
c o n t r i b u t i o n o f l o s s o f mi c r o p o r e v o l u me t o d e n s i t y c h a n g e . No
s u c h p o r e p l u g g i n g i s e x p e c t e d t o o c c u r i n t h e ( me s o p o r o u s )
c a t a l y s t ma t r i x o r i n t h e me s o p o r o u s ma t e r i a l t h a t i s g e n e r a t e d
d u r i n g c r y s t a l l i n e z e o l i t e d e s t r u c t i o n .
I t i s p o s s i b l e t o a t t r i b u t e t h e n e t d i f f e r e n c e b e t we e n t h e
c a l c u l a t e d a n d t h e o b s e r v e d d e n s i t y r a n g e t o mi c r o p o r e p l u g g i n g .
R e c a s t i n g t h e c a l c u l a t i o n s g i v e n i n Ap p e n d i x A s h o w t h a t t h i s
wo u l d r e q u i r e r e d u c i n g t h e o v e r a l l p a c k i n g f r a c t i o n f o r t h e l a r g e
c a g e s f r o m 6 7 % t o 3 1%. T h i s r e s u l t s u g g e s t s a t e n d e n c y f o r t h e
z e o l i t e t o s e l e c t i v e l y a d s o r b t h e l i g h t e r c o mp o n e n t , c a r b o n
t e t r a c h l o r i d e , wh i c h wo u l d r e s u l t i n s ma l l e r e s t i ma t e d p a c k i n g
f r a c t i o n s .
D e n s i t y V a r i a t i o n s f o r t h e He a v i e s t F r a c t i o n s - - R e mn a n t R a r e E a r t h
C a t a l y s t . T h e e s t i ma t e d d e n s i t y v a r i a t i o n s g i v e n i n T a b l e I X s h o w
t h a t t h e r e l a t i v e l y h i g h d e n s i t y e x h i b i t e d b y t h e s i n k F r a c t i o n H
i s a s s o c i a t e d w i t h t h e h i g h c o n c e n t r a t i o n s o f me t a l s p r e s e n t i n
t h i s f r a c t i o n ( T a b l e I I I ) . T h e h i g h c o n c e n t r a t i o n o f r a r e e a r t h
i n F r a c t i o n H, 0 . 6 8 wt %, i n d i c a t e s t h a t i t i s c o mp o s e d e n t i r e l y o f
t h e o l d c a t a l y s t ( s ) p r e s e n t i n t h e u n i t a t c h a n g e o v e r ( s e e
T a b l e I I ) . B y c o mp a r i s o n , f l o a t F r a c t i o n F , w i t h a r a r e e a r t h
c o n t e n t o f 0 . 16 wt %, i n c l u d e s a n a d mi x t u r e o f a b o u t 2 0 % o f t h e
p r i o r c a t a l y s t ( s ) . T h e p r e s e n c e o f t h e p r i o r r a r e e a r t h -
c o n t a i n i n g c a t a l y s t ( C a t a l y s t C, T a b l e I I ) i n t h e h e a v i e s t
F r a c t i o n s F , G, a n d H i s a l s o i n d i c a t e d b y t h e i n c r e a s e i n u n i t
c e l l s i z e e x h i b i t e d b y t h e s e f r a c t i o n s ( T a b l e I I I ) . R e c a l l i n g
t h a t t h e c h a n g e o v e r f o r t h e e q u i l i b r i u m c a t a l y s t o f t h i s s t u d y i s

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88% complete (Tab le II) , these res u l t s show that the major p ort i on
of the remnant rare earth-containing c at al y s t ( s ) i s sequestered
into the heaviest frac t i on s G and H.
Deactivation P rofi l e
Rate of Dealumination Compared with Rate of Zeol i t e Destruction.
The res u l t s developed earl i er for the n i c kel age of each c at al y s t
frac t i on can be used to q uantify and compare the rate of z eol i t e
dealumination with that for z eol i t e destruction. Upon
introduction of the c at al y s t to the FCU unit, the u n i t c e l l
dimension decreases from 24.40 angstroms to 24.31 angstroms
(Fraction A), i n d i c at i n g that about h al f of the ori g i n al framework
aluminum content (7) i s l os t i n the f i r s t s i x days. Dealumination
i s l arg el y complete for Fraction B (26 days residence), with a
0
-
24.27 angstroms representing retention of about 20% of the
ori g i n al framework aluminum content (7). Framework aluminum loss
continues at a slower rate for the t h i rd and fourth frac t i on s ,
which exh i b i t u n i t c e l l dimensions of 24.26 and 24.24 angstroms,
i n d i c at i n g that almost 90% of the ori g i n al framework aluminum
content has b een l os t (7).
Loss of micropore area/ z eolite c ry s t al l i n i t y i s a slow
process i n comparison with dealumination. Following an i n i t i a l
decline i n micropore area of 17% upon c at al y s t addition (Tab les
IV, V I), z eol i t e micropore area/ c ry s t al l i n i t y decreases by only an
ad d i t i on al 3% over the next 26 days (Fraction B, Tab le IV,
Figure 4), b y which time dealumination i s l arg el y complete. There
follows a steady rate of z eol i t e destruction which res u l t s i n an
ad d i t i on al 42% loss of c ry s t al l i n e z eol i t e ( rel at i v e to fresh
c at al y s t ) over the next 80 days (see Figure 4, Fractions B-F).
Frac t i on F, representing the end point of the USY c at al y s t
d i s t ri b u t i on , retains only 38% of the c ry s t al l i n i t y c h arac t eri s t i c
of fresh c at al y s t . Fractions A-D, representing the major portion
of t h i s eq uilib rium c at al y s t , exhib it rel at i v e c ry s t al l i n i t y
retentions ranging from 83 to 66%.
Comparison with Lab Steam Deactivations. Cataly st frac t i on s which
exh i b i t 50% or greater loss i n micropore v ol u me/ c ry s t al l i n i t y
comprise less than 15% of eq uilib rium c at al y s t . The major portion
of t h i s p art i c u l ar eq uilib rium c at al y s t i s remarkab ly s i mi l ar to
the material which res u l t s from increasingly severe lab oratory
steam deactivations at 815C or less (Tab les VI and V II) .
Dealumination i s rapid, the associated c ry s t al l i n i t y loss i s
small, and the matrix surface area shows l i t t l e change.
C ry s t al l i n i t y retention f a l l s below 70% only aft er dealumination
i s complete.
The comparison of phy sical properties of lab oratory -steamed
c at al y s t with those of eq uilib rium c at al y s t frac t i on s given i n
Tab le V II indicates that a wide range of steaming temperatures i s
necessary to reproduce the eq uilib rium c at al y s t deactivation
p rofi l e for lab steaming times of one day or l es s . These res u l t s
indicate that an improved c at al y s t aging procedure for simulating

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F CC c o n d i t i o n s w i l l i n v o l v e a p r o g r a m o f s t e a m t r e a t me n t s a t
d i f f e r e n t t e mp e r a t u r e s a s c o n t r a s t e d w i t h a r e c e n t s u g g e s t i o n t h a t
s t e a m t r e a t me n t b e c a r r i e d o u t a t c o n s t a n t t e mp e r a t u r e f o r v a r y i n g
t i me s ( 8 ) .
I t i s e v i d e n t f r o m t h e r e s u l t s p r e s e n t e d i n T a b l e V I I t h a t
s t e a mi n g t e mp e r a t u r e s o f 8 5 0 C o r e v e n h i g h e r a r e r e q u i r e d i n
o r d e r t o ma t c h t h e p h y s i c a l p r o p e r t i e s o f t h e o l d e s t F r a c t i o n F ,
wh i c h r e t a i n s o n l y 3 8 % o f t h e c r y s t a l l i n i t y e x h i b i t e d b y f r e s h
c a t a l y s t . T h i s d o e s n o t n e c e s s a r i l y s u g g e s t t h e p r e s e n c e o f l o c a l
h o t s p o t s i n t h e r e g e n e r a t o r , wh i c h a c t u a l l y o p e r a t e s a t
r e l a t i v e l y mi l d c o n d i t i o n s . T h e n e t 6 0 % l o s s i n c r y s t a l l i n i t y
d i s p l a y e d b y F r a c t i o n F i s mo r e p r o b a b l y t h e r e s u l t o f s t e a mi n g a t
6 8 0 C t o 7 0 5 C f o r l o n g t i me s . S i n c e t h e c a t a l y s t r e s i d e s i n t h e
r e g e n e r a t o r mo s t o f t h e t i me , i t i s e s t i ma t e d t h a t F r a c t i o n F h a s
b e e n s u b j e c t e d t o h i g h - t e mp e r a t u r e s t e a m t r e a t me n t f o r 8 0 d a y s o r
mo r e .
A c t i v i t y P r o f i l e f o r I n c r e a s i n g l y S e v e r e L a b D e a c t i v a t i o n s .
D e t e r mi n a t i o n o f t h e a c t i v i t y / s e l e c t i v i t y p r o f i l e e x h i b i t e d b y
s e p a r a t e d f r a c t i o n s f o r a f u l l r a n g e g a s o i l a wa i t s l a r g e r - s c a l e
s e p a r a t i o n . I n t h e me a n t i me , me a s u r e me n t s h a v e b e e n made a t a
mi c r o c r a c k i n g y i e l d s u n i t ( MY U) o n e a c h o f t h e l a b o r a t o r y s t e a me d
c a t a l y s t s r e p r e s e n t e d i n T a b l e V I I , wh i c h e x h i b i t e d p h y s i c a l
p r o p e r t i e s s i mi l a r t o t h o s e o f t h e s e p a r a t e d e q u i l i b r i u m F r a c t i o n s
A- D. R e s u l t s f o r c o n v e r s i o n a n d f o r i n d i v i d u a l y i e l d s o f
g a s o l i n e , l i g h t g a s , a n d c o k e , a r e g i v e n i n F i g u r e 6. F o r t h e
e a r l y p o r t i o n o f t h e d e a c t i v a t i o n p r o f i l e r e p r e s e n t e d b y t h e s e
i n v e s t i g a t i o n s , c o n v e r s i o n a n d g a s o l i n e y i e l d d e c r e a s e l i n e a r l y
w i t h t h e f r a c t i o n o f c r y s t a l l i n e z e o l i t e r e t a i n e d . T h u s , w i t h i n
t h i s r e g i o n , l o s s e s i n c r a c k i n g a c t i v i t y a n d i n g a s o l i n e
s e l e c t i v i t y c a n b e d i r e c t l y a t t r i b u t e d t o z e o l i t e d e s t r u c t i o n .
Ob s e r v i n g t h a t b o t h t h e r ma l c r a c k i n g a c t i v i t y a n d r e s i d u a l ma t r i x
a c t i v i t y c o n t r i b u t e t o c o n v e r s i o n a n d t o g a s o l i n e y i e l d , i t i s
c l e a r t h a t t h e l i n e a r r e l a t i o n s h i p s s h o wn i n F i g u r e 6 c a n n o t b e
ma i n t a i n e d i n t o t h e r e g i o n wh e r e t h e z e o l i t e d e s t r u c t i o n
a p p r o a c h e s c o mp l e t i o n . A c c o r d i n g l y , b o t h c o n v e r s i o n a n d g a s o l i n e
y i e l d a r e e x p e c t e d t o s h o w i n c r e a s i n g l y l e s s d e p e n d e n c e o n z e o l i t e
d e s t r u c t i o n i n t h e l a t e r s t a g e s o f d e a c t i v a t i o n . T h i s e x p e c t a t i o n
i s b o r n e o u t b y t h e p l o t s h o wn i n F i g u r e 6 a f o r t h e p s e u d o s e c o n d -
o r d e r p a r a me t e r , k i n e t i c s c o n v e r s i o n ( wt % c o n v e r s i o n / 1 0 0 - wt %
c o n v e r s i o n ) , wh i c h i n d i c a t e s mi n i ma l d e p e n d e n c e o n z e o l i t e c o n t e n t
a s c r y s t a l l i n i t y r e t e n t i o n f a l l s b e l o w 6 0 %.
T h e r e s u l t s f o r r e s i d u a l c a r b o n o n e q u i l i b r i u m c a t a l y s t
f r a c t i o n s ( F i g u r e 2 ) a n d f o r c u me n e c r a c k i n g o n r e g e n e r a t e d
e q u i l i b r i u m f r a c t i o n s ( T a b l e V ) a l s o i n d i c a t e t h a t c r a c k i n g
a c t i v i t y s h o ws l i t t l e d e p e n d e n c e o n z e o l i t e c o n t e n t f o l l o w i n g
c o mp l e t i o n o f f r a me wo r k d e a l u mi n a t i o n ( mi n i mu m u n i t c e l l s i z e ) .
A t t h i s p o i n t , t h e 6 0 t o 7 0 % o f c r y s t a l l i n e z e o l i t e t h a t r e ma i n s
c o n t a i n s a d i mi n i s h i n g l y s ma l l n u mb e r o f a c i d s i t e s , a n d f u r t h e r
z e o l i t e d e s t r u c t i o n h a s l i t t l e e f f e c t o n c r a c k i n g a c t i v i t y .
E x c e p t f o r t h e h i g h e s t c o n v e r s i o n wh e r e o v e r c r a c k i n g i s
p r e s u me d t o b e mo r e s i g n i f i c a n t , t h e l i g h t g a s y i e l d s ( T C2 ~,

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Deactivation Profile for Lab-Steamed Catalyst
60 70 80 90 100
Crystallinity Retention (%)
50 60 70 80 90 100
I
2
& 1
50 60 70 80 90 100
50 60 70 80 90 100
Catalyst Activity and Selectivity Losses
Follow the Loss in Zeolite Crystallinity
F i g u r e 6. ( a ) C o n v e r s i o n , ( b ) Ga s o l i n e Y i e l d ( C
5
- 2 2 0 C) ,
( c ) L i g h t Gas ( T C2 - ) Y i e l d , a n d ( d ) Co k e Y i e l d , e a c h
p l o t t e d v s . F r a c t i o n o f Z e o l i t e C r y s t a l l i n i t y t h a t i s
r e t a i n e d .

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8. BEYERLEIN ETAL. MonitoringFCC Deactivation Profile
131
F i g u r e 6 c ) , s h o w l i t t l e d e p e n d e n c e o n z e o l i t e c o n t e n t . T h i s
r e s u l t i s c o n s i s t e n t w i t h t h e r o l e o f C2 ~ a s a ma r k e r o f t h e r ma l
c r a c k i n g . I n i t i a l l y , c o k e y i e l d s ( F i g u r e 6 d) d r o p s h a r p l y w i t h
c r y s t a l l i n e z e o l i t e c o n t e n t , b u t l e v e l o f f a s c r y s t a l l i n i t y
r e t e n t i o n f a l l s b e l o w a b o u t 7 0 %, a b e h a v i o r s i mi l a r t o t h a t
d i s p l a y e d b y t h e p l o t o f t h e p s e u d o s e c o n d - o r d e r r a t e c o n s t a n t ,
k i n e t i c s c o n v e r s i o n , g i v e n i n F i g u r e 6 a . A c c o r d i n g l y , t h e c o k e
y i e l d s p l o t t e d i n F i g u r e 6 d mu s t r e p r e s e n t " c a t a l y t i c c o k e " ( 9 )
a n d , o f t h e ms e l v e s , c o mp r i s e a r e l i a b l e me a s u r e o f t h e
d e a c t i v a t i o n p r o f i l e a s s o c i a t e d wi t h t h e s e i n c r e a s i n g l y s e v e r e
l a b o r a t o r y d e a c t i v a t i o n s . T h e c l o s e c o mp a r i s o n o f t h e r e s u l t s f o r
c o k e y i e l d s v e r s u s c r y s t a l l i n i t y r e t e n t i o n p l o t t e d i n F i g u r e 6 d ,
w i t h t h e a n a l o g o u s r e s u l t s f o r r e s i d u a l c a r b o n o n e q u i l i b r i u m
c a t a l y s t g i v e n i n F i g u r e 2 a n d T a b l e I I I , f u r t h e r d e mo n s t r a t e t h e
s i mi l a r i t y b e t we e n t h e a s s o c i a t e d c a t a l y s t d e a c t i v a t i o n p r o f i l e s .
A n a l y t i c a l E l e c t r o n Mi c r o s c o p y I n v e s t i g a t i o n s o f E q u i l i b r i u m
C a t a l y s t F r a c t i o n s
Y o u n g F r a c t i o n - E x t e n s i v e Z e o l i t e C r y s t a l l i t e s . A n a l y t i c a l
e l e c t r o n mi c r o s c o p y ( AE M) was u s e d t o t r a c k z e o l i t e d e s t r u c t i o n
w i t h i n c r e a s i n g t i me i n t h e u n i t . I n t h e s e i n v e s t i g a t i o n s , t h e
US Y c r y s t a l l i t e s e mb e dde d i n e a c h mi c r o s p h e r o i d a l s p r a y - d r i e d
c a t a l y s t p a r t i c l e c o u l d b e d i s t i n g u i s h e d o n t h e b a s i s o f a
c o mb i n a t i o n o f l a t t i c e i ma g i n g , S i / A l r a t i o , a n d mo r p h o l o g y . A
l a t t i c e i mag e f r o m a US Y c r y s t a l l i t e ( F AU ma t e r i a l ) i n a c a t a l y s t
p a r t i c l e f r o m F r a c t i o n B i s s h o wn i n F i g u r e 7 b . T h e e x t e n t o f t h e
l a t t i c e l i n e s i n d i c a t e t h a t t h e c r y s t a l l i t e i s a t l e a s t 0 . 4
mi c r o n s i n s p a t i a l e x t e n t . C a t a l y s t mo r p h o l o g y i n t h i s r e g i o n i s
s h o wn i n t h e i n s e t , F i g u r e 7 a . L a t t i c e i ma g i n g t o g e t h e r w i t h
c o mp o s i t i o n a l a n a l y s i s ( e n e r g y d i s p e r s i v e X- r a y , E D X) was u s e d t o
d e mo n s t r a t e t h a t t h e z e o l i t e c r y s t a l l i t e s e x h i b i t e d h i g h e r S i / A l
t h a n t h e s u r r o u n d i n g ma t r i x , a s s h o wn b y t h e mi c r o g r a p h s i n
F i g u r e 8 , a n d t h e c o mp o s i t i o n a l a n a l y s i s s p e c t r a i n F i g u r e 9 f o r
F r a c t i o n F . T h e p a r t i c u l a r l a t t i c e i mag e s h o wn i n F i g u r e 8 b
o r i g i n a t e s f r o m a n i s o l a t e d , s ma l l r e g i o n o f c r y s t a l l i n e F AU
ma t e r i a l a s s h o wn i n t h e i n s e t , F i g u r e 8 a . R e s u l t s o f
c o mp o s i t i o n a l a n a l y s e s s h o w t h a t t h e F AU ma t e r i a l e x h i b i t s a
s i g n i f i c a n t l y h i g h e r S i / A l t h a n d o e s t h e s u r r o u n d i n g ma t r i x
( F i g u r e 9 ) .
O l d F r a c t i o n - I n t i ma t e Mi x t u r e o f C r y s t a l l i n e a n d C o l l a p s e d
Z e o l i t e . F r a c t i o n F e x h i b i t s a c h a r a c t e r i s t i c mo r p h o l o g y f e a t u r e
( n o t e t h e r e g i o n j u s t b e l o w a n d t o t h e r i g h t o f c e n t e r i n F i g u r e
10 a) n o t o b s e r v e d i n F r a c t i o n B. T h i s s t r u c t u r e i s i n d i c a t i v e o f
amo r p h o u s ma t e r i a l , b u t w i t h a n S i / A l t h a t i s c h a r a c t e r i s t i c o f
US Y z e o l i t e . F u r t h e r e x a mi n a t i o n o f t h i s l a r g e l y amo r p h o u s r e g i o n
r e v e a l s l a t t i c e i ma g e s f r o m s ma l l r e g i o n s o f c r y s t a l l i n e F AU
ma t e r i a l , a s s h o wn i n F i g u r e 10 b . A p p a r e n t l y , t h e s e p a r t i c u l a r
l a r g e l y amo r p h o u s r e g i o n s i n F r a c t i o n F r e p r e s e n t wh a t was o n c e
e x t e n s i v e c r y s t a l l i n e F AU ma t e r i a l wh i c h , a f t e r l o n g r e s i d e n c e
t i me ( a b o u t 10 0 d a y s f o r F i n c o mp a r i s o n w i t h 2 0 d a y s f o r B ) i n

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F i g u r e 7. ( a ) C a t a l y s t mo r p h o l o g y ( F r a c t i o n B) i n r e g i o n o f US Y
c r y s t a l l i t e , a n d ( b ) L a t t i c e i mag e o f US Y c r y s t a l l i t e
( F AU ma t e r i a l ) .

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F i g u r e 8. ( a ) I s o l a t e d US Y c r y s t a l l i t e w i t h i n F r a c t i o n F , a n d
( b ) L a t t i c e i mag e o f US Y c r y s t a l l i t e w i t h i n
F r a c t i o n F .

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134
F i g u r e 9. Co mp a r i s o n o f c o mp o s i t i o n a l a n a l y s i s d a t a f o r F AU a n d
ma t r i x .

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BEYERLEIN ET AL. MonitoringFCC Deactivation Profile
F i g u r e 10. ( a ) C h a r a c t e r i s t i c " amo r p h o u s " mo r p h o l o g y f e a t u r e
o b s e r v e d i n F r a c t i o n F , a n d ( b ) L a t t i c e i mag e o f F AU
c r y s t a l l i t e s w i t h i n a n " amo r p h o u s " r e g i o n o f
F r a c t i o n F .

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t h e F CU , h a s b e c o me a n i n t i ma t e mi x t u r e o f c r y s t a l l i n e F AU
ma t e r i a l a n d c o l l a p s e d z e o l i t e . T h e c o l l a p s e d o r d e s t r o y e d
z e o l i t e d o e s n o t p r o d u c e a l a t t i c e i mag e . I n s t e a d , i t d i s p l a y s a
f i n e l y d i v i d e d amo r p h o u s s t r u c t u r e .
T h e o b s e r v e d z e o l i t e d e s t r u c t i o n i s a l mo s t c e r t a i n l y c a u s e d
b y e x p o s u r e t o h i g h - t e mp e r a t u r e s t e a m i n t h e r e g e n e r a t o r s i n c e U S Y
z e o l i t e i s t h e r ma l l y s t a b l e i n d r y a i r t o t e mp e r a t u r e s i n e x c e s s
o f 10 0 0 C ( 1 0 ) . I t i s u n l i k e l y t h a t t h e s t e a m- i n d u c e d c o l l a p s e o f
c r y s t a l l i n e z e o l i t e i n t h i s US Y c a t a l y s t i s mu c h a f f e c t e d b y t h e
p r e s e n c e o f a l o w c o n c e n t r a t i o n o f v a n a d i u m
( 6 12 ppm V, T a b l e I I I ) . R e c e n t wo r k b y O c c e l l i a n d S t e n c e l ( 1 1 ) ,
a n d b y Mau g e e t a l . ( 12 ) o n b o t h US Y c r y s t a l s a n d c a l c i n e d r a r e
e a r t h - e x c h a n g e d Y ( CRE Y ) c r y s t a l s , s h o w t h a t , i n t h e p r e s e n c e o f
h i g h - t e mp e r a t u r e s t e a m ( 7 6 0 C) , v a n a d i u m h a s l i t t l e e f f e c t o n US Y
c r y s t a l l i n i t y u p t o a b o u t 0 . 6 wt % V, wh i l e wi t h o n l y 0 . 2 - 0 . 4 wt %
V, CRE Y b e c o me s e s s e n t i a l l y amo r p h o u s .
T h e i n t i ma t e mi x t u r e o f F AU ma t e r i a l a n d amo r p h o u s r e g i o n s
s e e n i n F i g u r e s 8 a n d 10 i n d i c a t e s t h a t h i g h t e mp e r a t u r e s t e a m
d e s t r u c t i o n o f z e o l i t e i n t h e F CU i s a c c o mp a n i e d b y e x t e n s i v e
c r y s t a l l i t e f r a c t u r i n g . T h i s o b s e r v a t i o n i s f u r t h e r s u p p o r t e d b y
t h e r e s u l t s o f x - r a y l i n e b r o a d e n i n g ( i n c r e a s e d x - r a y l i n e
b r o a d e n i n g i s o b s e r v e d f o r F r a c t i o n F i n c o mp a r i s o n w i t h
F r a c t i o n B ) a n d b y t h e f a c t t h a t t h e c r y s t a l l i n e r e g i o n s a r e mu c h
mo r e e x t e n s i v e i n t h e y o u n g e r f r a c t i o n ( B ) . T h e l a t t e r p o i n t i s
d e mo n s t r a t e d b y t h e c o mp a r i s o n g i v e n i n F i g u r e 11 o f l a t t i c e
i ma g e s f r o m F AU c r y s t a l l i t e s i n F r a c t i o n B ( t o p ) a n d F ( b o t t o m) ,
r e s p e c t i v e l y . Wh i l e h i g h t e mp e r a t u r e s t e a m d e s t r u c t i o n o f U S Y
z e o l i t e i n t h e F CU i s w e l l k n o wn , we b e l i e v e t h a t t h i s i s t h e
f i r s t r e p o r t e d d i r e c t o b s e r v a t i o n o f t h i s p h e n o me n o n o n
e q u i l i b r i u m c a t a l y s t b y e l e c t r o n mi c r o s c o p y . S i mi l a r me a s u r e me n t s
h a v e b e e n c a r r i e d o u t o n l a b o r a t o r y s t e a me d ( 8 0 0 C, 5 - h o u r ) L a - Y
c r y s t a l s ( 12 ) a n d o n a s t e a me d ( 7 7 0 C, 15 - h o u r ) i n d u s t r i a l F CC
c a t a l y s t ( 13 ) w i t h ma r k e d l y d i f f e r e n t r e s u l t s . F o r t h e s e t wo
c a s e s , l a t t i c e i ma g e s c o n t a i n e d l o w c o n t r a s t z o n e s o r h o l e s w i t h i n
t h e z e o l i t e g r a i n wh i c h we r e a t t r i b u t e d t o amo r p h o u s ma t e r i a l i n
t h e f o r me r c a s e ( 12 ) a n d t o me s o p o r e s i n t h e l a t t e r ( 1 3 ) .
C o n c l u s i o n s
A s u c c e s s f u l s e p a r a t i o n b y d e n s i t y i n t o f r a c t i o n s o f i n c r e a s i n g
ag e h a s b e e n o b t a i n e d f o r t h e US Y e q u i l i b r i u m c a t a l y s t o f t h i s
s t u d y . T h e n i c k e l l e v e l o n e a c h c a t a l y s t f r a c t i o n , wh i c h i s
e x p e c t e d t o f u r n i s h a s t a b l e ag e ma r k e r , i n c r e a s e s w i t h i n c r e a s i n g
d e n s i t y / a g e . T h e o b s e r v e d d e c r e a s e i n t h e V / N i r a t i o w i t h
i n c r e a s i n g ag e i s i n d i c a t i v e o f i n t e r p a r t i c l e v a n a d i u m mi g r a t i o n .
T h e t r e n d o f i n c r e a s i n g N i l e v e l wi t h i n c r e a s i n g d e n s i t y h a s b e e n
u s e d t o c o r r e l a t e i n c r e a s e s i n d e n s i t y w i t h " N i d a y s " i n t h e u n i t .
B o t h t h e r e s u l t s o f c u me n e c r a c k i n g i n v e s t i g a t i o n s o n
r e g e n e r a t e d f r a c t i o n s a n d o f r e s i d u a l c o k e d e t e r mi n a t i o n s o n
p r e c o k e d f r a c t i o n s i n d i c a t e t h a t r e l a t i v e l y h i g h a c t i v i t y i s
e x h i b i t e d b y o n l y t h e l i g h t e s t / y o u n g e s t f r a c t i o n s . I t f o l l o w s
t h a t a d i s p r o p o r t i o n a t e s h a r e o f c a t a l y s t a c t i v i t y i s a s s o c i a t e d

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F i g u r e 11. ( a ) L a t t i c e i mag e s h o wi n g e x t e n t o f a F AU c r y s t a l l i t e
i n F r a c t i o n B, a n d ( b ) I n t i ma t e mi x t u r e o f s ma l l F AU
c r y s t a l l i t e s a n d c o l l a p s e d z e o l i t e i n F r a c t i o n F .

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w i t h t h e y o u n g e s t 15 % o f t h e c a t a l y s t i n v e n t o r y . T h e i n i t i a l
r a p i d d e c l i n e i n c a t a l y s t a c t i v i t y c o i n c i d e s w i t h z e o l i t e
d e a l u mi n a t i o n wh i c h i s l a r g e l y c o mp l e t e d d u r i n g t h e f i r s t 3 6 d a y s
o f c a t a l y s t r e s i d e n c e . R e s u l t s o f mi c r o c r a c k i n g y i e l d s t e s t s o n a
s e r i e s o f l a b o r a t o r y s t e a me d c a t a l y s t s a r e i n q u a l i t a t i v e
a g r e e me n t wi t h t h i s p i c t u r e . F u r t h e r c o r r o b o r a t i o n , b a s e d o n
s i mi l a r i n v e s t i g a t i o n s o f e q u i l i b r i u m c a t a l y s t f r a c t i o n s , a wa i t s
l a r g e r - s c a l e s e p a r a t i o n s .
T h e d e a c t i v a t i o n p r o f i l e e x h i b i t e d b y t h e ma j o r i t y o f t h i s
e q u i l i b r i u m c a t a l y s t i s r e ma r k a b l y s i mi l a r t o t h a t r e s u l t i n g f r o m
i n c r e a s i n g l y s e v e r e l a b o r a t o r y s t e a m d e a c t i v a t i o n s . D e a l u mi n a t i o n
i s r a p i d , c r y s t a l l i n i t y r e t e n t i o n i s 7 0 % o r mo r e , a n d t h e r e i s
l i t t l e l o s s o f ma t r i x s u r f a c e a r e a . T h e wi d e r a n g e o f s t e a mi n g
t e mp e r a t u r e s n e c e s s a r y t o r e p r o d u c e t h e e q u i l i b r i u m c a t a l y s t
d e a c t i v a t i o n p r o f i l e i n d i c a t e s t h a t i mp r o v e d a g i n g p r o c e d u r e s w i l l
i n v o l v e t h e b l e n d i n g o f c a t a l y s t p o r t i o n s s t e a me d a t d i f f e r e n t
t e mp e r a t u r e s . A c c o r d i n g l y , t h e p r e s e n t s t u d y s u g g e s t s t h a t
e f f o r t s t o a c h i e v e i mp r o v e d c a t a l y s t a g i n g p r o c e d u r e s wh i c h r e l y
o n s i n g l e mo de d e a c t i v a t i o n o r o n s t e a m t r e a t me n t a t a s i n g l e
t e mp e r a t u r e f o r v a r y i n g t i me s w i l l b e l e s s s u c c e s s f u l .
L a t t i c e i ma g i n g s t u d i e s b y TE M o n a " y o u n g " f r a c t i o n s h o we d
e x t e n s i v e r e g i o n s o f c r y s t a l l i n i t y wi t h mi n i ma l e v i d e n c e o f
c r y s t a l l i t e f r a c t u r i n g . B y c o n t r a s t , s i mi l a r i n v e s t i g a t i o n s o f a n
" o l d " f r a c t i o n , c o mb i n e d w i t h i n s i t u c o mp o s i t i o n a l a n a l y s i s ,
r e v e a l e d s ma l l " i s l a n d s " o f c r y s t a l l i n i t y w i t h i n a " s e a " o f
d i s o r d e r e d ma t e r i a l t h a t was onc e c r y s t a l l i n e . F r a c t u r e l i n e s a t
c r y s t a l l i t e b o u n d a r i e s a r e a b s e n t . I n s t e a d , t h e s ma l l US Y
c r y s t a l l i t e s w i t h i n t h e " o l d " f r a c t i o n a r e i n i n t i ma t e mi x t u r e
w i t h t h e c o l l a p s e d z e o l i t e .
A " r e mn a n t " r a r e e a r t h c a t a l y s t f o u n d i n t h e h i g h - d e n s i t y
t a i l o f t h e d i s t r i b u t i o n i s a s s o c i a t e d w i t h i n c o mp l e t e c h a n g e o v e r
( 8 8 %) o f t h i s US Y c a t a l y s t . T h i s r e s u l t i n d i c a t e s t h a t d e n s i t y
s e p a r a t i o n may n o t y i e l d a g o o d ag e p r o f i l e i n t h o s e c a s e s wh e r e a
r a r e e a r t h c a t a l y s t h a s b e e n i n t r o d u c e d o v e r a z e r o r a r e e a r t h U S Y
c a t a l y s t . S i g n i f i c a n t i n h o mo g e n e i t y w i t h i n t h e p a r e n t ( f r e s h )
c a t a l y s t w i l l a l s o c o mp r o mi s e t h e a g e / d e n s i t y c o r r e l a t i o n .
T h e r e s u l t t h a t o n l y t h e y o u n g e s t ( mo s t a c t i v e ) f r a c t i o n s a r e
d e n s i t y - s e p a r a t e d o n t h e b a s i s o f a c t i v i t y f o r c o k i n g f r o m
i s o b u t e n e h a s l e d t o n e w i n s i g h t wh i c h p r o v i d e s a s o u n d b a s i s f o r
f u t u r e a p p l i c a t i o n o f f l o a t - s i n k d e n s i t y s e p a r a t i o n t e c h n i q u e s o n
e q u i l i b r i u m c a t a l y s t s c o n t a i n i n g h i g h p r o p o r t i o n s o f z e o l i t e . F o r
t h e ma j o r i t y o f s e p a r a t e d f r a c t i o n s , t h e g r a d u a l i n c r e a s e i n
s k e l e t a l d e n s i t y w i t h i n c r e a s i n g ag e a p p e a r s t o b e a s s o c i a t e d w i t h
t h e a p p a r e n t l o s s o f mi c r o p o r o s i t y ( z e o l i t e d e s t r u c t i o n ) wh i c h
o c c u r s w i t h i n c r e a s i n g t i me i n t h e u n i t . P r o v i d e d t h a t t h e p a r e n t
c a t a l y s t d o e s n o t i t s e l f e x h i b i t ma r k e d i n h o mo g e n e i t y , t h e
t e c h n i q u e s d e s c r i b e d h e r e c a n b e u s e d t o c o n s t r u c t a d e n s i t y / a g e
c o r r e l a t i o n f o r " h i g h c h a n g e o v e r " e q u i l i b r i u m c a t a l y s t .

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8. BEYERLEIN ET AL. Monitoring FCC Deactivation Profile 139
Ap p e n d i x A: F a c t o r s C o n t r i b u t i n g t o C a t a l y s t D e n s i t y Ch an g e
T h e a n a l y t i c a l d a t a o n s e p a r a t e d c a t a l y s t f r a c t i o n s g i v e n i n
T a b l e s I I I , I V , V I , a n d V I I c a n b e u s e d t o e s t i ma t e t h e
c o n t r i b u t i o n t o c a t a l y s t d e n s i t y c h a n g e f r o m 1) d e c r e a s e d a c t i v i t y
f o r c o k e d e p o s i t i o n , 2 ) i n c r e a s i n g me t a l s d e p o s i t i o n , a n d
3 ) e x c l u d e d v o l u me a s s o c i a t e d wi t h b o t h t h e s ma l l a n d l a r g e
z e o l i t e c a g e s .
E s t i ma t e s o f t h e c o n t r i b u t i o n t o c a t a l y s t d e n s i t y a s s o c i a t e d w i t h
e a c h o f t h e a b o v e f a c t o r s a r e c a r r i e d o u t b y i d e n t i f y i n g t h e
d e n s i t y d
f
( f - A, B , C, . . . ) o f a n i n d i v i d u a l c a t a l y s t f r a c t i o n w i t h
n e t c a t a l y s t d e n s i t y d
a v e
d e f i n e d a s f o l l o w s :
n
S d i V i
d
a v e
" 1=1 ( 2 )
n
2 V i
i =l
wh e r e d
i f
V i a r e , r e s p e c t i v e l y , t h e d e n s i t y a n d v o l u me a s s o c i a t e d
w i t h t h e i t h c o mp o n e n t o f t h e c a t a l y s t . Ob s e r v i n g t h a t
v
i
w
i / d i , wh e r e Wi we i g h t o f t h e i t h c o mp o n e n t , i t f o l l o w s
f r o m E q u a t i o n 2 t h a t
n
S Wi
d
a v e
= i =l = _W_ ( 3 )
n V
2 V i
i - 1
wh e r e W, V a r e , r e s p e c t i v e l y , t h e n e t s y s t e m we i g h t a n d t h e n e t
s y s t e m v o l u me .
I n c r e me n t a l A d d i t i o n o f He t e r o a t o m S p e c i e s
T h e e f f e c t o f i n c r e me n t a l a d d i t i o n o f h e t e r o a t o m s p e c i e s a s c o k e
o r me t a l s i s e s t i ma t e d u s i n g E q u a t i o n 3 :
n n
S V i = S Wi_ = V = W ( 4 )
i - 1 1- 1 d i d
a v e
wh e r e i = 1 i s n o w a s s o c i a t e d wi t h t h e b a s e c a t a l y s t , a n d
i - 2 , 3 , 4 , . . . i s a s s o c i a t e d wi t h i n c r e me n t a l a d d i t i o n o f
h e t e r o a t o m s p e c i e s . S i n c e t h e i n c r e me n t a l e f f e c t o n d e n s i t y o f

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8
e a c h h e t e r o a t o m s p e c i e s i s e x p e c t e d t o b e s ma l l , e a c h s p e c i e s c a n
b e t r e a t e d i n d i v i d u a l l y a c c o r d i n g t o t h e a p p r o x i ma t i o n
Wi/ 10 0 + v
2
/ 1 0 0 - 1 ( 5 )
F o r c o n v e n i e n c e , t h e n e t s y s t e m we i g h t W h a s b e e n s e t e q u a l t o
10 0 g .
E f f e c t o f Ca r b o n o n C a t a l y s t . Ob s e r v i n g t h a t t h e a v e r a g e H/ C mo l e
r a t i o f o r c o k e o n c a t a l y s t i s >1 a n d t h a t c o n d e n s e d p o l y a r o ma t i c s
w i t h s i mi l a r H/ C ( e . g . , p h e n a n t h r e n e , a n t h r a c e n e ) e x h i b i t
d e n s i t i e s i n t h e r a n g e 1 t o 1. 3 , a s k e l e t a l d e n s i t y o f 1. 2 g / c c i s
a s s u me d f o r c o k e o n c a t a l y s t ( 14 , 1 5 ) . T h e n f o r e a c h 1% a d d i t i o n
i n c o k e , f o r a n o mi n a l c a t a l y s t d e n s i t y o f 2 . 4 ,
0 . 9 9 + 0 . 0 1 - 1
2 . 4 1. 2 d
m
o r d
a v e
- 2 . 3 16 2
a n d Ad 0 . 0 2 3 8 g / c c f o r a d d i t i o n o f 1 wt % c o k e .
E f f e c t o f Me t a l s o n C a t a l y s t . N i c k e l a n d v a n a d i u m a r e as s u me d t o
b e p r e s e n t a s t h e o x i d e s N i O a n d V
2
0
4
w i t h d e n s i t i e s o f 6. 7 a n d
4 . 4 g / c c . F o r a n o mi n a l c a t a l y s t d e n s i t y o f 2 . 5 , t h e e s t i ma t e d
d e n s i t y f o r a 0 . 1% c h a n g e i n V c o n c e n t r a t i o n i s
Q - 0 . 0 0 1 x 1. 6 3 ^ + ( 0 . 0 0 1 x 1. 6 3 ) - 1_
2 . 5 4 . 4 d
a v e
d
a v e
- 2 . 5 0 17 6 a n d Ad - 0 . 0 0 18 g / c c f o r a 10 0 0 ppm
c h a n g e i n V c o n c e n t r a t i o n . T h e f a c t o r 1. 6 3
a c c o u n t s f o r t h e v a n a d i u m o x i d e / v a n a d i u m we i g h t
r a t i o . S i mi l a r l y , f o r a 0 . 1% c h a n g e i n N i
c o n c e n t r a t i o n ,
( 1 - 0 . 0 0 1 x 1. 2 7 ^ + ( 0 . 0 0 1 x 1. 2 7 ) - 1
2 . 5 6. 7 d
a v e
d
a v e
- 2 . 5 0 19 9 a n d Ad - 0 . 0 0 2 0 g / c c f o r a 10 0 0 ppm
c h a n g e i n N i c o n c e n t r a t i o n . T h e f a c t o r 1. 2 7
a c c o u n t s f o r t h e n i c k e l o x i d e / n i c k e l we i g h t
r a t i o . T h e n f o r a n i n c r e a s e i n me t a l s c o n t e n t
A ( N i + V ) - 10 0 0 ppm, t h e n e t d e n s i t y i n c r e a s e i s
e s t i ma t e d as Ad - 0 . 0 0 19 f o r A( N i +V ) -
10 0 0 ppm.

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8. BEYERLEIN ETAL. MonitoringFCC Deactivation Profile
141
S i mi l a r l y , i f t h e e f f e c t o f r a r e e a r t h i s mo d e l e d a s i f r a r e
e a r t h we r e p r e s e n t a s R E
2
0
3
, t h e e s t i ma t e d d e n s i t y c h a n g e f o r a
0 . 5 % c h a n g e i n RE c o n t e n t i s
1 - 0 . 0 0 5 x 1. 17 + 0 . 0 0 5 x 1. 17 - 1
2 . 5 6 . 7 5 d
a v e
o r d
a v e
- 2 . 5 0 9 2 4
a n d Ad - 0 . 0 0 9 2 g / c c f o r a 0 . 5 % i n c r e a s e i n r a r e e a r t h c o n t e n t .
S i mi l a r c a l c u l a t i o n s s h o w t h a t i f i r o n a n d t i t a n i u m a r e a s s u me d t o
b e p r e s e n t a s t h e o x i d e s a- F e 2 0 3 a n d T i 0 2 , w i t h d e n s i t i e s o f
5 . 2 4 g / c c a n d 4 . 2 g / c c , r e s p e c t i v e l y , t h e e s t i ma t e d Ad ' s a r e
Ad F e ( 5 0 0 0 ppm) - 0 . 0 0 9 4 g / c c
Ad T i ( 5 0 0 0 ppm) - 0 . 0 0 6 8 g / c c
E f f e c t o f E x c l u d e d V o l u me
As d i s c u s s e d i n t h e t e x t , a b o u t 12 . 5 % o f t h e t o t a l mi c r o p o r e
v o l u me o f z e o l i t e Y , 0 . 3 6 c c / g , i s a s s o c i a t e d w i t h t h e s ma l l
c a g e s . As s u me t h a t t h e s ame p r o p o r t i o n h o l d s f o r u l t r a s t a b l e Y
wh i c h , du e t o o c c l u d e d ma t e r i a l i n t h e mi c r o p o r e , t y p i c a l l y s h o ws
a me a s u r e d mi c r o p o r e v o l u me o f a b o u t 0 . 2 7 c c / g . A c c o u n t i n g f o r
t h e e x c l u d e d v o l u me i n t h e ( i n a c c e s s i b l e ) s ma l l c a g e s , t h e t o t a l
mi c r o p o r e v o l u me i s 0 . 2 7 / 0 . 8 7 5 - 0 . 3 1 c c / g . Ob s e r v i n g t h a t t h e X-
r a y d e n s i t y o f u l t r a s t a b l e Y i s a b o u t 1. 3 g / c c , t h e n e t v o i d
v o l u me i s 0 . 3 1 c c / g x 1. 3 g / c c 0 . 4 0 c c / c c . As s u mi n g t h a t t h e
s ma l l c a g e s o f c r y s t a l l i n e z e o l i t e a r e n e v e r f i l l e d a n d t h a t t h e
e x c l u d e d v o l u me i n t h e l a r g e c a g e s i s g i v e n b y ( 1 - F ) wh e r e F i s a
p a c k i n g f r a c t i o n , t h e o b s e r v e d d e n s i t y b e f o r e z e o l i t e d e s t r u c t i o n
6Z - 2 x 4 ( 0 . 12 5 x 0 + 0 . 8 7 5 #F ) x 0 . 4 0 g / c c + 1. 3 x 0 . 6 0 g / c c
wh e r e t h e s o l v e n t me di u m d e n s i t y 6 ^- 2 . 4 g / c c . T h e o b s e r v e d
d e n s i t y o f t h e me s o p o r o u s ma t e r i a l t h a t r e s u l t s f o l l o w i n g z e o l i t e
d e s t r u c t i o n i s
d ^ - 2 . 4 ( 0 . 12 5 + 0 . 8 7 5 ) 0 . 4 0 g / c c + 1. 3 x 0 . 6 0 g / c c
T h e c a t a l y s t d e n s i t y i n c r e a s e , A, a s s o c i a t e d w i t h t h e e f f e c t
o f e x c l u d e d v o l u me , i s
Ad , - R, ( c - 6 ^) - 2 . 4 R, ( 0 . 12 5 + ( 1 - F ) x 0 . 8 7 5 ) x 0 . 4 0 g / c c
wh e r e R, - f r a c t i o n o f c a t a l y s t c r y s t a l l i n i t y d e s t r o y e d .

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142
U p o n s t e a m t r e a t me n t a t 8 15 C f o r 5 h o u r s , t h e c r y s t a l l i n i t y
o f t h e f r e s h c a t a l y s t , a s d e t e r mi n e d f r o m mi c r o p o r e v o l u me ,
d e c r e a s e s f r o m 3 4 t o 2 4 % ( T a b l e V I ) . T h i s r e q u i r e s R, 0 . 1. T h e
a s s o c i a t e d me a s u r e d d e n s i t y i n c r e a s e i s 0 . 0 4 g / c c . S e t t i n g
Ad , - 0 . 0 4 g / c c g i v e s t h e r e s u l t F = 0 . 6 7 . I n o t h e r wo r d s , a
p a c k i n g f r a c t i o n o f 6 7 % i n t h e l a r g e c a g e s a c c o u n t s f o r t h e
d e n s i t y i n c r e a s e t h a t was o b s e r v e d u p o n s t e a m t r e a t me n t o f t h e
f r e s h c a t a l y s t .
T h e a b o v e e s t i ma t e f o r p a c k i n g f r a c t i o n / e x c l u d e d v o l u me i n
t h e l a r g e c a g e s i s b a s e d o n n o n - s e l e c t i v e a d s o r p t i o n . T h e
e s t i ma t e d v a l u e i s d e c r e a s e d i f , f o r a g i v e n p a c k i n g f r a c t i o n ,
t h e r e i s s e l e c t i v e a d s o r p t i o n b y t h e z e o l i t e o f t h e l i g h t e r
c o mp o n e n t , c a r b o n t e t r a c h l o r i d e .
S e l e c t i v e s o r p t i o n g i v e s r i s e t o a mb i g u i t y w i t h i n t h e mo d e l
j u s t d e s c r i b e d . F o r e x a mp l e , s u p p o s e t h a t t h e d e n s i t y o f t h e
s o l v e n t me di u m i s 2 . 4 g / c c . I t i s n o t p o s s i b l e t o d i f f e r e n t i a t e
b e t we e n a n a c t u a l l a r g e - c a g e p a c k i n g f r a c t i o n o f u n i t y i n
c o mb i n a t i o n w i t h a s e l e c t i v e l y a d s o r b e d s o l v e n t d e n s i t y o f
1. 6 1 g / c c a n d a n a c t u a l p a c k i n g f r a c t i o n o f 0 . 6 7 , t o g e t h e r w i t h a
n o n - s e l e c t i v e l y a d s o r b e d s o l v e n t d e n s i t y o f 2 . 4 g / c c .
As s u mi n g n o n - s e l e c t i v e a d s o r p t i o n a n d o b s e r v i n g t h a t t h e
e q u i l i b r i u m c a t a l y s t F r a c t i o n A e x h i b i t s a c r y s t a l l i n i t y o f 2 8 %
w i t h a mi c r o p o r e v o l u me o f 0 . 0 7 5 c c / g , t h e e x p e c t e d i n c r e a s e i n
d e n s i t y du e t o a g i v e n c h a n g e i n mi c r o p o r e v o l u me , Amp o r e , i s :
Ad - ( % c r y s t a l l i n i t y r e d u c t i o n ) 0 . 0 4 g / c c
10 0 R,
o r
Ad = Amp o r e x 0 . 2 8 ( 0 . 4 )
0 . 0 7 5
Amp o r e x 0 . 112 g / c c
0 . 0 7 5
wh e r e t h e q u a n t i t y z - 0 . 4 g / c c r e p r e s e n t s t h e d e n s i t y i n c r e a s e
R
x
t h a t wo u l d o c c u r u p o n c o mp l e t e d e s t r u c t i o n o f t h e n e a t z e o l i t e .
Ac k n o wl e d g me n t s
T h e a u t h o r s g r a t e f u l l y a c k n o wl e d g e J o h n F . N e wb u r y f o r p e r f o r mi n g
t h e s t e a m t r e a t me n t s o n f r e s h c a t a l y s t , J o h n P . Co mp a n i k f o r
c o l l e c t i n g t h e d a t a o n c u me n e c r a c k i n g , F r a n k S . Mo d i c a a n d D r .
E u g e n e H. Hi r s c h b e r g f o r man y h e l p f u l d i s c u s s i o n s , a n d D r . J ame s
A. K a d u k f o r g e n e r o u s a s s i s t a n c e a n d man y h e l p f u l d i s c u s s i o n s
c o n c e r n i n g t h e X- r a y d i f f r a c t i o n a n a l y s e s .

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8. BEYERLEIN ETAL. Monitoring FCC Deactivation Profile 143
RE F E RE NCE S
1. Palmer, J . L.; Cornelius, E. B. Applied Catalysis 1987, 35.
217-35.
2. Kugler, E. L.; Leta, D. P. J . Catal. 1988, 109, 387-395.
3. Johnson, M. F. I . J . Catal 1978, 52, 425-31.
4. Breck, D. W. Zeolite Molecular Sieves: R. E. Krieger:
Malabar, Florida, 1984; p 637.
5. The effective size of 1,1,2,2-tetrabromoethane was determined
using CHEM-X molecular modeling.
6. Barrer, R. M. In Zeolites and Clay Minerals as Sorbents and
Molecular Sieves. Academic Press: London, 1978; p 121.
7. Kerr, G. T. Zeolites 1989, 9, 350-51.
8. Keyworth, D. A .; Turner, W. J.; Reid, T. A. Oi l & Gas J .
1988, 86 (11) 65-8.
9. Rawlence, D. J.; Gosling, K. Applied Catalysis 1988, 43,
213-37.
10. McDaniel, C. V .; Maher, P. K. In Zeolite Chemistry and
Catalysis: Rabo, J. A ., Ed.; ACS Monograph 171; American
Chemical Society: Washington, DC, 1976; p 323.
11. Occelli, M. L.; Stencel, J . M. "Surface-Metals I nteraction
in Fluid Cracking Catalysts During the Upgrading of Vanadium-
Contaminated Gas Oils," in Proceedings of the I nternational
Zeolite Conference. Wurzburg, Germany, September 1988.
12. Mauge, F.; Courcelle, J . C.; Engelhard, Ph.; Gallezot, P.;
Grosmangin, J . In New Developments in Zeolite Science and
Technology: Murikami, Y .; I ijima, A .; Ward, J. W., Eds.; Stud.
Surf. Sci. Catal. 28; Kodansha, Tokyo; Elsevier, Amsterdam,
1986; pp 803-9.
13. Gallezot, P.; Feron, B.; Bourgogne, M.; Engelhard, Ph.
Zeolites: Facts. Figures. Future: Jacobs, P. A .;
van Santen, R. A ., Eds.; Stud. Surf. Sci. Catal. 49: Elsevier,
Amsterdam, 1989; pp. 1281-90.
14. Guisnet, M.; Magnoux, P.; Canaff, C. New Developments in
Zeolite Science and Technology: Murikami, Y .; I ijima, A .;
Ward, J. W., Eds.; Stud. Surf. Sci. Catal. 28: Kodansha,
Tokyo; Elsevier, Amsterdam, 1986; pp 701-07.
15. Magnoux, P.; Cartraud, P.; Mignard, S.; Guisnet, M. J . Catal.
1987; 106, pp 235-41.
RECEIVED J u n e 8, 1990

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Chapter 9
Translation of Laboratory Fluid Cracking
Catalyst Characterization Tests
to Riser Reactors
A. V. Sapre and T. M. Leib
Paulsboro Research Laboratory, Mobil Research and Development
Corporation, Paulsboro, NJ 08066
A theory has been developed which translates observed coke-
-conversion selectivity, or dynamic activity, from widely-used MAT or
fixed fluidized bed laboratory catalyst characterization tests to steady
state risers. The analysis accounts for nonsteady state reactor
operation and poor gas-phase hydrodynamics typical of small fluid bed
reactors as well as the nonisothermal nature of the MAT test.
Variations in catalyst type (e.g. REY versus USY) are accounted for by
postulating different coke deactivation rates, activation energies and
heats of reaction. For accurate translation, these parameters must be
determined from independent experiments.
This work provides conclusive evidence that transient catalyst
characterization tests can result in erroneous catalyst ranking. For
example, USY catalysts show higher activity than REY catalysts in the
laboratory tests but lower activity in a steady state riser. Although
emphasis in this paper is placed mainly on the coke-conversion
selectivity, the analysis is also extended to yields of other FCC
products.
While most catalyst vendors rely on fixed bed microactivity (MAT) tests, fixed fluid
bed (FFB) reactor experiments are widely used within Mobil to characterize FCC
catalysts. The amount of catalyst used is constant for each test, and products are
collected for a known period of time. In MAT experiments, catalyst bed is fixed while
in FFB test the catalyst bed is fluidized. As products are collected over the decay
cycle of the catalyst, the resulting conversion and coke yields are strongly influenced
by catalyst deactivation. Systematic differences exist between the measured
conversion or catalyst activity and coke yields for the MAT and FFB tests. The
magnitude of these differences varies depending on the type of catalyst being tested
(REY or USY). Experimental data in Figure 1 clearly show that FFB conversion is
higher than MAT conversion for USY catalysts. On the other hand, FFB conversion
is lower than MAT conversion for REY catalysts. Furthermore, the quantitative
0097-6156/9iy0452-0144$06.25A)

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SAPRE AND LEIB Translation of FCC Tests to Riser Reactors

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translation of the catalyst performance from these laboratory tests to steady state
riser is a strong function of catalyst type. Therefore, we recognized that a
fundamental approach relating laboratory catalyst screening tests to riser
performance is needed. In this paper we summarize a theory which quantitatively
accounts for these differences and give insights into interpreting laboratory test data.
Potential pitfalls exist in ranking catalysts based solely on correlations of
laboratory tests (MAT or FFB) to riser performance when catalysts decay at
significantly different rates. Weekman first pointed out the erroneous conversion
ranking of decaying catalysts in fixed bed and moving bed isothermal reactors (1-3).
Phenomena such as axial dispersion in the FFB reactor, the nonisothermal nature of
the MAT test, and feedstock differences further complicate the catalyst
characterization. In addition, differences between REY, USY and RE-USY catalyst
types exist due to differences in coke deactivation rates, heats of reaction, activation
energies and intrinsic activities.
In this paper, we will first illustrate the mathematical models used to describe
the coke-conversion selectivity for FFB, MAT and riser reactors. The models also
include matrix and zeolite contributions. Intrinsic activity parameters estimated from
a small isothermal riser will then be used to predict the FFB and MAT data. The
inverse problem of predicting riser performance from FFB and MAT data is
straightforward based on the proposed theory. A parametric study is performed to
show the sensitivity to changes in coke selectivity and heat of reaction which are
affected by catalyst type. We will highlight the quantitative differences in observed
conversion and coke-conversion selectivity of various reactors.
Theory
Coke-Conversion Kinetics. Coke formation kinetics and gas oil conversion are
represented by the following irreversible reactions (cracking and coking):
c r ac k i ng
gas o i l
>
pr od uct s (1)
\ /
coke
Based on Voorhies time-on-stream theory (4), catalytic coke is a function of catalyst
contact time:
Ac ^ At c " (2)
and the coke yield on fresh feed is given by:
coke = CCR + Ac[C/0] (3)
Typically less than 100% of the feed CCR goes to coke depending on the feedstock
and operating conditions. In Equation 3, however, for simplicity we assume that
100% of the feed CCR is deposited as coke on catalyst.

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9. S APRE AND LEIB Translation of FCC Tests to Riser Reactors
147
The reaction rate per unit volume for gas oil cracking is given by:
r = r
0
*(t) (4)
where r
0
is the initial cracking rate, and ( ) is the catalyst deactivation function. We
assume that the catalyst deactivates due to coke formation, and the cracking activity
declines in direct proportion to the rate of coke formation. The deactivation function
therefore may be written as:
*(t) = dAc/dt (5)
Similar dependence of catalyst deactivation on coke or catalyst residence time is
suggested by Corella et al. (5-7). The authors give details on possible mechanisms
of catalyst deactivation by coke, and also suggest, based on their data, that the
deactivation order may not be a constant. For our analysis, however, we will
assume that is constant and a function of catalyst type. Further theoretical
treatment of catalyst decay is given by Wojciechowski (8,9).
The effect of feedstock quality and oil partial pressure on coking is given by:
Ac = At
c
n
( a
+
k
A
C
A
) P
o i I
b
(6)
Blanding (10) first proposed the second order cracking kinetics for FCC. Krambeck
(11) theoretically demonstrated that conversion in systems with a large number of
parallel reactions can be approximated by simple second order kinetics. More
recently, Ho and Aris (12) have developed a further mathematical treatment of this
concept. An inhibition term was incorporated into the second order cracking kinetics
for gas oil conversion to account for competitive adsorption. The initial cracking rate
is then given by:
r
o =
k
Pb
c
A
2 /
( 1+k
H A
C
A
) (7)
Differences between various zeolites and matrix components of the catalyst
have been accounted for by fitting coke deactivation rates (exponent n), coking and
cracking activities (A and k), and adsorption coefficients (k
A
and k
HA
). Similar ideas
on deactivation of a composite cracking catalyst have been presented by Dean and
Dadyburjor (13). Coke on catalyst then becomes the sum of the coke on the matrix
and the coke on the zeolite:
Ac = ZACjZj (8)
Here Z
{
is the mass fraction of zeolite or matrix components.
And the deactivation functions become:
dACi/dt = î(t )(a
+
k
Ai
C
A
)P
0
i,
b
(9)
*j(t) = dACj/dt (10)
Similarly, the cracking reaction will be composed of the reactions occurring on the

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148
matrix and zeolite:
r = lrj (11)
where
n =Mi
z
i C
A
V (
1 +
W> A) (
12
>
Although the theory includes the impact of matrix contribution, we will restrict our
discussions primarily to low matrix activity catalysts, and highlight the differences in
zeolite type.
FFB Model. Use of FFB units in the industry for catalyst characterization is primarily
due to excellent temperature control and resulting isothermal reactor temperature.
The operating conditions of the FFB activity unit used in our study are given in Table
I. The material balance using a pseudo steady state assumption (at any given instant
the vapor is in contact with catalyst of almost uniform activity) gives:
*D
A
d
2
C
A
/ d z
2
- d(u C
A
)/dz = 2rj(C
A
,t) (13)
where r
;
is given by Equation 12. In the above equation, the hydrodynamics of FFB
reactors are represented by an axial dispersion model. The degree of bubbling, and
hence, the bypassing are reflected in the dispersion coefficient. The superficial gas
velocity u changes along the reactor due to molar expansion. Assuming u varies
linearly with conversion:
u = u
0
(1+y
A o
X) (14)
Where conversion X is given by
X = 1-uC
A
/(u
0
C
A o
) (15)
Danckwert's boundary conditions give:
@ z = 0 u(C
A o
-C
A
) = -eD
A
dC
A
/dz (16)
@z = Ld C
A
/d z = 0 (17)
Equations 13-17 expressed in dimensionless form give:
Pe"
1
d
2
y/dx
2
- d(v y)/dx = falê) (18)
v =1+y
A o
X (19)
X = 1-vy (20)
@ x = 0 v(1 -y) = -Pe
_ 1
dy/dx (21)
@x = 1 dy/dx = 0 (22)

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9. SAPRE AND LEIB Translation of FCC Tests to Riser Reactors 149
Here,
fj = G>
m
e
n
\-
1
; 6>j = kiAiniZj M
A
C
Ao
2
/(S
v
(1 +k
HA|
C
Ai
))
?i = t
n
r
1
; Pe = L u
0
/ ( eD
A
)
y = C
A
/ C
A o
; x = z/L
v = u/u
0
; $ = t/t
c
S
v
= (t
c
[C/0])
1
Solution of Equations 18 to 22 gives the instantaneous outlet concentration y, which
when integrated over the run length gives the average conversion (X):
X = 1-
1
vy d0 (23)
o
The crackability (Cr), or the second order conversion is given by:
Cr = X/(1-Xl (24)
A parameter k
c
representing coke-conversion selectivity, is defined as:
l^ = coke/Cr (25)
The use of k
c
in analyzing data from pilot units was proposed by Krambeck in the
early 1970's and has been used in Mobil since then. More recently, the same
concept has been published in the open literature, and the reciprocal of k
c
is defined
as UOP "dynamic activity" (14). The dynamic activity is now popularly used in the
FCC literature, and is even used to correlate catalyst performance with fundamental
catalyst parameters such as unit cell size (15). In this paper, however, we will use
the Mobil defined k
c
parameter.
Table I. FFB, MAT and Riser Operating Conditions
Reactor FFB
MAT (Davison)
Fixed Bed
Steady
State Riser
T. -F 850 930 1000
C/0,wt/wt 2 3 5
t
c
,s 300 75 3
Poil, psia 10 15 35
Light East
Gas Oil Texas < -W. Texas
>
C
A
,wt % 10 18 18
CCR, wt % .01 .40 .40
M
A
233 400 400

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MAT Model. The operating conditions of Davison's MAT unit (16) are given in Table
I. These conditions correspond to testing prior to the change in November 1988.
The material and energy balances, using pseudo steady state and adiabatic plug flow
assumptions give:
-d(u C
A
)/dz = Lr|(C
A
,T,t) (26)
w
c
c
p c
d T / a t + m
A
c
p A
L a T / d z 8 8
-M
A
VAHj r j (C
A
,T,t ) (27)
The inlet conditions are:
@ z = 0 C
A
= C
A o
, T = T
0
(28)
The partial differential Equation 27 can be simplified to an ordinary differential
equation in the independent variable z, by the following approximation: For typical
FCC catalysts and feedstocks, c
p A
- 3 x Cp
C
, and for the MAT test, [C/O] is 3 (Table
I). Hence, if we assume that the catalyst and oil temperatures are identical (no heat
transfer resistance between oil and catalyst), then as a first approximation, the
change in the energy content of the oil and of the catalyst are roughly the same over
the length of the run. Thus, the two terms on the left hand side of Equation 27 are
approximately the same magnitude. Therefore, the time derivative of T can be
lumped with the distance derivative. The right hand side of Equation 27 is divided by
2, and it becomes:
m
A
c
p A
Ld T/ d z = -M
A
VE(AH/2)rj (C
A
,T,t) (29)
This approximation of the energy balance may lead to inaccurate prediction of
the temperature profile as a function of time on stream. Thus, at short contact times
it may underpredict the temperature, while at long contact times it may overpredict
the actual temperature profiles. However, on the average, the model predictions are
good, as seen from the comparisons with data in subsequent sections. In our
opinion, the above simplifications are reasonable, especially since the reproducibility
of the MAT test is somewhat poor.
Normalizing Equations 27-29 gives:
-d(vy)/dx = y
2
Zfj(0)
ds/dx = y
2
E0jfi(0)exp(-e|/s)
@ x = 0 y = s = 1
(30)
(31)
(32)

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Here,
s = T/ T
0
0i = AH|/(2Cp
A
T
o
)
ei = Ei /(RT
0
) f^ f/expf-ej/s)
The other parameters are the same as for the FFB model. Similar to the FFB
model, Equations 30-32 give the instantaneous conversion; to obtain time averaged
values, integration is required for X (Equation 23) and T:
T = T 60
(33)
Forissier and Bernard (17), also give a model for the MAT test. However, since
they did not attempt to translate product selectivities from the MAT test to a steady
state riser, it is somewhat less complex.
Riser Model. The riser is represented by a steady state adiabatic plug flow model
with no slip between oil and catalyst (18). The material and energy balances give:
-d(u C
A
)/dz = Lrj (C
A
,T) (34)
(m
c
Cp
C
+m
A
c
p A
)LdT/dz = -M
A
VZAHj rj (C
A
,T) (35)
The inlet conditions are identical to Equation 28. Equations 28,34 and 35 can be
written in dimensionless form similar to Equations 30-32. The definition of the
dimensionless variables is identical to those of the MAT model, except for p{
0j = AH^CpATÎ+mcCpc/tmACpA)))
Since the riser operates at steady state no time averaging is required.
Numerical Method. Both the isothermal FFB and the adiabatic MAT models are very
stiff due to the coke deactivation terms <t>\. The spline orthogonal collocation
technique was used to solve the above models (19). Typically, the distance x was
divided into two regions (0<X<T and T<X<1, T 1) . with 6-8 collocation points in each
region. At the interface between the two regions, both the concentration and the
mass flux were taken as continuous. The value of 7 varied with the degree of
stiffness.
Comparison of Model Predictions and Experimental Data
Potential Erroneous Ranking of Catalysts. We ran a series of tests on equilibrium
REY [A], USY [B] and RE-USY [C] catalysts in an isothermal riser, an FFB and a
MAT unit. The experimental data are summarized in Table II:

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Table II. Catalyst Ranking Based on Experimental Data
FFB Test MAT Test Riser Results*
Conv. ,% k
c
Conv.
t
% k
c
Conv. ,% k
c
Catalyst [A]
Catalyst [B]
Catalyst [C]
63
65
68
0.53
0.38
0.42
66
62
67
1.39
0.98
1.04
70
64
67
1.47
1.20
1.33
Ranking
Ranking for Activity for Coke Selectivity
FFB Ranking
MAT Ranking
Riser Ranking
C B
C A
A C
A
B
B
B C A
B C A
B C A
k
c
= coke
crackability
Catalyst A - REY
Catalyst B - USY
Catalyst C - RE-USY
* At [C/O] of 5 and constant catalyst contact time and temperature.
For each test, the first column represents the observed catalyst activity and the
second column represents coke conversion selectivity given by Equation 25.
From the above table, the FFB test would rank the catalysts with respect to
decreasing catalyst activity in the order C, B, A. The MAT test on the other hand
would rank them in the order C, A, B. However, the true ranking, as seen in the riser
test, is A, C, B. Thus, both MAT and FFB rank the catalysts incorrectly with respect
to catalyst activity. Although the relative magnitude of k
c
parameters is different, the
rankings by coke conversion selectivity is correct for all tests. These results are not
unexpected and can be explained by the mathematical model presented above.
Quantitative Predictions. In this section we use the riser data to determine intrinsic
activity and coking parameters (k
jf
A
;
) in the model, and then predict MAT and FFB
conversion and coke yields. Typically, we will have either the MAT or FFB activity
and coke information and the task is to predict the riser performance. As the models
use intrinsic parameters, it is immaterial which test information is available. The
intrinsic parameters can be easily extracted by fitting the data to the appropriate
reactor model. We will use the riser data as it gives the intrinsic information directly.
The fitted rate parameters are summarized in Table III. The other model parameters,
such as the activation energies, heats of reaction, the coke deactivation exponent, n,
(also given in Table III), were estimated independently. The details of parameter
estimates are described in the Appendix.

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9. SAPRE AND LEIB Translation of FCC Tests to Riser Reactors
153
Table III/
1
) Key Rate Parameters for
Three Types of Catalysts
Model Parameters
E
1
Btu/lb mole
AH-j, Btu/lb
k
10
x10"
6
/ V? f Ibmol
\lbmoJ Ibcoke
A^ I O
8
s '
n
Ibcoke
Ibcat
(REY)
[A]
19,800
130
0.2
9.6
6.4
(USY)
[B]
27,000
200
0.4
96.0
2.4
(RE-USY)
[C]
23,400
180
0.4
16.0
3.3
I
1
' k
1 0
and A
1
are relative to k
H A 1
of Table V.
Comparison of predicted and experimental FFB and MAT conversions and
coke yields is given in Table IV.
Table IV. Comparison Between Predicted and
Observed Test Data
Catalyst A Catalyst B Catalyst C
Obs Pred Obs Pred Obs Pred
FFB Conversion, vol % 63 62 65 65 68 66
Coke, wt % 0.9 0.8 0.7 0.8 0.9 1.1
MAT Conversion, vol % 66 66 62 62 67 65
Coke, wt % 2.7 2.7 1.6 1.8 2.1 2.3
The conversions are predicted quite accurately over a wide range of coke
levels (from 0.7 to 2.7 wt %). There are some minor discrepancies in the coke
predictions. However, these predictions are within the experimental accuracies of the
tests. The FFB conversions are reproducible within 2 numbers, with 20%
accuracy for coke yields. Similarly, the MAT data are reproducible within 3
numbers with 30% accuracy for coke yields. These comparisons suggest that the
models could be used to fit the catalyst intrinsic parameters (kj, Aj) from the transient
tests and then predict the steady state riser performance. Indeed, we have done this
exercise and we predict a reverse ranking for catalysts A and C in going from
transient tests to the riser performance, as observed in the riser experimental data.
Parametric Studies. To provide a feel for the relative importance of some of the
model parameters, and to understand observed differences in performance between
REY and USY catalysts (Figure 1), key parameters such as the cracking and coking
intrinsic constants kj and A,, the heats of reaction AHj, and the order of coke
deactivation, n$, were varied. The base case model parameters and the rate

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constants for an REY catalyst (Catalyst D) were estimated from Mobil's precision test
runs and are summarized in Table V.
Table V. Estimated Relative Rate Constants and Parameters
For REY Catalysts
(Catalyst D)
Parameters Estimated Rate Constants^ >
Pe 5 k^ . f^ /l bmol 3.8
z
1
0.3 kH^ . ft fybmol 1
E
1 f
Btu/lbmol 19,800 k
1 0
/ f V Ibmol 8.4x10
6
Ibmol/ Ibcoke
AH
1 ?
Btu/lb 130
C
P A
, Btu/(lb F) 0.75 A-|, s'
n
Ibcoke 1.6x10
-8
Ibcat
C
P c
, Bt u/(l bF) 0.29 0.2
(
1
) Relative to the magnitude of k
H A 1
REY Catalysts. REY catalysts always give lower FFB conversions than MAT
conversions (Figure 1). To simulate the observed conversion differences in the MAT
and FFB units for REY catalysts, the intrinsic cracking activity kj is increased at
constant coking activity A;. This choice of parameters is a first order approximation
for the activity and coke-conversion selectivity variation of equilibrium catalysts.
Parameters summarized in Table V are used as the initial starting point.
The results of the simulation are shown by the curve marked REY in Figure 1,
and the curves of Figure 2. The results of Figure 1 agree with our experimental
observations, showing that the MAT conversion is always higher than the FFB
conversion for REY catalysts.
The lower FFB conversions in Figure 1 can be rationalized based on the
following nonidealities of the FFB test relative to MAT:
Backmixing (low Peclet No.).
Longer contact time resulting in lower time averaged conversion.
Lower temperature.
At high conversions, the adiabatic nature of the MAT reactor compensates
somewhat for the FFB nonidealities; thus, decreasing the difference between the
MAT and FFB conversions. Temperature drops of 60-150* F are not uncommon in
MAT units, Cronkright et al (20). Early on stream, the catalyst is very active resulting
in large endotherm (~100
-
F). As the catalyst deactivates, however, the temperature
profile is less steep and results in lower endotherm corresponding to lower

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conversions at the end of the run. As mentioned before, MAT activity is a time
averaged conversion corresponding to the temperature history of the run.
In Figure 2, we compare the coke-conversion selectivity behavior as a function
of activity for MAT, FFB and riser reactors. The k
c
is relatively flat for the FFB test,
with correspondingly higher negative slopes for MAT and steady state risers. The
riser results show the steepest slope indicating that even though the k
c
observed in
the FFB test is relatively independent of activity, the coke selectivity improves with
activity in a riser.
An important conclusion from these simulations is that neither the FFB nor the
MAT test simulates riser behavior, since neither of these tests reflects the intrinsic
catalyst activity and decay. These intrinsic parameters are masked by backmixing in
the FFB test and by a high temperature drop in the adiabatic MAT unit. In addition,
the time averaged values of the long contact time FFB and MAT tests over-
emphasize the low catalyst activity at long contact times, while the short contact time
riser is only exposed to initial activity and catalyst decay.
USY Catalysts. USY catalysts are advertised by catalyst vendors, as low coke/high
octane catalysts. This behavior results from the smaller zeolite unit cell size due to
dealumination (21,22). The controlled dealumination leads to fewer but stronger acid
sites resulting in increased cracking relative to H-transfer. The decrease in the extent
of the exothermic H-transfer reactions also results in net increase in the endothermic
heat of cracking for USY catalysts (21).
USY catalysts generally show higher FFB conversions than MAT conversions
(Figure 1). This trend is opposite of what was shown before for the REY catalysts.
We postulate that USY catalysts have lower coke deactivation rates and lower initial
activity than REY catalysts, as shown schematically in Figure 3. As mentioned
above, USY catalysts also exhibit higher heat of reaction (21), which results in a
larger temperature drop in the adiabatic MAT unit, and hence, in lower conversion.
Similarly, the lower deactivation rate benefits the longer contact time FFB unit relative
to the shorter contact time MAT unit. These two effects can compensate for the FFB
activity nonidealities listed before and effectively give higher conversion in the FFB
test relative to MAT.
Figures 4 and 5 show the effects of varying deactivation order, n and
endotherm AH, respectively, on the FFB and MAT conversions. In Figure 4, AH was
kept at the base value of 130 Btu/lb and only n was varied. As expected, with
increasing n, i.e. lower deactivation rate, the longer time on stream FFB test shows
higher conversion relative to MAT. In this specific simulation, for values of n>0.3,
FFB conversion is higher than MAT conversion. Similarly, at constant n of 0.2, AH is
varied in Figure 5. Here again, at high values of endotherm a lower average
temperature in the MAT tests results in lower MAT conversion relative to the FFB
test. From Figure 5, a 50% increase in the endotherm from 130 Btu/lb to 200 Btu/lb
would result in lower MAT conversions than FFB conversions. Thus, both a higher n
and AH for USY catalysts relative to REY catalysts would account for higher
observed FFB conversions than MAT conversions. We estimated values of n = 0.4
and AH = 200 Btu/lb for USY catalysts based on literature and Mobil data. The
simulated results are shown by the curve marked USY in Figure 1. Here again,
simulations match experimental observations quite well.

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156
Figure 3: A schematic representation of catalyst deactivation functions for REY
and USY catalysts.

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90
.1 .2 .3 .4
Deactivation Order (n)
Figure 4: Impact of catalyst deactivation rate on predicted MAT and FFB
conversions.
Figure 5: Impact of heat of reaction on predicted MAT and FFB conversions.

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In Figure 6, we show the results of a simulation in which the cracking activity kj
was varied while keeping the coking activity Aj constant (similar to the simulation
above for REY catalysts). It is interesting to note that for the choice of the
parameters noted above, k
c
values in MAT and riser closely trace each other. On
the other hand, FFB coke-conversion selectivity, k
c >
has somewhat lower slope.
Other Product Selectivities
In the preceding sections we concentrated mainly on the coke-conversion selectivity
aspects of various reactors. In this section we will briefly discuss the selectivities of
major FCC products: gasoline, LCO, HCO, and light gases in both transient and
steady state reactors. Weekman (1-3) has looked at steady state and transient
reactors for gasoline selectivity shifts. However, he did not include axial dispersion
effects in his analysis which are important for laboratory FFB reactors, and are
accounted for here.
Consider the following reaction network for gas oil cracking.
Each reaction in the above network is assumed to be a second order in the reactant,
and coking is assumed to deactivate all reactions identically. The dimensionless
continuity equations for each component, similar to Equation 18, are:
k1 k5
HCO - LCO - Gasol i ne
(A) (B) (C)
k2
(Gas + Coke
1
d 2
y
A
<* A
B
Pe d x
2
1 d
2
y
c
d y
c
Pe dx dx
- 1 - <y
A
+ y
B
+ y
c
>

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1 * A
B . C. : * X = 0 (1 - y
A
) - - p - g (36)
1 d y
B
1 d y
c
y
B
=
Pe 3 T '
y
C
=
Pe 35T
d y
A
d y
B
d y
c
e x = 1
a5r
=
ax-
=
ax-
= 0
n 1
k
i
A n
wher e, f . = W.IJ e '
w
1 1
I " "Sv"
y i y i y i y - nor mal i zed concent r at i ons of A , B , C, D
J
A V
j
C D, r es p ec t i v el y .
The time averaging equations are straightforward and will not be shown here.
A steady state equivalent of Equations (36) for the ideal plug flow riser reactor, Pe ->
oo
f
can be easily derived, and also will not be shown here. Equations (36) were
solved numerically using the spline collocation technique discussed before. The
product selectivities in various reactors for the following relative rates, k
4
/k
1
= 0.5;
k^/k-i = 0.7; k^ -j = 0.1 k
3
/k
1
= 0.05; kg/k^ = 0.035 are shown in Figure 7.
The product yields in Figure 7 correspond to steady state riser (Pe - ),
isothermal MAT (Pe - * ), and FFB (Pe - 1) reactors. The yields of desirable
products, gasoline and LCO are always lower in transient units due to time
averaging. The axial dispersion causes further decline in product selectivity. In
Figure 7, the maximum in gasoline yield occurs much earlier in the FFB reactor
compared to MAT, or steady state riser reactors. There are sufficient data in the
literature to verify that overcracking of gasoline occurs earlier in laboratory fluid bed
reactors than in risers [23,241. Thus, if laboratory reactors are used to rank catalysts
based on product selectivities, one should consider the above differences.
Furthermore, at conversions above those which give maximum gasoline yields, there
is a sharp increase in the light hydrocarbon yields and increased gasoline octanes.
The product qualities from the laboratory transient reactors, like octane for example,
should therefore be interpreted cautiously. At the same conversion level, Research
Octane numbers of the gasoline obtained from a transient laboratory reactor could be
higher than those of steady state risers.
The effect of time averaging on yields in transient tests can be minimized by
shortening the duration of the test. Al so, a fixed bed test is superior to an FFB
activity test in that backmixing is minimized. Furthermore, an isothermal fixed bed
test would be easier to interpret than the adiabatic MAT test. This work shows that
from the point of view of a catalyst characterization test, a small steady state riser will
give the most direct information for catalyst performance in a commercial riser.

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Crackability
Figure 6: Predicted coke-conversion selectivity as a function of catalyst activity
(crackability) for USY catalysts.
Fractional
Concentration
Average Conversi on, %
Figure 7: Predicted product selectivities as a function of conversion for three
different laboratory catalyst characterization test units.

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Summary
FCC catalyst testing prior to use in commercial reactors is essential for assuring
acceptable performance. Purely correlative relations for ranking catalysts based on
laboratory tests, however, can be erroneous because of the complex interaction of
the hydrodynamics in the test equipment with the cracking kinetics. This paper
shows how the catalyst activity, coke-conversion selectivity and other product
selectivities can be translated from transient laboratory tests to steady state risers.
Mathematical models are described which allow this translation from FFB and MAT
tests. The model predictions are in good agreement with experimental data on
identical catalysts run in the FFB, MAT and a laboratory riser.
Legend of Symbols
A
Intrinsic coking kinetic constant
Heat capacity at constant pressure
9A
Volumetric concentration of gas oil
c
A
Total carbon in aromatics
CCR Conradson carbon residue
Cr Crackability
C/O Catalyst/oil ratio, wt/wt
D
A
Axial dispersion coefficient
f Dimensionless reaction parameter for FAI
f Dimensionless reaction parameter for MAT and riser
*i
Dimensionless constants in Equation (36)
k Ratio of cracking to coking rate constants
k
A
Intrinsic coking reaction constant
k
c
Coke-conversion selectivity
k
HA
Adsorption constant
ko
Exponential factor of k
L Reactor height
m Mass flow rate
M
A Oil molecular weight
n Voorhies parameter
Pe Axial Peclet number
r Reaction rate per reactor volume
s Dimensionless temperature
s
v
Space velocity
t Time
c
Catalyst contact time
T Temperature
u Superficial vapor velocity
V Dimensionless vapor superficial velocity
V Reactor volume
w
c
Catalyst holdup in reactor
X Dimensionless axial distance

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X Conversion
y Dimensionless volumetric concentration
y
A
Fraction of oil in feed, mol/mol
y
B
Dimensionless concentration of LCO
YQ Dimensionless concentration of gasoline
y
D
Dimensionless concentration of gas
z Axial distance; fraction of zeolite in catalyst, wt/wt
Greek Letters
a Axial molar expansion coefficient
0 Dimensionless heat of reaction
e Dimensionless activation energy
AH Heat of reaction
Ac ACoke on catalyst
e Dimensionless time
(j Dimensionless reaction parameter
17 Dimensionless reaction parameter
7 Spline point
4 Coke deactivation function
Subscripts
A Oil
c Catalyst
1 1=zeolite, 2=matrix
0 feed
Appendix
Estimates of Model Parameters. The reactor models for FFB, MAT and riser include
important features for translating the MAT and FFB data to steady state riser
performance. A series of key parameters specific to a given zeolite and matrix
component are needed for a given catalyst. Such key parameters are intrinsic
cracking anc| coking activities (kj, Aj), activation energies and heats of reaction (Ej,
AHj), coke deactivation rate (exponents n,-), and axial dispersion in the FFB unit (D
A
).
Other feedstock dependent parameters include the inhibition constants (k
H A l
), the
coking constants (K
A i
), and the axial molar expansion factor (a).
It is the objective of the FFB or the MAT test to determine cracking and coking
activities of the catalyst (kj, Aj). Therefore, all other parameters should be known
from independent experiments or estimated prior to determining these intrinsic
catalyst parameters. These other parameter estimates are described below.
It can be shown, that the molar expansion parameter a is a function of the
charge stock and product molecular weights:
M
0
is the molecular weight of the charge stock, and M is the average molecular
weight of the product. The value of a varied from 2 to 6 in this study.

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An axial Pe number of 5 was estimated for the FFB unit, corresponding to a D
A
of -30 cm
2
/s. This estimate was based on dispersion data reported by Zenz (25) on
Geldart's Group A powders.
The coke deactivation exponent n, is typically estimated from riser pilot plant
experiments at varying catalyst contact time for different catalyst types. A value of n
of 0.2 was found for REY catalyst data base. For USY and RE-USY catalysts n was
estimated to be 0.4.
Heats of reactions were estimated from heats of formations and chemical
compositions of feed and product using standard procedures. For REY catalysts, we
estimated approximately 130 Btu/lb heat of reaction. The heat of reaction was close
to 200 Btu/lb for USY catalysts. These values are in close agreement with reported
data (21J. The activation energies for different catalyst types were estimated from
our extensive pilot plant data base, and found to be a weak function of catalyst type.
The adsorption constants and other kinetic parameters used in these simulations
were fitted to a large in-house data base. Typical parameter values are reported in
Tables III and V. The kinetic parameters (kj and Aj) are a strong function of catalyst
used, whereas the adsorption parameters were found to be relatively insensitive.
One could estimate these parameters even from a limited data base as illustrated
below for Catalyst D.
Table VI. Commercial Equilibrium REY Catalyst
(Catalyst D)
FFB Test MAT Test
Conversion Coke Conversion Coke
wt% wt% wt% wt%
63 0.43 66 1.56
63 0.44 68 1.51
64 0.47 69 1.59
64 0.49 71 1.51
64 0.50 71 1.51
65 0.51 72 1.85
66 0.55 72 1.59
A set of MAT and FFB data on a low metals equilibrium commercial REY
catalyst with a low matrix activity (Catalyst D) is summarized in Table VI. The range
of activities indicates varying steam deactivation levels in the commercial unit. These
data could be used to estimate the following four parameters: intrinsic cracking and
coking activities (kj, Aj) and feedstock parameters (k
H A
, k
A
). The feedstock
differences between Light East Texas Gas Oil (LETGO) and West Texas Gas Oil
used in the FFB and MAT tests, respectively, allows the determination of k
H A
and
k
A
. A modified Marquardt algorithm was used for parameter estimation. The fit was
meaningful at a 95% confidence level, and the correlation coefficient was 0.93.
These parameters are summarized in Table V. These parameter values were in
close agreement with other REY catalysts, for example Catalyst A in Table III.

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164
Acknowledgments
Useful discussions with F. J . Krambeck are sincerely appreciated. We thank D. M.
Nace for obtaining the experimental data. Also, D. H. Anderson's effort in
programming the spline orthogonal collocation technique is appreciated.
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5. Corella, J . and Menendez, M. CES, 1986,41.. 1817.
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1985, 24, 625.
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12. Ho, T. C. and Aris, R. Al ChE J . . 1987,33, (6), 1030.
13. Dean, J . W. and Dadyburjor, D. B. Ind. Eng. Chem. Res., 1989, 28, 271.
14. Moh, R. W. Oil & Gas Journal. 1987, January 26, 73.
15. Rajagopalon, K. and Peters A. W. Journal of Catalysis, 1982, 106, 410.
16. Davison Catalagram, 1988 Nov. 1.
17. Forissier, M. and Bernard, J. R. Al ChE Spring Meeting, 1989, Houston, April
2-6, Paper 84d.
18. Yen, L. C. , Al ChE Spring Meeting, 1989, Houston, April 2-6, Paper 84b.
19. Villadsen, J. and Michelsen, M. L. Solution of Differential Equation Models by
Polynomial Approximations. Prentice Hall, Inc., Englewood Cliffs, NJ, 1978.
20. Cronkright, W. A., Butler, M. M. and Harter, D. A. Ketjen Catalyst Symposium,
Kurhaus, The Netherlands, 1986, May 25-28.
21. Leuenberger, E. L. and Wilbert, L. J . Oil & Gas Journal. 1987, May 25, 38.
22. Desai, P. H. Oil & Gas Journal. 1986, September 22,42.
23. Creighton, J. E. and Young, G. W. ACS National Meeting, Philadelphia, 1984.
24. Gross, B., Nace, D. M. and Voltz, S. E. I&EC Proc. Des. & Dev., 1974,13, (3),
199.
25. Zenz, F. A. and Othmer, D. F. Fluidization and Fluid Particle Systems,
Reinhold Publishing Co. , New York, 1960, 300.

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9
Chapter 10
Analysis of the Riser Reactor
of a Fluid Cracking Unit
Model Based on Kinetics of Cracking
and Deactivation from Laboratory Tests
J. Corella and E. Francs
Department of Chemical Engineering, University of Zaragoza,
50009 Zaragoza, Spain
A model for the riser reactor of commercial fluid catalytic
cracking units (FCCU) and pilot plants is developed. This
model is for real reactors and feedstocks and for commercial
FCC catalysts. It is based on hydrodynamic considerations and
on the kinetics of cracking and deactivation. The microkinetic
model used has five lumps with eight kinetic constants for
cracking and two for the catalyst deactivation. These 10
kinetic constants have to be previously determined in labora-
tory tests for the feedstockcatalyst considered. The model
predicts quite well the product distribution at the riser exit. It
allows the study of the effect of several operational parame-
ters and of riser revampings.
Fluid catalytic cracking (FCC) of heavy oil fractions is a well-known process
in oil refineries. Numerous books (e.g., 13) and publications about the dif-
ferent aspects of this subject are available. This chapter is concerned with
the modeling of the transfer line or riser reactor of an FCC unit (FCCU)
or of a pilot plant. The riser reactor in FCCUs is a vertical pipe about 1 m
in diameter and 10-30 m in height. The hot catalyst coming from the
regenerator at about 710 C first comes in contact with steam and is fluid-
ized. Then, at a height of some meters above, the catalyst is mixed with the
preheated feedstock at about 300 C.
The first oil-catalyst contact is essential. The mixing temperature
(about 530-600 C) is very difficult to measure and is about 20-80 C
higher than the riser exit temperature (4, 5). The superficial gas velocity at
the inlet is several meters per second, much higher than the terminal velo-
city of the catalyst, which is about 0.20 m/s. The catalyst and the gas are
transported upwards together but at a different superficial velocity, u (6).
These two velocities are related by the slip velocity (sv), defined as follows:
0097-6156/91/0452-0165$06.00/0

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166
slip velocity (sv) ^ = (1)
u
catalyst *g
The value of sv in the riser makes the residence time or, better, the
space time different for the gas (t) and the catalyst (f
c
).
The riser reactor seems to be a very easy reactor. Its hydrodynamics
seems quite simple, and it could be studied with a simple piston-flow con-
sideration. But when the hundreds of cracking and coke-formation reac-
tions are considered with their very difficult kinetics and when the injection
or feeding point is studied in detail, this reactor becomes impossible to
model with 100% accuracy, at least today.
For these and other reasons, only a few papers have been devoted to
the modeling of FCC risers. The great economic importance of the FCC
process, the competition between companies, and the high cost of good
research on FCC have given rise to a lot of confidentiality in this field, and
thus many studies do not appear in the open literature.
Previous Models of FCC Risers
The best-known model for FCC risers may be that of Paraskos et al. (8)
and Shah et al. (8), although their valuable work is already a little old
(published in 1976-1977). They considered the riser to be isothermal (7)
and adiabatic (8). Besides piston flow in the riser, they assumed a deactiva-
tion order (d) of 1, which is, for us, an important error, and a slip velocity
of unity (in reality they only mention one time, their 17).
Other models are presented in references 914. Gates et al. (9) also
considered piston flow and d = 1. Van der Baan (10) considered piston
flow but with d undetermined. One patent (14) is based on piston flow, sv
= 1, d = 2.3 (9 = 0.76), and some corrective "scale factors." In our previ-
ous work on the subject (11), we considered piston flow, sv = 1, and d =
3. The recent work of Bernard et al. (12) points to the necessity of taking
into account radial velocity profiles. Finally, in an earlier work, Wollaston
et al. (13) used only an empirical equation relating conversion at the riser
exit and process severity.
All the works just cited have an important and common assumption:
the well-known, three-lump Weekman model with three kinetic constants.
This three-lump model was a significant achievement, but it lumps together
gas and coke, which are clearly different. Therefore, we consider it abso-
lutely necessary to expand this model by using a five-lump model with eight
cracking constants and the following definitions: A = feedstock (bp > 350
C), O = gas oil (bp 221-350 C), E = gasoline (bp 36-221 C), G =
gas (bp < 36
0
C), and C = coke (by combustion).
To our knowledge, the control of most FCCUs in refineries is based
today on a 10- or 11-lump model (14, 15) with 20 kinetic cracking con-
stants. We think that these 20 kinetic constants cannot be calculated with
precision from kinetic tests and that they are only empirical parameters

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10. CORELLA AND FRANCES Analysis of a Riser Reactor
167
used to adjust the operation of the FCCU. Besides, these models use scale
factors (14) or installation factors (15) to adjust the real yields at the
FCCU exit. So we prefer a model with only 5 lumps for which we can cal-
culate with accuracy and from laboratory tests the eight kinetic cracking
constants. Nevertheless, the optimal number of lumps to be used is a ques-
tion open to discussion and to more sophisticated kinetic techniques.
All the previously cited models and works also consider, and some
explicitly cite, this assumptionthat the catalyst activity varies with time-
on-stream (or with coke concentration [12]) in the same manner or with
the same deactivation function (tfi) for all reactions in the network. That is,
a nonselective deactivation model is always used. Corella et al. (16) have
recently demonstrated that in the FCC process this assumption is not true
and that it would be better to use a selective deactivation model. Another
work (17) also shows how this consideration, when applied to catalytic
cracking, influences the yieldconversion curves. Nevertheless, to avoid an
additional complication, we will use in this chapter a nonselective deactiva-
tion model with the same at
Q
kinetic equation and deactivation function
(tp) for all the cracking reactions of the network.
The radial catalyst density profiles or piston-flow deviations in FCC
risers have also been studied (9, 12, 18, 19, 20). The catalyst density is low
in the center and high near the wall, with gas velocities high at the center
and lower close to the wall. This factor could be modeled by using an axial
dispersion coefficient (9, 19), but in our opinion, the use of this coefficient
is not clear and important. So we will use piston flow. After comparing
results from this model with some plant data, we think that this assumption
is acceptable.
Assumptions of the Model
The following assumptions or considerations are made in the derivation of
the mathematical model:
1. Piston flow for gas and solid with a slip velocity that can vary with
the height of the riser.
2. Adiabatic riser with temperature (T) that varies with height. In each
height interval (three or four intervals throughout the riser), different
temperatures and kinetic constants can be used.
3. Temperature of the liquid-vapor the same as that of the catalyst. This
assumption is not true (21) particularly in the first meter of the riser.
This error is compensated if the kinetic constants have been calcu-
lated under the same or similar conditions or with a scale factor.
4. Good and instantaneous vaporization of the charge. In our opinion,
assumptions 3 and 4, which are due to the difficulty in modeling the
first meter or the first catalyst-feed contact, are the most important
ones.

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5. Five-lump model with eight kinetic cracking constants (k
t
) and two
kinetic deactivation constants (0 and d) (Scheme 1). These 10 con-
stants must be known beforehand and with accuracy for each
catalyst-feedstock used. One of the most important feature of our
model is that the k^values used come from modified MAT or labora-
tory tests and they are not simply empirical parameters obtained by
adjusting the FCCU data, as is commonly done in actual control
models (22). These kp V>> and d kinetic parameters clearly depend on
the catalyst-feedstock used. Details of how these kinetic parameters
(kp ij>, and d) are obtained have been previously shown (23). Of
course, there are more complex models for the stoichiometry of cata-
lytic cracking (24), but we do not know how the more than 100
cracking kinetic constants needed can be calculated simultaneously and
with precision from a laboratory kinetic test. For us, the work of
Liguras and Allen (24) is good in stoichiometry but weak in the
kinetic aspects.
6. Selective deactivation model (a
A
= a
Q
= a
E
= ...a [catalyst activity],
7. Microkinetic cracking model for A:
(-r
A
) = k
A
Y
2
A
a (2)
where
* A=* I + *2 + fr3 + fc
7
(
3
)
8. Riser height divided into zones. In each zone, the parameters (fc, ^,
C
A [
ex
P
a
nsion factor defined by equation 6], sv,...) and the diameter
or cross section (S) will have a constant value. These values can vary
from one zone to the other. If enough information is available about
the variation of these parameters with height, new equations relating
these variables with height could be introduced and an integration of
the equations along the riser height could be made. But, in our opin-
ion, with the present knowledge on these aspects, only some discrete
(not continuous) values can be used. In any case, the use of more
intervals does not offer mathematical problems. The change of S from
one zone to other will change the superficial velocity of the gas (w), a
very important parameter.
9. No lateral or secondary feed injections downstream of the feeding
point. This limitation and a constant cross section will be eliminated
in a forthcoming paper dealing with riser revamping with the model
presented in this chapter.

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169
Other Considerations
Expansion Factor: Flow Increase along Riser Height Because of cracking,
the flow rate, the volume, and the superficial velocity of the gas increase.
For mean molecular sizes, the following values can be used: A, 40; O, 20;
E, 9; and G, 3 (27). Then, for a given weight of feed (A), the volumetric
flow rate (Q) will be inversely proportional to these mean molecular sizes.
Thus:
Go oc
40
G(at*
A
)oc>l
40 20 9 3
(4)
(5)
Thus, the flow rate is not directly proportional to the conversion X
A
=
(1 - Y
A
), but the influence of the other products (Y
Q
, Y~, and Y
Q
) is
clear. As a result, the expansion will not be linear, as Figure I indicates. To
approximate this situation, we can consider several zones along the riser
height. For each zone, equation 6 applies:
G = Co(l + * A* A) = Go + Go*A*A (6)
c
A
can vary with X
A
because of the cracking mechanism; therefore, for each
zone we can use a different c
A
, a low value for the first zone and about 4
for the last zone.
When the proposed model is solved for each zone, the product distri-
bution at the exit of the zone is calculated, and a better value for can
be then calculated. For simplicity, we suggest using initially equation fywith
only one or two values of e
A
for the whole length of the riser. When the
model is well understood and managed, a new value for c
A
can be calcu-
lated and used for each zone. For this purpose, equation 7 applies:
G = GH
2
+ GH
2
S + Gsteam + Gc, + GQ + Gc
3
- + (?)
+ GE + GO + GA (nonconverted)
These flow rates can be calculated if Q
Q
and X
A
and Y. at different riser
heights are known. c
A
can also vary from one feedstock to another.
Mean Molecular Weight of Feedstock. The mean molecular weight (MW)
affects at least two factors: (1) the kinetic constants k
i
and ^ (usually, when
MW increases, k. decreases) and (2) the number of moles and the flow rate

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h
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zone 1 i zone 2
\ or riser height
Figure 1. Variation of flow rate with riser height.

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10. CORELLA AND FRANCES Analysis of a Riser Reactor 171
(14). For a given flow (in tons per day) of feedstock to be processed, if
MW increases, the number of moles decreases, the superficial velocity of
the gas decreases, and the residence time of the gas in the riser increases.
These two effects are then opposed: the first decreases X
A
and the second
increases it. In any case, the MW of the feedstock must be known or
estimated.
Temperature along the Riser Height Temperature (T) affects the cracking
(k.) and deactivation (0) constants (or functions). It also influences the gas
density and, as a consequence, the flow rates, the superficial velocities, and
the residence time of the gas in the riser. Its effect on k. makes the pro-
duct distribution (gas, coke, etc.) dependent on T.
The riser could be considered isothermal, but if the values for E, E^,
AH
r
, etc., are known, it is better to use a nearly adiabatic regime. A
rigorous calculation of the temperature profile in the riser (indicated, for
instance, in Figure 2 of reference 4) is in reality quite difficult and may be
impossible. In the riser, a temperature difference of 20-60 C between the
mixing point and the top has to be considered. Our solution is to divide
the riser into several zones (four or five zones are recommended). In each
zone, T will be different. Thus, different values of k
A
, ^, and k
(
will have to
be used. Then by calculating the AY. in each zone and by assuming an
adiabatic regime, AT can be calculated/ Thus, the estimated T of the zone
can be checked.
The initial basis will be that T at the top is known (515 C for
instance) and that at the feed injection point the mix temperature is
560-570 C (this T can also be calculated by a heat balance).
Residence Time of the Catalyst in the Riser. The residence time of the
catalyst in the riser, f
c
, can be calculated from equations 8 and 9
dW
c
= Cdt
c
(9)
in which C is the flow rate of catalyst (in kilograms per second) and W
Q
is
the weight of catalyst in the riser. Because it is difficult to determine W
Q
, t
Q
is calculated from equation 10:
t
c
= svfg = sv = sv (10)
u
g . v \ . Gsteam
8
A,o(l + *A*A> + 7~
According to reference 6, sv can have values between 1.05 and 1.15.

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Kinetics of deactivation. On the basis of findings of Corella et al. (25) and
Espinosa et al. (26), we are convinced that
or, in integrated form for d ^ 1
a
= TTZ ' 1\J(d-\) (
12
)
Equation 12 is equivalent to equation 13
a = -
r
(13)
(1 + Gf)>
commonly used by Wojciechowski (27) and in some FCC control models.
As written in equation 12, ^ and d have a clear physicochemical signifi-
cance and their values can be interpreted and discussed. In equation 13, G
and j only have empirical significance.
Calculation of Product Distribution from X*. The kinetic equations of the
network allow Y
Q
, Y
E
, and Y
Q
to be calculated versus X
A
(= 1 - Y
A
) or
versus riser height.
Flow Rates at Riser Inlet If the ideal gas law can be applied, the flow
rates of feedstock (Q
AQ
) and steam ( G
V o
) and the total flow rate (Q
Q
; in
cubic meters per second) are easily calculated from equations 14-16.
^ - v t ^ r f / M - a a o g ^ , ^
( 1 5 )
Go = GAO + Gsteam (16)
The superficial velocity of the gas at the inlet is given by equation 17:
_ (GAP + Gvo) n - v

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10. COREL L A AND FRANCES Analysis of a Riser Reactor 173
Weight Fraction of A at the Inlet The weight fraction of A at the inlet,
Y
A o
, is defined by equation 18:
* Ao =
O
(O + m
w
)
(18)
Because steam is introduced at the bottom (my), Y
Ao
1.
For the catalyst activity at the riser inlet (a
Q
), it will be supposed that
The conversion (Y
A
) is defined by equation 19:
v
YAO - ? A
1
* A
A
A = v = 1 - w
*Ao
r
Ao
(19)
Modeling the Riser
Mass Balance for A in dL. With an assumed piston flow (Figure 2), a mass
balance for A in dL (in which there is a catalyst of weight dW^ gives equa-
tion 20:
-OdY
A
= (k
A
Y
2
A
a)-dW
c
(20)
By substituting equation 12 in equation 20 and separating variables, equa-
tion 21 is obtained:
dY
A
l
(21)
By substituting the value of dW
Q
given by equation 9 and integrating equa-
tion 21, equation 22 is obtained:
_ i i _,
v
- (C/O)
^ As >Ao
A
V - 2)*
(22)
+(d- l ^ e ) ^ ) ^ "
1
) Mo
4
"
2
)
(valid for d 1 and d 2)
From this basic equation, (and then is calculated. To do this,
it is necessary to know a
o
, Y^ , kinetic parameters for the

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h
0
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0
catalyst-feedstock system used (0, d, and Jfc
A
), C/O, and t
c
(which implies
knowing e
A
, equation 10). It is also necessary to know the cross section (S)
and height (L) of the riser.
Method
The riser will be considered as divided into zones that can be represented
by a battery of piston-flow reactors in series (Figure 3). Each zone will
have a length of L
v
L
2
, Ly etc. The following relations will apply:
Zone 1, c
A1
(small), T
v
(fc
A
, ^,...,0) at 7^
Zone 2, (bigger), T
T
(fc
A
, ^,...,0) at T
T
etc.
Zone 1. The inlet conditions are given by equations 14-18. To calculate Y
A
at the exit of zone 1 (1^) with equation 22, 5j, the mean superficial gas
velocity at zone 1, has to be estimated. As a first trial we propose using
equation 23:
(u
1
)e = 1.2
Wo
(23)
With equation 10, the mean residence time of the catalyst in zone 1(t
Q
^ is
calculated by using equation 24:
'c i ="i - ^ 7 - (24)
( l ) e
With this value and equation 17, Y
A
(and X^J) and a at point m are
calculated with equations 22 and 12, respectively. Tne superficial velocity of
the gas at point m (u
m
) and the mean velocity in zone 1 (5i) can be calcu-
lated by using equations 25-27:
Qv
"m = WA,o(l + * Al * Am) + ~ (
25
)
1 = "A, o( l + CA1 - * Al ) + (26)
when
*M - ^ (27)
given that X
AQ
= 0.

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c
h
0
1
0
d L, dW
f
d y
C A
0=m
j
C=m
c
Figure 2. Scheme of the riser.
Products
Feedstock(O)
+
steam
l^cl
Zone 2
Zone 1
T
y ; X ; u ;a ;u ;T
A,s A,s A,s s s s
u ; X ;(u ) ; T e
g,2 A,2 g,2 e 2
A
*
-m ^ y ; X ; u ;a ;u ;T
A,m A,m A,m m m m
u =X ;(u ) ; T
g,1 A,1 g,1 e 1 ' t
A 1
y ; X ;a ;u ;T
A,o A,o o o o
Catalyst (C) + steam
Figure 3. Nomenclature for the riser (only two zones are shown).

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.
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0
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-
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-
0
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5
2
.
c
h
0
1
0
The calculated ui value from equation 26 and the assumed (or
estimated) value, C"i)e are
n o w
compared. If they are the same, the
assumption was correct and the calculation passes to zone 2. If (ui)
e
the calculation is repeated by using equation 24 with a new value for (5i)
e
,
the calculated ffj. This iterative method is continued until two consecutive
values appear to be the same.
With the calculated correct or definitive X*^ a simple heat balance,
and the known AH, AT in zone 1 is calculatedTAr is obtained from T
m
= T
Q
- AT.
Zone 2. The inlet conditions of zone 2 are those of point m (exit of zone
1). The calculation for this case is the same. The values for c
A
, k
A
, k., ifr,
sv, etc., are those corresponding to 7
2
.
The superficial velocity of the gas at the exit of zone 2 (w
s
) and the
mean velocity in zone 2 (u
2
) are given by equations 28 and 29:
w
s
="Ao
2 = "Ao
where
l Qv
1 + CAl ^ Am +
e
Al (
X
As ~ Âm) I + "~^T" (28)
1 + * Al * Am + *A2(*A2 " * Am)] + ^ (29)
XA2 = ^ ^ L (30)
The first estimate of the mean superficial velocity of the gas in zone 2,
(u
2
)
e
, is determined as for zone 1 (equation 31):
(u
2
)
e
= 1.2a
m
(31)
With the value of t
c2
(equation 32)
L
2
*c,2 = sv
2
(32)
(2)e
and equation 22 and with Y
A o
= Y^, Y^ is calculated. With Y^, X^ is
obtained. With this value and equations 29 and 30, u
2
is calculated and
compared with (u
2
)
e
. If 5
2
^ (
2
)
e
, the calculation is repeated, with
u
2
= (u
2
)
e
and equation 22.
Zones 3, 4, 5,... If we prefer to use several more zones, the calculation is
repeated. For each zone, a different T with different values of k
A
, kp

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.
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h
0
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0
10. C O R E L L A A N D F R A N C E S Analysis of a Riser Reactor 177
kp...
A
, and sv must be used. The X
A
at the exit of the last zone con-
sidered is X
A
at the riser exit (X^).
Product Distribution at the Riser Exit With X
M
or Y
M
calculated, Y
Q
, Y
9
Y
0
and Y^ at the riser exit must be now be computed. This can be done
by integrating the kinetic equations by numerical methods with the follow-
ing boundary conditions: Y
A
= Y
A o
and Y
Q
= Y
E
= Y
Q
- Y~ = 0.
The integration, between Y
A
= Y. and Y
A
= Y^ , can be carried out
by the Runge-Kutta-Merson method. For good accuracy, the intervals have
to be very small. For this calculation, the correct values of ky-fc
g
must be
known. If periodic deviations are obtained between the experimental (from
the FCCU) yields and the yields predicted by this model, a corrective factor
in these k. values can be introduced.
Data Input to the Program or Model
To the program or model it is necessary to give the following data:
Operating parameters
1. u superficial velocity of the gas at the bottom of the riser
(feedstock injection point)
2. f i
st eam
CN
s t e a m o r
N
2
flow rates at the bottom of the riser
3. p total pressure
4. CATOIL or C/O ratio of catalyst to oil flow rates
Feedstockcatalyst parameters
1. fc
A
, fcj-fcg values of the cracking kinetic constants
2. V value of the deactivation kinetic constant
3. d deactivation order
Dimensions of the riser
1. S section
2. L height
Hydrodynamic parameters
1. c
A
expansion factor
2. sv slip velocity
Example
Input File. The following data are used with the program.
Mass flow rate of the distillate or feedstock (A) in the inlet = 3358
tons per day

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k
-
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9
9
1
-
0
4
5
2
.
c
h
0
1
0
Flow rate of steam in the inlet = 150.4 tons per day
CATOIL or C/O = 5.9
Average molecular weight of distillate (MW) = 450 g/mol
Pressure in the riser = 3.09 bar
Average temperature in each zone = 814, 792, 790, 789, and 789 K.
Deactivation kinetic constant (0) in each zone = 0.50/s
Slip velocity in each zone = 1.02, 1.04, 1.06, 1.08, and 1.1
Expansion factor (c) in each zone = 4.17
Cracking order for distillate = 2
Allowed error = 0.00001
Output File. The output is given in Table 1.
These results agree quite well with the experimental values from an
FCCU.
Another Example
The model can be used to study, for instance, the influence of the total
pressure. For the same conditions used for the first example, Figure 4
shows this influence in the conversion at the riser exit.
Table 1. Output from Model
Var iabl e Zone 1 Zone 2 Zone 3 Zone 4 Zone 5
Riser height 1.0 5.0 10.0 19.0 28.0
ôutlet
0.959 0.834 0.723 0.571 0.478
"outlet (
m e t e r s
per second)
9.52 12.27 13.71 14.40 14.37
f
g
in each zone
(second) 0.131 0.367 0.385 0.698 0.603
tc (second) 0.132 0.382 0.408 0.753 0.664
r
g
total
(second) 0.131 0.498 0.883 1.581 2.184
0.665 0.397 0.291 0.207 0.172
Y
o
0.083 0.144 0.162 0.170 0.169
y
e
0.200 0.358 0.417 0.462 0.478
y
g
0.048 0.094 0.119 0.149 0.168
y
c
0.006 0.017 0.025 0.037 0.044

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.
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h
0
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0
X
A 0,971 -
0,951 -
0,931
179
0,911
0,891
0,871
1,75 2,25 2,75 3,25 3,75 4,25
Pressure (atm)
Figure 4. Influence of the total pressure in the riser in the conversion at
the exit for a give mass flow rate of A.
Nomenclature
A
a
a
o
d
E
G,j
k k k
K
V *8'
K
i
mass flow rate of A, in kilograms per second
catalyst activity at some riser height, defined by
r
A
/(
r
p)
0
catalyst activity at bottom of riser or feedstock inlet
catalyst activities for the cracking reactions of A, O,
and E, respectively
deactivation order, defined by equation 11
deactivation orders for the cracking reactions of A, O,
and E, respectively
activation energy according to Arrhenius law for the
disappearance (cracking) of A, in kilocalories per mole
deactivation energy, in kilocalories per mole
empirical parameters of equation 13
kinetic cracking constants for reactions 1, 8, and /,
respectively, in reciprocal second
overall kinetic cracking constant for the cracking of A,
in reciprocal second
height from the feedstock injection point (m) in the
riser

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2
.
c
h
0
1
0
180
Q total volumetric flow rate, in cubic meters per second
Q
Q
total volumetric flow rate at feedstock inlet, in cubic
meters per second
2
A
, Q
Y
, Q
WQ
total volumetric flow rates of A, of steam, and of steam
at feedstock inlet, respectively, in cubic meters per
second
r
A
reaction rate of A, in kilograms of A per kilogram of
catalyst per second
r
c
, f
g
residence times in the riser of the catalyst and the gas,
respectively, in seconds
u superficial velocity, in meters per second
X
A
feedstock conversion
Y
A
, Y Q, Y
E
, Y
G
weight fractions of unreacted A, gas oil, gasoline, and
gas, respectively
Y
A o
weight fraction of unreacted A at the feedstock inlet
Y ^ weight fraction of unreacted A at the riser exit
A
expansion factor, defined by equation 6
V> deactivation kinetic constant or function, defined by
equation 11, in reciprocal second
0
A
, Vo> deactivation kinetic constants for the cracking reactions
of A, O, and E, respectively, in reciprocal second
r j , $ parameters described in references
Acknowledgments
We thank our colleagues from the CRAL of BP France at Lavdra (France),
whose friendship encouraged us to write this chapter. The discussions with
P. Vernet, M. Provost, A. Espinosa, and A. Priou were particularly stimu-
lating.
Literature Cited
1. Venuto, P. B.; Habib, E. T. Fluid Catalytic Cracking with Zeolite
Catalysts; Marcel Dekker, New York, 1979.
2. Fluid Catalytic Cracking: Role in Modern Refining; Occelli, M. L., Ed.;
ACS Symposium Series 375; American Chemical Society: Washington,
DC, 1988.

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0
.
1
0
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/
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-
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9
9
1
-
0
4
5
2
.
c
h
0
1
0
10. CORELLA AND FRANCES Analysis of a Riser Reactor 181
3. Gates, B. C.; Katzer J. R.; Schuit, G. C. A. Chemistry of Catalytic
Processes; McGraw-Hill, New York, 1989; Chapter 1.
4. Mauleon, J. L.; Sigaud J. B. Proc. 12th World Petroleum Congress,
1987, 4, 71-81.
5. O'Connor, P.; Hartkamp, M. B. (Akzo Chemical Division, The Neth-
erlands), personal communication.
6. Whittington, E. L.; Murphy, J. R.; Lutz, I. H. Book of Abstracts, Sym-
posium on Advances in Gasoline Technology (ACS National Meeting,
New York), 1972, pp B66-B82.
7. Paraskos, J. A.; Shah, Y. T.; Mckinney, J. D.; Carr, N. L. Ind. Eng.
Chem. Process Des. Dev. 1976, 15(1), 165-169.
8. Shah, Y. T., Huling, G. P.; Paraskos, J. A.; Mckinney, J. D. Ind. Eng.
Chem. Process Des. Dev. 1977, 16(1), 89-94.
9. Gates, B. C.; Katzer, J. R.; Shuit, G. C. A. Chemistry of Catalytic
Processes; McGraw-Hill, New York, 1989; pp 90-99.
10. Van der Baan, H. S. In Chemistry and Chemical Engineering of Cata-
lytic Processes; Prins, R. and Schuit, G. C. A., Eds.; Sijthoff and
Noordhoff: The Netherlands, 1980; pp 217-233.
11. Corella, J.; Fernandez, A.; Vidal, J. M. Ind. Eng. Chem. Product Res.
Dev. 1986, 25, 554-562.
12. Turlier, P.; Forissier, M.; Bernard, J. R. (ELF France); work presented
at the CCRE meeting in Lyon, June 1989 and at the AlChE meeting
in Houston.
13. Wollaston, G.; Haflin W. J.; Ford, W. D.; D'Souza, G. J. Hydrocarbon
Proc. 1975, September, 93-100.
14. Gross, B.; Jacob, S. M.; Nace, D. M.; Volz, S. E. U.S. Patent 3 960
707, June 1976.
15. Xinjun, M.; Shunsheng, W.; Huixin, W. J. East China Inst. Chem.
Tech. 1988, 14(4), 409-417.
16. Corella, J.; Morales, F. G.; Provost, M.; Espinosa, A.; Serrano, J. In
Recent Advances in Chemical Engineering; Saraf, D. N. and Kunzru, D.,
Eds.; Tata McGraw-Hill: New Delhi, 1989; pp 192-210.
17. Shaikn, A. A.; Carberry, J. J. Chem. Eng. Res. Dev. 1984, 62, 387-390.
18. Shuurmans, H. J. A. Ind. Eng. Chem. Process Des. Dev. 1980, 19,
267-271.
19. Dry, R. J.; White, C. C. Powder Tech. 1989, 58, 17-23.
20. Saxton, A. L.; Warley A. C. Oil Gas J., 1979, October, 71-82.
21. O'Connor, P.; Gevers, A. W. (Akzo Chemical Division, The Nether-
lands), private communication.
22. Bartholomew, K. D.; Soudek, A. Oil Gas J. 1989, October, 57.
23. Corella, J.; Provost, M.; Espinosa, A.; Gutierrez-Morales, F. In
Proceedings, XI Iberoamerican Symposium on Catalysis, Guajanato,
Mexico; Cossio, F. et al., Eds.; IMP Mexico: Mexico, 1988; pp
415-421.

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h
0
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0
24. Liguras, D. K.; Allen, D. T. Ind Eng. Chem. Res. 1989, 26, 665.
25. Corella, J.; Bilbao, R.; Molina, J. A.; Artigas, A. Ind Eng. Chem.
Process Des. Dev. 1985, 24, 625-636.
26. Espinosa, A.; Provost, M.; Corella, J.; Francs, E. (BP France,
Lavra), private communication, 1989.
27. Wojciechowski, B. W. Canad J. Chem. Eng. 1968, 46, 48.
RECEIVED March 12, 1990

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Chapter 11
Fluid Cracking Catalyst
Metals Passivation
Development and Application
Robert W. Bohmer, Dwight L. McKay, and Kelly G. Knopp
Phillips Petroleum Company, Bartleville, OK 74004
Passivation of metals on equilibrium catalytic
cracking catalyst is widely and successfully applied
operating practice within the refining industry. The
technology is effective over a broad range of
catalysts metals concentrations, oil feed
compositions, operating conditions and types of
catalytic cracking units. Practice of antimony
metals passivation technology increases FCC unit oil
feed capacity, significantly decreases the yields of
hydrogen and coke and increases the yield of
gasoline. Lower quality oil feedstocks can be
cracked. Options for maximizing metals passivation
benefits are illustrated with examples from refinery
units.
The use of met al s p as s i v at i on t o reduce t h e u n d es i red e f f e c t s of
n i c k e l and vanadium on f l u i d c a t a l y t i c c rac ki n g c a t a l y s t s has
b ecome an es t ab l i s h ed op erat i n g p r a c t i c e wi t h i n t h e r e f i n i n g
i n d u s t ry . S ev eral op erat i n g t ren d s wi t h i n t h e i n d u s t ry , such as
i n c reas ed r e s i d c rac ki n g and h i g h er reg en erat or t emp erat u re
op erat i on , are r e l a t e d t o t h e b e n e f i t s p rov i d ed b y met al s
p a s s i v a t i o n ( 1 ) . Over t h e 14 y ears s i n c e i t was f i r s t c ommerc i al l y
i n t rod u c ed , met al s p as s i v at i on has p l ay ed a key r o l e i n al l owi n g
r e f i n e r s t o maximiz e p r o f i t s wh i l e c rac ki n g r e s i d .
P h i l l i p s P et rol eu m Company d i s c ov ered and d ev el op ed t h e
antimony met al s p as s i v at i on p roc es s i n t h e e a r l y 1970's, and
s u c c e s s f u l l y ap p l i ed t h e p roc es s at i t s B org er, Texas heavy o i l
c rac ker (HOC) i n 1976 (2) . For c a t a l y t i c c rac ki n g u n i t s wi t h
contaminant met al s prob lems, met al s p a s s i v a t i o n wi t h antimony
s i g n i f i c a n t l y d ec reas es t h e y i e l d s of hy drogen and coke, and
i n c reas es t h e y i e l d of g as ol i n e. For a u n i t op erat i n g ag ai n s t a
l i m i t e d gas compressor or reg en erat or a i r b l ower, d ec reas es i n
y i e l d s of hy drogen and coke al l ow f o r any of t h e fol l owi n g
0097- 6156/ 91/ 0452- 0183$06. 00/ 0
1991 Ame r i c an Ch e mi c al S o c i e t y

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1
b e n e f i t s : i n c reas ed t h rou g h p u t , i n c reas ed c on v ers i on , or
s u b s t i t u t i o n of low v al u e r e s i d f o r some gas o i l feed . Wi t h t h es e
p erforman c e b e n e f i t s , met al s p as s i v at i on i s wi d el y used and
ac c ep t ed .
Op t i mi z i n g p as s i v at i on performance i s an i mp ort an t
c on s i d erat i on as r e f i n e r s maximiz e t h rou g h p u t t o c a t a l y t i c c rac ki n g
u n i t s and c h arg e g reat er q u a n t i t i e s of r e s i d . Met al s p a s s i v a t i o n
s h ou l d now b e i n t eg rat ed i n t o o v e r a l l r e f i n i n g op t i mi z at i on models.
Models used t o p r e d i c t c a t a l y t i c c rac ki n g y i e l d s b as ed on feed s t oc k
p rop ert i es and op erat i on al parameters can b e used e f f e c t i v e l y t o
ev al u at e t h e r e a l b en efi t s of ad d i t i v es and methods f o r en h an c i n g
t h e p erforman c e of met al s p as s i v at i on . Models are b ei n g used as
wel l as advanced l ab orat ory methods t o d ev el op t ec h n i q u es f o r
i mp rov i n g t h e commercial performance of met al s p a s s i v a t i o n .
S p e c i f i c commercial performance b e n e f i t s ob t ai n ed wi t h t h e
antimony met al s p a s s i v a t i o n p roc es s and methods used f o r ev al u at i n g
p o t e n t i a l b en efi t s are d i s c u s s ed . Op t i on s f o r maxi mi z i n g b e n e f i t s
are a l s o p res en t ed .
E a r l y Development and I n i t i a l A p p l i c a t i o n
Res earc h and Development. Res earc h s t u d i es were c a r r i e d ou t i n
l ab orat ory u n i t s d es i g n ed t o meet p a r t i c u l a r needs i n t h e area of
heavy o i l c rac ki n g and contaminant met al s on c rac ki n g c a t a l y s t s .
These reac t or sy stems were d es c ri b ed i n e a r l y p ap ers ( 3 -5) . Met al s
p a s s i v a t i o n ag en t s were ev al u at ed i n s c reen i n g t e s t s . Commercial
eq u i l i b ri u m c a t a l y s t s and c a t a l y s t s c on t ami n at ed wi t h n i c k e l and
vanadium i n t h e l ab orat ory were used t o c rac k gas o i l s or r e s i d s .
The p a s s i v a t i o n ag en t s were p r i m a r i l y organo met al compounds or
oxi d es of t h e elements s t u d i ed . The effec t i v en es s of s ev eral
elements f o r t h e red u c t i on of t h e y i e l d of hy drogen i s shown i n
T ab l e I . Antimony c on t ai n i n g compounds were t h e most e f f e c t i v e
met al s p a s s i v a t i o n ag en t s . Al t h ou g h n ot d i s c u s s ed i n t h i s p ap er,
met al s p a s s i v a t i o n s t u d i es have b een made u s i n g c omb i n at i on s of
el emen t s .
E q u i l i b ri u m c a t a l y s t from a heavy o i l c a t a l y t i c c rac ker was
used t o c rac k 20 API g r a v i t y West Texas Long Res i d . The c a t a l y s t
c on t ai n ed 3100 ppm n i c k e l and 4500 ppm vanadium; t h e c on c en t rat i on
of antimony was v a r i e d . E v al u at i on r e s u l t s f o r 75 volume p erc en t
c on v ers i on are i l l u s t r a t e d i n Fi g u re 1. The d i s t r i b u t i o n of
c rac ked p rod u c t s improved as antimony on t h e c a t a l y s t i n c reas ed .
A d d i t i on of 0.25 weight p erc en t antimony red u c ed t h e y i e l d of
hy drogen ab out 50 p erc en t , red u c ed t h e y i e l d of coke ab out 20
p erc en t , and t h e y i e l d of g as ol i n e i n c reas ed 10 p erc en t . Larg er
s c al e t e s t s i n a t r a n s f e r l i n e c a t a l y t i c c rac ki n g p i l o t p l an t
c on fi rmed t h e ou t s t an d i n g res p on s e when t h e met al s on t h e c a t a l y s t
were p as s i v at ed wi t h a compound c on t ai n i n g antimony .
A p l an aimed at commercial a p p l i c a t i o n of met al s p a s s i v a t i o n
t ec h n ol og y was implemented. T oxi c ol og y , i n d u s t r i a l h y g i en e, and
en v i ron men t al q u es t i on s r e l a t i v e t o t h e use of antimony or
p a s s i v a t i o n of met al s on c a t a l y s t i n FCC u n i t s were ad d res s ed .
P roc ed u res f o r i n j e c t i o n of antimony compounds i n t o FCC u n i t s were

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11. BOHMERETAL. FCC Metals Passivation
185
Tab le I. Passivation of Metals on FCC Cataly sts
Ranking of Elements for Reduction of Hydrogen
Hydrogen Reduction Relative To
Element Antimony Passivation
Sb 1.0
TI . 8
B i .7
P .6
Sn . 5
In .4
Ca .4
Te . 3
Ba . 3
Oe .2
Al .2
S i .2
0 0.1 0.2 0.3 0.4 0.5
ANTIMONY ON CATALYST, WT.%
F i g u r e 1. 75 V o l % c o n v e r s i o n i n p i l o t p l a n t o p e r a t i o n .
( Re pr o du c e d wi t h p e r mi s s i o n f r o m r e f . 2. Co p y r i g h t 1977 Gu l f
P u b l i s h i n g Co . )

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186
d ev el op ed , and extended p i l o t p l an t t e s t s demonstrated o p e r a b i l i t y .
Assessment of a l l i n format i on i n d i c at ed t h at , when ap p l i ed
p rop erl y , met al s p as s i v at i on wi t h antimony c ou l d b e c a r r i e d ou t
s a f e l y i n r e f i n e r y FCC u n i t s . The p o t e n t i a l economic b e n e f i t s were
l arg e, so a commercial t e s t i n a heavy o i l c a t a l y t i c c rac ker was
u n d ert aken . A p roj ec t team p rep ared t h e commercial t e s t p l an ,
p a r t i c i p a t e d i n c on d u c t i on of t e s t s , and ev al u at ed t h e t e s t
i n format i on .
Commercial A p p l i c a t i o n . The commercial t e s t showed ou t s t an d i n g
b e n e f i t s . Comparison of i n format i on from t h e heavy o i l c rac ker f o r
s ev eral months b efore and a f t e r p a s s i v a t i o n of t h e met al s on t h e
c a t a l y s t demonstrated l on g term, t rou b l e-free a p p l i c a t i o n of met al s
p a s s i v a t i o n t ec h n ol og y . P as s i v at i on of t h e met al s on t h e c a t a l y s t
wi t h antimony improved c a t a l y s t s e l e c t i v i t y t o g as ol i n e, and
red u c ed p rod u c t i on of gas and coke. Many d e t a i l s of t h e t e s t
program and t h e demonstrated b en efi t s ac h i ev ed have b een rep ort ed
(2, 6-8) . Commercial b en efi t s of met al s p as s i v at i on were s i m i l a r
t o t h e b en efi t s p red i c t ed from res earc h and development
i n format i on .
E f f e c t s on Environment, I n d u s t r i a l Hy giene, and Met al l u rg y . The
e f f e c t s of met al s p as s i v at i on wi t h antimony on t h e environment,
i n d u s t r i a l h y g i en e and met al l u rg y were s t u d i ed b y P h i l l i p s
P et rol eu m Company and b y independent t e s t i n g l a b o r a t o r i e s . The
t o x i c o l o g i c a l and en v i ron men t al i n format i on r e l a t e d t o antimony
met al s p a s s i v a t i o n has b een s t u d i ed b y s p e c i a l i s t s rep res en t i n g
ov er s ev en t y r e f i n e r i e s . The g u i d el i n es f o r s afe p r a c t i c e of
met al s p a s s i v a t i o n wi t h antimony have b een demonstrated i n
commercial exp eri en c e. (6, 9 ) .
Mechanism. The i n t e r a c t i o n of antimony wi t h s u p p ort ed n i c k e l
p a r t i c l e s was s t u d i ed wi t h X-ray d i f f r a c t i o n (XRD) ( 1 0) . These
s t u d i es s u g g es t ed t h at a h i g h l e v e l of antimony i s p res en t on t h e
s u rfac e of Ni-Sb a l l o y s . Fu rt h er s t u d i es of t h e Ni-Sb a l l o y , u s i n g
X-ray p h ot oel ec t ron s p ec t ros c op y (XPS) and Auger e l e c t r o n
s p ec t ros c op y (AES), c on fi rmed t h e p res en c e of an antimony en ri c h ed
s u rfac e (11) The s u rfac e enrichment of antimony on t h e Ni-Sb
a l l o y would b e exp ec t ed t o s i g n i f i c a n t l y a l t e r t h e c a t a l y t i c
a c t i v i t y of n i c k e l , as i n d eed oc c u rs when antimony i s added t o
n i c k e l l ad en c rac ki n g c a t a l y s t s .
E f f e c t of Antimony on CO Comb ustion Promoters and S0
X
C a t a l y s t s .
P a r t i a l p a s s i v a t i o n of CO comb ustion c a t a l y s t may oc c u r when
an t i mon y -c on t ai n i n g met al s p as s i v at i on ag en t s are i n j e c t e d i n t o
c a t a l y t i c c rac ki n g u n i t s . A d ec reas e i n CO comb ustion may b e most
n ot i c eab l e d u ri n g t h e fron t end l oad i n g p eri od of h i g h antimony
i n j e c t i o n (12) Technology has b een d ev el op ed t o overcome t h e
d ec reas ed a c t i v i t y of t h e comb ustion c a t a l y s t s . P as s i v at i on of
met al s on c a t a l y s t wi t h antimony i s r o u t i n e l y p r a c t i c e d i n
c a t a l y t i c c rac ki n g u n i t s u s i n g CO comb ustion c a t a l y s t f o r complete

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11. BOIIMER ET AL. FCC Metal s Passivation
187
o r p a r t i a l CO c o mb u s t i o n . P a s s i v a t i o n o f me t a l s w i t h an t i mo n y d o es
n o t a f f e c t t h e p e r f o r ma n c e o f t h e S O
x
r e d u c t i o n c a t a l y s t s ( 13 ) .
I n d u s t r y Wi d e A c c e p t a n c e
A n t i mo n y me t a l s p a s s i v a t i o n t e c h n o l o g y h as b een u t i l i z e d i n a
v a r i e t y o f FCC u n i t d e s i g n s , w i t h a wi d e r an g e o f FCC c a t a l y s t s
( 14 , 9) . I n a d d i t i o n , an t i mo n y me t a l s p a s s i v a t i o n h as b een
c o mme r c i a l l y p r o v e n o v e r a b r o a d r an g e o f c a t a l y s t me t a l s
c o n c e n t r a t i o n s . As t h e c a t a l y s t me t a l s l e v e l i n c r e a s e s , t h e
p a s s i v a t i o n p e r f o r ma n c e i mp r o v e s . A s t u d y o f o v e r 25 c o mme r c i a l
t r i a l s r e v e a l e d t h a t t h e av er ag e h y d r o g en r e d u c t i o n i mp r o v ed f r o m
35% t o 45% as t h e me t a l s l e v e l s i n c r e a s e d f r o m l e s s t h a n 6000 ppm
(4Ni +V) t o o v e r 9000 ppm ( 4 Ni +V) , F i g u r e 2 .
Me t a l s p a s s i v a t i o n c o mp l i men t s t h e l a t e s t g e n e r a t i o n s o f FCC
c a t a l y s t s : o c t a n e c a t a l y s t s b a s e d o n USY z e o l i t e t e c h n o l o g y an d
c h e mi c a l d e a l u m i n a t i o n . Oc t an e c a t a l y s t s e q u i l i b r a t e a t l o w e r u n i t
c e l l s i z e s , r e s u l t i n g i n mi n i mi z a t i o n o f h y d r o g e n t r a n s f e r
r e a c t i o n s (15). Co mmer c i al t e s t s h av e d e mo n s t r a t e d t h a t an t i mo n y
d o es n o t a f f e c t t h e z e o l i t e u n i t c e l l s i z e ( 9) .
Cas e S t u d i e s . As shown i n F i g u r e 2, me t a l s p a s s i v a t i o n i s u t i l i z e d
e f f e c t i v e l y w i t h 4Ni +V c o n c e n t r a t i o n s l e s s t h a n 6000 p p m. S p e c i f i c
b e n e f i t s o f an t i mo n y me t a l s p a s s i v a t i o n f o r t wo r e f i n e r y FCC u n i t s
o p e r a t i n g a t l e s s t h a n 6000 ppm 4Ni +V a r e d i s c u s s e d b e l o w .
Th e f i r s t ex amp l e i s a FCC u n i t o p e r a t i n g a g a i n s t i t s wet g as
c o mp r e s s o r c o n s t r a i n t . Th e FCC c a t a l y s t c o n t a i n e d 900 ppm n i c k e l
an d 600 ppm v an ad i u m; t h e s e me t a l s c a t a l y z e d a s i g n i f i c a n t
p r o d u c t i o n o f h y d r o g e n . I n t r o d u c t i o n o f an t i mo n y d r a m a t i c a l l y
i mp r o v ed t h e u n i t p e r f o r ma n c e . Hy d r o g en p r o d u c t i o n d e c r e a s e d 31%,
y i e l d o f c o k e d e c r e a s e d 5%, an d y i e l d o f g a s o l i n e i n c r e a s e d 1. 5%.
T h e d e c r e a s e i n h y d r o g en p r o d u c t i o n u n l o a d e d t h e wet g as
c o mp r e s s o r , an d e n a b l e d s u b s t i t u t i o n o f 2. 5% o f t h e g as o i l f e e d
w i t h l o w e r v a l u e r e s i d . Th e b e n e f i t t o c o s t r a t i o o f t h e s e
i mp r o v emen t s was g r e a t e r t h a n 3 0 .
T a b l e I I , t h e s ec o n d ex amp l e, s hows t h e b e n e f i t s o f me t a l s
p a s s i v a t i o n a t a FCCU i n a r e f i n e r y o p e r a t i n g t o max i mi z e
t h r o u g h p u t . Th e FCC c a t a l y s t c o n t a i n e d 490 ppm n i c k e l an d 1200 ppm
v an ad i u m, an d t h e u n i t was o p e r a t i n g a g a i n s t b o t h i t s a i r b l o w e r
an d g as c o mp r e s s o r l i m i t s . Hy d r o g en p r o d u c t i o n was 92 SCF p e r
b a r r e l o f FCCU f e e d ; w i t h t h i s amount o f h y d r o g e n i n t h e g as t o t h e
c o mp r e s s o r , i t was d i f f i c u l t t o ma i n t a i n t h e c o mp r e s s o r g o v e r n o r o n
c o n t r o l . Th e h i g h c o n c e n t r a t i o n o f h y d r o g en i n t h e f u e l g as a l s o
a f f e c t e d t h e s t e a d y s t a t e o p e r a t i o n o f t h e h e a t c o n t r o l o f o t h e r
p r o c e s s i n g u n i t s .
When an t i mo n y was i n j e c t e d , h y d r o g en p r o d u c t i o n d e c r e a s e d t o
58 S C F / B F F , an d t h e l o a d o n t h e c o mp r e s s o r was e a s e d . Co k e
p r o d u c t i o n d e c r e a s e d as e v i d e n c e d by a d e c r e a s e d l o a d o n t h e a i r
b l o w e r an d t h e 17 F d e c r e a s e i n r e g e n e r a t o r t e mp e r a t u r e . A s t h e
l o a d o n t h e c o mp r e s s o r was e a s e d , t h e c o mp r e s s o r s p eed c o n t r o l l e r
was e f f e c t i v e , an d t h i s s t a b i l i z e d t h e r e f i n e r y s t eam b a l a n c e .
O v e r a l l , t h e u n i t o p e r a t e d c l o s e r t o s t e a d y s t a t e , an d t h i s h e l p e d

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| 1 H2, S C F / B F F r ^ ^ j H2, S C F / B F F
1 1
NO MP WITH MP
140 1
< 6000 6000 - 9000 >90O0
4NI y PPM
F i g u r e 2 . Hy d r o g e n mak e wi t h me t a l s p a s s i v a t i o n .
Tab le I I . Antimony Metals Passivation Effec t s on Charge Rate
Charge, B/D
Feed API Gravity
Feed Carb on Residue, Wt%
Regenerator Bed, F
Metals on Cataly st, PPM
Ni c kel
Vanadium
Aft er
Before Passivation
30,774 32,943
28.2 27.5
0.38 0.63
1302 1285
489 611
1203 1585
Hydrogen, $CF/BFF
C
2
& Lighter, LB/BFF
C
3
& C
4
Ol efi n s , LV%FF
I C 4 , LV%FF
Oasoline, LV%FF
LCO, LV%FF
Coke, LB/BFF
92
14.3
12.8
3.1
56.2
24.3
19.7
58
14.7
13.2
2.9
54.3*
26.5
18.3
*Separations conditions were changed to increase the y i el d of LCO
during the l at e f a l l and winter months.

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11. BOHMER ET AL. FCC Metals Passivation
189
s mo o t h o u t t h e o v e r a l l r e f i n e r y o p e r a t i o n s . Wi t h t h e d e c r e a s e d
l o a d o n t h e c o mp r e s s o r , t h e c h a r g e was i n c r e a s e d f r o m 3 1, 0 0 0 BPD t o
3 3 , 0 0 0 B PD. T h e r e f i n e r y was a l s o a b l e t o c h a r g e a p o o r e r q u a l i t y
f e e d t o t h e u n i t ; t h e me t a l s i n t h e f e e d i n c r e a s e d as d i d t h e
me t a l s o n t h e c a t a l y s t . Th e y i e l d o f g a s o l i n e was l e s s a f t e r t h e
a d d i t i o n o f an t i mo n y t o t h e u n i t , d u e p r i m a r i l y t o a c h an g e i n
f r a c t i o n a t i o n o f l i q u i d p r o d u c t s .
Me t a l s p a s s i v a t i o n a l l o w s r e f i n e r s t o max i mi z e t h e c h a r g e o f
l o w e r v a l u e f e e d s . I n j e c t i o n o f an t i mo n y i n t o t h e P h i l l i p s Sween y ,
T e x a s HOC d e c r e a s e d u n i t h y d r o g en p r o d u c t i o n an d d e c r e a s e d t h e
p r o c e s s g as c o mp r e s s o r s p eed ab o u t 500 r p m. T h i s e n a b l e d t h e
r e f i n e r y t o i n c r e a s e t h r o u g h p u t 10% an d p r o c e s s a mo r e d i f f i c u l t t o
c r a c k f e e d s t o c k (J L4 ) . F i f t e e n p e r c e n t o f O r i e n t e c r u d e f r o m
Ec u a d o r was b l e n d e d i n t o t h e P h i l l i p s B o r g e r , T ex as r e f i n e r y c r u d e
s l a t e w i t h t h e u s e o f me t a l s p a s s i v a t i o n a t i t s HOC. Me t a l s i n t h e
HOC f e e d an d o n t h e HOC c a t a l y s t i n c r e a s e d s i g n i f i c a n t l y , b u t y i e l d
o f h y d r o g e n was s t i l l l e s s t h an i t h ad b een p r i o r t o me t a l s
p a s s i v a t i o n ( 6 ) .
Me t a l s p a s s i v a t i o n a l s o a l l o w s r e f i n e r s t o i n c r e a s e r e a c t o r
s e v e r i t y t o i n c r e a s e FCCU c o n v e r s i o n . One r e f i n e r y i n c r e a s e d C 4
p r o d u c t i o n ( v a l u a b l e a l k y l a t i o n f eed ) 17. 2% b y i n c r e a s i n g
c o n v e r s i o n w i t h t h e i n j e c t i o n o f a n t i mo n y . A n o t h e r r e f i n e r was
a b l e t o i n c r e a s e t h e FCCU r i s e r o u t l e t t e mp e r a t u r e 8 F t h r o u g h
d e c r e a s e d d r y g as p r o d u c t i o n w i t h me t a l s p a s s i v a t i o n . Y i e l d o f
g a s o l i n e i n c r e a s e d , an d g a s o l i n e RON c l e a r i n c r e a s e d 0 . 7 .
Ot h e r t y p e s o f o p e r a t i o n s wh er e me t a l s p a s s i v a t i o n h as b een
s u c c e s s f u l a r e FCC u n i t s t h a t o p e r a t e t o max i mi z e d i s t i l l a t e
p r o d u c t i o n an d T h er mo f o r C a t a l y t i c Cr a c k i n g U n i t s ( T CCU) . A
r e f i n e r o p e r a t i n g a FCCU a t c o n v e r s i o n s l e s s t h a n 60 l i q u i d v o l u me
p e r c e n t o f t h e o i l f e e d o b s e r v e d a 56% d e c r e a s e i n h y d r o g e n
p r o d u c t i o n w i t h me t a l s p a s s i v a t i o n . Y i e l d s o f l i q u i d p r o d u c t s
i n c r e a s e d . I n a TCCU a p p l i c a t i o n , i n j e c t i o n o f an t i mo n y d e c r e a s e d
y i e l d o f c o k e , as e v i d e n c e d by a 70 F d e c r e a s e i n r e g e n e r a t i o n
t e mp e r a t u r e , an d d e c r e a s e d t h e H 2 / C H 4 mo l e r a t i o i n t h e o f f g as
13. 7%.
C a t a l y s t V / N i Ra t i o Ef f e c t s o n Hy d r o g en Ge n e r a t i o n . Muc h o f t h e
l i t e r a t u r e o n an t i mo n y me t a l s p a s s i v a t i o n f o c u s e s o n t h e e f f e c t o f
an t i mo n y o n n i c k e l . L i t t l e i s men t i o n ed ab o u t t h e i n t e r a c t i o n o f
an t i mo n y an d v an ad i u m. Van ad i u m h as b een shown t o s t a b i l i z e n i c k e l
c o k i n g a c t i v i t y t o m i l d s t eam d e a c t i v a t i o n . Ev i d e n c e f o r t h i s
i n t e r a c t i o n came f r o m c o k i n g e x p e r i me n t s , X- r a y d i f f r a c t i o n , an d
t emp er at u r e- p r o g r ammed r e d u c t i o n s t u d i e s ( 16 ) . S t a b i l i z a t i o n o f
n i c k e l b y v an ad i u m s u g g e s t s t h a t i n a d d i t i o n t o t h e d i r e c t e f f e c t
o f an t i mo n y o n v an ad i u m, t h e p r e s e n c e o f v an ad i u m w i l l i n f l u e n c e
t h e i n t e r a c t i o n o f an t i mo n y an d n i c k e l . F i g u r e 3 s hows t h e
p e r c e n t a g e h y d r o g e n d e c r e a s e w i t h an t i mo n y me t a l s p a s s i v a t i o n i n
c o mme r c i a l u n i t s v s . FCC c a t a l y s t v an ad i u m t o n i c k e l r a t i o s . Th e
d a t a i n d i c a t e t h a t t h e r a t i o o f v an ad i u m t o n i c k e l o n t h e c a t a l y s t
i s n o t a s i g n i f i c a n t c o n t r o l l i n g f a c t o r i n t h e p e r f o r ma n c e o f
an t i mo n y me t a l s p a s s i v a t i o n .

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190
A s t u d y o f t h e v an ad i u m c a t a l y z e d d e n y d r o g e n a t i o n r e a c t i o n
s h o wed an t i mo n y i n t e r a c t s w i t h v an ad i u m an d d e c r e a s e s i t s
d e h y d r o g e n a t i o n a c t i v i t y . Cr a c k i n g c a t a l y s t was c o n t a mi n a t e d w i t h
v an ad i u m i n t h e l a b o r a t o r y . A p o r t i o n o f t h i s c o n t a mi n a t e d
c a t a l y s t was t h e n t r e a t e d w i t h an an t i mo n y c o n t a i n i n g c o mp o un d t o
p a s s i v a t e v an ad i u m. Th e c a t a l y s t s wer e e v a l u a t e d b y c r a c k i n g g as
o i l . T h e y i e l d o f h y d r o g e n f o r p a s s i v a t e d c a t a l y s t a v e r a g e d
f i f t e e n p e r c e n t l e s s t h a n f o r t h e u n p a s s i v a t e d c a t a l y s t .
T e c h n o l o g y i s Ef f e c t i v e l y T r a n s f e r r e d t o Co mmer c i al Us e
B a s e d o n p i l o t p l a n t an d c o mme r c i a l me t a l s p a s s i v a t i o n e v a l u a t i o n s ,
a p r o c e d u r e was d e v e l o p e d f o r e s t i m a t i n g p o t e n t i a l c o mme r c i a l
b e n e f i t s o f t h e p r o c e s s . Th e e s t i m a t i o n p r o c e d u r e u t i l i z e s p l a n t
d a t a s u c h as c a t a l y s t me t a l s c o n c e n t r a t i o n s , FCCU h y d r o g e n
p r o d u c t i o n , f e e d t y p e , an d r e a c t o r s e v e r i t y t o d e t e r mi n e p o t e n t i a l
ec o n o mi c b e n e f i t s ( 17 ) .
F i g u r e 4 s hows t h a t t h e mag n i t u d e o f b e n e f i t s o b s e r v e d i n
c o mme r c i a l o p e r a t i o n s i s c l o s e t o t h e mag n i t u d e o f b e n e f i t s
o b s e r v e d i n t h e p i l o t p l a n t an d t h e mag n i t u d e o f b e n e f i t s
p r e d i c t e d . I n c a s e 1, t h e c o mme r c i a l h y d r o g e n p r o d u c t i o n d e c r e a s e
w i t h me t a l s p a s s i v a t i o n was 42%, an d t h e p i l o t p l a n t p r e d i c t e d
d e c r e a s e was 35%. I n c a s e 2 , t h e c o mme r c i a l , p i l o t p l a n t , an d
p r e d i c t e d d e c r e a s e s i n h y d r o g e n p r o d u c t i o n wer e 36%, 41% an d 39%
r e s p e c t i v e l y . I n c a s e 3 , t h e c o mme r c i a l an d p i l o t p l a n t d e c r e a s e s
i n t h e y i e l d o f h y d r o g e n wer e 46% an d 28% r e s p e c t i v e l y . I n c a s e 4
t h e c o mme r c i a l , p i l o t p l a n t , an d p r e d i c t e d d e c r e a s e s i n h y d r o g e n
p r o d u c t i o n wer e 34%, 38% an d 36% r e s p e c t i v e l y . Es t i m a t i o n s o f
c h an g es i n y i e l d o f c o k e wer e a c c e p t a b l e . Ch an g es i n y i e l d s o f
o t h e r p r o d u c t s wer e d i f f i c u l t t o e s t i ma t e .
O p t i m i z a t i o n o f Me t a l s P a s s i v a t i o n B e n e f i t s
Ma i n t e n a n c e o f Pr o p e r A n t i mo n y C o n c e n t r a t i o n . C l o s e mo n i t o r i n g o f
t h e an t i mo n y c o n c e n t r a t i o n o n t h e c a t a l y s t w i l l a s s u r e t h a t maxi mum
b e n e f i t s a r e d e r i v e d f r o m a me t a l s p a s s i v a t i o n p r o g r a m. Th e
a n t i m o n y - t o - n i c k e l r a t i o o n t h e e q u i l i b r i u m c a t a l y s t h as b een
c o r r e l a t e d w i t h h y d r o g e n p r o d u c t i o n i n c o mme r c i a l o p e r a t i o n s
( F i g u r e 5 ) . Th e n o n - l i n e a r s h ap e o f t h e h y d r o g e n p r o d u c t i o n c u r v e
h as b een c o n f i r me d i n p i l o t p l a n t t e s t s ( F i g u r e 1) . Th e
r ec o mmen d ed an t i mo n y c o n c e n t r a t i o n c o r r e s p o n d s t o a p o i n t b ey o n d
t h e b r e a k p o i n t o f t h e c u r v e . A " c u s h i o n " i s d e s i r e d t o a l l o w
f l u c t u a t i o n s i n t h e s y s t em w i t h o u t maj o r i n c r e a s e s i n t h e y i e l d s o f
h y d r o g e n an d c o k e .
T y p e o f A n t i mo n y . Th e t y p e o f an t i mo n y a d d i t i v e s e l e c t e d w i l l
a f f e c t t h e p e r f o r ma n c e o f a me t a l s p a s s i v a t i o n p r o g r a m. A n t i mo n y
a d d i t i v e s a r e g e n e r a l l y c a t e g o r i z e d as o r g a n i c o r i n o r g a n i c . Ga l l ,
e t . a l . c o mp ar ed t h e p a s s i v a t i o n p e r f o r ma n c e o f an o r g a n o - a n t i mo n y
a d d i t i v e , an t i mo n y t r i s d i p r o p y l d i t h i o p h o s p a t e , w i t h an t i mo n y
p e n t o x i d e i n a f l u i d i z e d p i l o t p l a n t ( 14 ) . T h e o r g a n o - a n t i mo n y
g av e b e t t e r p a s s i v a t i o n p e r f o r ma n c e b e n e f i t s t h a n t h e i n o r g a n i c

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BOHMER ET AL. FCC Metals Passivation
80
z
2
iu$ 60
g
40
20
% H2 DECREASE IN
COMMERCIAL UNITS
0.0 1 1.5 2 2.5 3
FCC CATALYST V/NI RATIO
3.5
F i g u r e 3 . C a t a l y s t V / N i e f f e c t s o n h y d r o g e n g e n e r a t i o n .
PILOT PLANT PREDICTED COMMERCIAL
CASE 1 CASE 2 CASE 3 CASE 4
F i g u r e 4 . Co mp a r i s o n o f p i l o t p l a n t , p r e d i c t e d , an d c o mme r c i a l
b e n e f i t s .

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c o mp o u n d . I t h as b een s u g g e s t e d t h a t o r g a n o - a n t i mo n y a d d i t i v e s l a y
d own o n t h e c a t a l y s t mor e e f f e c t i v e l y t h a n t h e i n o r g a n i c c o mp o u n d s .
Mi l l e r , e t . a l . p r e s e n t e d c o mme r c i a l c o mp a r i s o n s o f an t i mo n y
p e n t o x i d e an d an o r g a n o - a n t i mo n y a d d i t i v e ( 18) . T h e d a t a s h o wed a
s i g n i f i c a n t i mp r o v emen t i n l a y - d o w n e f f i c i e n c y f o r t h e
o r g a n o - a n t i mo n y c o mp o u n d , b u t t h e a u t h o r s c o n c l u d e d t h a t t h e
an t i mo n y p e n t o x i d e was p r e f e r r e d d u e t o l o w e r a d d i t i v e c o s t s .
P h i l l i p s u s e s o r g a n o - a n t i mo n y a d d i t i v e s i n i t s c o mme r c i a l
a p p l i c a t i o n s b a s e d o n a c o s t / b e n e f i t ec o n o mi c o p t i m i z a t i o n .
Co mmer c i al Me t a l s P a s s i v a t i o n Sy s t ems
Me t a l s p a s s i v a t i o n i s an a r e a o f a c t i v e r e s e a r c h an d d e v e l o p me n t ,
an d s e v e r a l p a s s i v a t i o n s y s t ems h av e b een c o m m e r c i a l i z e d .
Co mme r c i a l i z e d s y s t ems i n c l u d e a d d i t i o n o f e l e me n t s an d
c o mb i n a t i o n s o f el emen t s t o FCC c a t a l y s t s , s u c h as a n t i mo n y ,
an t i mo n y p l u s p h o s p h o r u s ( 6 , . 14), an t i mo n y p l u s p h o s p h o r o u s p l u s
t i n , an t i mo n y p l u s t i n , t i n ( 19- 2 1) , an d b i s mu t h ( 2 2 , 23. ). Ot h e r
c o mme r c i a l i z e d s y s t ems i n c l u d e p r o c e s s c h an g es o r c a t a l y s t c h an g es
s u c h as t h e u s e o f s t eam o r l i g h t h y d r o c a r b o n s as d i l u e n t s i n t h e
r e a c t o r ( 4 ) an d v an ad i u m t r a p s ( 2 5 ) . A n t i mo n y h as b een u s e d
s u c c e s s f u l l y i n c o n j u n c t i o n w i t h t h e s e s y s t e ms . A n o t h e r me t a l s
p a s s i v a t i o n a d d i t i v e , c o n t a i n i n g i n g r e d i e n t s t h a t a r e p r o p r i e t a r y ,
h as a l s o b een i n t r o d u c e d c o mme r c i a l l y ( 2 6 ) .
T h e c o mb i n a t i o n o f an t i mo n y an d t i n r e d u c e s t h e y i e l d o f
h y d r o g e n an d c o k e , an d i n c r e a s e s t h e y i e l d o f g a s o l i n e when
c o mp ar ed w i t h t h e u s e o f an t i mo n y a l o n e . Th e r e s i s t a n c e o f t h e
c a t a l y s t t o d e a c t i v a t i o n by v an ad i u m may a l s o b e i mp r o v e d . Th e
c o mb i n a t i o n o f an t i mo n y an d t i n h e l p e d ma i n t a i n c a t a l y s t a c t i v i t y
f o r s e v e r a l c o mme r c i a l c a s e s . Wi t h c o mp ar ab l e f e e d s t o c k an d
p r o c e s s c o n d i t i o n s , t h e c o n v e r s i o n i n c r e a s e d up t o t h r e e p e r c e n t ,
t h e y i e l d o f g a s o l i n e i n c r e a s e d up t o 2 . 4 p e r c e n t , an d t h e y i e l d o f
c o k e d e c r e a s e d u p t o 0 . 5 w ei g h t p e r c e n t .
F u t u r e A p p l i c a t i o n an d Dev el o p men t
Ec o n o mi c p r e s s u r e s f o r h i g h e r g a s o l i n e o c t a n e an d i n c r e a s e d
t h r o u g h p u t a s s u r e t h a t p a s s i v a t i o n o f me t a l s o n c r a c k i n g c a t a l y s t s
w i l l r e ma i n an i mp o r t a n t t e c h n o l o g y i n t h e r e f i n i n g i n d u s t r y . Wor k
c o n t i n u e s o n i mp r o v emen t s t o t h e p a s s i v a t i o n p r o c e s s . Th e
d i c h o t o my a t h i g h an t i mo n y c o n c e n t r a t i o n l e v e l s b et ween i n c r e a s i n g
b e n e f i t s an d d e c r e a s i n g l ay d o wn e f f i c i e n c y h as b een d o c u men t ed
( 2 7 ) . Met h o d s t o i mp r o v e t h e r e t e n t i o n o f an t i mo n y o n t h e c a t a l y s t
w o u l d r e s u l t i n t h e s h i f t i n g o f t h e ec o n o mi c o p t i mu m t o a h i g h e r
an t i mo n y c o n c e n t r a t i o n . Th e d y n ami c s b et ween t h e an t i mo n y l ay d o wn
mec h an i s ms an d t h e u n i t o p e r a t i o n s mus t b e c o n s i d e r e d .
I mp r o v emen t s i n an t i mo n y l ay d o wn e f f i c i e n c y o f 35 t o 40 p e r c e n t
h av e b e e n o b s e r v e d i n t e s t s o f new an t i mo n y c o n t a i n i n g a d d i t i v e
s y s t e ms .
S t u d i e s w h i c h a p p l y s u r f a c e s c i e n c e t e c h n o l o g y a r e b e i n g
u t i l i z e d t o d e v e l o p a b e t t e r u n d e r s t a n d i n g o f me t a l s p a s s i v a t i o n
mec h an i s ms . T r a n s p o r t e x p e r i me n t s i n t h e l a b h av e shown t h a t

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11. BOHMERETAL. FCC Metal s Passivation
193
d u r i n g s t e a m- a g i n g i n t r a p a r t i c l e t r a n s f e r o f V o c c u r s an d t h a t
m i g r a t i n g V c a n be i r r e v e r s i b l y s o r b e d b y a me t a l t r a p s u c h as
s e p i o l i t e i n t h e f o r m o f a h eat s t a b l e v a n a d a t e . T h e mec h an i s m o f
V p a s s i v a t i o n an d t h e n a t u r e o f t h e c o mp o und f o r med d u r i n g
V - c a t a l y s t i n t e r a c t i o n h as b een s t u d i e d b y XRD, XPS an d l a s e r Raman
s p e c t r o s c o p y ( 2 8- 3 1) . L e a an d K u g l e r (32) s t u d i e d e q u i l i b r i u m FCC
c a t a l y s t s b y i ma g i n g s e c o n d a r y i o n mas s s p e c t r o me t r y ( SI MS) . I n
Ag r eemen t w i t h l a b r e s u l t s o f O c c e l l i (28) v an ad i u m was f o u n d t o b e
p a r t i a l l y f r e e t o move f r o m p a r t i c l e t o p a r t i c l e as w e l l as w i t h i n
a p a r t i c l e . Wo o l e r y , e t . a l . i n v e s t i g a t e d t h e o x i d a t i o n s t a t e an d
l o c a l s t r u c t u r e o f v an ad i u m an d n i c k e l i n FCC c a t a l y s t (33) . T h e i r
d a t a s u g g e s t t h a t o x i d a t i o n o f V t o V+5 i s n o t a s u f f i c i e n t
c o n d i t i o n f o r c a t a l y s t d e a c t i v a t i o n . Ot h e r f a c t o r s s u c h as
v an ad i u m l o c a t i o n an d m o b i l i t y p l a y a r o l e i n t h e d e a c t i v a t i o n o f
c a t a l y s t by v an ad i u m ( 2 8) .
As mar k et d emand s s h i f t t h e d e s i r e d FCC y i e l d s l a t e , t h e
e c o n o mi c s o f a me t a l s p a s s i v a t i o n p r o g r am a l s o c h a n g e . I n d u s t r y
t r e n d s i n c l u d e h i g h e r r e a c t o r t e mp e r a t u r e s ( g r e a t e r t h a n 10 0 0 F ) t o
max i mi z e C 2 - C 4 o l e f i n s , h i g h e r t h r o u g h p u t , an d l o w er q u a l i t y
f e e d s t o c k s . Me t a l s p a s s i v a t i o n t e c h n o l o g y c a n b e u s e d t o i mp r o v e
t h e l i g h t en d p r o d u c t q u a l i t y at h i g h r e a c t o r t e mp e r a t u r e s . P i l o t
p l a n t t e s t s a t 10 5 0 F r e a c t o r t e mp e r a t u r e w i t h c a t a l y s t c o n t a i n i n g
10 , 0 0 0 ppm me t a l s r e v e a l e d t h a t , i n a d d i t i o n t o r e d u c t i o n s i n
y i e l d s o f h y d r o g e n an d c o k e , a p a s s i v a t i o n ag en t r e d u c e d t h e
b u t a d i e n e y i e l d 90%, i n c r e a s e d t h e p r o p y l e n e y i e l d 20%, an d t o t a l
b u t y l e n e s i n c r e a s e d 10%. A v a r i e t y o f p a s s i v a t i o n t e c h n i q u e s may
b e u s e d t o c u s t o mi z e t h e t o t a l p r o d u c t s l a t e f o r a p a r t i c u l a r u n i t
c o n f i g u r a t i o n .
Th e Mo d e l i n g o f Me t a l s P a s s i v a t i o n Ef f e c t s
Mo d el s h av e b een d e v e l o p e d t o p r e d i c t c a t c r a c k e r y i e l d s b a s e d o n
o p e r a t i n g p a r a me t e r s an d f e e d s t o c k p r o p e r t i e s (^34) . T h e s e h av e
a i d e d i n a p p l i c a t i o n an d e v a l u a t i o n o f me t a l s p a s s i v a t i o n b e n e f i t s .
Mi l l e r an d Pa w l o s k i (35) r e p o r t e d t h e u s e o f ma t h e ma t i c a l mo d el s t o
c a l c u l a t e t h e b e n e f i t s o f v an ad i u m p a s s i v a t i o n , an d T e r a n (27)
r e p o r t e d t h e n eed f o r FCCU h y d r o g en mo d e l i n g an d me t a l s t r a c k i n g t o
o p t i m i z e p a s s i v a t i o n b e n e f i t s .
I n i n s t a n c e s wh er e r e f i n e r s max i mi z e c h a r g e o f l o w e r q u a l i t y
f e e d , o b s e r v e d s e l e c t i v i t y c h an g es w i t h p a s s i v a t i o n a r e s o met i mes
n o t as e x p e c t e d . I n o n e c o mme r c i a l a p p l i c a t i o n , h y d r o g e n
p r o d u c t i o n d e c r e a s e d 34% w i t h t h e a d d i t i o n o f a n t i mo n y , b u t t h e
y i e l d o f c o k e i n c r e a s e d 5. 6%, n o t an e x p e c t e d r e s u l t . Th e
d e c r e a s e d h y d r o g e n p r o d u c t i o n r emo v ed t h e FCCU g as c o mp r e s s o r
r e s t r a i n t , a l l o w i n g t h e r e f i n e r y t o i n c r e a s e FCCU c o n v e r s i o n an d
c h a r g e a l o w e r q u a l i t y f e e d . T h es e o p e r a t i o n a l c h an g es i n f l u e n c e d
y i e l d s s i g n i f i c a n t l y . Mo d el s wer e u s e d t o p r o j e c t wh at t h e y i e l d s
w o u l d h av e b een w i t h t h e c h an g e i n f e e d s t o c k , h ad t h e r e b een no
i n j e c t i o n o f a n t i mo n y . Th e s ec o n d c o l u mn o f T a b l e I I I c o mp ar es t h e
a c t u a l y i e l d s w i t h me t a l s p a s s i v a t i o n , t o t h e y i e l d s p r o j e c t e d b y
t h e mo d el h ad t h e r e b een no me t a l s p a s s i v a t i o n . T h i s s hows t h a t
me t a l s p a s s i v a t i o n b e n e f i t s wer e g r e a t e r when t h e l o w e r q u a l i t y

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1
-
0
4
5
2
.
c
h
0
1
1
1800 PPM < Nl < 2000 PPM
+ 100
SO-
IL
CO BASE
CM
X
-50
SB/NI
F i g u r e 5. Co mme r c i a l r e s p o n s e o f h y d r o g e n p r o d u c t i o n t o v a r i a -
t i o n s i n c a t a l y s t S b / N i r a t i o .
Tab le III. The Effec t s of Feedstock Quality on Passivation
Percent Change
With Metals
Passivation
Percent Change
With Metals
Passivation
Considering Feed
Quality Changes
Gasoline
C
4
LPG Gas
Coke
LCO
H
2
+1.3
+17.2
+5.6
-13.6
-33.6
+3.8
+9.6
-8.9
+7.1
-33.6
Benefits/ Costs 6.4 17.9

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11. BOHMERETAL. FCC Metals Passivation 195
f e e d was c o n s i d e r e d . Th e b e n e f i t t o c o s t r a t i o o f me t a l s
p a s s i v a t i o n was b e t t e r , 17. 9 v s . 6 . 4 , when a c c o u n t i n g f o r
o p e r a t i o n a l an d f e e d c h a n g e s .
S i m i l a r mo d el s wer e u s e d t o a i d i n e v a l u a t i n g t h e b e n e f i t s o f
an t i mo n y an d t i n c o mp ar ed w i t h an t i mo n y a l o n e . I n o n e c o mme r c i a l
t r i a l , a d d i t i o n a l b e n e f i t s a c h i e v e d w i t h t h e a n t i m o n y - t i n s y s t em
i n c l u d e d 2 . 9 p e r c e n t h i g h e r c o n v e r s i o n , 2 . 2 p e r c e n t i n c r e a s e i n t h e
y i e l d o f g a s o l i n e w i t h o n l y a 0 . 2 p e r c e n t i n c r e a s e i n t h e y i e l d o f
c o k e . When v a r i a t i o n s i n f r e s h f e e d p r o p e r t i e s , s l u r r y r e c y c l e an d
o t h e r p r o c e s s i n g c o n d i t i o n s wer e i n c l u d e d i n d a t a e v a l u a t e d w i t h
t h e mo d e l , b e n e f i t s w i t h t h e a n t i m o n y - t i n s y s t em i mp r o v ed t o 4 . 4
p e r c e n t h i g h e r c o n v e r s i o n , 2 . 6 p e r c e n t i n c r e a s e i n y i e l d o f
g a s o l i n e , an d t h e y i e l d o f c o k e o n l y i n c r e a s e d 0 . 3 w e i g h t p e r c e n t .
I n c o r p o r a t i o n o f me t a l s p a s s i v a t i o n t e c h n o l o g y i n t o p l a n t FCC u n i t
o p e r a t i o n mo d el s an d i n t o o v e r a l l r e f i n e r y e c o n o mi c s mo d el s i s
e x p e c t e d t o s i g n i f i c a n t l y e x t e n d t h e d o c u men t ed b e n e f i t s o f me t a l s
p a s s i v a t i o n .
Summar y
P a s s i v a t i o n o f me t a l s o n e q u i l i b r i u m c a t a l y t i c c r a c k i n g c a t a l y s t i s
an e s t a b l i s h e d o p e r a t i n g p r a c t i c e w i t h i n t h e r e f i n i n g i n d u s t r y .
T h e t e c h n o l o g y i s e f f e c t i v e o v e r a b r o a d r an g e o f c a t a l y s t
c o n t a mi n a n t me t a l s c o n c e n t r a t i o n s , p r o c e s s o p e r a t i n g c o n d i t i o n s an d
t y p e s o f c a t a l y t i c c r a c k i n g u n i t s . P r a c t i c e o f an t i mo n y me t a l s
p a s s i v a t i o n t e c h n o l o g y i n c r e a s e s FCC u n i t o i l f e e d c a p a c i t y ,
d e c r e a s e s t h e y i e l d s o f h y d r o g en an d c o k e an d i n c r e a s e s t h e y i e l d
o f g a s o l i n e . L o wer q u a l i t y o i l f e e d s t o c k s c a n b e c r a c k e d .
Co mmer c i al b e n e f i t s o b t a i n e d w i t h t h e p r a c t i c e o f me t a l s
p a s s i v a t i o n t e c h n o l o g y an d t h e a p p l i c a t i o n o f mo d el s f o r ma x i mi z i n g
me t a l s p a s s i v a t i o n b e n e f i t s a r e i l l u s t r a t e d w i t h ex amp l es f r o m
r e f i n e r y u n i t s .
Literature Cited
1. Stokes, O. M., Davison Catalagram No. 77 (1988).
2. Dale, O. H. , and McKay, D. L . , Hydrocarbon Processing, 56 (9),
97-102 (1977).
3. McKay, D. L., and Bertus, B. J., PREPRINTS, Div. of Petrol.
Chem., ACS, 24 (2), 645 (1979).
4. McKay, D. L . , Schaffer, A. M., and Bertus, B. J., Southwest
Catalysis Society Symposium, Fall 1980 Meeting, Houston, TX.
5. Lee, F. M., Ind. Eng. Chem. Res., 28, 920-925 (1989).
6. Dale, G. H. , Rogers, C. L . , Nielsen, R. H. , McKay, D. L., and
Davis, E. D., API 43rd Midyear Meeting, Toronto, Canada, May
8-11, 1978, Proceedings-Refining Department, 57, 432-438
(1978).
7. Rush, J. B. , Chemical Engineering Progress, 77 (12), 29-32
(1981).
8. Rush, J. B., AM-81-43, NPRA Annual Meeting, March 29-31, 1981,
San Antonio, TX.

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9. Bohmer, R. W., McKay, D. L., and Knopp, K. G., AM-89-51, NPRA
Annual Meeting, March 19-21, 1989, San Francisco, CA.
10. Drei l i n g , M. J. , and Schaffer, A. M., J. Cat al ., 56, 130-133
(1979) .
11. Parks, G. D., Applications of Surface Science, 5, 92-97
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12. Transcript of NPRA Question and Answer Session on Refining and
Petrochemical Technology , 40-41 (1980), 50-51 (1982), 68
(1984), 62 (1987).
13. Pettersen, F. A., and Blanton, W. A., Paper 37e, AICHE, Summer
National Meeting, 1986, Boston, MA
14. Gal l , J. W., Nielsen, R. H., McKay, D. L., and Mi t c h el l , N.
W., AM-82-50, NPRA Annual Meeting, March 21-23, 1982, San
Antonio, TX.
15. Pine, L. A., Maher, P. J. and Wachter, W. A., J. Cat al ., 85,
466-476.
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27, 1595-1599 (1988).
17. McCarthy, W. C., Hutson, T. Jr. , and Mann, J. W., Kat al i s t i ks
3rd Annual Fl u i d Cat Cracking Symposium, May 1982, Amsterdam,
The Netherlands.
18. Mi l l er, R. F., Blaschke, M. W., and Pawloski, J. N., AM-88-72,
NPRA Annual Meeting, March 20-22, 1988, San Antonio, TX.
19. Denison, F. W. III, Hohnholt, J. F., English, A. R., and
Krishna, A. S., AM-86-51, NPRA Annual Meeting, March 23-25,
1986, Los Angeles, CA.
20. English, A. R., and Kowalcz ych, D. C., Oi l and Gas J. ,
127-128, (July 16, 1984).
21. Anderson, M. W., Oc c el l i , M. L., and Suib , S. L., J. Cat al .,
118. 31-42 (1989).
22. Ramamoorthy, P., English, A. R., Kennedy, J. V., Lossens, L.
W., and Krishna, A. S., AM-88-50, NPRA Annual Meeting, March
20-22, 1988, San Antonio, TX.
23. Kennedy, J. V., and Jossens, L. W., Paper 60a, AICHE, Spring
National Meeting, 1990, Orlando, FL.
24. Cab rera, C. A., Helmer, C. L., and Davis, J. P., Paper 14,
Kat al i s t i ks 8th Annual Fl u i d Cat Cracking Symposium, June 1-4,
1987, Budapest, Hungary.
25. Upson, L. L., Paper 18, Kat al i s t i ks 8th Annual Fl u i d Cat
Cracking Symposium, June 1-4, 1987, Budapest, Hungary.
26. Barlow, R. C., and Li p i n s ki , J. J. , AM-89-17, NPRA Annual
Meeting, March 19-21, 1989, San Francisco, CA.
27. Teran, C. K., AM-88-70, NPRA Annual Meeting, March 20-22,
1988, San Antonio, TX.
28. Oc c el l i , M. L., i n "Fl u i d Cat al y t i c Cracking: Role i n Modern
Refining," ACS Sympsoium Series, V ol . 375: M. L. Oc c el l i ,
Ed., ACS, Washington, D. C., p. 162 (1989).
29. Oc c el l i , M. L. and Stencel, J. M. i n "Fl u i d Cat al y t i c
Cracking: Role i n Modern Refining," ACS Sympsoium Series,
V ol . 375: M. L. Oc c el l i , Ed., ACS, Washington, D. C., p. 195
(1989).

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11. BOHMER ET AL. FCC Metals Passivation 197
30. Oc c el l i , M. L. and Stencel, J. M. i n "Zeol i t es as Cataly sts,
Sorb ents and Detergent Builders." H. O. Karge and J. Weitkamp
Eds.; El s ev i er, p. 127 (1989).
31. Oc c el l i , M. L. and Stencel, J. M. i n "Zeol i t es . Facts,
Figures. Future." P. A. Jacob s, P. A. V anj arter, Eds.,
El s ev i er, Part B, p. 1311, 1989.
32. Let a, D. P., and Kugler, E. L., PREPRINTS, Div. of P et rol .
Chem., ACS, 33 (4), 636-641 (1988).
33. Woolery, O. L., Chin, A. A., Kirker, G. W., Huss, A. Jr. , and
Chester, A. W., PREPRINTS, Div. of P et rol . Chem., ACS, 33 (4),
648.
34. Wenig, R. W., White, M. G., and McKay, D. L., PREPRINTS, Div.
of P et rol . Chem., ACS, 28 (4), 909-919 (1983).
35. Mi l l er, R. F. and Pawloski, J. N., Paper 18b, AICHE., Spring
National Meeting, 1988, New Orleans, LA.
RECEIVED J u n e 8, 1990

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Chapter 12
Selectivity of Silica-Alumina Matrices
W-C. Cheng and K. Rajagopalan
Davison Chemical Division, W. R. Grace and Company-Conn.,
Columbia, MD 21044
Amorphous silica-aluminas containing 13, 27 and 59 wt%
A l2O 3 were prepared by precipitating alumina onto silica
gel, followed by hydrothermal treatment. These materials
were characterized by
27
Al NMR and ESCA and evaluated
in gas oil cracking. NMR revealed the presence of
tetrahedral, pentacoordinated and octahedral Al species in
the steamed SiO
2
- A l2O 3 samples with 27 and 13% A l2O 3.
The sample containing 59% A l2O 3, however, showed the
presence of only tetrahedral and octahedral Al species and
a 3-fold enrichment of Al at the surface. In gas oil cracking,
the activity of the catalyst per unit surface area increased
with increasing A l2O 3 content. NMR analysis indicated
that different types of Al species (eg., tetrahedral,
octahedral) played a role in gas oil cracking. The catalysts
with 13 and 27% A l2O 3 showed equivalent selectivity
while the catalyst with 59% A l2O 3 yielded higher coke, H
2
,
gasoline and LCO and lower C
3
and C
4
olefins at constant
conversion. The differences in activity and selectivity can
be attributed to increase in acid site density with increase in
alumina content of these catalysts.
Commercial fluid cracking catalysts are comprised of faujasite zeolite
dispersed in an inorganic mixed oxide matrix (1). X-ray amorphous silica-
aluminas are generally used as matrix components. Cracking of large
molecules present in a resid feed is limited by diffusion within a zeolite
crystallite. As a result, the amorphous silica-alumina matrix plays a major
role in cracking of these feed components (2). Cracking activity of
amorphous silica-alumina is related to its acidity (3). Acidity and
hydrocarbon cracking activity of amorphous silica-alumina catalysts of
varying composition and preparation methods have been reported (4 - 7).
Hydrothermal pretreatment of cracking catalysts has been employed as a
0097-6156/91A)452-0198$06.00/0

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12. CHENG AND RAJAGOPALAN Selectivity of Silica-Alumina Matrices 199
method to simulate aging in a commercial FCC unit (1). The objective of
this work is to determine gas oil cracking activity and selectivity for silica-
aluminas of varying composition. Hydrothermal pretreatment under
varying conditions was employed to generate catalysts of the same
composition with varying surface area. NMR and ESC A characterization of
the silica-aluminas were employed to elucidate the nature of active site for
gas oil cracking and determine catalyst structural properties that influence
selectivity.
Experimental Methods
Amorphous silica-alumina catalysts of varying composition (13 to 59 wt%
A I 2O 3) were prepared following the method described by Magee and Blazek
(8). Catalysts are designated by their alumina content as SA-13, SA-27 and
SA-59. The catalysts were washed free of soluble salts and spray dried.
Properties of the fresh catalysts are described in Table I. Catalysts were
hydrothermally pretreated at 1090K with 100% steam for varying periods
(2 to 16 hours). The pretreated catalysts were characterized by ESCA and
solid state NMR. ESCA analyses were carried out on a PHI 5400 XPS with a
Mg Ka X-ray source. The surface Al/Si was taken as the ratio of the peak
areas of the Al 2P and Si 2P peaks. Solid state
27
Al NMR analyses were
performed using a Bruker AM-400 spectrometer (
27
A1 frequency, 104.25
MHz). About 1000 scans were accumulated before Fourier transformation.
A line broadening of 100 Hz was used to eliminate the high frequency noise
without affecting peak widths. A 2 (is pulse (10 degree) was used with a
repetition time of 0.1 s between pulses. Chemical shift was referenced to
hexaquo aluminum ion. Solid state
29
Si NMR was carried out on a Bruker
MSL-200 spectrometer (
29
Si frequency, 39.76 MHz). An average of 1600
scans were collected. A line broadening of 50 Hz was used. Chemical shift
was referenced to tetramethylsilane. In all experiments, the samples were
equilibrated with a 50% relative humidity atmosphere for 16 hours and
spun at the magic angle at a frequency between 4-8 kHz.
Table I: Properties of Catalysts
Description : SA-13 SA-27 SA-59
wt% Na20 : .08 .04 .02
wt%S04 : .07 .16 .70
wt% A I 2O 3 : 12.7 27.1 58.6
BET Surface AreaHm^-
1
)
: 417 320 504
'Measured after activating the catalyst for 3 hours at 810K.

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200
A fixed bed reactor described by ASTM Method No. D3907 was employed
for catalytic testing. A sour, imported heavy gas oil with properties
described in Table II was used as the feedstock. Experiments were carried
out at a reactor temperature of 800K and catalyst residence time (9) of 30
seconds. Liquid and gaseous products were analyzed with gas
chromatographs. Carbonaceous deposit on the catalyst was analyzed by
Carbon Determinator WR-12 (Leco Corp., St. Joseph, MI). The Weight
Hourly Space Velocity (WHSV) was varied at constant catalyst contact time
to generate selectivity data of various products as a function of conversion.
For certain experiments, conversion was also varied by varying the catalyst
pretreatment conditions.
NMR and ESCA Characterization. Increasing the duration of
hydrothermal pretreatment reduced the surface area of the silica-alumina
catalysts (Figure 1). By varying the duration of pretreatment, catalysts of
varying surface area were obtained for characterization and evaluation.
Twelve catalysts of varying composition and surface area were analyzed
(Table HI). For the purpose of illustration,
27
A1 and
29
Si NMR spectra of
three of those catalysts are shown as Figures 2 and 3.
27
Al NMR analyses
(Figure 2) indicated the presence of three lines for the pretreated SA-13 and
SA-27 catalysts. The approximate chemical shift values for the lines were 0,
30 and 60 ppm. These lines were attributed to octahedral, pentacoordinated
and tetrahedral Al respectively (10). The SA-59 catalyst exhibited only two
Table II: Properties of Sour, Imported Heavy Gas Oil
API gravity at 16C
Sulfur (wt%)
Nitrogen (wt%)
Conradson Carbon (wt%)
Aniline Point (C)
K Factor
D-1160 (C)
IBP
22.5
2.6
.086
.25
73
11.6
217
307
324
343
382
423
472
500
524
5
10
20
40
60
80
90
95

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300
STEAMING TIME AT 1090 K/h
Figure 1. Effect of the time of pretreatment on surface area of catalysts.
A SA-13; O SA-27; SA-59

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lines near 70 ppm and 0 ppm (Figure 2). The chemical shift of about 70 ppm
observed in SA-59 is characteristic of tetrahedral Al observed in y- AI2O3
(11), indicative of Al-O-Al species, while the chemical shift of about 60 ppm
observed in SA-13 and SA-27 is characteristic of tetrahedral Al present in
zeolites, indicative of Al-O-Si species. These results imply that the
pentacoordinated Al is not present in the pretreated SA-59 catalyst.
Integrated line intensities for the NMR peaks for the catalysts after various
pretreatments are summarized in Table EI. These intensities are designed to
be a qualitative measure of changes in the type of Al species as a function of
composition and pretreatment. The results indicate that the distribution of
Al species in SA-13 and SA-27 catalysts changed significantly with changes
in pretreatment conditions. For example, increasing the duration of
hydrothermal treatment of SA-13 increased pentacoordinated Al at the
expense of tetrahedral Al. However, the surface composition of the
catalysts, as measured by ESCA, did not change significantly with changes
in pretreatment conditions.
Table EI: Characterization of Steamed Silica-Alumina Catalysts
Relative Intensities -
27
A1 NMR
ESCA
Description Al/Si Tetrahedral Pentacoordinated Octahedral
SA-13-2hrs. .17 .67 .06 .27
SA-13-4hrs. .18 .33 .31 .36
SA-13-8 hrs. .19 .32 .41 .27
SA-27-2hrs. .68 .35 .42 .23
SA-27-4hrs. .67 .33 .39 .28
SA-27-8 hrs. .75 .36 .37 .27
SA-59-2hrs. 4.5 .31 0 .69
SA-59-4hrs. 4.2 .27 0 .73
SA-59-8hrs. 4.6 .29 0 .71
The ^Si NMR Spectra (Figure 3) for SA-13 and SA-27 exhibited a broad
peak at a chemical shift of - 110 ppm, indicative of silicon species with zero
nearest Al neighbors, Si (OA1)
0
(12). Shoulders at a chemical shift of 100 to
105ppm suggest that a small amount of SHOAl^ species are also present.
The SA-59 sample, exhibited the peak at 110 ppm and several other broad
peaks up to a chemical shift of 82 ppm, suggesting that this sample
contained the full range of structures from Si(OAl)
0
to Si(OAl)
4
. The higher
alumina content of SA-59 apparently resulted in the presence of significant
concentrations of Si(OAl)
2
, Si(OAl)
3
and Si(OAl)
4
species.

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400 200 0 -200
CHEMI CAL SHIFT/ppm
Figure 2.
27
Al NMR spectra for hydrothermally pretreated (1090 K)
catalysts, SA-13 (above), SA-27 (middle) and SA-55 (below).

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12. CHENG AND RAJAGOPALAN Selectivity ofSilica-Alumina Matrices 205
Activity per Unit Surface Area for Gas Oil Cracking. A second order kinetic
conversion parameter (conversion +100 - conversion) was used (13) to
monitor gas oil cracking activity. The activity relationship as a function of
surface area and catalyst composition is described in Figure 4. As expected,
activity increased linearly with surface area. Activity per unit surface area
depended on composition and increased with increasing alumina content.
A catalyst with 27 wt% A I 2O 3 was more active for cumene cracking than a
catalyst with 13 wt% A I 2O 3 (6). An activity maximum at 30 wt% A I 2O 3 was
reported with thermally pretreated, cogelled silica-alumina catalysts for
n-octane cracking and propylene polymerization (4). Propylene
polymerization and n-octane cracking activity declined at higher alumina
content. In the current work with hydrothermally pretreated catalysts, we
observe the highest gas oil cracking activity per unit surface area at the
highest (59 wt%) alumina content that was examined. Differences in
catalyst preparation methods between the current and previous (4) work
(cogellation or impregnation), could have influenced the activity -
composition relationship.
For a given composition, when the catalyst surface area was varied by
varying the pretreatment conditions, the distribution of Al species within
the catalyst (tetrahedral, pentacoordinated, octahedral) varied significantly
(Table HI) without a significant change in activity per unit surface area
(Figure 4). Cracking activity in amorphous silica-alumina has been
attributed to tetrahedrally coordinated Al (14). The above NMR and activity
results indicate that activity does not correlate with concentration of Al
species of any particular coordination. This implies that Al that is not
tetrahedrally coordinated in the catalyst also plays a role in gas oil cracking.
Effect of Composition and Pretreatment on Coke and H 2 Selectivity. We
examined the effect of catalyst composition and pretreatment on the
selectivity for coke and H2. Results (Figures 5 and 6) indicate higher yields
of coke and H 2 at constant conversion for SA-59 relative to catalysts with
lower alumina content. Pretreatment conditions influenced coke, H 2 yields
indirectly by influencing surface area and gas oil conversion. Thus, coke
and H 2 selectivity was not influenced by pretreatment conditions. We
conclude that coke and H 2 selectivity does not correlate with the
concentration of Al species of a particular coordination (eg., tetrahedral).
The activity per unit surface area as well as selectivity for coke and H 2
were higher for SA-59 relative to catalysts of lower alumina content. Coke
selectivity of various Y-faujasite catalysts has been related to density of acid
sites (13). Perhaps the density of acid sites per unit surface area in these
amorphous silica-alumina catalysts increase with A I 2O 3 concentration. The
higher density of sites in SA-59 can explain its higher activity per unit
surface area as well as higher coke yields at constant conversion. Increasing
site density in faujasite catalyst resulted in lower selectivity for light olefins
(eg., butylene) and higher selectivity for gasoline (15). Hence, we examined
the detailed selectivity for all the cracked products with the amorphous
silica-alumina catalysts.

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206
z
o
55
oc
Ul
>
z
o
o
o
UJ
z
5
2.0
1.5
1.0
0.5
0.0

I I I 1 I 1 1 I i i i i i i
100
200
BET SURFACE AREA/m
2
g'
1
3 00
Figure 4. Activity of catalysts of varying surface area. Surface area was
varied by varying the duration of hydrothermal pretreatment.
A SA-13; SA-27; 0 SA-59
0.25
40 50
WT% CONVERSION
70
Figure 5. Hydrogen selectivity of catalysts. Conversion was varied by
varying the duration of hydrothermal pretreatment
A SA-13; SA-27; 0 SA-59

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KINETIC CONVERSION
Figure 6. Coke selectivity of catalysts. Conversion was varied by varying
the duration of hydrothermal pretreatment.
ASA-13; SA-27; OSA-59
Product Distribution as a Function of Composition. Pretreatment
conditions for the catalysts of varying composition were adjusted to achieve
catalysts of comparable activity. Thus, the more active SA-59 catalyst was
pretreated longer (16 hrs.) than the less active SA-13 catalyst (2 hrs.). This
was considered acceptable as results reported earlier indicate that activity
per unit surface area and coke, H 2 selectivity are not influenced by the
pretreatment conditions. Gas oil conversion was varied by varying the
space velocity. Results summarized in Figures 7 and 8 indicate that SA-59
yielded more coke, H 2, gasoline and light cycle oil (LCO) at constant
conversion than SA-13 and SA-27. SA-13 and SA-27 were more selective for
propylenes and butylenes relative to SA-59. Selectivity for C 2-
hydrocarbons of all the catalysts were equivalent. The selectivity of SA-59
for gasoline at the expense of propylenes and butylenes is consistent with
the hypothesis of higher acid site density in SA-59. With high acid site
density bimolecular hydrogen transfer reactions compete with unimolecular
cracking reactions (15) resulting in increased yield of intermediate cracked
products like gasoline and LCO at the expense of fully cracked products like
propylenes and butylenes. The high site density also favors bimolecular
reactions that facilitate formation of coke precursors (13).
Conclusions
The distribution of Al species of varying coordination (tetrahedral,
pentacoordinated and octahedral) can be influenced by changing the
conditions of hydrothermal pretreatment of amorphous silica-alumina
catalysts. However, for a given composition, activity per unit surface area
and selectivity were independent of pretreatment conditions. Thus, gas oil
cracking activity and selectivity in amorphous silica-alumina cannot be

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ascribed to Al species of a particular coordination (eg., tetrahedral). Al that
is not tetrahedrally coordinated in the catalyst also plays a role in gas oil
cracking. Activity per unit surface area and selectivity for the production
coke, gasoline, LCO and light olefins were influenced by the composition
(alumina content) of the catalyst. The activity and selectivity results can be
explained by suggesting that the catalyst with the highest alumina content
(SA-59) has the highest density of acid sites. Higher site density resulted in
increased selectivity for gasoline, LCO and coke at the expense of light (C3,
C4) olefins. The selectivity trends are consistent with reported effects of site
density on selectivity in faujasite.
2 3 4 5
CATAL YST/ OI L
UJ
82
0 >
0
n -
40 50 60 70
WT% CONVERSI ON
0.3
40 50 60 70
WT% CONVERSI ON

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12. CHENG AND RAJAGOPALAN Selectivity ofSilica-Alumina Matrices
. o 40,
209
w 35
O
CO
30
C?25
40 50 60
WT% CONVERSI ON
70
40 50 60 70
WT% CONVERSI ON
Figure 7. Activity and selectivity of hydrothermally pretreated (1090K)
catalysts. Conversion was varied by varying weight hourly
space velocity.
ASA-13 (2 hrs.); DSA-27 (8 hrs.); OSA-59 (16 hrs.)
o
0
<
D
> D
40 50 60 70
WT% CONVERSI ON
(Figur e continued)

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* 8
<
AO
0
_ Y
40 50 60 70
WT% CONVERSI ON
O
0
A D
0
b.
40 50 60 70
WT% CONVERSI ON
0
J*
40 50 60 70
WT% CONVERSI ON
0
0
0
A
40 50 60
WT% CONVERSI ON
70

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h
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2
CO
LU
H
3
C

CO
<
A
40 50 60
WT% CONVERSI ON
70
Figure 8. Light hydrocarbon selectivity of hydrothermally pretreated
(1090K) catalysts. Conversion was varied by varying weight
hourly space velocity.
ASA-13 (2 hrs.); SA-27 (8 hrs.); 0 SA-59 (16 hrs.)
Acknowledgments
The authors are grateful to M. P. Shatlock for the solid state NMR spectra,
B. J. Rees for the ESCA work and to the Davison Chemical Division of
W. R. Grace & Co.-Conn. for permission to publish this work.
Literature Cited
1. Venuto, P. B.; Habib, Jr., . T. Fluid Catalytic Cracking with zeolite
Catalysts; Marcel Dekker, Inc.: New York, 1979.
2. Young, G. W.; Rajagopalan, K. Ind. Eng. Chem. Proc. Pes. Dev. 1985,
24,995.
3. Tamele, M. W. Disc. Faraday. Soc. 1950, 8, 270.
4. Holm, V. C. F.; Clark, A. T. Catal. 1963, 2, 16.
5. Holm, V. C. F; Baily, G. C.; Clark, A. J. Phys. Chem. 1959, 63, 129.
6. Marczewski, M.; Wojciechowski, . W. Can. T. Chem. Eng. 1982, 60,
617.
7. Murrell, L. L.; Dispenziere, N. C. J. Catal. 1989, 117, 275.
8. Magee, J. S.; Blazek, J. J. Preparation and Performance of Zeolite
Cracking Catalysts in "Zeolite Chemistry and Catalysis" J. A. Rabo,
Ed. ACS Monograph, ACS, Washington, D.C. 1976, 171, 615.
9. Weekman, Jr., V. W. Ind. Eng. Chem. Proc. Pes. Dev. 1968, 7, 90.
10. Gilson, J-P.; Edwards, G. C; Peters, A. W.; Rajagopalan, K.;
Wormsbecher, R. F.; Roberie, T. G.; Shatlock, M. P. J. Chem. Soc.
Chem. Comm. 1987, 91.
11. John, C. S.; Alma, N. C. M. ; Hays, G. R. Appl. Catal. 1983,6,341.
12. Klinowski, J.; Thomas, J. M. ; Fyfe, C. .; Hartman, J. S. J. Phys. Chem.
1981,85,2590.
13. Rajagopalan, K.; Peters, A. W. T. Catal. 1987, 106, 410.
14. Thomas, C. L. Ind. Eng. Chem. 1949, 41, 2564.
15. Pine, L. .; Maher, P. J.; Wachter, W. A. J Catal. 1984, 85, 466.

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5
2
.
c
h
0
1
2
Chapter 13
Solid-Solid Reaction Between Y-Zeolite
and Vanadium Pentoxide
C. Marchal, J. Thoret, M. Gruia, C. Dormieux-Morin, and J. Fraissard
Laboratoire de Chimie des Surfaces, associ au Centre National
de la Recherche Scientifique, URA 870, Universit Pierre et Marie Curie,
4 Place Jussieu, 75252 Cedex 05, Paris, France
X-ray diffractometry, spectrometric techniques (
29
Si high-resolution
NMR, adsorbed

129Xe NMR, and electron paramagnetic resonance),
and transmission electron microscopy (TEM) have been used to
study solid-state reactions occurring between NaY zeolite and V
2
O
5
at 700 K. When the ratio R (V atom number/[Al + Si] atom
number) is 0.2, the zeolite lattice collapses. However, when R ~
0.05, the lattice remains. The interaction is interpreted in terms of
sodium vanadate (containing VVand V
IV
atoms) formation.
Zeolite modifications have been the subject of extensive studies. Some
research deals with the replacement of lattice silicon or aluminum by
another element (18). The motivation for such studies is that, even for a
low substitution ratio, the modified zeolites would acquire specific catalytic
properties. In fact, the location of the heteroatoms is generally uncertain, a
fact bringing to question whether the heteroatoms really enter the lattice or
lie in cavities or channels to generate compounds of potential interest to
industries.
In his monograph (9), Rabo reported the first studies of solid-state
reactions between zeolites, mainly Y zeolite, and some salts. These studies
revealed either ion exchange or more or less reversible occlusion of the
salt. In cases of occlusion, the salt anion (halide, nitrate, or oxygenated
chlorine anions) was usually located in sodalite cavities.
Recently, Karge et al. reported results of solid-state ion exchange
between alkaline chlorides and HZSM-5 (or NH
4
ZSM-5) (10) and between
alkaline earth chlorides and mordenite (77). They used IR spectroscopy (to
monitor OH groups), thermogravimetric analysis, titration of the evolved
gases, and mass spectrometry associated with temperature-programmed gas
evolution. The mass spectrometric technique enabled them to distinguish
between low- and high-temperature exchange reactions. Subsequently, they
0097-6156/91/0452-0212$06.00/0

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13. MARCHAL ET AL. Reaction Between Y-Zeolite and Vanadium Pentoxide 213
studied the solid-state interaction of HZSM-5 with several oxides (MnO,
Cu
2
0, CuO, and NiO) and chlorides of the same metals (72). The degrees
of exchange of zeolite protons with the oxides were considerably lower than
those for the corresponding chlorides.
Kucherov and Slinkin reported solid-state reactions of H-mordenite and
HZSM-5 zeolites with metallic oxides such as CuO (73), CÔ-, Mo0
3
, and
V
2
0
5
(14-17). The resulting samples were studied by EPR (electron
paramagnetic resonance) spectrometry. The authors have shown that the
metal cations migrate to cationic sites, where they are coordinately unsa-
turated.
When V
2
O
s
is used, vanadyl ions (V0
2+
) that are formed interact
strongly with lattice aluminum atoms located in acidic site vacancies of the
ZSM-5 lattice (14, 16).
In this chapter, we report the results of some solid-state experiments
on NaY zeolite and vanadium pentoxide, V
2
0
5
(18).
Experimental Procedures
NaY zeolite (LZY-52 from Union Carbide Corporation) and V-O^ (from
Prolabo) were used. Mixtures were prepared by using ratios calculated as
follows
V atom number
R =
(Al + Si) atom number
for the same NaY zeolite unit (for example, the unit cell).
Samples weighing 2 g were prepared each time. The samples were
ground by hand in an agate mortar for 15 min and then heated in air (at
150 K/h) in a refractory nacelle to 690-750 K. The materials were kept at
this temperature for 16 h. The samples were then allowed to remain at
ambient temperature in air to rehydrate freely.
X-ray diffractograms were obtained with a Philips NP 760 apparatus
using the K
a
radiation of cobalt or copper. The value of the cubic-unit-cell
parameter was determinated from an internal silicon standard.
The pretreatment temperature of the sample submitted to xenon
adsorption and NMR experiments was low enough (393 K) to prevent any
hydrolysis. Evacuation to 10"
4
torr ( 1 torr = 133.322 Pa) for 15 h at this
temperature ensures the elimination of most of the water of hydration.
Moreover, GeWon et al. (79) showed that when NaY is less than 15%
hydrated the remaining water molecules are in the sodalite cages. Such a
small amount of water cannot affect xenon adsorption, which occurs only in
the supercages.
Measurements of xenon gas adsorption isotherms were performed at
temperatures between 273 and 299.5 K (this latter temperature being that
of the
129
Xe NMR probe).

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214 FLUID CATALYTIC CRACKING : CONCEPTS IN CATALYST DESIGN
129
X e NMR experiments were performed according to previously
described methods (19) on a Bruker CXP 100 apparatus at 24.3 MHz. The
chemical shift (6) of adsorbed xenon is given relative to the value for gase-
ous
129
X e extrapolated to zero pressure.
29
Si magic-angle-spinning (MAS) solid-state NMR spectra were
obtained with a Bruker MSL 400 apparatus at 79.5 MHz. The Si/Al ratios
were calculated by the usual method (20) after simulation of the experimen-
tal spectra.
EPR spectra were obtained with a Varian CSE 109 apparatus at 9.277
GHz. The g reference value was 2.0037 for DP. Commercial NaY zeolite
could not be used because it contains too much iron, and so the experi-
ments were performed with a noncommercial zeolite containing only 28
ppm of iron.
TEM results were collected on a Jeol JEM 100 CXII high-resolution
apparatus with an acceleration voltage of 100 kV. The samples were
prepared on a copper grid from an aqueous suspension. The magnification
varied from 3 l( r to 9 10
5
.
The X-ray spectra of the heated samples (Figures 1 and 2 and Tables I and
II) show different results depending on R.For samples with R < 0.05, the
spectrum contains the characteristic lines of the NaY zeolite and no addi-
tional lines. In particular, no lines characteristic of V
2
0
5
are observed. The
cubic-unit-cell parameter rises from 2.4639 0.0005 nm for NaY zeolite to
2.4673 0.0015 nm for the sample with R= 0.05.
For 0.05 < R < 0.2, the structure of NaY zeolite is almost retained,
but some weak lines of ~0
5
can be identified in the spectrum.
For 0.2 < R < 0.6, the NaY zeolite lines are weak, and V
2
0
5
is still
visible; an amorphous phase exists, and the lines of the sodium vanadate
NaV^VÔ^ containing some tetravalent V
I V
are detected. When the
sample with = 0.6 is heated to 810 again for 9 h, a new sodium vana-
date, Na
5
V
v
1 1
V
I V
0
3 2
, crystallizes. X-ray spectroscopy clearly attests to a
chemical interaction between NaY zeolite and V
2
Oj.
The
29
Si NMR spectrum determined that the Si/Al ratio for NaY zeol-
ite is 2.45 0.12. Because of this experimental error, no significant modifi-
cation of this ratio can be observed for the sample with R = 0.05. For
treated samples containing an amorphous phase, the
29
Si NMR signal can-
not be used for two reasons: the resolution is reduced and the interpreta-
tion is not clear.
Because it would be difficult to compare isothermal adsorption results
for multiphase samples, the studies were restricted to NaY zeolite and the
compound for which R= 0.05. For both solids, the logarithmic representa-
tions for the relation log = / (log P), where is the number of
adsorbed xenon atoms per gram of dehydrated zeolite and is the xenon
equilibrium pressure, are straight lines. The line for the sample with R =
0.05 is below that of NaY zeolite (Figure 3). The log value extrapolated
to zero abscissa is smaller, and the slope is only a little larger.

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13. MARCHALETAL. Reaction Between Y-ZeolUe and Vanadium Pentoxide 215
Figure 1. X-ray data for NaY zeolite-V
2
O
s
: (a) sample with R =
0.05, (b) sample with R = 0.10, and (c) sample with R = 0.60. For all
samples, Co K
a
radiation was used. Symbols are defined as follows: *,
NaY zeolite; A, V
2
O
s
; and , NaV
6
0
15
.

Figure 2. X-Ray data for NaY zeolite-V
2
O
s
(R = 0.50, Cu K
a
radia-
tion). Symbols are defined as follows: *, NaY zeolite; A, V, 0
5
; and
NaV
6
0
15
.

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3
Tab le I. X-Ray data
Samples e In t en s i t i es
k,l<
A
>
NaY New V
2
0
5
phase
h , k, l h , k, l h , k, l
3. 57 TF 14.364 111
5. 89 m 8. 716 220
6. 91 m 7. 434 311
9. 07 F 5. 688 331
10. 86 m 4. 747 511
11. 84 F 4. 359 440
13. 26 m 3. 899 620
NaY-V
2
0
5
13. 74 F 3. 766 533
R=0.05 14. 58 f 3. 553 444
15. 02 f 3. 451 551
Co K 15. 74 F 3. 294 642
rad i at i on 16. 18 f 3. 209 731
17. 28 m 3. Oi l 733
17. 92 m 2. 906 660
18. 29 F 2. 850 555
18. 92 m 2. 758 840
19. 29 f 2. 706 911
19. 89 m 2. 630 664
3. . t>7
T F
14.364 111
5, ,91 m 8.687 220
6, .93 m 7.413 311
9. .10 F 5.655 331
10, .87 m 4.743 511
11, .84 F 4.358 440
12. .65 m 4.080
13, .27 m 3.896 620
NaY-V
2
0
5
13. .76 F 3.760 533
R=0.10 14, .57 f 3.555 444
15. .01 f 3.453 551
Co K
a
15.
rad i at i on 15.
.22 f 3.407 Co K
a
15.
rad i at i on 15. .75 F 3.295 642
16. .175 f 3.2108 731
17. .275 m 3.012 733
17 , .194 m 2.9038 660
18. .31 F 2.846 555
18. .93 m 2.757 840
19. .32 f 2.703 911
19. .90 m 2.627 664
001
101
110

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1
3
13. MARCHALETAL. Reaction Between Y-Zeolite and Vanadium Pentoxide 217
Tab le I I . X-Ray data
NaY New V
2
0
5
Samples 0 In t en s i t i es ^h
f
k
f
l^^ phase
h , k, l h , k, l h , k, l
6. .06 F 7. .292 002
6, .22 f 7. .013 102
7, .76 m 5. .702 331
9, .30 m 4, .762 511 200
10, .10 m 4, .371 440
11, .50 f 3. .867 104
11, .70 m 3, .76 533
12. .20 f 3. .643 004
12. .78 m 3. .482 202
13. .12 F 3. .391 111
NaY-V
2
0
5
13. .40 m 3. .305 642
R=0.5 13, .88 m 3, .20 111
14, .50 F 3, .07 104
Cu K
a
15,
rad i at i on l 5,
.25 F 2, .928 304 Cu K
a
15,
rad i at i on l 5, .55 m 2, .87 555
16, .17 f 2, .76 840
16, .37 m 2, .73 213
17 , .20 f 2 .63 113
17, .78 m 2, .52 106
18 .30 m 2 .45 311
18, .88 m 2 .38 404
19 .82 m 2 .271 311
20 .70 F 2 .18 106
5. .42 f 9.48 100
7. ,09 m 7.25 002
7. ,40 f 6,97 102
10 .86 f 4.75 200
11, .85 f 4.35
NaY-V
2
0
5
13 .30 f 3.88 104
R=0.6 14, .30 f 3.64 004
15 .00 f 3.46 202
Co K
a
15
rad i at i on 1 6
.35 m 3.38 111 Co K
a
15
rad i at i on 1 6 .25 f 3.25 111
16 .50 f 3.16 300
17 .02 m 3.06 104
17 .25 m 2.90 304
19 .25 m 2.72 213

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These results would mean that part of the zeolite lattice is damaged,
that some of the lattice cavities are blocked, or that the diameter of the
cavities is reduced.
One observes also the smaller absolute initial adsorption energy value
for the NaY zeolite-V
2
O
s
product (12.1 0.8 kJ/mol) compared with that
for NaY zeolite (18.8 0.2 kJ/mol) at 273-299.5 K.
The adsorbed-
129
Xe NMR spectrum allows us to choose between these
interpretations. The chemical shifts extrapolated to N = 0, (6), are 59.6
and 58.0 0.5 ppm for NaY zeolite and NaY zeolite-V
2
0
5
(R = 0.05),
respectively. Although the difference between these values is small, it may
be associated with a difference in the Na
+
concentration (19). However,
according to the relationship between S
&
and the pore free space (19), this
result proves that the size of cavities where xenon is adsorbed remains
unchanged. On the other hand, the variation of 6 with N (6 = f[N\) is rec-
tilinear, with good correlation coefficients (0.9998; 6) for NaY zeolite and
the sample with R = 0.05 (Figure 4).
The slope of these straight lines is significantly larger for the treated
zeolite (4.52 x 10"
20
ppm/atom) than for NaY zeolite (3.51 x 10"
20
ppm/atom). Because the xenon chemical shift change is due mainly to
XeXe interaction (79), the xenon density inside any supercage cavity must
be higher. Consequently, the number of these undamaged cavities per gram
is lower (much lower than would result from the small reduction of zeolite
mass because of the introduction of VÔ^.
r
^
n e
porosity of bulk V
2
0
5
would possibly give another distinct
129
Ae signal, which, however, is not
detected here.
The samples corresponding to R = 0.05 and 0.005 were studied by EPR
spectrometry. For both mixtures, an isotropic signal with a g value of 1.973
and a width (AH) of 75 gauss observed before heating indicates the usual
V
I V
impurities in V
2
0
5
crystals (27). The corresponding hyperfine structure
would be detected at low temperature. After being heated, the sample with
R = 0.05 gives a room-temperature spectrum showing a hyperfine structure
that is hardly visible because of strong interactions between the neighboring
tetravalent V atoms (less than 1 nm distant) (21). For this reason, a much
more dilute vanadium sample was needed.
Under the same experimental conditions, the spectrum of the sample
with R = 0.005 gave a better resolved hyperfine structure because of the
relative decrease in the dipolar interaction. The 77-K spectrum of this sam-
ple shows enhanced hyperfine structure (Figure 5). However, with nine
lines, the spectrum demonstrates that the V
I V
atoms have axial symmetry.
The spectrum, looks qualitatively like that obtained by Kucherov and Slin-
kin (16) (although less resolved) for the sample obtained by HZSM-5 and
V
2
0
5
interaction. The similarity confirms this symmetry, but a quantitative
interpretation of our spectrum would not give the same characteristic values
as Kucherov and Slinkin's. The vanadium atom environment is different.
This interpretation would require spectrum simulation and will not be given
in this discussion.

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220
N Xa adsorbed par g of anhydrous zaolita
Figure 4.
129
Xe chemical shift versus the number of adsorbed xenon
atoms per gram of anhydrous zeolite N.

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In conclusion, the EPR results demonstrate the presence of tetravalent
vanadium atoms in some sites of the sample. The V
I V
atoms could be
included in a new compound, as in the NaV^
v
V
, v
0
1 5
vanadate identified
in the sample by X-ray spectroscopy. They could also interact with the zeol-
ite surface as reported for V
2
0
5
supported on silica or 7 alumina (22) and
titania surfaces (23).
TEM photographs of the modified zeolite with R = 0.05 have been stu-
died. The zeolitic lattice is visible at the beginning of the experiment, but
later on, it is destroyed by the electron beam (24). In some cases, crystals
with different morphologies appear with no zeolitic particles because they
are too large to be inserted in the zeolite lattice. They could contain part
or all of the vanadium atoms, which would then be outside the lattice.
Conclusions
NaY zeolite and V
2
0
5
react at temperatures as low as 700 K, although
both compounds are stable at this temperature. For low R values, the V
2
0
5
structure disappears, whereas that of the zeolite does not seem to be dam-
aged nor is the cavity size reduced. However some cavity entrances are
blocked by a compound containing vanadium atoms and, in particular, a
few tetravalent vanadium atoms. Some tetravalent vanadium atoms have
also been observed by Occelli and Stencel (25, 26) in much more complex
reaction mixtures.
We have not determined the number of V
I V
species. We assume that
they come from two distinct sources. Some of them may already be present
in the V
2
0^ samples (21). Most of them come from a reaction between
V~0
5
and Na
+
of NaY zeolite crystals giving vanadium bronze phases
(27-29) among; which two crystalline phases were identified: NaV
v
5
V
l v
0
1 5
and Na
5
V
v
1 1
Y
l v
0
3 2
.
We therefore propose the following simplified reaction process: V2p
5
reacts as an acidic medium with the zeolite to give sodium vanadates. For
R = 0.05, about 1.6 Na
+
of the 56 in the zeolite lattice unit would be used
to transform all VÔ^ into NaV
v
5
V
I V
Ojj. The small difference obtained
for the 6
S
values is in agreement with this process. The growth of the
hydrated zeolite cubic lattice parameter (0.14%) may be associated with two
phenomena: the change in the Na
+
content of the zeolite, these ions being
replaced by protons during the free rehydration, or Si
I V
-V
I V
substitution in
the zeolite framework. However, we have no experimental support for such
a substitution. When the R value is higher, the zeolite lattice is no longer
in electrostatic equilibrium, and partial breakdown occurs.
Literature Cited
1. Flaningen, E. M.; Lok, B. M.; Patton, R. L.; Wilson, S. T. In New
Developments in Zeolite Science and Technology; Studies in Surface Sci-
ence and Catalysis, Vol. 28; Proc. 7th Int. Zeolite Conf.; Murakami,
Y.; Iijima, A.; Ward, K. W., Eds.; Elsevier: Amsterdam, 1986; p 103.

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222
2. Guth, J. L.; Kessler, M.; Wey, R. In New Developments in Zeolite Sci-
ence and Technology; Studies in Surface Science and Catalysis, Vol. 28;
Proc. 7th Int. Zeolite Conf.; Murakami, Y.; Iijima, A.; Ward, K. W.,
Eds.; Elsevier: Amsterdam, 1986; p 121.
3. Coudurier, G.; Vdrine, J. C. In New Developments in Zeolite Science
and Technology; Studies in Surface Science and Catalysis, Vol. 28;
Proc. 7th Int. Zeolite Conf.; Murakami, Y.; Iijima, A.; Ward, K. W.,
4. Newsam, J. M.; Vaughan, D. E. W. In New Developments in Zeolite
Science and Technology; Studies in Surface Science and Catalysis, Vol.
28; Proc. 7th Int. Zeolite Conf.; Murakami, Y.; Iijima, A.; Ward, K.
W., Eds.; Elsevier: Amsterdam, 1986; p 457.
5. Inui, I.; Miyamoto, A.; Matsuda, H.; Nagata, H.; Makino, Y.; Fukuda,
K.; Okazumi F. In New Developments in Zeolite Science and Technol-
ogy; Studies in Surface Science and Catalysis, Vol. 28; Proc. 7th Int.
Zeolite Conf.; Murakami, Y.; Iijima, A.; Ward, K. W., Eds.; Elsevier:
Amsterdam, 1986; p 859.
6. Mostowicz, R.; Dabrowski, A. J.; Jabonski, J. M. In Zeolites: Facts,
Figures, Future; Studies in Surface Science and Catalysis, Vol. 49; Proc.
8th Int. Zeolite Conf.; Jacobs, P. A.; van Santen, R. A., Eds.; Elsevier:
7. Skeels, G. W., Flaningen, E. M. In Zeolites: Facts, Figures, Future; Stu-
dies in Surface Science and Catalysis, Vol. 49; Proc. 8th Int. Zeolite
Conf.; Jacobs, P. A.; van Santen, R. A., Eds.; Elsevier: Amsterdam,
1989; p 331.
8. Davies, M. E.; Montes, C.; Hathaway, P. E.; Garces, J. M. In Zeolites:
Facts, Figures, Future; Studies in Surface Science and Catalysis, Vol.
49; Proc. 8th Int. Zeolite Conf.; Jacobs, P. A.; van Santen, R. A.,
9. Rabo, J. A. In Zeolite Chemistry and Catalysis; Rabo, J. A., Ed.; ACS
Monograph 171; American Chemical Society: Washington, DC, 1976;
pp 332-349.
10. Beyer, H. K.; Karge, H. G.; Borbly, G. Zeolites 1988, 8, 89.
11. Karge, H. G.; Beyer, H. K.; Borbly, G. Catalysis Today 1988, 3, 41.
12. Wicherlova, B.; Beran, S.; Karge, H. G. In Zeolites for the Nineties:
Recent Research Reports; presented during the 8th Int. Zeolite Conf.,
Amsterdam, 1989; Jansen, J. C.; Moscou, L.; Post, M. F. M., Eds.;
13. Kucherov, A. V.; Slinkin, A. A. Zeolites 1986, 6, 175.
17. Kucherov, A. V.; Slinkin, A. A.; Beyer, G. K.; Borbly, G. In Zeolites
for the Nineties, Recent Research Reports; presented during the 8th Int.
Zeolite Conf., Amsterdam, 1989; Jansen, J. C.; Moscou, L.; Post, M.
F. M., Eds.; Amsterdam, 1989; p 89.

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h
0
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13. MARCHAL ET XL Reaction Between Y-Zeolite and Vanadium Pentoxide 223
18. Dormieux-Morin, C.; Fraissard, J.; Gruia, M.; Marchal, C.; Rafarahar-
imbola, J.; Thoret, J.; 4th Meeting of the French Zeolite Group
(Eveux, France), 1988.
19. Fraissard, J.; Ito, T. Zeolites 1988, 8, 350 and references therein.
20. Engelhardt, G.; Lohse, U.; Lippma, E.; Tarmak, M.; Mgi, M. Z.
Anorg. Allg. Cliem. 1981, 482, 49.
21. Gillis, E.; Boesman, E. Phys. Status Solidi 1966, 14, 337.
22. Taouk, M. B. Ph. D. Thesis, Lille-Flandre-Artois University, France,
1988.
23. Jammul, N. Ph. D. Thesis, Pierre and Marie Curie University, Paris,
1989.
24. Bursill, L. .; Lodge, . .; Thomas, J. M. Nature (London) 1980,
286, 111.
25. Occelli, M. L.; Stencel, J. M. In Zeolites: Facts, Figures, Future; Studies
in Surface Science and Catalysis, Vol. 49; Proc. 8th Int. Zeolite Conf.;
Jacobs, P. .; van Santen, R. ., Eds.; Elsevier: Amsterdam, 1989;
1311.
26. Occelli, M. L.; Stencel, J. M. In Zeolites as Catalysts, Sorbents, and
Detergent Builders; Studies in Surface Science and Technology, Vol. 46;
Applications and Innovations, proceedings of an international sympo-
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27. Hardy, .; Galy, J.; Casalot, .; Pouchard, M. Bul l . Soc. Chim. Fr.
19654, 1056.
28. Perlstein, J.; Sienko, M. J. J. Chem. Phys. 1968, 48, 174.
29. Chakrabarty, D. K.; Dipak G.; Bismas, A. B. J. Mater. Sci 1976, 11,
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Chapter 14
Luminescence as a Probe of Metal Effects
in Fluidized Cracking Catalysts
L. K. Kurihara
1
, M. L. Occelli
2
, and S. L. Suib
1
1
Department of Chemistry, U-60, University of Connecticut,
Storrs, CT 06269-3060
2
Science and Technology Division, Unocal Corporation, Brea, CA 92621
Naphthenate, phthalocyanine and porphyrin ligands have been
used to represent vanadium contaminants in petroleum
feedstocks. Lanthanum HY zeolites were then V-loaded with
each of these species and the vanadium deposited was
passivated with tetraphenyl tin. Materials were studied by
luminescence emission and lifetime measurements after drying,
calcination and steam aging. Results suggest that
naphthenates are degraded most readily followed by
phthalocyanines and by porphyrins. Vanadium, after the
oxidative decomposition (in air) of naphthenate and
phthalocyanine ligands, forms V
2
O5. When vanadyl
mesotetraphenyl porphyrin was used to metal load LaY
crystals, V
2
O
5
formation was observed only after steam-aging.
Tin addition prevents (minimizes) vanadia formation
irrespective of the vanadium contaminant used. Luminescence
can detect V
2
O
5
formation when LRS (and XRD) cannot.
In fluid catalytic cracking, the high boiling components of crude oils are cracked
into gasoline and other light hydrocarbon fuels. The fluidized cracking of
petroleum fractions is still the main process for large-scale gasoline production and
it represents the main commercial use of zeolites. In fact, 95% of all refineries use
zeolite-containing catalysts in their fluidized cracking units. The savings in
petroleum resources in the U.S. through the use of zeolite catalysts over the last
15 years has been estimated at three billion barrels (1).
During the 1970's, the limited availability of crude oil led to the refining of heavier
fractions (resids); today, economic incentives have kept the petroleum engineer's
interest in cracking metal-contaminated crudes. When cracking resids, metals (such
as Ni, V, Cu, Fe) are continuously deposited on fluid cracking catalysts (FCC).
These metals can increase hydrogen and coke production in the cracking unit.
Furthermore, vanadium irreversibly destroys the zeolite thus eliminating the FCC
cracking activity. Techniques to avoid metal effects on FCC selectivities and
0097-6156/91/0452-0224$06.00A)

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14. KURIHARA ET AL. Luminescence as a Probe of Metal Effects 225
activity properties include varying process conditions (2-4), modifying the catalyst
composition (5-10), feed pretreatment (11,12,13,14), and the use of passivating
agents (15-21). Recently, it has been shown that at microactivity test conditions
addition of diluents capable of selectively sorbing metal contaminants from gas oils,
can form dual function cracking catalysts (DFCC) that retain most of their useful
cracking activity even in the presence of 1.0-1.5% V (22-25).
Modern spectroscopic techniques have been proven particularly useful in studying
metal-FCC interactions. In fact, Tin-119 Mossbauer spectroscopy has indicated
that Sn-V interactions take place only during steam-aging (26). EPR data have
shown that tin seems to promote the oxidation of VO
+ 2
to V
+ 5
during steam aging,
forming complexes that minimize V-zeolite interactions (27). Luminescence
emission and lifetime experiments have been used in determining the identity of
metal contaminants, quenching effects on rare earth zeolite Y emission and as
indicators of degradation of initial cracking activity (28). Luminescence can
provide useful information on the environment of the rare earth cations present
in the zeolite and it can be used to monitor V-migration between the zeolite and
the catalyst matrix (29).
It is the purpose of this paper to investigate and report the use of luminescence
techniques to follow the mechanism of metals deposition and passivation in a
zeolite when the three vanadium precursors shown in Figure 1 are used.
Experimental
Catalyst Preparation. Ammonium zeolite Y (Linde LZY-62) was exchanged with
La
3+
cations by stirring 3.0g of zeolite in 300 mL of 0.1 M La(NO
3
)
3
.6H
2
0 at room
temperature for 24 hours. After the exchange, the zeolite was washed with 3 x 25
ml of distilled deionized water to remove excess nitrates and dried in a 60C oven
for 20 hours. Vanadyl naphthenate (3%; K & Labs), Vanadyl phthalocyanine
(Kodak) and vanadyl mesotetraphenyl porphyrins were dissolved in a minimum
amount of hot benzene and added to LaY via incipient wetness. Excess benzene
was removed under reduced pressure. The metal loaded zeolite contained about
2.3% V
2
0
5
, 17.7% La
2
0
3
and a residual 1.76% Na
2
0. The LaY was loaded with
1 wt% Sn using a hot solution of tetraphenyl tin (Alfa) in benzene. Calcination
was at 540C for 10 hours in flowing air. Steam deactivation was performed at
730C for lOhr with 95% steam/5% nitrogen at a flow of 4mL liquid water per
hour.
Laser Raman spectroscopy (LRS) measurements were performed on a Spex
Ramalog 1403 spectrometer described in detail elsewhere (23). Powder diffraction
measurements were obtained with a Siemens D-500 diffractometer at a scan rate
of l/min using monochromatic Cu-Ka radiation.
Luminescence. Both excitation and emission spectra were recorded using a Spex
Fluorolog 202 B double monochromator fluorescence spectrometer. The
spectrometer was operated in the front face mode with bandpass slits of 1.0 nm.
Excitation spectra were recorded using a Rhodamine B solution as a reference to
correct for variations in the arc lamp intensity. All samples were sealed in
evacuated quartz tubes.

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H H
I I
H - C ^
C s
C '
C
^ C - H
i n i
H
"
C
^ c ^
C s
c ^
C
"
H
I I
H H
NAP
Figure 1. Organic precursors used in this study, NAP = naphthenate, PTC =
phthalocyanine, and POR = porphyrin.

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14. KURIHARA ET AL. Luminescence as a Probe of Metal Effects 2 11
Luminescence Lifetime. Luminescence lifetime measurements were made with a
PRA Model 3000 system. A block diagram of the system is given in Figure 2. The
excitation source is a hydrogen arc lamp operated at 30,000 Hz. Data were
collected on a Tracor-Northern multichannel analyzer and were transferred to a
Digital Corporation PDP-1103 computer for storage and fitting. Statistical analysis
was performed using the software package Decay 3.0 purchased from PRA
Corporation.
Results
With 1.29% V, the LaY crystals lose most (>80%) of their initial crystallinity,
Figure 3B. With 5.0% V, the steam aged LaY samples collapse and new phases
are formed, Figure 3A In the diffractogram shown in Figure 3A, reflections at
d = 3.41 A, 3.22A and 3.00A indicate the presence of monoclinic LaV0
4
. Additional
peaks at d = 23.8A and 17.9A have been attributed to the presence of smaller
amounts of tetregonal LaV0
4
. Some mullite (Al
6
Si
2
0
13
) is also present, Figure 3A
Raman results are shown in Figure 4. With 5.0% V a spectrum similar to the one
for unsupported LaV0
4
is obtained, Figure 4A At lower V-levels (1.29% V), a
non-descriptive spectrum with a broad and very weak band centered near 850 cm"
1
is seen; Figure 4B.
Emission spectra of vanadyl naphthenate on LaY after various treatments are
shown in Figure 5. The dried sample spectrum consists of a strong band centered
at 365nm, indicative of the naphthenate moiety, Figure 5a. After calcination, the
intensity of the naphthalene band is greatly reduced and a broad weak band begins
to appear in the 500-575nm region, Figure 5b. The hydrothermally treated sample
does not show the naphthalene band and the broad spectral band in the 500-575
region becomes dominant, Figure 5c. The effects of tin addition can be seen in
Figure 6. Tin treated (calcined or steamed) samples do not luminesce in the 400-
500 nm region.
Emission spectra of vanadyl mesotetraphenyl porphyrin on LaY, when excited at
310 nm, are shown in Figure 7. After calcination and hydrothermal treatment, the
porphyrin band in the 350 nm region is still present (Figures 7b and 7c); the
spectrum for the dried sample shows more fine structure in the 330-370 nm range,
Figure 7a. After calcination, some of the fine structure is lost and there is a slight
decrease in intensity of the spectral bands. In the dried and in the calcined
samples, evidence of metal free porphyrin is indicated by the broad band in the
390-475 nm region. The effects of tin addition are shown in Figure 8. The tin
loaded LaY sample exhibits, after calcination, a weak band at 370 nm. After steam
aging, fine structure appears in the 340-425nm region.
Vanadyl porphyrin on LaY, when excited at 468 nm, gives the spectra shown in
Figure 9. The dried and the calcined samples give similar spectra, Figures 9a-b.
The bands in the 640-750 nm range correspond to porphyrin and at liquid nitrogen
temperatures fine structure is seen in these bands, Figure 10. Steam-aged vanadyl
porphyrin does not luminesce in this region and the spectrum is dominated by a
broad band near 530 nm. Both the calcined and steam aged tin loaded samples
exhibit very weak spectra that are one quarter the magnitude of the samples free

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228
POWER
SUPPLY
FOR
FLASHLAMP
START
PMT
EXCITATION
FILTER
EMISSION
FILTER
100 MHZ
DISCRIMINATOR
CONSTANT
FRACTION
DISCRIMINATOf
STOP
PMT
DELAY
CABLE
TI ME- TO-
AMPLITUDE
MULTICHANNEL
ANALYZER
COMPUTER
AND
PLOTTER
Figure 2. Schematic diagram of a single-photon counting nanosecond
fluorometer.

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i 1 i i i i i i
300 500 700 900 1100
WAVENUMBERS (cm1)
Figure 4. Laser Raman spectra of LaHY crystals steam-aged in the
presence of: (A) 5% and (B) 1.2% vanadium.

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WAVELENGTH (nm)
Figure 5. Luminescence spectra for vanadyl naphthenate on LaY: (A)
before and (B) after calcination and (C) steam aging. The excitation
wavelength was 300 nm.
WAVELENGTH (nm)
Figure 6. Luminescence spectra of vanadyl naphthenate on LaY steam
aged: (A) without and (B) with tin addition. The excitation wavelength
was 300 nm.

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^50 400 450 500 550
WAVELENGTH (nm)
Figure 7. Luminescence spectra of vanadyl porphyrin on LaY: (A) before
and (B) after calcination and (C) after steam aging. Excitation wavelength
was set at 310 nm.
i i 1 1
350 400 450 500 550
WAVELENGTH (nm)
Figure 8. Luminescence spectra of tin loaded LaY at 77 K after vanadyl
porphyrin impregnation and calcination; (A) was taken before and (B)
after steam aging. The excitation wavelength was set at 300 nm.

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WAVELENGTH (nm)
Figure 9. Luminescence spectra of vanadyl porphyrin on LaY: (A) before
and (B) after calcination and (C) steam aging. Excitation wavelength was
set at 468 nm.
WAVELENGTH (nm)
Figure 10. Luminescence spectrum of calcined vanadyl porphyrin on LaY at 77K
with the excitation wavelength set at 468 nm.

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of tin, Figure 11. The calcined tin loaded LaY has a broad band centered near
540 nm; a shoulder in the 700 nm region suggests the presence of residual
porphyrin, Figure 11a. Porphyrin moieties are not present in hydrothermally
treated samples containing tin, Figure lib.
Vanadyl phthalocyanine freshly deposited on LaY shows a broad weak band at 450
nm, Figure 12a. Upon calcination more fine structure appears; steam aging
increases band intensity five-fold, however the shoulder at 415nm remains, Figure
12c. Tin addition decreases band intensity by a magnitude of four; nonetheless,
some of the fine structure is still present. The emission spectra of vanadyl
phthalocyanine, when the excitation is set at 400 nm, are shown in Figure 13. A
broad band centered at 470 nm dominates the spectra of the dried and calcined
phthalocyanine samples, Figure 13a. Upon calcination the band nearly doubles in
intensity, Figure 13b. Steam aging broadens this band. Tin addition results in a
very weak spectrum without luminescent behavior in the 500-575 nm region,
Figure 14. At 650-675nm, a new band begins to emerge.
For comparison purposes, the spectrum of LaV0
4
(excited at 330 nm) is given in
Fig. 15. The spectra for steam aged LaY crystals containing low (1.29%) V levels
is shown in Fig. 16. Luminescent lifetime data are given in Tables I and II. In
all cases there are two components, (T
t
and a T
2
), present. The T
2
species are very
short often exceeding limits of detection.
TABLE I. LUMINESCENCE LIFETIME DATA FOR LaY
V Precursor Treatment
l i I2
NAP Fresh 3.46 0.47 1.5
PTC Fresh 3.74 0.40 1.4
POR Fresh 4.85 0.17 1.1
NAP Calcined 4.86 0.85 1.2
PTC Calcined 5.71 0.31 1.1
POR Calcined 6.37 0.21 1.3
Vanadia Calcined 5.24 0.34 1.2
LaV0
4
Neat 2.16 0.85 1.3
Calcined = 540C, in air, 10 hr.
Steamed = 740C, 95% steam, 5% N
2
, 10 hr.
Tj and T
2
in nanoseconds.

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WAVELENGTH (nm)
Figure 11. Luminescence spectra of tin loaded LaY impregnated with
vanadyl porphyrin: (A) calcined and (B) steam aged. The excitation
wavelength was set at 468 nm.
WAVELENGTH (nm)
Figure 12. Luminescence spectra of vanadyl phthalocyanine on LaY: (A)

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KURIHARA ET AL. Luminescence as a Probe of Metal Effects
WAVELENGTH (nm)
Figure 13. Luminescence spectra of vanadyl phthalocyanine on LaY: (A)
o
g
J
1 . r-
d 500 600 700
WAVELENGTH (nm)
Figure 14. Luminescence spectra of vanadyl phthalocyanine on steam aged
LaY: (A) without and (B) with tin addition.

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236
Figure 16. Luminescence emission of steam aged LaY crystals loaded with
1.29% V. The excitation wavelength was 330 nm.

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TABLE II. LUMINESCENCE LIFETIME DATA FOR Sn
PASSIVATED SAMPLES
V Precursor Treatment
l i 22
NAP Sn, Fresh 4.01 0.57 l. l
PTC Sn, Fresh 3.12 0.59 0.9
POR Sn, Fresh 4.85 0.17 1.1
NAP Sn, Calcined 5.59 0.34 1.6
PTC Sn, Calcined 6.07 0.24 1.2
POR Sn, Calcined 7.50 0.07 1.5
NAP Sn, Steamed 6.37 0.46 1.2
PTC Sn, Steamed 2.94 0.04 1.3
POR Sn, Steamed 7.26 0.41 1.5
Calcined
Steamed
= 540C, in air, 10 hr.
= 740C, 95% steam, 5% N* 10 hr.
Discussion
In agreement with published results (25) steam-aging LaHY crystals containing
high (5.0%) V-levels caused a total collapse of the faujasite structure with
formation of LaV0
4
and some mullite (36,37), see Figure 3a. Vanadate formation
can be easily observed also by LRS, Figure 4a. At lower (1.29%) V-levels the
steam aged crystals retain some crystallinity; however V-compounds such as V
2
0
5
or LaV0
4
could not be observed either by XRD or LRS, see Figures 3b; 4b.
These compounds, in samples containing low concentrations of V, can be observed
by luminescence techniques.
The spectrum for LaY impregnated with vanadyl naphthenate shows a
characteristic band at 365nm that loses most of its intensity after calcination, Figs.
5a, 5b. This is not surprising since Pompe et al (30), using TGA/DTA data,have
shown that the oxidative decomposition of the vanadyl naphthenate is complete
at 500C. Electron paramagnetic resonance (EPR) studies have shown that
vanadium (after calcination) is stabilized mainly in the form of vanadyl (V0
2+
)
cations in the zeolite supercages (29).
The naphthenate band at 365 nm disappears after steam aging the V-loaded
(1.29%) catalysts and a broad band in the 450-575nm region is formed, Fig 5C;
both V
2
0
5
and LaV0
4
exhibit spectral bands in this region. In the present study,
V
2
0
5
formation has been ascertained by taking the luminescence spectrum at 77 K.
The presence of V
2
0
5
(together with EuV0
4
) has also been observed by Anderson
et al (29) after steam-aging vanadyl naphthenate on EuY crystals. Roozenboom

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238
et al (31) have shown that V
2
0
5
forms on the surface of Si0
2
and A1
2
0
3
. Iwamoto
et al. (32) and Anpo et al. (33) have reported the phosphorescence spectrum of
V
2
0
5
observed when vanadyl naphthenate was steam aged. The generation of a
V
2
0
5
phase on several supports (free of RE-ions) impregnated with vanadyl
naphthenates and steam aged has also been observed using Laser Raman
spectroscopy for V concentrations above 4% (22-25). Mauge et al (34), using
SEM, TEM and energy dispersive X-ray emission (EDX) have shown than when
LaY crystals are loaded with naphthenate, steaming induced a reaction between
the La
+ 3
ions and vanadium with formation of a LaV0
4
phase.
Spectral bands in the 500-575 nm region are quenched when the LaY zeolite is
loaded with 1% tin, suggesting that tin addition minimizes V
2
0
5
formation.
Mossbauer studies have indicated that tin is in the +4 state after calcination (26-
31); the reduction in intensity seen when comparing Figures 6a and 6b could be
due to the formation of V
+5
-0-Sn
+4
linkages (26).
After deposition, vanadyl porphyrin (like vanadyl naphthenate) covers the LaY
surface, Figs. 7-10. EPR results have indicated that, again, V in these samples is
in the +4 state. A similar conclusion was also reached by Roth et al (35) after
depositing vanadyl porphyrin on NdY crystals. FTIR results were reported (35)
that indicated loss of porphyrin structure after calcination. DTA data (35) were
used to show that the porphyrin moiety lost aromatic structure after heating in the
200-300C temperature range; vanadyl porphyrin fully decomposed in air below
500C (30). In LaY crystals, residual porphyrins are still present after calcination
at 540C, but totally disappear after steam aging; a broad band centered between
400-550 nm (attributed to V
2
0
5
) is observed, Fig. 7. In the presence of both Sn
and V, samples give a spectrum with weak bands in which neither porphyrins or
V
2
0
5
bands can be observed, Fig. 8.
Luminescence spectra in Fig. 9 show strong bands for the vanadyl mesotetraphenyl
porphyrin moiety after deposition and after calcination indicating little degradation
of the complex after thermal treatment. On steaming there is considerable loss of
band intensity between 640 and 750 nm. These bands (not seen in Figs. 7,8) are
now observable since the excitation wavelength used corresponds to direct
excitation of the porphyrin, Fig. 9. Luminescence data taken at 77 K for the
calcined vanadyl mesotetraphenyl porphyrin loaded LaY crystals show fine
structure of the porphyrin ring again indicating that little breakdown of this
complex had occurred, Fig. 10.
Spectra of tin loaded LaY containing vanadyl mesotetraphenyl porphyrin show a
significant decrease in luminescence intensity with respect to tin free samples after
calcination (27). These data suggest that tin deposition influences the emissive
properties of the porphyrin perhaps by quenching. It is not believed that Sn
deposition catalyzes the breakdown of the porphyrin. On steaming there is
significant intensity in the 550-750 nm region indicating that some porphyrin is still
present, Fig. lib.
The phthalocyanine band increases in intensity and acquires a shoulder near 420
nm on calcination, Fig 12. There is almost a ten-fold increase in band intensity
after steam aging, Fig 12c. In contrast to what is shown in Figs. 5 and 7, band

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intensity for vanadyl phthalocyanine increases after steam aging, Fig. 12. This
luminescence enhancement has been attributed to the phosphorescence of
benzene containing fragments resulting from the thermal degradation of the
phthalocyanine moiety, Fig. 12. The luminescence enhancement after calcination
could be due to self absorption effects. Vanadyl phthalocyanine appears to be less
stable than vanadyl mesotetraphenyl porphyrin complexes, Figs. 7, 12. These
results are consistent with bioinorganic literature data. When the excitation
wavelength is set at 400 nm (instead of 365 nm) a band at 470 nm appears, Figs
13a, 13b; this band broadens and shifts to near 530nm after steaming, Fig. 13c.
Spectra for calcined (or steamed) samples containing tin do not exhibit a band
near 470 nm; however, a peak in the 650-725nm region begins to appear, Fig. 14.
Loss of structure in the 520-550 nm region of the luminescence emission spectrum
is apparent after tin addition, Figs. 7-14. This vibrational structure is indicative of
V
2
0
5
and is inhibited by tin addition. On the other hand, samples containing both
Sn and V show quenched luminescence emission in the 520 - 550 nm region. These
data suggest that a V
2
0
5
-like environment is present in these materials which may
have tin incorporated into V
2
0
5
. This Sn-0-V species is amorphous and may be
responsible for V passivation in these LaY samples. Luminescence lifetime data
are in agreement with this suggestion. The luminescence emission spectra of
steamed samples containing both Sn and V show that a vanadium oxide-like
environment has been formed. The luminescence emission spectra of this species
do not have vibrational fine structure even when data are collected at liquid
nitrogen temperature indicating that V
2
0
5
itself is not present; a conclusion
supported also by lifetime data.
Luminescence lifetime behavior in all samples showed two species, Table 1. The
T
2
is very short, often exceeding the instrumental limits. In all cases the lifetimes
changed after calcination and steam aging suggesting the formation of different
vanadium species. The calcined samples have T
t
values that approach that of
calcined V-loaded LaY. Tin addition affects the lifetimes of the vanadium species,
Table 2. When the naphthenate was used as the precursor all the tin treated
samples exhibited higher T
t
values than tin-free samples. Steam aging the
porphyrin-containing samples changed T
1
by one half. When phthalocyanine was
used to load V, tin addition had little effect on the samples' T
t
values.
Unsupported LaV0
4
crystals have an emission band at 610 nm, Fig. 15. This band
is not observed in any V loaded LaY crystals. The emission of the vanadia-like
specie at 540 nm is so intense that it extends past 600 nm toward the red region,
Fig. 16. Thus the emission of any LaV0
4
formed when steam aging V-loaded LaY
could have been covered by the strong emission of the V
2
0
5
-like phase.
In conclusion, luminescence can be used as a probe for tracking V
2
0
s
formation
and for monitoring disappearance and changes in the state of the organic
precursor. The nature of the vanadium precursor controls the stage at which the
ligand leaves. Naphthenate is lost at much lower temperatures and treatment
times than porphyrin or phthalocyanine ligands. In all tin-free supports tested,
vanadia forms either during calcination (naphthenate, phthalocyanine) or steaming
(porphyrin). These data suggest that porphyrin precursors are most stable. In all
cases, tin addition results in reactions with vanadium with concomitant prevention
(or minimization) of V
2
0
5
formation.

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Luminescence is more sensitive than LRS and can detect the presence of V
2
0
5
in
V-loaded LaY crystals even at low (~1% V) levels. Luminescence lifetime
experiments at 610 nm will need to be performed with a more powerful light
source and with a monochromator placed between the sample and the detector in
order to observe LaV0
4
formation at low V concentrations. Such experiments are
now in progress in our laboratory.
Acknowledgments
Support for this research was from the National Science Foundation under the
Kinetics and Catalysis Program through grant CBT-08814974.
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25. Occelli, M. L. and Stencel, J. M. in "Proc. 8th IZA Meeting," Amsterdam,
The Netherlands (in press).
26. Anderson, M. W.; Occelli, M. L.; Suib, S. L.; J. Mol. Catal. (In press).
27. Anderson, M. W.; Occelli, M. L.; and Suib, S. L.; J. Catal., 112, 375 (1990).
28. Occelli, M. L.; Psaras, D.; Suib, S. L., J. Catal. 96, 336 (1986).
29. Anderson, M. W.; Occelli, M. L.; Suib, S. L. J. Catal. 1989,118, 31.
30. Pompe, R.; Jaras, S. and Vannenberg, N., Appl. Catal., 13, 171 (1984).
31. Roozenboom,F.; Mittelmeijer-Hazeleger, M. C.; Moulign, J. A; Mecima, J.;
deBeer, V. H. J.; Gellings, P. J. J. Phys. Chem. 1980, 84, 2783.
32. Iwamoto, M.; Furukawa, H.; Matsukami, K.; Tekenaka, T.; Kakawa, S. J.
Am. Chem. Soc. 1983, 105, 3719.
33. Anpo, M.; Tanahashi, I.; Kubokawa, Y. S. J. Phys. Chem. 1980, 84, 3440.
34. Mauge, F.; Courcelle, J. C.; Engelhard, Ph.; Gallezot, P. Grosmanging, J.
Proceedings of the 7th Int. Zeolite Conf. Murakami, Y.; Iijima, A. T.;
Word, J. W. Eds. 1986.
35. Marshall, C. L.; Delgass, W. N. J. Catal. 1987, 108, 214.
36. Yoshimura, M., and Sata, T., Bull. Chem. Soc. Japan 42, 3195 (1969).
37. Le Flem G., and Olazcuaga R., Bill. Soc. Chem. Fran. 2769 (1968).
RECEIVED August 28, 1990

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Chapter 15
Vanadium-Contaminated Aluminas
and Aluminosilicate Gels
51
V NMR Spectroscopic Characterization
P. S. Iyer
1
, H. Eckert
2
, M. L. Occelli
1
, and J. M. Stencel
3
1Science and Technology Division, Unocal Corporation, Brea, CA 92621
2
University of California, Santa Barbara, CA 93106
3
Center for Applied Energy Research, University of Kentucky,
Lexington, KY 40506
51
V wideline solid state NMR spectroscopy has been used
to differentiate between various vanadium (V
+5
) species
present on vanadium-loaded pseudo-boehmite and
aluminosilicate gels. The observed speciation has been
found to be sensitive to vanadium loadings and to hydro-
thermal and dehydration pre-treatments. Low loadings
(<2%V) result in the formation of 4-coordinate surface
species. Higher loadings (>2%V) favor 6-coordinate
vanadium species formation. Dehydration studies have
confirmed that hydrous species such as H
2
O and/or OH do
indeed participate in some of these 6-coordinate
environments. The relative amounts of 4- and
6-coordinate vanadium species is principally governed by
the support surface area retention after calcination and
steaming. The aluminosilicate gel, on the other hand,
responds to hydrothermal treatment by forming a new,
highly hydrated, V
2
O
5
-like phase, that has not been
identified before by NMR studies.
Recent s t ud i es at mi c r o ac t i v i t y t es t (MAT) c o n d i t i o n s have shown
t hat VO -Napht henat e decomposes on f l u i d i z ed c r ac k i n g c at al y s t s
(FCC) f or mi ng vanadi um s p ec i es t hat d ur i ng st eam agi ng al l ow i n t r a
p ar t i c l e t r an s f er of V t o occur (1- 3). Once on t he c at al y s t
s u r f ac e, V can d r amat i c al l y r ed uce c r ac k i ng ac t i v i t y by d ec r eas i ng
t he c r y s t a l l i n i t y of i t s c r ac k i ng c ent er s (t he z eo l i t e) . Mi gr at i ng
Note: Based in part on a paper presented at the 1989 Fall Meeting of the California
Catalysis Society, University of California at Los Angeles, Los Angeles, CA
0097-6156/91/0452-0242$06.00/0

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15. IYER ET A L . Vanadium-Contaminated Aluminas 243
vanadi um can be s el ec t i v el y sor bed and p as s i v at ed by ad d i ng t o t he
FCC a second p ar t i c l e cap abl e o f f or mi ng unr eac t i v e and heat s t abl e
vanadi um compounds (4-6). By p r ev ent i ng (or mi ni mi zi ng) vanadi um
fr om r eac hi ng t he FCC, i t has been p o s s i b l e t o gener at e dual
f u n c t i o n c r ac k i ng c at al y s t s (DFCC) mi xt ur es cap abl e o f r et ai n i n g
70-80% of t h ei r o r i g i n al c r ac k i ng ac t i v i t y even i n t he p r esence of
hi gh (1. 0-1. 5%) vanadi um l ev el s (7- 9). Vanadi um t r an s p o r t and t he
s el ec t i v e s o r p t i o n of vanadi um by a second p ar t i c l e (al umi na) has
r ec en t l y been obser ved by Kugl er and Let a (10) i n t h ei r SIMS
an al y s i s of eq u i l i b r i u m FCC fr om a US r ef i n er y . Vanad i um-al umi na
i n t er ac t i o n s have al s o been i n v es t i g at ed by XPS, Raman (4-6,11) and
V NMR (12) s p ec t r o s c o p y .
So l i d s t at e NMR of quad r up ol ar n uc l ei has become an
i n c r eas i n g l y p op ul ar t ool t o pr obe t he s t r u c t u r e o f met al oxi d e
s ur f ac e s p ec i es on c at al y s t s (12-17). Al t h o u g h
5
t h e V n u c l i d e has
f av o r abl e NMR c h ar ac t er i s t i c s , t he number^ o f V s o l i d s t at e NMR
ap p l i c at i o n s t o t he c h ar ac t er i z at i o n of V oxi d e s ur f ac e phases on
c at al y s t s has been somewhat l i mi t ed (12-15). Rec ent l y , ext ens i v e
s t ud i es o f c r y s t al 1g r ap h i c al l y wel l - d ef i n ed model compounds have
shown t hat t he an i s o t r o p i c V chemi cal s h i f t t ens or s obt ai ned fr om
s t at i c (wi d el i ne) NMR exper i ment s at hi gh f i e l d s t r engt hs (> 7 Jl
can d i s t i n g u i s h unambi guousl y bet ween f o ur - and s i x - c o o r d i n at e V
envi r onment s (12). These i n s i g h t s have hel ped t o c l a r i f y t he
s t r u c t u r al p r o p er t i es o f t he V s ur f ac e oxi d e phases p r esent on a
v ar i et y o f met al oxi d e sup p or t s (12). The p r esent st ud y ext end s
t h i s work t o t he hyd r at ed and d ehyd r at ed for ms of pseudo boehmi t e
and al u mi n o s i l i c at e g el s of t he t ype used i n p r ep ar i ng V- r es i s t an t
c r ac k i n g c at al y s t mi xt ur es (5).
Exper i ment al
Room t emper at ur e wi d el i ne and MAS s o l i d s t at e NMR measurement s were
c ar r i ed out usi ng a Gener al El ec t r i c GN-300 s p ec t r omet er , equi pped
wi t h an Exp l o r er hi gh speed d i g i t i z e r and a 7 mm mu l t i - n u c l ear
MAS-NMR pr obe ( z i r c o n i a s t at o r and s p i nner ) fr om Dot y Sc i e n t i f i c .
Ambi ent sampl es were s t ud i ed wi t h i n z i r c o n i a s p i n n er s , whi l e
d ehyd r at ed sampl es were s t ud i ed i n f l ame- s eal ed evacuat ed pyr ex
ampul es. The 90 p ul s e l engt h f o r l i q u i d V0C1- was measur ed t o be
7-8. 5 us. Sp ec t r a were t y p i c al l y obt ai ned usi r i g a si mp l e one- p ul s e
sequence (Bl och decay) usi ng a p ul s e l engt h o f 1 /i s and a p r e-
ac q u i s i t i o n d el ay of 10/xs wi t h a dwel l t i me o f 1-2/xs. Rel axat i on
d el ay s of 1 second were u s u al l y found s u f f i c i en t f o r q u an t i t at i v e
s i gnal d et ec t i o n i n al l t he sampl es. Al t hough t he use o f Bl och
d ecays wi l l r es u l t i n somewhat d i s t o r t ed l i nes h ap es wi t h more
accent uat ed v al l ey s bet ween peaks and s h o ul d er s , i t i s t he p r ef er r ed
met hod her e, s i n c e i t av oi d s c o mp l i c at i o ns ar i s i n g fr om v ar y i ng
d egr ees o f ex c i t at i o n s el ec t i v i t y t hat become i mpor t ant wi t h t he
l onger p ul s e l engt hs needed t o gener at e 90 and 180 p ul s es f o r s p i n
ec hoes . A l l chemi cal s h i f t s ar e r ep or t ed wi t h l i q u i d V0C1- as a
r ef er en c e.
Det ai l ed d es c r i p t i o n s of t he c at al y s t s ' p r o p er t i es as wel l as
d es c r i p t i o n s of t he method o f p r oced ur es used i n p r ep ar i ng
V-cont ami nat ed mat er i al s , has been gi v en el sewher e (18).

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Dehyd r at i on o f t he al umi na samp l es, p r i o r t o V NMR an al y s i s , was
per f or med f o r 22 hour s at ~200C under -10 t o r r p r es s u r e. The gel
sampl es were d ehyd r at ed at ~150
W
C f o r 4 hour s under t he same vacuum.
Res ul t s and Di s c us s i o n
NMR s p ec t r a o f quad r up ol ar nuc l ei ar e i nf l uenc ed by t he i n t er ac t i o n
of t he nuc l ear e l e c t r i c quad r upol e moment wi t h el ec t r o s t at i c f i e l d
gr ad i ent s gener at ed at t he nuc l ear s i t es by asymmet r i c el ec t r o n
d i s t r i b u t i o n s due t o chemi cal bond i ng. To a f i r s t or d er
ap p r oxi mat i on t he ener gy l ev el s of a s p i n s p l i t y i el d i n g 21
t r an s i t i o n s ; I i %,t he nuc l ear spi n-quant um number. For h al f - i n t eg er
n uc l ei such as V (1=7/2), t he c ent r al +1/2 t o - 1/ 2 t r an s i t i o n
r emai ns un af f ec t ed . Pr ev i ous
5
s t u d i es (12) have shown t hat t h i s
s i t u at i o n i s u s u al l y v al i d f o r V NMR obt ai ned at s u f f i c i e n t l y hi gh
f i e l d s (>7 T ) , where s ec ond - or d er ef f ec t s on exp er i ment al l y obser ved
l i nes h ap es can be negl ec t ed (12). However, as p r ev i o u s l y d es c r i b ed ,
even i n t h i s l i mi t t he quad r up ol ar i n t er ac t i o n mani f es t s i t s e l f i n
t he p ul s ed ex c i t at i o n behav i or . The s el ec t i v e ex c i t at i o n o f t he
c en t r al +1/2 t o - 1/ 2 t r an s i t i o n t hus af f ec t s t he nuc l ear p r ec es s i o n
f r equency o f t he s p i ns i n t he ap p l i ed r ad i o f r equency f i e l d
necessar y f o r NMR d et ec t i o n . As d es c r i bed bel ow, t h i s ef f ec t wi l l
be us ed . However, t he mai n f ocus wi l l be on chemi cal s h i f t
i nf or mat i on av ai l ab l e fr om t he s t at i c NMR l i n es h ap es . In t h i s
p ap er , r es u l t s obt ai ned on V s ur f ac e oxi d e d ep o s i t ed on pseudo
boehmi t e and al u mi n o s i l i c at e g el s wi l l be d i s c us s ed and compar ed.
51
Vanadi um and Pseudo-Boehmi t e Al umi na. The 79 MHz wi d el i ne V NMR
s p ec t r a o f t hese st eam aged sampl es c o n t ai n i n g onl y 0. 5 t o 5.0% V
(l oad ed us i ng VO -Napht henat e) ar e shown i n Fi gur e 1. Two
p r i n c i p al s i gn al component s, " t ype a" (f av or ed at hi gh s ur f ac e
cover ages and assi gned t o d i s t o r t ed - o c t ah ed r al V s p ec i es ) and
" t ype b" (f av or ed at l ow s ur f ac e cover ages and i n d i c at i v e o f a
d i s t o r t ed t et r ah ed r al envi r onment ) can be eas i l y d i s t i n g u i s h ed . The
r el at i v e s i gnal i n t en s i t y r at i o s o f t hese two s p ec i es ar e s i mi l ar t o
t hose obser ved by Ec k er t and Wachs (12) where VO ( OC- H, ) - i n
met hanol was used t o l oad 7 -al umi na powders (Fi gur e 2). The
s i mi l ar i t y i n t he s p ec t r a i s p ar t i c u l ar l y i n t er es t i n g c o n s i d er i n g
t he d i f f er en c es i n t he nat ur e o f t he p r ec u r s o r , al umi na sup p or t and
t he f ac t t hat i mpr egnat i on was si mp l y f ol l owed by c al c i n at i o n at
450C f o r 16 h; st eam agi ng was not per f or med (12). The mai n
d i f f er en c e bet ween bot h s et s o f sampl es i s t he vanadi um l ev el needed
bef or e c r y s t al l i n e V
2
0c i s d et ec t ed e. g . 5% i n t he p r esent st ud y vs
11.2% V i n t he case or 7 -al umi na s up p or t . Th i s i s l ar g el y due t o
t he r ed uc t i o n o f t he s ur f ac e ar ea encount er ed upon st eami ng, and i s
a c l ear mani f es t at i o n o f t he d et r i ment al ef f ec t o f vanadi um on t he
s t a b i l i t y o f t he suppor t s ur f ac e (see Tabl e 1, Ref . 18).
At t he l owest l o ad i n g s , 4- c o o r d i nat e vanadi um i s i n d i c at ed by a
br oad " t y p e- b" s i g n al . T Ms r esonance i s much br oad er t han u s u al l y
obser ved f o r monomeri c (p ' ( e. g . - o t h o v an ad at e, VO- " ) and d i mer i c
(T ' ( e. g . p yr ov anad at e, 0
3
V- 0 - V0
3
) s p ec i es , whi ch show onl y smal l
d i f f er en c es bet ween t he chemi cal y i i f t component s a,,,
a n c
*
a
33*
As d i s c u s s ed p r ev i o u s l y f o r V oxi d e on 7 -al umi na (12), t ne

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15. IYER ETAL. Vanadium-Contaminated Aluminas 245
0 -400 -800 -1200
CHEMICAL SHIFT(PPM)
1.0(0.12)
0.5(0.06)
5 L
Fi gur e 1.
J 1
V wi de l i n e NMFLspect r a at 79 MHz f o r al umi nas
(boehmi t e) Y- l oad ed wi t h VO napht henat e i n benzene and st eam
aged . The numer al s i n d i c at e V l oad i ngs and (e) s ur f ac e cover age
by V.
4.2 (0.38)
2.8 (0.25)
1.1 (0.10)
0.6 (0.05)
0 -200 -400 -600 -800 -1000-1200
CHEMICAL SHIFT(PPM)
51,
Fi gur e 2. V wi de l i n e NMR s p ec t r a at 79 MHz f o r 7 -al umi nas
met hanol and c al c i n ed at 4 5 0 C/ 16 h
V l oad i ngs and (e) s ur f ac e cover age
by V.
V- l oad ed wi t h V0 ( 0 C
3
H
7
)
3
i n rr
(12). The numer al s i n d i c at e

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s p ec t r o s c o p i c par amet er s ar e most c o n s i s t en t wi t h a Q
v 1
s p ec i es .
It was not p o s s i b l e t o achi ev e l i n e nar r owi ng by MAS, i n d i c at i n g t he
p r esence o f a wi de chemi cal s h i f t d i s t r i b u t i o n . Th i s d i s t r i b u t i o n
p r obabl y al s o i nc l ud es vanadi um atoms wi t h d i f f er en t numbers o f
no n- br i d gi ng oxygen at oms.
The i n t en s i t y of t he " t ype a" s i gnal i nc r eas es monot oni c al l y
wi t h i n c r eas i n g V- l o ad i n g s , Fi gur es 1,2. Ref er ence t o t he
ap p r o p r i at e model compounds i n d i c at e t hat t he l o c al s t r u c t u r e of
t h i s s p ec i es i s q ui t e d i f f er en t fr om t hat o f c r y s t al l i n e V
2
0
5
and
suggest s a d i s t o r t ed oct ahed r al s t r u c t u r e s i mi l ar t o t hat obser ved
i n Zn V
2
0
f i
, Pb V
2
0
g
and N a
g
V
1 0
0
2 8
- 18 H
2
0. At 5% l o ad i n g , t he NMR
sp ect nmi shows xhat t he Maj o r i t y af vanadi um i s p r esent as
c r y s t al l i n e V
2
0 g . Th i s i s accompani ed by a t o t al s t r u c t u r al
c o l l ap s e o f thie sup p or t wi t h f or mat i on o f a bul k ^ -al umi na p hase.
For mat i on of bul k A1V0. was not obser ved i n any o f t he sampl es
s t u d i ed . Whi l e s i g n i f i c an t s i gnal i n t en s i t y i s obser ved i n t he
r egi on near 800 ppm (whi ch ov er l ap s wi t h t he chemi cal s h i f t r ange
f o r A1V0- ), we bel i ev e t hat t h i s s i gnal i s si mp l y due t o t he u p f i el d
component of t he chemi cal s h i f t ani s ot r op y powder p at t er n bel ongi ng
t o t he oc t ahed r al V s p ec i es .
5 1
As obser ved p r ev i o u s l y f o r 7 -al umi na, V NMR s p ec t r a of
s ur f ac e V oxi d e on pseud o-boehmi t e ar e v er y s en s i t i v e t o t he s t at e
of h y d r at i o n , Fi gur e 3. The sampl e c o nt ai ni ng 5% vanadi um r emai ns
u n af f ec t ed , as expect ed f o r a s i t u at i o n where most o f t he s i gn al i s
due t o bul k c r y s t al l i n e V
2
0r. At l ower l o ad i ngs t he oc t ahed r al
s p ec i es d i mi ni s hed d r amat i c al l y upon d ehy d r at i on i n v acuo. The
ext r emel y br oad s i g n al s obser ved f o r t he 3% and 4% sampl es i n d i c at e
t hat d ehy d r at i on i n vacuum c ai ^ es t he f or mat i on o f a d i s t r i b u t i o n o f
d i f f er en t f o u r - c o o r d i n at e V s p ec i es , whi ch span a v er y wi de
chemi cal s h i f t r ange. A nar r ower and more wel l - d ef i n ed s i gnal
(" t ype c" ) i s obser ved at 2% l o ad i n g . The l i nes hap e i n d i c at es an
ap p r oxi mat el y axi al chemi cal s h i f t t en s o r , c o n s i s t en t wi t h a
vanadi um (V) envi r onment t hat p ossesses a l o c al uni que axi s (12).
Such symmet r i c un i t s c oul d al s o be p r esent at hi gher l o ad i n g s , but
cannot be d i s c er ned c l ear l y fr om t he br oad l i nes h ap es obser ved i n
t hose c as es , see ot her t r ac es i n Fi gur e 3. Recent i n - s i t u Raman
r es u l t s , obt ai ned on d ehyd r at ed V(V) oxi d e s ur f ac e phases on v ar i o us
met al oxi d e s up p o r t s , show Raman bands i n t he 1020-1040 cm r eg i o n ,
i n d i c at i n g t hat t he vanadi um s p ec i es p ossesses a s i n g l e s t r ong V=0
bond (19-21). These s p ec i es ar e al s o obser ved on V-l oad ecL
st eam-aged pseud o-boehmi t e al umi nas (met al l oad ed wi t h V0
napht henat e i n benzene) but onl y af t er s ur f ac e d ehy d r at i on (18).
Al u mi n o s i l i c at e g el s . Fi gur e 4 shows t he
5 1
V NMR r es u l t s obt ai ned
on v anad i a- l oad ed al u mi n o s i l i c at e g el s . Whi l e no r ead i l y appar ent
t r end i s v i s i b l e , i t has t o be bor ne i n mi nd t hat t he i n t er p r et at i o n
o f t he s p ec t r a i s comp l i cat ed her e by t he l i mi t ed hyd r ot her mal
s t a b i l i t y of t he gel when l oad ed wi t h V, (18). Due t o t hese
c o mp l i c at i o n s , onl y t he s p ec t r a obt ai ned at t he l owest s ur f ac e
cover ages (0.5% and 1%) ar e i n t er p r et ab l e i n t er ms o f s ur f ac e- V
oxi d e s p ec i es . Fi gur e 4 r ev eal s t hat t he d i s t o r t ed oc t ahed r al
envi r onment s (" t ype a" s i g n al s ) domi nat e at t hese V- l o ad i n g s . As
t he vanadi um l o ad i ng i nc r eas es t he gel s t r u c t u r e c o l l ap s es r ap i d l y ,
e . g . , wi t h onl y 1.25% V t her e i s a 46% r ed uc t i o n i n s ur f ac e ar ea,

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15. WERETAL Vmmmumt-Cutmtmn^dtmmimos 247
Fi gur e 3.
5 1
V wi de' l i n e NMR s pec t r a at 79 MHz of V l oaded
al umi nas a f t e r dehydr at i on i n vacuo at 220C.
Figure 4
5 1
V wide line NMR spectra at 79 MHz of V loaded
aluminosilicate gels.

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accompanied by the formati on of bul k phases such as mul l i t e and
t r i dymi t e t hat can be easi l y
5
obser ved by XRD (18).
As i n the case of V on pseudo boehmite, t hi s st r uct ur al
col l apse i s induced by the steaming process r at her than the
cal ci nat i on st ep. Accor di ngl y, the spect ra observed f or samples
wi th V-cont ent s exceedi ng lwt.%, show two new types of si gnal s: a
sharp feat ure near 500 ppm (" type d " ; symbol o i n Fi gure 4) and an
extremel y broad si gnal (" type e") whose spect r al parameters are
remi ni scent of V
2
0
5
. Based on i t s spect r oscopi c parameters, the
sharp 500 ppm feat ure i s assi gned to a t et r ahedr al V speci es. It
most l i k el y ar i ses from V i ncorporat ed i n one of the bul k phases,
whose format i on i s induced by the presence of vanadium upon
st eami ng. Thi s assignment i s fur t her supported by the fact t hat
surface dehydrat i on has no i nfl uence on t hi s si t e (vi de i nf r a).
The broad " type e" si gnal , whose cont r i but i on i ncreases wi th
i ncr easi ng V cont ent , shows NMR behavi or t hat i s consi st ent wi th the
presence of bul k V
2
0
5
: (1) the wi del i ne NMR pat t ern resembles t hat
of cr y st al l i ne V
2
6
5
f (2) i nt ense spi nni ng si deband pat t erns are
present under MMS condi t i ons (not shown) and (3) the pul sed
exci t at i on behavi or i ndi cat es weak quadrupol ar coupl i ng si mi l ar to
t hat observed i n cr yst al l i ne V
2
0r. Fi gure 5 i l l ust r at es t hat i t i s
possi bl e t o det ect t hi s si grfar sel ect i vel y by usi ng pul ses of
suf f i ci ent l engt h t o cause r el axat i on of the ot her NMR si gnal s i n
the r ot at i ng frame of the appl i ed radi o frequency f i el d . Thus, at a
gui se l engt h of 7/xs, the sharp 500 ppm feat ur e, which ar i ses from
V nucl ei wi th si gni f i cant l y st ronger quadrupol ar i nt er act i ons,
remains undet ect ed.
Al though the presence of a V
2
0
5
- l i k e phase i s det ect ed by Raman
anal ysi s (18), t here was no Evi dence f or the format i on of a
cr y st al l i ne phase by XRD. Thus, i n spi t e of the anal ogi es between
the speci es gi vi ng r i se to the " type e" NMR si gnal and cr yst al l i ne
V
2
0
5
, the si gnal i s assi gned t o an amorphous V
2
0
5
phase.
5 1
Furt her i nsi ght i nt o t hi s problem i s provi ded by the V NMR
spect r a of the correspondi ng dehydrated sampl es, Fi gure 6. As
observed f or V l oaded al umi nas, the oct ahedral " type a" surface
speci es, seen at low coverages, has-been repl aced by the t et r ahedr al
" type c" speci es (most l i k el y a Q* ' uni t ). The same type of uni t
appears t o ar i se from dehydrat i on of samples cont ai ni ng the
amorphous V
2
0
5
pr ecur sor , i ndi cat i ng t hat t hi s phase must be hi ghl y
hydrated unaer ambient condi t i ons. Fi nal l y , the t et r ahedr al " type
d" speci es, al ready i d ent i f i ed as a si gnal ar i si ng from the bul k i n
the ambient samples remains unaffect ed upon dehydrat i on of the
surface (see symbol o i n Fi gure 6.)
Summary and Concl usi ons
51
V wi del i ne sol i d st at e NMR has proven to be a very useful
techni que for d i f f er ent i at i ng between vari ous vanadium (V ) surface
speci es present on vanadi a-l oaded metal oxi de subst r at es. The
r esul t s confi rm the previ ous t rends observed for vanadium on alumina
and t i t ani a support s, which can be summaraized as fol l ows:
(1) low surface coverages favor the formati on of a hi ghl y
di sor der ed four -coor di nat ed vanadium speci es;

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15. IYER ET AL. Vanadium-Contaminated Aluminas 249
-500 -1000 -1500
CHEMI CAL SHIFT (PPM)
C 1
Fi gur e 5. Ef f ec t s of p ul s e l engt h on V wi d el i ne NMR s p ec t r a
o f al u mi n o s i l i c at e gel s c o n t ai n i n g : (a) 5% V, 7/xS p ul s e l en g t h ,
r es u l t i n g i n ex c l u s i v e d et ec t i o n of bul k Vp 0
5
; (b) 3% V, 7/xs
p ul s e l en g t h , r es u l t i n g i n ex c l u s i v e d et ec t i o n of amorphous V
9
0,
and (c) 3% V, 1/iS p ul se l en g t h , r es u l t i n g i n a spect r um
r ep r es en t at i v e of al l V s p ec i es p r es ent .
2
U
5
i
-500
-1000
CHEMICAL SHIFT(PPM)
51,
Fi gur e 6. V wi de l i n e NMR s p ec t r a at 79 MHz of V l oad ed
al u mi n o s i l i c at e gel s af t er d ehy d r at i on i n vacuo at 15 0 C/ 4 h .

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(2) as t he s ur f ac e cover age i n c r eas es , an i n c r eas i n g amount of
vanadi um i s p r esent i n a s i x - c o o r d i n at e envi r onment under
ambi ent c o n d i t i o n s ;
(3) hydr ous s p ec i es (FLO and / or OH) p ar t i c i p at e i n t h i s s i x -
c o o r d i nat e envi r onment , and upon d ehy d r at i on a h i g h l y
c h ar ac t er i s t i c V oxi d e wi t h an ax i al l y symmet r i c V(V) p o i nt
symmet ry i s f or med .
Beyond c o nf i r mat i o n of t hese p r ev i o u s l y obt ai ned r es u l t s , t he
p r esent st ud y al s o i l l u s t r at es t he u t i l i t y of V NMR t o pr obe t he
p r oc es s es t hat l ead t o t he c o l l ap s e of v anad i a- l oad ed s ur f ac es upon
hyd r ot her mal t r eat ment . In t he case of pseudo boehmi t e, t he f o u r -
and s i x - c o o r d i n at e V oxi d e s ur f ac e s p ec i es si mp l y r ed i s t r i b u t e t o
account f o r t he gr ad ual l o s s i n s ur f ac e ar ea upon st eami ng, y i el d i n g
r es u l t s i n c l o s e anal ogy t o t hose obt ai ned on c al c i n ed (but
unst eamed) samp l es. In c o n t r as t , t he al u mi n o s i l i c at e gel r espond s
t o hyd r ot her mal t r eat ment by f or mi ng a new amor phous, h i g h l y
hy d r at ed , V
2
0c - l i k e p hase, whi ch has not been i d en t i f i ed bef or e by
NMR s t ud i es or ot her s u b s t r at es . Fur t her d et ai l s o f t he mechani sm
o f c at al y s t d eac t i v at i o n by V ar e
5 1
t h e s ubj ec t o f c o nt i nui ng
i n v es t i g at i o n s i n our l ab o r at o r i es by V s o l i d s t at e NMR, XPS, and
Raman s p ec t r o s c o p y .
Acknowl edgment
The aut hor s t hank Mr . R. Or t i z and Dr . M. So l l b er g er f o r as s i s t an c e
i n sampl e p r ep ar at i o n .
Ref er ences
1. Occel l i , M. L. in " Fl uid Catal yti c Cracking: Role in Modern
Refi ni ng." ACS Symposium Seri es, Vol . 375: M. L. Occel l i , Ed. ,
ACS, Washington, D. C. , p. 162 (1989).
2. Occel l i , M. L. and Swift H. E. U. S. Patent No. 4, 466, 884
(1984).
3. Occel l i , M. L. in "Advances in Catal yti c Chemistry IV" Snowbird,
Utah (1989).
4. Occel l i , M. L. And Stencel , J . M. in Fl ui d Catal yti c Cracking:
Role in Modern Refi ni ng." ACS Symposium Seri es, Vol . 375; M. L.
Occel l i Ed. , ACS Washington, D. C. , p. 195 (1989).
5. Occel l i , M. L. and Stencel , J . M. in " Zeolites as Catal yst,
Sorbents and Detergent Bui l ders," H. G. Karge and J. Weitkamp
Eds.; El sevi er, p. 127 (1989).
6. Occel l i , M. L. and Stencel , J . M. " Proc. 8th IZA" Amsterdam
(1989).
7. Occel l i , M. L. and Kennedy, J . V. in G. B. Patent No. 2, 116,
062A (1983).
8. Occel l i , M. L. and Kennedy, J . V. in U. S. Patent No. 4, 465,
588 (1984).
9. Occel l i , M. L. in U. S. Patent No. 4,615,996 (1986)
10. Kugler, E. L. and Leta, D. P., J. Cat al . 109, 387 (1988).
11. Repeli n, Y. , Husson, E. , Abel l o, L. and Lucazeau, G. ,
Spectrochim. Acta, 41A, 993 (1985).

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15. IYER ETAL. Vanadium-Contaminated Aluminas 251
12. Eckert, H. and Wachs, I. E. , J. Phys. Chem. 93, 6796, 1989.
13. Eckert, H. and Wachs, I. E. , Mater. Res. Soc. Symp. Proc. 111.
455 (1988).
14. Le Costumer, L. R., Taouk, B., Le Meur, M., Payen, E. , Guelton,
M. and Grimblot, J., J. Phys. Chem. 92, 1230 (1988)
15. Taouk, B., Guelton, H., Grimblot, J . and Bonnelle, J . P., J.
Phys. Chem. 92, 6700 (1988).
16. Cheng, J. T. and El l i s, P. D., J. Phys. Chem. 93, 2549 (1989).
17. Morri s, H. D. and El l i s , P. D., J. Am. Chem. Soc. 111, 6045
(1989).
18. Occel l i , M. L. , and Stencel , J . M., This Volume.
19. Went, G. and Bel l , A. , personal communication, J . Phys. Chem.
1990, in press.
20. Wachs, I. E., J. Cat al , 1990 (in press).
21. Wachs, I. E. , Chem. Eng. Science, 1990 (in press).
RECEIVED Au g u s t 2 8 , 19 9 0

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Chapter 16
Laser Raman and X-ray Photoelectron
Characterization of V-Contaminated Components
of Fluidized Cracking Catalysts
M. L. Occelli
1
and J. M. Stencel
2
1
2
Center for Applied Energy Research, University of Kentucky,
Lexington, KY 40506
In r ecent year s , a var i et y o f s pec t r o s c o pi c t ech ni ques
have been used t o st udy t he nat ur e o f t he compounds
f ormed f rom vanadi um d epo s i t i o n on met al oxi de s u r f ac es .
Usi ng l as er Raman spect r o sco py (LRS) it was obser ved t h at
V, when d epo s i t ed on l ayer ed magnesium silicates (such as
sepiolite), i s pas s i vat ed i n t he f orm o f -Mg
2
V
2
O
7
and
t h at t he nat ur e o f t he vanadat e f ormed depends on t he
clay co mpo si t i o n (1). Roozenboom et al (2) have proposed
t h at on al umi na, t et r ah ed r al l y c o o r d i nat ed vanadi a
monomers and o c t ah ed r al l y c o o r d i nat ed vanadi a o l i go mer s
are f ormed at l ow V- l o ad i ngs . At hi gh V l o ad i ngs , a
crystalline
V2
O
5
phase has been observed by sever al
i nves t i gat o r s ( 2-6) . Wachs et al (6) have proposed t h at
t he observed monomeri c s pec i es are di oxovanadat es a
c o nc l us i o n support ed al s o by EXAFS measurement s ( 7, 8) .
However, sever al o t h er aut hors have proposed i ns t ead t h at
t he monomeri c s pec i es f ormed at l ow V- l o ad i ng on al umi na
s ur f ac es are mai nl y monoxovanadyl groups bonded t o t he
s ur f ac e by Al -O-V l i nkages ( 9-13) . The dependence o f t he
nat ur e o f t he V s pec i es f ormed and V- l o ad i ng on al umi na
gr anul es ( af t er st eam agi ng at 7 6 0 C/ 5h , 100% st eam) , has
r eveal ed t h at at l eas t t h r ee t ype o f V s pec i es can be
pr es ent , ( 4) . Vanadyl s ( VO+2) gr o ups, V
2
O
7
- gr o u ps (wi t h
at l eas t t h r ee d i f f er ent V-O-V bond angl es) and a
crystalline V2O5 phase have been observed when t he
V-l o ad ed al umi na co nt ai ned <1%, 1% t o 4% and >4%
vanadi um, r es pec t i vel y ( 4) . Monomeri c vanad yl s , one and
two di mensi onal vanadat e c h ai ns , and crystallites o f V
2
O
5
have been f ound t o f orm as t he V l o ad i ng is i nc r eas ed on
SiO
2
, TiO
2
and Al 2O
3
suppor t s ( 14) .
Spec t r o s c o pi c and mo d el l i ng s t ud i es o f V
2
O
5
xer o gel s have
compr ehensi vel y exami ned t he vi br at i o nal c h ar ac t er i s t i c s o f
V
2
O
5
. nH
2
O gel s ( 21-24) . These gel s c o nt ai n broadened vi br at i o nal
bands as compared t o c r y s t al l i n e V
2
0
5
. Vanadi a gel s wi t h n > 0. 5
0097-6156/91/0452-0252$06.00/0

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16. OCCELLI AND STENCEL Raman & X-ray Photoelectron Characterization 253
have been d es c r i bed as havi ng a two d i mensi onal f i b er or r i bbon
s t r u c t u r e. For n = 1.6 t hese r i bbons have been measur ed t o be 2. 7
x 0. 36 x 100 nm (a x b x c) i n s i z e and t o o r i en t wi t h l ay er s
p ar al l el t o t he smooth s ubs t r at es on whi ch t hey ar e d ep o s i t ed
(21-23). The pr esence o f FLO, ei t h er as t r ap p ed mol ecul es bet ween
t he l ay er s o f V
2
0
5
, or t er nr i nal l y bonded t o V
2
0r c r y s t a l l i t e s , or
i n t er ac t i n g wi t n I n d i v i d u al V-0 bonds i n v anad i a g el s , has been
shown t o pr oduce a Raman band on t he hi gh f r equency s i d e o f t he
nor mal l y i nt ens e 998 cm V=0 s t r et c h i n g band (24-27). Thus , t he
pr esence of bands (or s houl d er s ) i n t he 1010 - 1040 cm" r egi on of
s p ec t r a showi ng V
2
0
5
s p ec i at i o n have been at t r i b u t ed t o HgO
p r esent i n t he vanad i a s t r u c t u r e. Th i s t ype of ' b l u e s h i f t ' i n
v i b r at i o n al f r equency i n d i c at ed t hat H
2
0, bes i d es weakeni ng V=0
bonds by p i back d onat i on (t her eby d ec r eas i ng V=0 s t r et c h i n g
f r eq u en c i es ) , can al s o st r engt hen ot her V=0 t er mi nal bond s. The
pur pose o f t h i s paper i s t o i n v es t i g at e V- i n t er ac t i o n s on
st eam-aged al u mi n o s i l i c at es of t he t ype used i n FCC p r ep ar at i o n .
The p r o p er t i es of t he V s p ec i es for med wi l l be compared t o t hose
of V compounds obser ved on s i mi l ar l y pr epar ed V- l oad ed al umi na
samp l es.
EXPERIMENTAL
Cat al y s t s Pr ep ar at i on
Vanadyl napht henat e (i n benzene) was used t o met al l oad al umi nas
and al u mi n o s i l i c at e g el s ac c or d i ng t o an es t ab l i s h ed p r oced ur e
(15); t he napht henat e was obt ai ned fr om Pf al t z and Bauer , I n c . ,
and c ont ai ned 2. 9 wt% V. Decomposi t i on of t he napht henat e was
per f or med by c al c i n i n g t he i mpr egnat ed mat er i al s f o r 10 hour s at
540C i n a i r . A l l c at al y s t s were t hen st eam-aged f o r f i v e hour s
wi t h -100% st eam at 760C i n a f l u i d i z ed bed .
The amorphous al u mi n o s i l i c at e gel (AAA-al umi na) used i n t h i s st ud y
c ont ai ns about 80.4% S i 0
2
, 19.4% A1
2
0~ and 0. 0562 Na
2
0. Mer cur y
p or osi met r y measurement s have i n d i c at ed a 479 m / g s ur f ac e ar ea
and 1.67 c c / q por e vol ume; t he aver age por e d i amet er of t he d r i ed
gel was 134 A.
The 100 x 325 mesh gr anul es of Cat apal SB Al umi na used gave an
x - r ay p at t er n i n ex c el l en t agreement wi t h JCPDS ( J o i n t Commi t t ee
on Powder Di f f r ac t i o n St and ar d s) p at t er n No. 21-1307 f o r A100H
(boehmi t e); mi nor amounts of A1(0H)
3
( no r d s t r and i t e wi t h p o s s i b l e
g i b b s i t e pol ymor phs) ar e al s o p r es ent . Af t er st eam-agi ng
( 76 0 C/ 5 h ) t h i s al umi na had a mer cur y s ur f ac e ar ea o f 118 m / g and
por e vol ume o f 0. 98 c c / g .
Cat al y s t s Ch ar ac t er i zat i o n
(i ) XPS Measur ement s. Mat er i al s were anal y zed by X- r ay
p h o t o el ec t r o n s p ec t r os c op y (XPS) af t er c al c i n at i o n ( C) , st eami ng
(S) and af t er H
2
- t r eat ment ( H
2
) . Powders were p r es s ed i n t o t h i n ,
13-mm d i amet er waf er s and t hen mounted on a heat abl e sampl e pr obe
at t ached t o a Leybol d -Her eaus LHS- l l j XPS/ Aug er / I SS i ns t r ument . The
i nst r ument base p r es s ur e was 2 x 10 bar ; sampl es were g en er al l y

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254
anal y zed at a p r es s ur e o f 2 x 10 bar . Dur i ng Hp -t r eat ment ,
mat er i al s were exposed t o 25 ml /mi n f l owi ng H
2
at a p r es s u r e o f
2. 5 bar and at t emper at ur es o f 325- 400 C f o r p er i od s o f 15 t o 120
mi nut es i n a hi gh p r es s ur e- h i gh t emper at ur e r eac t o r at t ached t o
t he s i d e of t he LHS-11 an al y s i s chamber . Af t er exposur e t o Hp,
t h
2
sampl es were c ool ed whi l e t he r eac t o r was evacuat ed t o
10" bar . Then t he sampl es were moved i nt o a p r ep ar at or y chamber
and f i n a l l y i nt o t he an al y s i s chamber . A t y p i c al t i me t o c o o l ,
evacuat e and move t he sampl e t o t he an al y s i s p o s i t i o n was 10
mi nut es.
A l l bi nd i ng ener gi es r ep or t ed have been c o r r ec t ed f o r c har gi ng by
compar i ng t he l o c at i o n of t he Cl s bands wi t h t hat f o r Al 2p.
Co r r ec t i o n o f t he Al 2p band t o 74. 7 eV c o i n c i d ed wi t h peak
f i t t i n g o f t he C Is bands i n whi ch a pr omi nent car bon peak was
wi t h i n 0. 3 eV o f t he ubi q ui t ous C Is assumed t o be at 284. 6 eV.
Hence, peak p o s i t i o n s f o r vanadi um were c o r r ec t ed us i ng t he Al 2p
at 74. 7 eV.
The V 2p i s a d o ubl et , t he 2p
A
peak o f whi ch i s obscur ed by t he 0
Is peak whi l e a oxygen s a t e l l i t e i s l o c at ed bet ween t he V ZPo/o
and 2pi p eak s. Hence, mani p ul at i on of t he s p ec t r a i n c l ud ed r ' a
s a t e l l i t e el i mi n at i o n r o u t i n e, f ol l owed by a n o n l i n ear backgr ound
s u b t r ac t i o n , t o pr oduce a wel l - s ep ar at ed V 2 p
3
,
2
peak on whi ch an
es t i mat i o n of t he pr esence o f mu l t i p l e o x i aat i o n s t at es f o r
vanadi um was made. Th i s es t i mat i on i nv ol v ed t he d ec onv ol ut i on o f
t he V 2 p
3
y
2
t o
i nc l ud e ei t h er a s i n g l et , d o ubl et , or t r i p l e t
Gaussi an f i r . The number o f peaks used i n t h i s f i t t i n g p r oced ur e
was d et er mi ned by compar i ng t he FWHM of t he f i t t ed V peaks t o
t hose obt ai ned f o r t he Si and Al p eak s, r el at i n g f i t t ed peak
p o s i t i o n s t o t hose fr om s t and ar d s , and by mi ni mi zi ng t he l eas t
squar es d i f f er en c e bet ween f i t t ed and exper i ment al d at a.
( i i ) Raman Sp ec t r os c op y . Raman s p ec t r a were r ecor d ed on a
Spex Ramal og 1403 sp ect r omet er (Spec I n d u s t r i es , Met uchen, NJ)
equi pped wi t h a c ool ed RCA GaAs p h o t o mu l t i p l i er t ube (CA
31034-02). The 488nm l i n e o f a model 165 Ar l as er (Sp ec t r a
Ph y s i c s , Mount ai n Vi ew, CA) was used t o gener at e Raman s c at t er ed
l i g h t . The l as er power i mpi ngi ng on t he sampl e was l i mi t ed t o
ap p r oxi mat el y 50 mW,. A l l s p ec t r a were r ecor d ed wi t h a s p ec t r al
r es o l u t i o n of 5 cm (350 /xm s l i t wi d t h ). Si gnal p ul s es fr om t he
p h o t o mu l t i p l i er t ube were passed t hr ough a model 1182
amp l i f i er / d i s c r i mi n at o r (Pr i nc et on Ap p l i ed Res ear c h, Pr i n c et o n ,
NJ) and count ed by a Ni c o l et 1280 d at a syst em ( Ni c o l et Inst r ument
Co r p . , Mad i son, WI). T y p i c al l y , 50-100 scans per sampl e were
aver aged i n or d er t o obt ai n s p ec t r a wi t h adequat e, s i g n al - t o - n o i s e
r at i o s . A d at a p oi nt was ac q ui r ed ever y 0. 7 cm" . Sampl es were
p r ep ar ed f o r Raman measurement s by g r i n d i n g t he c at al y s t s i n an
agat e mor t ar and p es t l e. The powdered sampl es were t hen p r essed
i n t o 1 cm d i amet er waf er s under a p r es s ur e of ap p r oxi mat el y 1000
p s i . Each waf er was mounted i n a s p i nni ng sampl e hol d er and
p l ac ed i n t he sp ect r omet er sampl e chamber . The angl e bet ween t he
i n c i d en t l as er beam and t he sampl e s ur f ac e was 3 0 ; sampl es were
spun at ap p r oxi mat el y 500 rpm t o mi ni mi ze t her mal mo d i f i c at i o n s .

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Sur f ac e Pr o p er t i es
The boehmi t e used (Cat apal SB Al umi na) af t er V- l o ad i n g and
c al c i n at i o n i n ai r (at 540 C) for med some p o o r l y c r y s t al l i z ed
d el t a- al umi n a (4); t he BET s ur f ac e ar ea o f t he c al c i n ed mat er i al
r emai ned es s en t i al l y unchanged f o r V l oad i ngs up t o 5%, t ab l e 1.
Af t er st eam-agi ng ( 7 6 0 C/ 5 h ,
2
100% st eam) t he al umi na s ur f ac e ar ea
(SA) d ecr eased t o 130 m/ g and t he c r y s t a l l i n i t y o f t he
d el t a- al umi n a phase i mpr oved (4). Dur i ng st eam ag i n g , t he s ur f ac e
ar ea monot oni c al l y d ecr eased wi t h V- l o ad i n g , t abl e 1. Wi t h 4% V,
t he st eam aged al umi na r et ai ned 76% o f i t s i n i t i a l s ur f ac e ar ea.
Above 4% V, t her e i s a c o l l ap s e o f t he mi cr op or ous s t r u c t u r e.
Wi t h 5% V, t he s ur f ac e ar ea d ecr eased t o 18 m2/g and f or mat i on o f
a c r y s t al l i n e VJdr phase t oget her wi t h (wel l c r y s t al l i z ed )
d el t a- al umi n a couf d T)e obser ved i n t he x - r ay d i f f r ac t o gr ams o f t he
sampl e (4); f or mat i on o f A1V0- was not obser ved i n any o f t he
V- l oad ed al umi nas s t ud i ed (4).
The hi gh f i e l d al umi num-27 MAS NMR spect r um of t he al u mi n o s i l i c at e
gel under st ud y c ont ai ns r esonances near 0 ppm 30 ppm and 58 ppm
i n d i c at i n g t he pr esence o f al umi num i n o c t ah ed r al , p ent ahed r al and
t et r eh ed r al c o o r d i n at i o n (16, 17), see F i g . 1. Lumi nescence as
wel l as EPR d at a have shown t hat af t er met al d ep o s i t i o n , t he
vanad yl i ons (VO ) for med ar e q ui t e mobi l e (18,19) and abl e t o
mi gr at e p o s s i b l y t o char ge compensat e Al (I V) p r esent i n t he gel
t her eby f or mi ng Si - O- Al ( I V) - 0V0 gr oups (20).
It i s bel i ev ed t h at , when st eami ng t he gel at hi gh t emp er at ur es,
t he V0 at t ac k s and br eaks t he Si - 0 - A l bonds pr omot i ng mu l l i t e
f or mat i on and t he c o l l ap s e of t he gel macr opor ous s t r u c t u r e (3).
The XRD p at t er n i n Fi g . 2B shows t hat mu l l i t e f or mat i on i n t he gel
can be obser ved wi t h onl y 1.5% V and when t h i s o c c u r s , t her e i s a
81% d ecr ease i n s ur f ac e ar ea, Tabl e 1. Mu l l i t e l ev el i nc r eas ed
wi t h V- l o ad i n g s , see F i g . 2. Dat a i n t he l i t er at u r e (20)
i n d i c at es t hat when t he st eami ng t emper at ur e i s d ecr eased t o 730C
fr om 760
P
C (as i n t he p r esent work) gel s t a b i l i t y t o V i mpr oved
and onl y a 23% r ed uc t i on i n s ur f ac e ar ea was obser ved i n a s i mi l ar
gel l oad ed wi t h 1.5% V. Al u mi n o s i l i c at e g el s ar e c l ear l y l es s
r es i s t an t t han al umi nas t o V at t ac k at hyd r ot her mal c o n d i t i o n s ,
Tabl e 1.
Laser Raman Sp ect r oscop y
Laser Raman s p ec t r a of st eamed ( 76 0 C/ 5 h r ) pseudoboehmi t e al umi nas
met al l oad ed wi t h s o l u t i o n s o f vanadyl napht henat e i n benzene ar e
shown i n F i g . 3; band p o s i t i o n s ar e l i s t e d i n Tabl e 2. Some of
t hese r es u l t s have al r ead y been d i s c us s ed i n d et ai l s el sewher e
( 3, 4) . At l ow V- l o ad i n g s , t he spect r um i s c h ar ac t er i zed by an
i nt ens e band near 925 c m , F i g . 3B. Th i s band has been
at t r i b u t ed t o V=0 s t r et c h i n g modes r es u l t i n g fr om t he p r esence o f
i s o l at ed vanadyl i ons on t he al umi na s u r f ac e. Hydr ogen bond i ng,
r es u l t i n g fr om st eami ng, i s bel i ev ed r es p o n s bi l e f o r t he br oad
nat ur e o f t h i s band .

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256
TABLE 1. St eami ng ( 7 6 0 C/ 5 h , 100% st eam) ef f ec t s on t he s ur f ac e
ar ea (SA, m2/g, 5%) of V- l oad ed al umi nas and al u mi n o s i l i c at e g el s
(AAA-al umi na). Dat a obt ai ned fr om N
?
- p o r o s i met r y measur ement s.
Wt% Suppor t
V Al umi na
Gel
C S C S
0. 0 238 130 480 191
0. 25

166
0. 5 232 126

146
1.0 232 124 448 127
1.25

88
1.5 230 116

35
2. 0 229 113 424 33
3. 0 228 109 396 22
4. 0 227 96 392 17
5. 0 224 18 371 13
C = c al c i n ed at 540 C/ 10h i n ai r : S = st eamed at 76 0 C/ 10 h ,
100% st eam at 1 at m.
As t he V- l ev el s on t he al umi na suppor t i n c r eas e, t he band at 925
cm" d ecr eases i n i n t en s i t y and s h i f t s t p hi gher wav el engt hs;
s i mul t aneous l y new bands i n t he 300 cm" , t o 850 cm" r egi on
ap p ear , Fi g s . 3C-3D. The band near 790 cm has been at t r i b u t ed
t o t he f or mat i on o f oc t ahed r al - 1 i k e s p ec i es and t o V-0 s t r et c h i n g
v i b r at i o n al modes (4). It has been pr oposed t hat f o r V
c o nc ent r at i o ns bet ween 1% and 4%, d i mer i c s p ec i es such as :
ar e for med on t he al umi na sur f ace, (4). Bands near 660 cm" and
bands i n t he 350 cm" - 600 cm r egi on have been assi gned t o
V- 0- V asymmet r i c and symmet r i c s t r et c h i n g modes; t hese V^ O, u n i t s
p r obabl y have t hr ee d i f f er en t V0V bond angl es (4). Iff sampl es
c o n t ai n i n g more t han 4% V, st eami ng cause a d r as t i c r ed uc t i o n i n
t he al umi na s ur f ac e ar ea (Tabl e 1) and f or mat i on o f V
2
0
5
, F i g . 3
H. Th i s Vp 0
R
phase i s al s o eas i l y obser ved by XRD (4).

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OCCELLI AND STENCEL Raman & X-ray Photoelectron Characterization 257
-i i 1 1 1 1 1
150 100 50 0 -50 -100 -150
CHEMI CAL SHIFT(PPM)
Figure 1. Aluminum 27 MAS NMR spectrum at 130 MHz of the parent
aluminosilicate gel.
TWO-THETA (DEGREES)
Figure 2. X-ray Diffractograms of steam aged aluminosilicate gels loaded
with (A) 1.0%; (B) 1.5%; (C) 2.0%; (D) 3.0%; (E) 4.0% and (F) 5.0%
vanadium.

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258
I 1 I i ! . I I I I i I i 1 i
200 300 400 500 600 700 800 900 1000 1100
WAVELENGTH(c m
1
)
Figure 3. Laser Raman spectra of Catapal SB alumina (A) after loading
with : (B) 0.5%; (C) 1.0%; (D) 1.5%; (E) 2.0%; (F) 3.0%; (G) 4.0%; (H)
5% V and steaming (4).

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The LRS o f s i mi l ar l y pr epar ed V- l oad ed al u mi n o s i l i c at e g el s
(AAA-al umi nas) ar e shown i n Fi g . 4; band p o s i t i o n s ar e l i s t e d i n
Tabl e 3. These s p ec t r a ar e es s en t i al l y f eat u r el es s f o r V
c o nc ent r at i o ns bel ow t he 1%V l e v e l , Fi g . 4 . For l o ad i ngs i n t he
1.0 t o_3. 0% V r ange, r el at i v el y i nt ens e bands near 517 cm" and
700 cm" , t oget her wi t h a br oad shoul d er cent er ed near 815 cm"
and a ver y weak band near 1020 cm" can be seen i n t he Raman
s p ec t r a o f t hese samp l es, Fi g s . 4B-4D. Rec ent l y , Wokaun, et . a l .
(25) have shown Raman s p ec t r al c h ar ac t er i s t i c s f o r Si 0
2
s up p or t i ng
l ow V l o ad i ngs whi ch ar e s i mi l ar t o t hose i n F i g . 4 T)ut d i d not
i n d i c at e whet her H
2
0 i nf l uenc ed t h ei r r es u l t s .
For st eamed g el s c o nt ai ni ng more t han 3%V, Raman s p ec t r a show
f or mat i on o f a suppor t ed V
?
0r phase, Fi g s . 4E- 4F. When V l oad i ngs
i nc r eas ed t o 5% fr om 4%, t he r el at i v e i n t en s i t y r at i o of t he 525
cm" t o t he 475 cm" band ( i . e . I C O R / ^ T R ) i nc r eas es t o 1.83 fr om
1. 35. Fur t her mor e, t he i n t en s i t y o f xl re 405 cm band changed
r el at i v e t o t he i n t en s i t y of t he 525-475 cm" d oubl et as l o ad i ng
o f V i nc r eas ed t o 5%.
Sp ec t r a o f al u mi n o s i l i c at es gel c o nt ai ni ng 4% and 5%, V ex h i b i t a
s t r ong band at 995 cm wi t h a shoul d er at 1020 cm" , Fi g s . 4E, 4F.
The hi gh f r equency band i s d i f f er en t fr om t hat r es u l t i n g fr om t he
p r esence o f monomeri c vanadyl s p ec i es obser ved at l ow V l o ad i ngs
(21) and has been at t r i b u t ed t o wat er sor bed i n t he V
2
0
5
- l i k e
phase d ur i ng st eam- agi ng.
TABLE 2. Raman Band Po s i t i o n s f o r t he V-Load ed Al umi nas shown i n
Fi g . 3 .
% v Positions (cm"
1
)
0.5 --- --- --- ---
...
842 890 925 978
...
1.0 --- 528 560 665 790 835 895 928 978
...
1.5 352 535 560 665 785 835 890 930 978
...
2.0 355 532 555 660 780 828 888
...
978
...
3.0 350 540
...
660 777
... ... ...
978
...
4.0 --- 480 535 --- 670 770
... ... ...
978 1000
5.0 405 485 530 704 ---

978 997
Vanadi um s p ec i at i o n f o r c o nc ent r at i o ns bel ow 4%V i s not eas i l y
as c er t ai n ed . In g en er al , f o r V- c o n t ai n i n g compounds, t er mi nal V=0
band f r eq uenc i es have v al ues gr eat er t han 900 cm" ; t hese bands
appear onl y when t he p r esence of V
?
0
R
i s obs er v ed , Fi g s . 4E- 4F.

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260
200 300 400 500 600 700 800 900 1000 1100
WAVENUMBER
Figure 4. Laser Raman spectra of an aluminosilicate gel after loading with
(A) 1.0%; (B) 1.5%; (C) 2.0%; (D) 3.0%; (E) 4.0%; (F) 5% V and
steaming.

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TABLE 3. Raman Band Po s i t i o n s f o r t he V-Load ed Al u mi n o s i l i c at e
Gel s i n F i g . 4.
% V Positions (cm" )
1.0% 517
1.5% 265 --- 517 (685),715 805 (1020)
2.0% 264 --- 517 (685),715 805 (867) (968) --- (1020)
3.0% 265 --- 517 707 805 (1020)
4.0% --- 405 482,527 704 995 1020
5.0% 282 405 485,527 704 994 1020
Tet r ahed r al (V0-) " s p ec i es i n aqueous s o l u t i o n s c o nt ai n an i nt ens e
V-0 s t r et c h i n g v i b r at i o n al band , at 827 cm and r el at i v el y i nt ens e
V-0 bend i ng modes near 330 cm (26). In condensed V0
4
syst ems,
t he V-0 s t r et c h i n g v i b r at i o n i nc r eas es i n p o s i t i o n and has a r ange
of v al ues fr om 830 t o 915 cm (27). In met avanad at es, ( i . e . ,
MV0~-t ype mol ecul es whi ch c o n s i s t o f V
?
0
6
c hai ns connect ed by VO-
gr oups) t he i nt ens e bands i n t he 890 t o 950 cm r egi on Jâve been
as s i gned t o V-0 s t r et c h i n g v i b r at i o n s (28-30). In ad d i t i o n ,
met avanadat e chai n s t r u c t u r es pr oduce r el at i v el y i nt ens e
v i b r at i o n al bands due t o V-0-V s t r et c h i n g i n t he 500 and 200-300
cm" r eg i o n s (28-30). I nt ense bands i n t he 820-950 cm or i n t he
200-300 cm" r egi on were not obser ved i n t he gel s p ec t r a f o r
V- l o ad i n g s bel ow 4%, ( Fi g s . 4A- 4F) . Thus c o nc ent r at i o n of
condensed V0- or Vp 0
g
c hai ns i s expect ed t o be i n s i g n i f i c an t i n
t hese st eam-aged al o mi n o s i l i c at es c o n t ai n i n g l es s t han 4% V.
When V- l ev el s d ecr eased t o 3% fr om 4% V, t he i nt ens e bands at 995
cm" and 405 cm d i sap p ear ed and a s i n g l et at 517 cm" for med fr om
t he d oubl et at 482 cm" and ,527 cm" seen i n Fi g s . 4E, 4F.
Fur t her mor e, t he band at 704 cm d ec r eas ed j n i n t en s i t y f or mi ng a
band near 715 cm" wi t h shoul d er at 685 cm" . Sampl es c o n t ai n i n g
1-3% V ex h i b i t al s o a (weak) br oad band i n t he 725-925 cm" r eg i o n ,
see Fi g s . 4B-4D. These s p ec t r al changes ar e s i mi l ar t o t hose
r ep or t ed f o r V
2
0
5
. n H
2
0 xer ogel s wi t h n>0 (21-24).
Ch ar ac t er i s t i c bands f o r al u mi n o s i l i c at es c o n t ai n i n g l e s s t h a n 4% V
t hat can be r easonabl y assi gned ar e i n t he 400 and 750 cm" r eg i o n .
For V0c t hese bands ar e assi gned t o V-0 s t r et c h i n g v i b r at i o n s
(685- A)? c m ) and - V- 0 bendi ng v i b r at i o n s (480-500 c m ) . The
s t r u c t u r al model of v anad i a gel s i nv o l v es r el at i v el y l ong V-0-V
c hai ns whi ch c ont ai n f our c oor d i nat ed V havi ng d i s t o r t ed
t et r ah ed r al symmet r y. Such a c hai n s t r u c t u r e n ec es s i t at es
r el at i v el y i nt ens e v i b r at i o n al bands i n t he 100-350 cm" r egi on
whi ch ar e t he r es u l t of concer t ed v i b r at i o n al mot i ons o f 0 and V
atoms i n t he c h ai n .

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262
However , t he mu l t i c i p l i c i t y o f bands and r el at i v el y i nt ens e
c h ar ac t er o f t hese c onc er t ed v i b r at i o n al modes ar e not obser ved i n
t he V l oad ed g el s under s t ud y . Thus, s i g n i f i c an t devel opment of
l ong r i bbons o f V
2
0
5
. n H
2
0 , or a p ol y mer i c nat ur e o f t h i s s ur f ac e
s p ec i es , i s not e^ ec t ed r t o ex i s t i n t he V- l oad ed al u mi n o s i l i c at es
under s t ud y .
In summary, i t i s pr oposed t hat at l ow V l e v e l s , st eam-agi ng
( 76 0 C/ 5 h ) gener at es h i gh l y hyd r at ed v anad i a i s l an d s c o n t ai n i n g
d i s t o r t ed t et r ah ed r al and oct ahed r al V atoms (31). Hy d r at i on
woul d change t er mi nal V-0 bond or d er s and / or cap t er mi nal vanadyl
gr oups (21, 22), t her eby r emovi ng st r ong Raman bands above 850
cm" , br oad eni ng V-0 s t r et c h i n g bands i n t he 700-900 cm r egi on
and weakeni ng bands bel ow 350 cm" . Vanad i a f or mat i on i s f av or ed
by t he l i mi t ed hydr ot her mal s t a b i l i t y of t he g e l , Tabl e 1. The
VpOg s t r u c t u r e at l ow V c o nc ent r at i o ns woul d sup p or t eas i l y t he
devel opment o f t hr ee d i mensi onal V
?
0
5
as t he V c o nc ent r at i o n i s
i nc r eas ed t o 4%. Hence, a hyd r at ed l ay er ed v anad i a model i s
env i s i o ned whi ch does not c ont ai n t er mi nal vanadyl gr oups because
of H-bond i ng ef f ec t s and d ecr eased V-0 bond or d er due t o H
2
0
sor bed d ur i ng st eami ng. Thus, t he v anad i a p r esent woul d be a
h i g h l y d i s o r d er ed or p oor l y condensed phase s i mi l ar i n s t r u c t u r e
t o V
2
0
5
. n H
2
0 where n > 1. 6.
XPS Res ul t s
XPS r es u l t s f o r (st eam aged) V- l oad ed al u mi n o s i l i c at e g el s and
al umi nas ar e shown i n Fi q&. 5-8. At l ow (0.5%) V l e v e l s , t he two
sup p or t s c o nt ai n bot h V and V s p ec i es i n t he n ear - s u r f ac e
r eg i o n ; V f or mat i on i n sampl es c o nt ai ni ng as l i t t l e as 0.5% V
has been obser ved al s o by V-NMR (31). Sur f ac e c o nc ent r at i o n o f
V r ap i d l y d ecr eases wi t h V- l o ad i n g s , F i g . 5. Wi t h 2% V onl y V
4
i s obser ved on t he gel ancj
5
5% V i s needed bef or e al l t he V
p r esent i s o x i d i zed t o V on t he al umi na s u r f ac e, F i g . 5.
El ec t r o n par amagnet i c (EPR) s t ud i es o f g el s cont ami nat ed wi t h 1% V
have i n d i c at ed t h at , f o l l o wi n g t he o x i d at i v e d ecomp osi t i on o f t he
nap t ht henat e, 95% o f t he vanadi um was p r esent as V (18). Af t er
st eam ag i n g , t he sampl e, assumed a y el l o w/ gr een c o l o r at i o n
i n d i c at i v e o f t he pr esence of V
2
0
5
whi ch c oul d be v er i f i ed al s o by
Lumi nescence t echni q ues (19).
Tbe r e d u c Un l i t y o f t he vanadi um on t he gel ( i . e . , t he amount o f
V or V obser ved i n H
2
t r eat ed sampl es) i s l es s t han t hat on
t he al umi na; V f or mat i of f i s obser ved onl y at 5% V l o ad i n g s , F i g .
6. Th i s d i f f er en c e can be eas i l y obs er v ed , - i n Fi g . 7 where t he
p er cent age of t he V o r i g i n at i n g onl y fr om V i s p l o t t ed . At 5%
V l o ad i n g , and af t er H
2
t r eat ment , some o f t he vanadi um on t he gel
r emai ned i n t he V st at e-wher eas on t he A1
2
0~ al l o f t he vanadi um
was conv er t ed t o ei t h er V or V , F i g . 6. Hence, c onv er s i on (or
nuc l eat i o n) o f vanadi um t o a V
2
0
5
s p ec i es was p r obabl y more
compl et e on t he A1
2
0~ t han on t he g e l . Th i s c onv er s i on d i f f er en c e
t o V
2
0
5
at a 5% \ r f oad i ng can al s o be i n f er r ed fr om Raman d at a
were t t i e s i g n al - t o - n o i s e (S/N) f o r 5% V/ A1
2
0
3
i s s i g n i f i c a n t l y

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6
OCCELLI AND STENCEL Raman & X-ray Photoelectron Characterization 263
100 \ -
V - LOADING (%)
Figure 6. Percent distribution of V
+ 5
(), V
+ 4
fo) and V
+ 3
() after
reducing in H
2
steam aged V-loaded aluminas. Data for similarly prepared
gels is indicated by () V
+ 5
, (A) V
+ 4
and (#) V
+ 3
.

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264
+ 100 -
>
o
V - LOADING (%)
Figure 7. Reducibility in of steam aged V-loaded aluminas to V
+ 4
(o )
and (#) V
+ 3
. Data for similarly prepared gels is indicated by (A) V
+ 4
and(B) V
+ 3
.
Figure 8. Surface V/Al and V/Si+Al ratios in V-loaded and steam aged
alumina and aluminasilicate gels before [ , ] and after [ O > ]
reduction in H~.

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bet t er t han t he S/N f o r 5%V/gel and conf i r ms t he amorphous nat ur e
of t he V
2
0g p r esent on t he al u mi n o s i l i c at e mat r i x.
Compar i son o f V/ Al at omi c r at i o s f o r A 1
2
0
3
and V/ ( Si +Al ) at omi c
r at i o s f o r V- l oad ed g el s ar e p r esent ed fn F i g . 8. Ov er al l , and
somewhat i nd epend ent o f whet her or not t he sampl es have been
s ubj ec t ed t o HL r ed u c t i o n , t hese r at i o s f o r t he gel ar e
ap p r oxi mat el y 30% s mal l er t han t he v al ues obser ved f o r V on A 1
2
0
3
.
The l eas t squar es l i n ear r egr es s i o n f i t s t o t he V/ A1
2
0 - aat a
ex t r ap o l at es near t he o r i g i n whereas t he c or r es p ond i ng Xiaxa f o r
V/ gel does no t , F i g . 8. Hence, V d i s p er s i o n on t he gel s u r f ac e,
as moni t or ed by XPS, i s l ower t han on A 1
2
0
3
. The hyd r ot her mal
i n s t a b i l i t y o f V l oad ed gel (Tabl e 1) i s pr ot r abl y r es p o n s i b l e f o r
t he l ower V d i s p er s i o n and f o r t he l ower V/ Al +Si r at i o s seen i n
F i g . 8.
Raman and NMR (31) d at a i n d i c at e t hat wi t h up t o 2% V, a
s i g n i f i c an t amount of t he vanadi um i s i n t et r ah ed r al c o o r d i n at i o n
on bot h s up p o r t s . That i s , p oor l y for med Vp 0
5
nH
2
0 (n > 0) on
t he gel and V compounds on t he al umnus* i r r t et r ah ed r al
c o o r d i n at i o n . At l oad i ngs above 2%, t he c o o r d i n at i o n o f vanadi um
on A 1
2
0
3
becomes more oct ahed r al but , u n t i l a l o ad i ng of
ap p r oxi mat el y 4%, c ont ai ns i s o l at ed V
2
0
7
un i t s i ns t ead o f a
condensed V
2
0
5
net wor k. Hence, c o n s i d er i n g t he XPS d at a on
r e d u c i b i l i t / and t he Raman d at a, i t seems t o be p o s s i b l e t o
s t ab i l i z e V agai ns t H
2
r ed uc t i o n whi l e havi ng vanadi um i n
d i f f er en t c o o r d i n at i o n and s p ec i at i o n , but es s en t i al l y i n
i d en t i c al d i s p er s i o n and i s o l at ed u n i t s .
SUMMARY AND CONCLUSIONS
XRD, XPS, and Raman c h ar ac t er i z at i o n of V sup p or t ed on
pseudoboehmi t e al umi na or on amorphous al u mi n o s i l i c at e g el s (met al
l oad ed wi t h a s o l u t i o n of VO Napht henat e i n benzene) have
i n d i c at ed t he pr esence o f t et r ah ed r al l y and o c t ah ed r al l y
c oor d i nat ed vanadi um (31) havi ng s p ec i at i o n and d i s p er s i o n t hat
depends on vanadi um c o nc ent r at i o n (an.d s ur f ac e ar ea) p r esent on
t he st eamed ( 76 0 C/ 5 h ) sampl es.
Oxy cat i ons o f V (V0
2
or VO ) can eas i l y p enet r at e t he gel
mi cr osp ace and br eak Si - O- Al bonds c aus i ng t he c o l l ap s e o f t he gel
mi c r o s t r uc t ur e and mu l l i t e f or mat i on even at l ow (1.5%) V l e v e l s .
Excess V gener at es an x- r ay amor phous, V
2
0
5
- l i k e s p ec i es whi ch i s
h i g h l y hyd r at ed and l es s s u s c ep t i b l e t o cnemi cal r ed uc t i o n t han bul k
In (pseudoboehmi t e) al umi na, A1-0-A1 bonds ar e not eas i l y br oken
by oxy c at i ons o f V and condensed s p ec i es , - ( V- O- V) - , r es i s t an t t o
r ed uc t i o n ar e f or med . In f ac t , i t i s bel i ev ed t hat f o l l o wi n g t he
o x i d at i v e d ecomp osi t i on of t he napht henat e p r ec u r s o r , VO c at i o n s

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266
ar e~d ep os i t ed on t he al umi na s ur f ac e where t hey can be o x i d i zed t o
VO s p ec i es (scheme I and II)
0 0
ii
II
V
/
V
0 0
02 0 0 0
Al Al
Al
1
Al
1
Al
/ \ / \
/ \
(I) (II)
In t he p r esence o f st eam (760' C/5h) hydr oxy vanad yl i ons (and
ot her p r ot onat ed s p ec i es ) ar e for med (scheme III and scheme IV)
0 o
0
o
0
II II II / \ II
H O - V - O H H O - V - O H - ^ H O - V V - O H "V2O 5"
1 1 1 1
o o 0 0
Al Al Al Al
/ \ / \ / \ / \
(IV) (V)
As V l o ad i ngs i n c r eas e, cond ensat i on o f t hese monomeri c s p ec i es
y i e l d d i v anad at es un i t s ( V
2
0
7
) t hat at hi gh (5%) V l ev el s c o l l ap s e
t he al umi na mi cr osp ace and for m a c r y s t al l i n e V
2
0
5
p hase.
Sur f ac e vanadi um appear s t o be most s t abl e (t o r ed uc t i on) at l ow
(<1%) V c o nc ent r at i o n when p r esent as monomeri c vanad yl u n i t s . I t s
s t a b i l i t y d ecr eases wi t h i n c r eas i n g V l e v e l s . It i s l eas t s t ab l e
(t o r ed uc t i on) at hi gh (5%) V l ev el s when p r esent as a sup p or t ed
Vanad i a p hase. Th i s d i f f er en c e i n r eac t i v i t y wi t h V
c o nc ent r at i o ns i s bel i ev ed r es p o n s i bl e f o r t he r ap i d d ec l i n e i n
c r ac k i n g ac t i v i t y obser ved i n dual f un c t i o n c r ac k i n g c at al y s t s
c o n t ai n i n g al umi na when V s t ar t t o exceed t he 1. 0-1. 25 wt.% l ev el
(4). Fur t her d et ai l s of t he mechani sm o f c at al y s t d eac t i v at i o n by
V ar e t he s ubj ec t o f c o nt i nui ng i n v es t i g at i o n s i n our l ab o r at o r i es
by V s o l i d s t at e NMR, XPS, and Raman s p ec t r o s c o p y .
Acknowl edoment s
The aut hor s g r at ef u l l y acknowl edge t he hel p r ec ei v ed fr om Mr . R.
Or t i z d ur i ng sampl e p r ep ar at i o n . Sp ec i al t hanks ar e due t o Dr . P.
S. I yer f o r p r o v i d i n g NMR d at a and t o Dr . P. Ri t z f o r LRS
measur ement s.

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Ref er ences
1. Occel l i , M. L. in " Fl ui d Catal yti c Cracking: Role in Modern
Refi ni ng." ACS Symposium Seri es, Vol . 375: M. L. Occel l i ,
Ed. , ACS, Washington, D. C. , p. 162 (1989).
2. Rooseboom, F. ; Mittelmeijer-Hazeleger, M. C. Moul i j n, J . A. ;
Medema, J.; de Beer, V. H. J.; Gel l i ngs, P. J. J. Phys, Chem.
1980, 84, 2783.
3. Occel l i , M. L. and Stencel , J . M. in " Zeol ites as Catal yst,
Sorbents and Detergent Bui l ders," H. G. Karge and J. Weitkamp
Eds.; El sevi er, p. 127 (1989).
4. Occel l i , M. L. and Stencel , J . M. " Zeol i tes: Facts, Figures,
Future" P. A. Jacobs and R. A. Van Santen, Eds.: El sevi er, p.
1311 (1989).
5. Wachs, I. E. , Hardcastle, F. D. and Chan, S. S. , Mat. Res.
Soc. Symp. Proc. Vol . III, 353 (1988).
6. Wachs, I.E.; Saleh, R. Y. ; Chan, S. S. ; Cherisch, C. C. Appl.
Cat. 1985, 15, 339.
7. Kozlowski, R.; Pet t i fer, R. F.; Thomas, J. M. J. Phys. Chem.
1989, 87, 5176.
8. Haber, J.; Kozlowska, A. ; Kozlowski, R. J. Cat al . 1986, 102,
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3440.
10. Anpo, M.; Sunamoto, M.; Che, M. J. Phys. Chem. 1989, 93, 1187.
11. Anpo. M.; Suzuki, T. ; Yamada, Y. ; Che, M. Proc. 9th Int. Cong.
Cat al . 1988, 1513.
12. Cr i st i ani , C. ; Forzat t i , P.; Busca, G. J. Cat al . 1989, 116,
586.
13. Oyama, S. T. ; Went, G. T. ; Lewis, K. B.; Bel l , A. T. ; Somorjai,
G. A. ; J. Phys. Chem. 1989, in press.
14. Went, G. T. , Oyama, S. T. And Bel l , A. T. J. Phys. Chem.
(submitted)
15. Mi t chel l , B. D. Ind. Eng. Chem. Prod. Res. Dev. 19, 209 (1980)
16. Gi l son, J. P.; Edwards, G. C. ; Peters, A. K.; Rajagopalan, K.;
Wormsbecher 4, R. F. ' Roberie, T. G. ; Shatlock, M. P., J. Chem.
Soc. Chem. Comm. 1987, 91.
17. Samoson, A. ; Lippmaa, E. ; Engelhardt, G. ; Lohse, D.;
Jerschwitz, H. g. , Chemical Physics Letters 1987, 134, 589.
18. Anderson, M. W.; Occel l i , M. L. ; Suib, S. L. , J. Cat al . , in
press.
19. Anderson, M. W.; Occel l i , M. L. ; Suib, S. L. , J. Cat al . , in
press.
20. Occel l i , M. L. and Stencel , J . M. in " Proc. 9th Int. Congress
Catal ysts," Phi l l i ps, M. J. and Ternan, M., Eds.; Vol . 1, p.
214 (1988).
21. Abel l o, L. , Husson, E. , Repelin, Y. and Lucazeau, G. , J. Sol i d
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Spectrochim. Acta, 41A, 993 (1985).
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Spectrochim, Acta, 39A, 641 (1983).

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24. Sanchez, C. , Livage, J . and Lucazeau, G. , Raman Spectrosc.
12, 68 (1982).
25. Wokaun, A. , Schraml, M. and Baiker, A. , J. Cat al . 116, 595
(1989).
26. Vi l chez, F. G. and Gr i ffi t h, W. P., J . C. S. , Dalton, 1416
(1972).
27. Gr i f f i t h, W. P. and Lesniak, P. J. B., J. Chem. Soc. (A),
1066 (1969).
28. Park, Y. S. and Shurwell, H. F. , J. Raman Spectrosc. 18, 247
(1987).
29. Baran, E. J., Cabello, C. I. and Nord, A. G. , J . Raman
Spectrosc. 18, 405 (1987).
30. Seetharaman, S. , Bhat, H. L. and Narayanan, P. S. , J. Raman
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31. Iyer, P. S. , Eckert, H., Occel l i , M. L. and Stencel , J. M.,
t hi s volume.

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Chapter 17
Petroleum Cracking Catalyst Characterization
Secondary Ion Mass Spectrometry Imaging
Processing Methods
D. P. Leta, W. A. Lamberti, M. M. Disko, E. L. Kugler
1
,
and W. A. Varady
Exxon Research and Engineering Company, Annandale, NJ 08801
The characterization of petroleum cracking cat al yst s,
with which a thi rd of the world's crude oi l i s processed,
presents a formidable anal yti cal challenge. The catal yst
part i cl es are in the form of microspheres of 60-70 micron
average diameter which are themselves composites of up to
fi ve di fferent micron and submicron sized phases. In
refi nery operation the catal ysts are poisoned by trace
concentrations of ni ckel , vanadium and other contaminant
metals. Due to the replacement of a small portion of
equilibrium catal yst each day (generally around 1% of the
total reactor inventory) the catal yst part i cl es in a
reactor exi st as a mixture of di fferi ng part i cl e ages,
poisoning l evel s and act i vi t i es.
Direct imaging SIMS has been shown to be capable of
viewing both the phases and contaminants within individual
catal yst part i cl es, and differences from part i cl e to
part i cl e. Multiple image processing techniques now allow
the rapid analysis of the rel at i ve concentrations of
several elements (normally 6-8) on a large number of part-
i cl es (50-100) using multiple low magnification SIMS
images. Using the fact that nickel concentrations
increase systematically with a par t i cl e' s age permits the
analysis of poisoning and elemental composition as a
function of a par t i cl e' s "time in the reactor." Within
individual part i cl es, SIMS views coupled with elemental
image rati os and overlays have also allowed the measure-
ment of the quantity of each phase (such as zeol i t e and
alumina) and the di st ri but i on of nickel and vanadium
poisons in rel ati onshi p to those phases.
The t echni que of Imagi ng Secondar y Ion Mass Spect r omet r y (SIMS) has
pr oven t o be ver y wel l s ui t ed t o t he c h ar ac t er i z at i o n of f l u i d i z ed
p et r ol eum c r ac k i ng c at al y s t s ( FCC) . U" 4 ) The a b i l i t y t o vi ew
1
Current address: West Virginia University, Morgantown, WV 26506
0097-6156/91/0452-0269$07.00/0

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270
el ement al d i s t r i b u t i o n s wi t h 0. 5 mi cr on s p at i al r es o l u t i o n at
c o nc ent r at i o ns i n t he ppm r ange i s wel l s u i t ed t o t he an al y s i s of
t he submi cr on phases and l ow c o nc ent r at i o n cont ami nant s p r esent i n
commer ci al mul t i -component FCC p ar t i c l es . The use o f u l t r a- l o w
l i g h t l ev el i magi ng syst ems(S) wi t h t he i n t r i n s i c a l l y s en s i t i v e
SIMS t echni que makes r eal t i me vi ewi ng o f many o f t he el ement s
i mpor t ant i n FCC c at al y s t s p o s s i b l e. Al umi num, s i l i c o n and t he
r ar e ear t h el ement s ser v e t o d ef i ne t he maj or phases p r esent wi t h i n
each c at al y s t p a r t i c l e , whi l e t he t r an s i t i o n row el ement s and al l
of t he al k al i and al k al i n e el ement s may be seen at t r ac e c o n c en t r a-
t i o n s . Of p ar t i c u l ar i mpor t ance i s t he use of t he t echni que t o
st ud y t he d i s t r i b u t i o n s of n i c k el and vanadi um whi ch ar e t he most
d el et er i o u s of t he cont ami nant met al s . (
6
) Modern i mage p r o c es s i ng
comput er s and sof t war e now al l ow t he r ap i d q u an t i t at i v e an al y s i s o f
SIMS el ement al i mages i n or d er t o more c l ear l y r ev eal t he l o c at i o n s
o f t he c at al y s t phases and t he q u an t i t at i v e d i s t r i b u t i o n s o f t he
cont ami nant met al s on t hose p hases. Al t hough t he an al y s i s t ec h -
ni ques d i s c us s ed i n t h i s st ud y may be ap p l i ed t o any o f t he
cont ami nant el ement s, f o r s i mp l i c i t y we wi l l l i mi t our exampl es t o
t he maj or c at al y s t el ement s, and t he n i c k el and vanadi um
cont ami nant s.
EXPERIMENTAL METHODS
Cat al y s t Pr ep ar at i o n . A l l of t he FCC c at al y s t sampl es used i n t h i s
st ud y were pr epar ed by embeddi ng t he as - r ec ei v ed p ar t i c l es i n
t her mos et t i ng copper doped epoxy (commer ci al l y av ai l ab l e fr om
met al l u r g i c al sup p l y d i s t r i b u t o r s ) t o p r ov i d e el ec t r i c al c o n d u c t i v -
i t y . The har dened epoxy bl oc k s were t hen p o l i s h ed t o expose t he
i n t er i o r s o f t he c at al y s t p ar t i c l es (appr oxi mat e c r o s s - s ec t i o n s )
us i ng s i l i c o n c ar bi d e paper t o 600 g r i t . The p o l i s h i n g i s c ar r i ed
out wi t hout wat er t o av oi d t he p o s s i b i l i t y o f el ement al r e d i s t r i b u -
t i o n . Pr i o r t o d at a c o l l ec t i o n i t i s necessar y t o p r e- s p ut t er
ar eas o f i n t er es t f o r 10-15 mi nut es, whi ch at o mi c al l y removes
s ev er al mi cr ons of mat er i al , c l eani ng away embedded p o l i s h i n g g r i t
and exp osi ng t he und i st ur bed p ar t i c l e i n t er i o r s .
SIMS I ns t r ument at i on. A CAMECA IMS-3f i on mi c r op r obe/ mi c r os c op e,
mod i f i ed by t he ad d i t i o n o f a hi gh s en s i t i v i t y v i d eo based i magi ng
syst em(5) was used f o r el ement al v i ewi ng o f t he FCC p a r t i c l e s .
Oxygen as 0 2
+
was used as t he pr i mar y bombar di ng i o n , at an i mpact
ener gy o f 10. 5 keV and p o s i t i v e second ar y i ons were used f o r d at a
c o l l e c t i o n . Gen er al l y , i n t eg r at i o n t i mes of 8-30 seconds were
s u f f i c i en t t o obt ai n good s i g n al - t o - n o i s e c h ar ac t er i s t i c s i n t he
i mages. A l l o f t he i mages i n t h i s st ud y were c o l l ec t ed usi ng
ei t h er a nomi nal 150 or 400 mi cr on f i el d - o f - v i ew . The t ype o f
i mage i n t eg r at i o n used s et s t he f i n al i n t en s i t y of t he b r i g h t es t
p i x el i n each i mage t o a st and ar d v al ue, ens ur i ng v i ewab i l i t y . As
s uc h , t he br i gh t nes s wi t h i n one i mage may be used t o gauge an
el ement ' s r el at i v e c o nc ent r at i o n fr om r egi on t o r eg i o n , but no
c o n c l u s i o n s shoul d be drawn bet ween d i f f er en t i mages wi t hout us i ng
t he mass s p ec t r al count r at es and compar i son t o s u i t ab l e s t and ar d s .
For t h i s s t ud y , t he d i g i t i z ed br i ght nes s wi t h i n t he i mages were

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17. LETAETAL. PetroleumCracking Catalyst Characterization
271
used wi t hout at t empt t o conv er t t o act ual c o n c en t r at i o n , and as
such al l v al ues r ep r es ent " r el at i v e c o n c en t r at i o n . "
Image Pr o c es s i n g . In our i mage p r o c es s i n g / c o l l ec t i o n syst em t he
SIMS i ns t r ument ' s i n t er n al mul t i channel p l at e / f l u o r es c en t scr een
i s vi ewed usi ng an u l t r ah i g h gai n v i d eo camera cap abl e o f v i ewi ng
t he bur s t s o f l i g h t gener at ed by i n d i v i d u al i o n s . Th i s anal og
v i d eo s i gnal i s d i g i t i z ed and i nt egr at ed us i ng a " Cr y s t al " i mage
p r o c es s o r (MCI Cons ul t ant s ) and t he i nt egr at ed i mages s t or ed as
anal og s i g n al s us i ng an Op t i c al Laser Di sk whi ch p r ov i d es i nexp en-
s i v e h i - f i d e l i t y i mage s t o r age. Post an al y s i s i mage p r o c es s i n g i s
accomp l i shed by r e - d i g i t i z i n g t he i mages wi t h a Mi cr ovax II host ed
Goul d /DeAnza 8500 i mage p r o c es s i ng comput er syst em and us i ng a
combi nat i on o f i n- hous e and commer ci al sof t war e r o u t i n es . Pr i o r t o
t he use of any i mage compar at i ve c al c u l at i o n s , s et s o f i mages ar e
ac c ur at el y r eg i s t er ed wi t h each ot her us i ng c r o s s - c o r r el at i o n
t ec h ni q ues . For al l st ep s o f i mage hand l i ng and p r o c es s i n g ,
r es o l u t i o n s o f ap p r oxi mat el y 512x512 wi t h 256 br i gh t nes s l ev el s ar e
mai nt ai ned .
Di s t r i b u t i o n s Wi t hi n Si n g l e Cat al y s t Par t i c l es
Si l i c o n/ Al umi num Rat i o Images. Many t yp es o f FCC c at al y s t
p ar t i c l es ar e het er ogeneous mi xt ur es o f z eo l i t e, c l ay , al umi na and
s i l i c a/ al u mi n a bi nd er p hases. Each o f t hese phases c o nt ai ns
s i l i c o n and al umi num as t he maj or el ement s, wi t h v ar y i ng Si / A l
r at i o s i n each p hase. It i s p o s s i b l e t o gener at e a " phase map" o f
s i n g l e c at al y s t p ar t i c l es by t ak i ng advant age o f t hese d i f f er i n g
Si / A l r at i o s . Di v i s i o n of t he SIMS Si i on i mage by t he Al i on
i mage pr od uces a Si / A l i n t en s i t y r at i o i mage whi ch of t en c l ear l y
shows t he p o s i t i o n s o f t he p hases. Image d i v i s i o n al s o p r ov i d es
t he ad d i t i o n al ben ef i t o f el i mi n at i n g most o f t he i n t en s i t y v a r i a -
t i o n s caused by t opogr aphy or by nonuni f or m pr i mar y beam i l l u mi n a-
t i o n o f t he sampl ed r eg i o n .
Fi gur e l a and l b show 150 mi cr on f i el d - o f - v i ew Si and Al i on
i mages, r es p ec t i v el y , t aken of a f r es h FCC c at al y s t p ar t i c l e of a
t ype whi ch c ont ai ns no r ar e ear t h exchanged z e o l i t e s . When r ar e
ear t h el ement s ar e p r esent (see l at er d i s c u s s i o n ) t hey g r eat l y
s i mp l i f y t he i d en t i f i c at i o n o f t he z eo l i t e p hase. I ns p ec t i on of
t he Si and Al i mages shows t hat al t hough br i gh t nes s v ar i at i o n s ar e
p r esent i n bot h i mages i t i s ver y d i f f i c u l t t o " see" where t he
v ar i o us phases r es i d e. Di v i s i o n o f t he Si i mage by t he Al i mage
y i el d s f i g u r e l c whi ch shows t he Si / A l i n t en s i t y r at i o i mage, r e-
nor mal i zed t o a vi ewabl e br i g h t n es s . In t h i s r at i o i mage t he
v ar i o us gr ey l ev el s (br i ght nes s es ) c or r es p ond i ng t o t he d i f f er en t
phases may be much more c l ear l y d i s c er n ed . S i l i c a (as s i l i c a
i mp ur i t i es or as aggr egat ed bi nd er phase) gi v es t he hi ghes t Si / A l
r at i o s and i s t h er ef o r e t he br i g h t es t i n t he i n t en s i t y r at i o i mage,
f ol l owed by z eo l i t e > c l ay > added bul k al umi na.
The use o f l i n e p r o f i l e met hods t o d et er mi ne t he d i g i t al gr ey
l ev el s (0-255) p r esent ac r os s t he r at i o i mage i s d emonst r at ed i n

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f i g u r e I d . At t h i s p oi nt i n t he an al y s i s i t i s nec essar y t o
d et er mi ne t he " c ut o f f " gr ey l ev el s whi ch demark each o f t he p hases.
Our exp er i enc e has shown t hat al t hough t he eye seems t o be r eas o n -
abl y abl e t o " see" t he p o s i t i o n o f t he phases i n t he Si / A l
i n t en s i t y r at i o i mage, per haps because of t he b r ai n ' s a b i l i t y t o
see " o bj ec t s " i ns t ead of " gr ey l ev el s " , i t i s of t en d i f f i c u l t t o
ac c u r at el y p i c k t he gr ey l ev el c u t o f f s f o r each p hase. Abs ol ut e
compar i son of t he gr ey l ev el s p r esent i n a set of i mages wi t h t hose
d et er mi ned us i ng st and ar d s i n g l e phase sampl es i s d i f f i c u l t due t o
" d ay - t o- d ay " changes i n i nst r ument t r an s mi s s i o n , p r i mar y i on beam
s t a b i l i t y and u n i f o r mi t y , and t o t he " aut or angi ng" of t he i mage
c o l l ec t i o n syst em (whi ch i nc r eas es t he sy st em' s gai n f o r weaker
s i g n al s t o make t he f i n al i mages v i ewabl e). For compar i son t o
sep ar at e s t and ar d s , no r mal i zat i o n o f t he br i ght nes s l ev el s us i ng a
sep ar at e measurement of t he i on c o unt s - p er - s ec o nd f o r each el ement
ar i s i n g fr om t he en t i r e f i e l d o f vi ew must be d one. For t hese
r easons i t i s best and most conv eni ent t o use known phases wi t h i n
t he an al y s i s f i e l d o f vi ew i t s e l f , ei t h er wi t h i n t he p ar t i c l es
bei ng anal yzed or added as " i nt er nal st and ar d s" t o t he mount i ng
mat er i al , t o d et er mi ne t he gr ey l ev el s r ep r es en t at i v e of each
p hase. Af t er t he gr ey l ev el r ep r es en t at i v e of each phase i s
d et er mi ned fr om l ar ge and wel l d ef i ned r egi ons t he d i f f i c u l t y s t i l l
r emai ns as t o how t o as s i gn t he " p i x el s " whose v al ues f a l l bet ween
t he gr ey l ev el s d et er mi ned as " aver age" f o r each p hase. Due t o t he
l i mi t s o f r es o l u t i o n of t he t echni que (about 0. 5 mi c r o n) , t he
i nt i mat e mi xi ng of t he p hases, and t he ubi q ui t ous p r esence of
bi n d er , t her e ex i s t s a r ange o f measur ed gr ey l ev el s f o r each
p hase. Nor mal l y t he s el ec t i o n of a gr ey l ev el ev enl y spaced
bet ween t he aver age o f two phases may be used as a c u t o f f l ev el t o
d el i n eat e t he bound ar i es o f each p hase. Fi gur e l e shows t he gr ey
l ev el c u t o f f s chosen t o i n d i c at e t he hi gh s i l i c a (cl umped b i n d er ) ,
z eo l i t e, c l ay and al umi na phases p r esent i n t h i s c at al y s t p a r t i c l e .
Exp er i ence has shown t hat t he aver age ar ea c o nc ent r at i o ns
d et er mi ned on st and ar d mat er i al s wi t h known c o nc ent r at i o ns of
z eo l i t e and al umi na phases agr ees wi t hi n +20-30% r el at i v e once t he
c onv er s i on fr om wei ght c o nc ent r at i o n t o vol ume c o nc ent r at i o n has
been made. Improvement , aut omat i on, and mat hemat i cal j u s t i f i c a t i o n
of t h i s p r ocess wi l l be a goal of f ut ur e s t ud y .
Once t he gr ey l ev el s r ep r es ent i ng each of t he phases have been
d et er mi ned , a " s emi - q uan t i t at i v e phase map" such as t hat shown i n
f i g u r e I f may be gener at ed . The whi t e ar eas i n t h i s i mage show t he
hi gh s i l i c a p hase, t he l i g h t gr ey shows t he z eo l i t e p hase, t he d ar k
gr ey t he c l ay phase and t he ver y d ar k gr ey t he added bul k al umi na.
From such an an al y s i s bot h t he p o s i t i o n and t he " ar ea
c o n c en t r at i o n " f o r each phase may be d et er mi ned . It must be kept
i n mi nd t hat t he ar ea c onc ent r at i ons o f each phase d et er mi ned by
v i ewi ng c r o s s - s ec t i o n ed c at al y s t p ar t i c l es ar e p r o p o r t i o nal t o t he
oc c up i ed vol ume f r ac t i o n s but must be c o r r ec t ed bot h f o r a p has e' s
abs ol ut e and " packed " d en s i t i es bef or e compar i ng t he " ar ea
c o n c en t r at i o n s " t o c onv ent i onal wei ght f r ac t i o n s .
Di s t r i b u t i o n o f Ni c k el and Vanadi um Between Phases. Al ong wi t h t he
d et er mi nat i on o f t he amount of each phase p r esent i n i n d i v i d u al
c at al y s t p ar t i c l es i t i s v er y us ef ul t o be abl e t o q uant i f y t he

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17. LETA ET AL. Petroleum Cracking Catalyst Characterization 273
Fi gur e 1. Phase i d en t i f i c at i o n us i ng Si / A l r at i o i mages,
a) s i l i c o n b) al umi num c) Si / A l r at i o i mage d) Si / A l
i n t en s i t y p r o f i l e e) s el ec t i o n o f i n t en s i t y c u t - o f f s
f ) " s emi - q uan t i t at i v e" phase map

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274
d i s t r i b u t i o n o f t r ac e p oi sons such as n i c k el and vanadi um bet ween
t hose p hases. Of p ar t i c u l ar i mpor t ance i s t he d egr ee t o whi ch
vanadi um r es i d es on t he z eo l i t e phase o f a c at al y s t . It has been
f ound t hat vanadi um d eac t i v at es c r ac k i ng c at al y s t s by d e c r y s t a l l i z -
i ng t he z eo l i t e component . (7) In g en er al , we have seen t hat t he
gr eat er t he f r ac t i o n of vanadi um whi ch r es i d es on t he z eo l i t e phase
t he gr eat er t he ac t i v i t y l o s s s uf f er ed due t o vanadi um at t ac k .
Th i s i s t r ue f o r bot h l abo r at o r y doped and eq u i l i b r i u m c at al y s t s .
Al t hough l abo r at o r y met hods o f vanadi um d opi ng may not q u an t i -
t at i v el y mi mi c t he d i s t r i b u t i o n s of vanadi um found i n eq u i l i b r i u m
c at al y s t s , f i n al vanadi um d i s t r i b u t i o n s as d i s c er n i b l e by i magi ng
SIMS i n ei t h er s i t u at i o n seem t o c o r r el at e wel l wi t h t he d egr ee o f
d eac t i v at i o n exp er i enced (i n t hat s i t u at i o n ) . We have al s o seen
t hat whi l e vanadi um has a s i g n i f i c an t d egr ee of mo b i l i t y bot h
wi t h i n and bet ween p ar t i c l es under normal FCC c o n d i t i o n s , n i c k el
t end s t o be i mmobi l i zed once d ep o s i t ed . As s uc h , n i c k el d i s t r i b u -
t i o n s may be used t o bot h d et er mi ne t he appr oxi mat e t i me a p ar t i c l e
has been r ec i r c u l at i n g i n an FCC u n i t (
8
) , as wel l as t o show on
whi ch phases t he c r ac k i ng occur s f o r t he n i c k el p or p hy r i n t ype
mol ecul es p r esent i n FCC f eed s .
At t h i s p oi nt i t may be ap p r op r i at e t o b r i ef l y d i s c u s s t he
mechani sm o f s i gnal f or mat i on i n t he SIMS p r o c es s . A p r i mar y i on
beam i mpi nges upon t he sampl e s ur f ac e and causes t he s p u t t er i n g of
atoms and smal l mol ec ul ar c l u s t er s , some o f whi ch ar e i o n i zed by
t he ener gy of c o l l i s i o n , u s u al l y s ev er al t housand s o f eV. The i ons
t hus c r eat ed ar e av ai l ab l e f o r an al y s i s by c o l l ec t i o n usi ng
el ec t r o s t at i c ac c el er at i o n and mass s p ec t r o met r i c s ep ar at i o n
f ol l owed by s eq uent i al i on c ount i ng or d i r ec t i mage f or mat i on (t he
t ype o f i nst r ument used i n t h i s st ud y ac t u al l y keeps t he s p ut t er ed
i ons f oc us s ed as t hey ar e mass sep ar at ed t hr ough t he use o f i on
l en s es ) . In t he s p ut t er i n g event i t s e l f a s i g n i f i c an t amount of
at omi c mi xi ng o f t he out er 20-30 angst r oms o f a mat er i al o c c u r s ,
c r eat i n g an amorphous and wel l - mi xed r eg i o n . It i s fr om t he t op
few at omi c l ay er s of t h i s r eg i o n , whi ch i s i n st ead y s t at e wi t h t he
s ev er al angst r oms per second s p ut t er i n g r ec es s i o n o f t he s u r f ac e,
t hat t he c o l l ec t ed i ons ar e c r eat ed . The r ap i d s p u t t er i n g and
mi xi ng s i t u at i o n p r ev al ent i n t he " dynami c SIMS" p r oc es s her e has
s ev er al b en ef i c i al c h ar ac t er i s t i c s when ap p l i ed t o t he c h ar ac -
t er i z at i o n of FCC c at al y s t p ar t i c l es . F i r s t , t he r ap i d s p ut t er i n g
al l ows t he t op s ev er al mi cr ons of pr epar ed c r o s s - s ec t i o n al s ur f ac e
t o be removed i n a r easonabl e p er i od o f t i me, t hus at o mi c al l y
r emovi ng mi xi ng and smear i ng ef f ec t s whi ch mi ght have oc c ur r ed
d ur i ng p o l i s h i n g . Sec ond l y , t he at omi c mi xi ng o f t he s ur f ac e t end s
t o el i mi n at e " o v er l ay er " ef f ec t s whi ch mi ght cause one el ement t o
" c o nc eal " anot her . T h i r d l y , i n t he case o f oxi d e c at al y s t s such as
t h es e, t he at omi c mi xi ng phenomena t end s t o d i s t r i b u t e oxygen
t hr oughout t he s p ut t er i n g r egi on i n a r el at i v el y uni f or m manner ,
where i t has t he ef f ec t o f " bu f f er i n g " any mat r i x ef f ec t s on
el ement al i on y i e l d s . Al t hough t he i on y i el d s f o r t he el ement s
( i . e . t he i ons c r eat ed r at i o ed t o t he atoms sp ut t er ed ) v ar y g r eat l y
fr om el ement t o el ement , f o r any one el ement t h i s oxi d e b u f f er i n g
ef f ec t mi ni mi zes t he changes i n i on y i e l d fr om phase t o phase t hus
g r eat l y r ed uc i ng t he d i f f i c u l t i e s nor mal l y encount er ed i n maki ng
SIMS r es u l t s even " s emi - q u an t i t at i v e. "

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275
SIMS i on i mages t aken of t he A l , S i , La, V and Ni d i s t r i -
but i ons on s ev er al p ar t i c l es of eq u i l i b r i u m c at al y s t ar e shown i n
Fi gur e 2a-2e, r es p ec t i v el y . Th i s c at al y s t i s o f t he t ype d esi gned
t o c r ac k vacuum gas o i l s and c ont ai ns onl y r ar e ear t h exchanged
z eo l i t e, c l ay and bi nd er . In t h i s c at al y s t t y p e, much o f t he
z eo l i t e i s p r esent i n 5-10 mi cr on d i amet er cl ump s. Th i s cl umpi ng
makes t he v i s u al i z at i o n o f t h i s phase p o s s i b l e ei t h er as d ar k gr ey
ar eas i n t he al umi num i mage or as t he br i gh t ar eas i n t he l ant hanum
i mage whi ch d i r ec t l y shows t he r ar e ear t h d op i ng i n t he z e o l i t e s .
Q u al i t at i v el y , vanadi um may be seen t o be p r esent at hi gher c onc en-
t r at i o n s ( br i gh t er ) i n t he r egi ons o f t he p ar t i c l es whi ch c o nt ai n
z eo l i t e, whi l e n i c k el shows a st r ong " r i m" d i s t r i b u t i o n on t hese
c r o s s - s ec t i o n al v i ews. Cl o s er i n s p ec t i o n of t he n i c k el i mage al s o
r ev eal s t hat whi l e much o f t he i n t er i o r o f t he p ar t i c l es has a l ow,
but v i s i b l e amount o f n i c k e l , t he r egi ons where z eo l i t e i s p r esent
show al most no n i c k el s i g n al . As p r ev i o u s l y s t at ed n i c k e l ' s
appar ent l ac k o f mo b i l i t y , her e d emonst r at ed even wi t h i n i n d i v i d u al
c at al y s t p a r t i c l e s , has caused t he n i c k el t o be found i n t he
l o c at i o n s where t he p or p hy r i n mol ecul es were c r ac k ed . Ver y r eas o n -
ab l y , i n t h i s case where t he z eo l i t e c r y s t al s ar e cl umped t oget her
and al l ow l i t t l e access t o t h ei r ext er nal s ur f ac e ar eas , t he n i c k el
may be seen t o be excl ud ed fr om t hese r egi ons because o f t he l ar ge
p or p hy r i n mo l ec ul es ' i n a b i l i t y t o d i f f u s e i nt o z e o l i t i c c h annel s .
Fi gur e 3a-3e d emonst r at es an i mage p r o c es s i n g met hodol ogy
us ef ul f o r t he gener at i on of " bi nar y phase masks" whi ch may be used
t o d ef i ne ar eas fr om whi ch t he i nt egr at ed i n t en s i t i es of ot her
el ement s, such as n i c k el and vanadi um, may be d et er mi ned . Fi gur e
3a shows a bi nar y i mage gener at ed by us i ng ei t h er t he Si or t he Al
i mage and s et t i n g al l i n t en s i t y v al ues above a c u t o f f v al ue t o
whi t e, t o d ef i n e t he r egi ons o f t he i mages r ep r es ent i ng t he en t i r e
c at al y s t p a r t i c l e s . Vanadi um and n i c k el i nt egr at ed i n t en s i t i es
(summed gr ey l ev el s ) fr om wi t hi n t h i s r eg i o n , d i v i d ed by t he number
of p i x el s i n t he r eg i o n , i . e. t he mean p i x el i n t en s i t y v al u e, gi v es
t he t o t al " r el at i v e c o nc ent r at i o n" of t he el ement s on t he c at al y s t
p a r t i c l e s . Gener at i on o f a bi nar y map o f t he z eo l i t e phase i s t he
next st ep i n d et er mi ni ng t he t r ac e el ement phase d i s t r i b u t i o n s .
Si nc e t he bi nd er phase i s ver y homogeneousl y d i s t r i b u t ed (as i s
nor mal l y t he case) i t wi l l not be c ons i d er ed as a sep ar at e phase
( p r i mar i l y due t o our i n ab i l i t y t o s ep ar at el y vi ew i t ) . Thus t he
d et er mi nat i on o f t he z eo l i t e d i s t r i b u t i o n wi l l subt end t he i mages
i n t o two p hases, z eo l i t e and c l ay .
As p r ev i o u s l y d i s c u s s ed , t he f or mat i on o f a Si / A l i n t en s i t y
r at i o i mage gi v es a us ef ul map of t he phases wi t h i n t he c at al y s t
p a r t i c l e s . Regi ons o f hi gh Si / A l such as z eo l i t e and cl umped
bi nd er phases show up as br i gh t ar eas i n t he r at i o i mage. Fi gur e
3b shows such an i mage f o r t hese " gas o i l " c at al y s t p a r t i c l e s .
Cons er v at i v e s el ec t i o n of a hi gh c u t o f f v al ue t o i nc l ud e bot h t he
z eo l i t e and bi nd er r egi ons l ead s t o t he gener at i on o f t he bi nar y
i mage shown i n f i g u r e 3c . Si nc e t h i s t ype o f c at al y s t c ont ai ns
r ar e ear t h exchanged z eo l i t es , we may al s o use t he La i on i mage t o
d ef i ne r egi ons of z eo l i t e p hase. Gener at i ng a bi nar y mask fr om t he
La i mage l ead s t o f i g u r e 3d . We have found t hat al t hough t he La
i mage i t s e l f shoul d p r ov i d e a good mask o f t he z eo l i t e p hase, due
t o t he weak s i g n al s o f t he r ar e ear t h el ement s, each of t en p r esent

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Fi gur e 2. Ion i mages o f eq u i l i b r i u m "VGO t yp e" c at al y s t
p a r t i c l e s , a) al umi num b) s i l i c o n c) l ant hanum d) vanadi um
e) n i c k el

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LETA ET AL. Petroleum Cracking Catalyst Characterization 277
Fi gur e 3. B i nar y phase masks of eq u i l i b r i u m VGO c at al y s t
i mages. a) p ar t i c l e l o c at i o n mask b) Si / A l i n t en s i t y r at i o
c) hi gh Si / A l r at i o mask d) hi gh l ant hanum mask e) z eo l i t e
mask ( l o g i c al AND of c & d)

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278
at t ent hs of p er cent c o n c en t r at i o n s , t he i mages may not show
s u f f i c i en t c l a r i t y t o p r o p er l y d ef i ne t he z eo l i t e r eg i o n s .
Per f or mi ng a " l o g i c al and" op er at i on on t he two bi nar y masks, 3c
and 3d , el i mi n at es bot h t he r egi ons of hi gh bi nd er c o nc ent r at i o n
shown i n t he Si / A l bi nar y i mage and t he r egi ons i n t he La bi nar y
i mage whi ch ar e caused by i mp er f ec t i on o f f o c u s . Such an i mage,
whi ch d ef i n es t he z eo l i t e p hase, and by d i f f er en c e t he c l ay p hase,
i s shown i n f i g u r e 3e.
TABLE 1
EQUILIBRIUM " GAS OIL" CATALYST
Phase Ar ea Cone. % o f V ( RO % o f Ni (RC)
13.4% 17.4% (1. 30) 6.2% (0. 46)
86.4% 82.6% (0. 96) 93.8% (1. 09)
EQUILIBRIUM " RESID RESISTANT" CATALYST
Phase Ar ea Cone. % o f V (RC) % o f Ni (RC)
24.3% Zeo l i t e 28.1% (1. 16) 24.4% (1. 00)
3.8% Bul k Al umi na 5.0% (1. 32) 5.9% (1. 55)
71.9% Cl ay 66.9% (0. 93) 69.7% (0. 97)
Measur i ng t he t o t al s i gnal i n t en s i t i es o f vanadi um and n i c k el
wi t h i n t he t o t al p ar t i c l e mask and t he z eo l i t e mask r egi ons al l ows
t he q u an t i f i c at i o n o f t he phase d i s t r i b u t i o n s o f t hese el ement s.
The t op h al f o f Tabl e 1 p r esent s t he r es u l t s o f such an an al y s i s on
t hese i mages o f gas o i l c at al y s t . The number o f p i x el s c ont ai ned
i n t he z eo l i t e mask d i v i d ed by t he number o f p i x el s i n t he p ar t i c l e
mask d i r ec t l y gi v es t he " ar ea p er cent " o f t he z eo l i t e p hase, and by
d i f f er en c e t hat o f t he c l ay (t he v al ues f o r c l ay i nc l ud e most of
t he c o n t r i b u t i o n s o f t he bi nd er p has e). The f r ac t i o n o f t he
vanadi um and n i c k el i n t he d ef i ned z eo l i t e r egi ons d i v i d ed by t he
s i g n al s fr om t he p ar t i c l e mask r egi ons gi v es t he numbers r ep or t ed
i n t he t abl e as "% o f V" (or Ni ) . Th i s f i g u r e i s t he p er cent age o f
t he t o t al q uant i t y o f t he t r ac e el ement whi ch r es i d es on t he
z eo l i t e p hase. " RC" i n t he t abl e i s used t o i n d i c at e t he " r el at i v e
c o n c en t r at i o n " f ac t o r , whi ch i s t he p er cent age o f t he el ement on a
phase d i v i d ed by t he ar ea f r ac t i o n of t hat p hase. Her e an RC v al ue
of 1.00 woul d mean t hat t he phase c ont ai ns a c o nc ent r at i o n of t he
el ement whi ch i s equal t o t he aver age c o nc ent r at i o n o f t he el ement
on t he t o t al p ar t i c l e. RC f ac t o r s gr eat er t han 1.0 mean t hat t he
phase has a hi gher t han aver age c o nc ent r at i o n (and c o nv er s el y f o r
v al ues of l es s t han 1. 0). It may be seen t hat i n t h i s c as e,

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17. LETAETAL. Petroleum Cracking Catalyst Characterization 279
vanadi um i s s i g n i f i c an t l y accumul at ed on t he z eo l i t e p hase, wi t h an
RC f ac t o r o f 1. 3. As was seen q u al i t at i v el y however , n i c k el i s
most l y excl ud ed fr om t he z eo l i t e r egi ons wi t h an RC f ac t o r o f 0. 46.
SIMS el ement al i mages t aken of a second t ype o f eq u i l i b r i u m
commer ci al c at al y s t , mar ket ed as " r es i d r es i s t an t " , ar e shown i n
f i g u r e 4. Car ef ul i n s p ec t i o n of t he Al and Si i mages r ev eal s t he
p r esence of d ar k r egi ons i n t he Si i mage and c or r es p ond i ng l i g h t
r egi ons i n t he Al i mage. These r egi ons ar e bul k al umi na whi ch has
been added t o t he c at al y s t d ur i ng manuf act ur e. The use o f i mage
s u b t r ac t i o n , as d emonst r at ed i n t he Si - A l i mage ( f i g . 4 c ) , q u i c k l y
r ev eal s t he l o c at i o n s of t h i s al umi na p hase. In t he s ubt r ac t ed i on
i mages t he al umi na appear s as bl ac k r eg i o n s . In our syst em, as
wel l as many commer ci al i mage p r o c es s i ng syst ems, i mage s u bt r ac t i o n
(as opposed t o t he more c al c u l at i o n i n t en s i v e i mage d i v i s i o n
op er at i ons ) may be per f or med at v i d eo r at es whi ch makes t he i d e n t i -
f i c at i o n of added al umi na i n FCC p ar t i c l es p o s s i b l e i n r eal t i me
whi l e c o l l ec t i n g t he SIMS d at a. The l ant hanum i on i mage ( f i g . 4d)
shows t hat i n t h i s c at al y s t t ype t he d i s t r i b u t i o n o f t he z eo l i t e
phase i n t h i s c at al y s t i s much more homogeneous t han t he p r ev i o u s l y
c i t ed exampl e. The vanadi um i on i mage ( f i g . 4e) shows t hat t he
al umi na phase has get t er ed t he vanadi um, whi ch shows t he b r i g h t es t
ar eas i n t he l o c at i o n s of t he al umi na. The al umi na i n t he
c at al y s t , i n ad d i t i o n t o l i k e l y p r o v i d i n g i nc r eas ed " bot t oms
c r ac k i n g " , i s maki ng t he c at al y s t somewhat " r es i d r es i s t an t " by
g et t er i n g a f r ac t i o n of t he vanadi um. It must be not ed , however ,
t hat t he z eo l i t e phase ( f i g . 4d) i s al s o " t r ap p i ng" a s i g n i f i c an t
p o r t i o n of t he vanadi um. The n i c k el c o nc ent r at i o ns ( f i g . 4f )
v ar i es somewhat fr om p ar t i c l e t o p ar t i c l e due t o t he p a r t i c l e s '
d i f f er en t r es i d enc e t i mes (ages) i n t he u n i t , but wi t h i n each
p ar t i c l e n i c k el may be seen t o r es i d e t o a s i g n i f i c an t d egr ee on
t he al umi na phase and " c l o s er t o t he o ut s i d e" of t he p a r t i c l e s .
Once agai n , t he n i c k el d i s t r i b u t i o n i s l i k e l y i n d i c at i n g t he
l o c at i o n s wi t h i n t he p ar t i c l es where t he o r gano met al l i c n i c k el
s p ec i es were decomposed.
Image p r o c es s i ng met hod ol ogy, s i mi l ar t o t hat d es c r i bed
e a r l i e r , may be used t o q uant i f y t he phase d i s t r i b u t i o n s of t he
n i c k el and vanadi um i n t hese i mages. The q u an t i t at i v e r es u l t s of
such an an al y s i s may be found i n t he bot t om of Tabl e 1. Her e, t he
RC f ac t o r f o r vanadi um on t he z eo l i t e has been l ower ed fr om t he
1.30 obser ved i n t he gas o i l c at al y s t exampl e t o 1. 16. Th i s may be
p o s t ul at ed t o be due t o t he t r ap p i ng of some o f t he vanadi um by t he
al umi na p hase, whi ch, wi t h an RC of 1.32 i s ac t i n g as a s i nk f o r
vanadi um. Even i f t he t r ap p i ng ef f ec t of t he al umi na i s a
t empor ar y one, i t d ecr eases t he ef f ec t i v e ac t i v i t y o f t he vanadi um
i n t he r egener at o r . Al t hough t he q uant i t y of vanadi um t r ap p ed by
t he smal l q uant i t y of al umi na i n t h i s c at al y s t i s onl y 5% o f t he
t o t a l , i t may be t hat t h i s mechani sm hel p s r ed uce t he ac t i v i t y o f
t he mobi l e vanadi um i n t he r egener at or enough t o make a d i f f er en c e.
As not ed bef o r e, t he n i c k el i s al s o l o c at ed on t he al umi na phase
and her e shows a 1.55 RC f ac t o r . The n i c k e l ' s RC o f 1.00 on t he
z eo l i t e phase (aver age n i c k el c o n t en t ) , as opposed t o bei ng r ed uced
as shown f o r t he gas o i l c at al y s t , may be due t o t he more
ac c es s i b l e ext er nal r eac t i v e s ur f ac e of t he wel l - d i s t r i b u t ed
z eo l i t e c r y s t al s i n t h i s c at al y s t t y p e.

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Fi gur e 4. Ion i mages o f eq u i l i b r i u m " Resi d t yp e" c at al y s t
p a r t i c l e s , a) al umi num b) s i l i c o n c) s i l i c o n mi nus al umi num
d) l ant hanum e) vanadi um f ) ni c k el

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17. LETA ET AL. PetroleumCracking Catalyst Characterization
Di s t r i b u t i o n s From Par t i c l e t o Par t i c l e
281
One o f t he pr i mar y ben ef i t s i n t he use o f t he i magi ng SIMS
t echni que t o vi ew FCC c at al y s t p ar t i c l es l i e s i n i t s a b i l i t y t o
i d en t i f y p ar t i c u l ar c at al y s t p ar t i c l es or t yp es i n mi xt ur es . Th i s
i s p ar t i c u l ar l y i mpor t ant i n c h ar ac t er i z i n g eq u i l i b r i u m c at al y s t
p ar t i c l es where t her e ex i s t s a r ange o f p ar t i c l e ages ( i . e . , t i me
i n t he uni t ) as wel l as t he p o s s i b i l i t y of c at al y s t s fr om d i f f er en t
vend or s and / or sep ar at e ad d i t i v e- c o n t ai n i n g p a r t i c l e s . Used at l ow
mag n i f i c at i o n s and wor ki ng wi t h p ar t i c l es embedded at r easonabl y
hi gh d en s i t i es , i t i s p o s s i b l e t o s i mul t aneous l y vi ew as many as
one hundr ed p ar t i c l e c r o s s - s ec t i o n s . Al t hough at l ow
mag n i f i c at i o n s i t may not be p o s s i b l e t o vi ew t he phases wi t h i n
each c at al y s t p ar t i c l e, c o l l ec t i n g i mages o f al l o f t he el ement s of
i n t er es t i n a s i n g l e r egi on f ol l owed by q u an t i t at i v e i mage
p r o c es s i ng p r ov i d es t he eq ui v al ent of as many as one hundr ed mu l t i -
el ement an al y s es .
Q u a! i t at i v e Obs er v at i o ns . As an exampl e of mu l t i - p ar t i c l e i magi ng
SIMS an al y s i s , eq u i l i b r i u m c at al y s t sampl ed fr om an FCC uni t whi ch
had r ec en t l y begun ad d i ng f r es h c at al y s t fr om a d i f f er en t vendor
has been chosen. In t h i s s i t u at i o n , we have a hand l e on t he
maximum l engt h o f t i me whi ch a new t ype c at al y s t p ar t i c l e has been
i n t he r eac t o r , as wel l as t he minimum t i me f o r an o l d t ype
c at al y s t p ar t i c l e. (Al t hough mi xi ng i n t he f r es h c at al y s t f eed
s i l o adds unc er t ai nt y t o t he s i t u at i o n , as wi l l be seen i n t he
f o l l o wi n g an al y s i s . )
A set of ~400 mi cr on f i el d - o f - v i ew SIMS i mages o f an e q u i l i -
br i um sampl e t aken ap p r oxi mat el y f our weeks i nt o a c at al y s t t ype
change i s shown i n Fi gur e 5. It may be seen t hat t he l ant hanum
(5b) and cer i um (5d) d i s t r i b u t i o n s ar e not i d en t i c al . Usi ng t he
mass s p ec t r al mode of SIMS an al y s i s on sep ar at e sampl es of t he o l d
and new c at al y s t t yp es i t was found t hat t he o l d c at al y s t (l onger
r es i d enc e t i me i n t he uni t ) had a l ant hanum t o cer i um r at i o of
ap p r oxi mat el y t wi ce t he new t y p e. Th i s d i f f er en c e may be used t o
r ap i d l y i d en t i f y t he vendor o f each i n d i v i d u al p a r t i c l e . Fi gur e 5f
shows t he " cer i um mi nus l ant hanum" i mage i n whi ch t he o l d p ar t i c l es
appear ver y d ar k and t he new p ar t i c l es appear whi t e. The n i c k el
i n t en s i t i es (5e) ar e, q u al i t at i v el y , t he i nv er s e of t h i s s ubt r ac t ed
i mage. That i s , t he p ar t i c l es known t o be o l d er may be seen t o
c o nt ai n more n i c k el . The vanadi um i mage (5c) al s o shows a c o r r e l a -
t i o n wi t h age, but t he c o nt r as t fr om o l d t o new p ar t i c l es i s much
l es s t han f o r n i c k el . Th i s may be i n t er p r et ed t o d emonst r at e t hat
vanadi um has ex h i bi t ed a s i g n i f i c an t , but f i n i t e , d egr ee of
p ar t i c l e t o p ar t i c l e mo b i l i t y i n t he FCC u n i t .
Q uan t i t at i v e Mu l t i - p ar t i c l e An al y s i s . In or d er t o d et er mi ne t he
r el at i v e c o nc ent r at i o ns o f each of t he el emen t s - o f - i n t er es t (her e
t aken t o mean a d i mens i onl es s measure o f t he v ar i at i o n s of each
el ement ' s c o nc ent r at i o n fr om p ar t i c l e t o p ar t i c l e wi t h i n t he
f i el d - o f - v i ew ) , t he s i l i c o n i mage i s used t o gener at e a bi nar y mask
whi ch d ef i n es t he p o s i t i o n of each o f t he c at al y s t p a r t i c l e s . In
cases where t he p ar t i c l es ar e t o uc h i n g , i t i s ad d i t i o n al l y
necessar y t o manual l y draw a l i n e of s ep ar at i on bet ween t hem. Once

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Fi gur e 5. Low magn i f i c at i o n i on i mages o f eq u i l i b r i u m c at al y s t
p ar t i c l es sampl ed f our weeks i nt o a c at al y s t t ype change,
a) s i l i c o n b) l ant hanum c) vanadi um d) cer i um e) ni c k el
f ) cer i um mi nus l ant hanum

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17. LETA ETAL. PetroleumCracking Catalyst Characterization 283
t h i s p ar t i c l e mask i s gener at ed , t he mean i n t en s i t y o f each of t he
el emen t s - o f - i n t er es t i s d et er mi ned wi t h i n each of t he " p ar t i c l e"
r egi ons ( p r o p r i et ar y s of t war e). In t h i s c as e, t he r el at i v e c onc en-
t r at i o n s of S i , A l , La, Ce, Ni and V on each p ar t i c l e were d et er -
mi ned . To show t he p o t en t i al o f such an al y s i s , t he r el at i o n s h i p o f
vanadi um t o t he ot her el ement s was d et er mi ned i n or d er t o gai n
i n s i g h t i nt o t he f ac t o r s c o n t r o l l i n g i t s f i n al d i s t r i b u t i o n .
Fi gur e 6 shows t he r el at i o n s h i p o f vanadi um t o n i c k el f o r t he
sampl e ment i oned above, t aken f our weeks af t er t he c at al y s t t ype
change. Not e t hat t he uni t s on t h i s , and t he f o l l o wi n g f i g u r es ,
ar e t he mean gr ey l ev el s fr om each p ar t i c l e, r angi ng fr om 0-255,
whi ch were d i g i t i z ed fr om t he SIMS i on i mages. The new c at al y s t
p a r t i c l e s , as d et er mi ned by t h ei r l ower c al c u l at ed La/ Ce r at i o s ,
ar e i d en t i f i ed by a " * " .
In f i g u r e 6 t he ni c k el c o n c en t r at i o n , shown on t he X- ax i s , i s
i nt end ed t o i n d i c at e t he " age" of t he i n d i v i d u al p a r t i c l e s .
Al t hough t he n i c k el c onc ent r at i on o f t he p ar t i c l es i s c er t ai n l y
p r o p o r t i o nal t o t h ei r age, i t i s l i k e l y t hat t he r el at i o n s h i p i s
not exac t , and may be af f ec t ed by p ar t i c l e s i z e. It has been shown
t hat n i c k el i s o f t en , but not al ways, found t o r es i d e i n a " r i m"
d i s t r i b u t i o n on t he c r o s s - s ec t i o n ed c at al y s t p a r t i c l e s . Th i s
i n d i c at es t hat t he n i c k el - c o n t ai n i n g mol ecul es of t en c r ac k r ap i d l y ,
r el at i v e t o t h ei r speed of d i f f u s i o n i nt o t he c at al y s t p a r t i c l e s .
Th i s d i f f u s i o n l i mi t at i o n l ead s t o t he p o s s i b i l i t y t hat t he " quant -
i t y o f n i c k el on a p ar t i c l e per t he p a r t i c l e ' s ext er nal s ur f ac e
ar ea" (her e meani ng t he ar ea of t he s ur f ac e o f t he ~30-90 mi cr on
s p her es , not t he " s ur f ac e ar ea" of t he c at al y s t ) woul d be a more
c o r r ec t d et er mi nant of age t han woul d t he n i c k el per vol ume, whi ch
i s t he c o n c en t r at i o n . Two f ac t o r s have pr event ed us fr om ap p l y i ng
t he ef f ec t s o f t h i s d i f f u s i o n l i mi t at i o n , whi ch may l ead t o l ar g er
p ar t i c l es showi ng l ower c onc ent r at i ons of n i c k el at equal age t han
s mal l er ones, i n t he c al c u l at i o n of t he p a r t i c l e s ' age d i s t r i b u -
t i o n s . F i r s t , we have seen t hat t he d egr ee of " r i m" d i s t r i b u t i o n
f o r n i c k el v ar i es among d i f f er en t eq u i l i b r i u m c at al y s t samp l es,
p r obabl y due t o d i f f er en c es i n t he d i f f u s i o n l i mi t at i o n s o f t he
c at al y s t t y p es . Sec ond l y , al t hough we do d et er mi ne t he vi ewed ar ea
of each of t he p ar t i c l es , we have no way of d et er mi ni ng t o what
p o i nt i n i t s c r o s s - s ec t i o n an i n d i v i d u al p ar t i c l e has been
p o l i s h ed . Th er ef o r e, onl y a s t a t i s t i c a l an al y s i s o f l ar ge numbers
of p ar t i c l es , combi ned wi t h q u an t i t at i v e d et er mi nat i on of t he
r ad i al d i s t r i b u t i o n f unc t i o ns f o r n i c k el , woul d al l ow t he p r op er
use o f a f ac t o r exp r es s i ng t he mi x bet ween Ni /v ol ume and Ni / s u r f ac e
ar ea t o be used . Combi ned wi t h t he necessar y assumpt i on t hat t he
c o nc ent r at i o n o f ni c k el i n t he FCC u n i t ' s f eed has been ver y
c onst ant over a y ear - l o n g p er i od (of t en known t o be f al s e) l ead s us
t o mer el y use t he ni c k el c o nc ent r at i o n as t he i n d i c at o r o f age.
Ret ur ni ng t o f i g u r e 6, we may not e t hat even wi t h al l o f t hese
c av eat s , t he use of mean ni c k el i n t en s i t y as t he age i n d i c at o r has
gi v en a ver y good s ep ar at i on of t he new p ar t i c l es (" *" ) on t he
l e f t , fr om t he o l d p ar t i c l es on t he r i g h t . Not e t he one " new"
p ar t i c l e on t he ext r eme r i g h t o f t he p l o t . Al t hough i t appear s
t hat t h i s p ar t i c l e i s mi sp l aced on t he p l o t , an an al y s i s of i t s
Si / A l r at i o shows i t t o be d i f f er en t fr om t he ot her new p a r t i c l e s .
A check o f t he r ef i n er y ' s r ec or d s r ev eal ed t hat al t hough t hey had

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17. LETA ET AL. PetroleumCracking Catalyst Characterization 285
been usi ng t he " o l d " t ype of c at al y s t f o r about a y ear , p r i o r t o
t hat t i me t hey had been usi ng a c at al y s t fr om t he same vendor as
t hat o f t he " new" t y p e. Th i s " ol d o l d " c at al y s t was o f a d i f f er en t
bi nd er t y p e, ex p l ai n i n g i t s d i f f er en t Si / A l r at i o , but bei ng fr om
t he same v end or , happens t o have t he same La/ Ce r at i o as our new
c at al y s t p a r t i c l e s .
From t he vanadi um c onc ent r at i ons shown i n t he f i g u r e, we
i mmed i at el y d i s c er n two f ac t s . F i r s t , even at v er y s hor t t i mes i n
t he uni t t he p ar t i c l es have become i mpr egnat ed wi t h a s i g n i f i c an t
q uant i t y of vanadi um. Sec ond l y , t h i s r ap i d d i f f u s i o n o f vanadi um
does not l ead t o a t o t al homogenei t y o f vanadi um c o nc ent r at i o n
r eg ar d l es s o f age. It woul d seem l i k e l y t hat s ev er al mechani sms o f
vanadi um bi nd i ng or t r ans p o r t ar e o c c u r r i n g , l ead i ng t o a mi xt ur e
o f s hor t and l ong vanadi um i mpr egnat i on k i n et i c s .
Fi gur e 7 shows a s i mi l ar an al y s i s o f anot her sampl e t aken fr om
t he same uni t f o ur weeks l at er . Al t hough not as t i g h t l y sep ar at ed
i n t o o l d and new p ar t i c l es , t he same gener al obs er v at i ons s t i l l
h o l d . It i s bel i ev ed t hat some of t he mi xi ng o f o l d and new t ype
p ar t i c l es i s r e a l , o c c ur r i n g due t o t he mi xi ng of o l d and new
c at al y s t t yp es i n t he " f r es h c at al y s t f eed s i l o " l ead i ng t o a
gr ad ual change t o t he new c at al y s t t y p e, and t hat some of t he
mi xi ng i s due t o t he d i f f i c u l t i e s encount er ed wi t h c o r r ec t l y
d et er mi ni ng a p a r t i c l e ' s age. The l ar ge number of p ar t i c l es
sampl ed i n t h i s case (71) as wel l as t he more even mi xt ur e of
s ev er al c at al y s t t y p es , makes t h i s d at a bet t er s u i t ed f o r use as a
d at a base f o r an emp i r i c al vi ew of t he f ac t o r s af f ec t i n g vanadi um
c o nc ent r at i o ns on i n d i v i d u al p ar t i c l es .
In or d er t o emp i r i c al l y remove t he ef f ec t s o f age, as d et er -
mi ned by t he n i c k el c o n c en t r at i o n , fr om t he vanadi um d i s t r i b u t i o n ,
a r eg r es s i o n o f t he d at a was per f or med t o d et er mi ne a best f i t
f un c t i o n al for m r el at i n g vanadi um wi t h n i c k e l . Wi t h t he f o r c ed use
o f a zer o i n t er c ep t , f o r t h i s case (and s ev er al o t h er s , not shown)
best r es u l t s were obt ai ned f o r f unc t i o ns o f t he t y p e:
V = A * ( N i V 3 ) .
No fundament al exp l anat i on f o r t h i s emp i r i c al l y d er i v ed r e l a -
t i o n s h i p has y et been p o s t u l at ed . The gener al shape o f t h i s t ype
o f f un c t i o n i s r easonabl e i f one c o ns i d er s t he mo b i l i t y o f vanadi um
and t he l ac k o f mo b i l i t y o f n i c k el . The const ant " A" must be such
t hat young p ar t i c l es have a gr eat er V/ Ni r at i o t han t hat of t he
f eed and o l d p ar t i c l es have a l ower V/ Ni r at i o t han t hat o f t he
f eed . Gi ven q u an t i t at i v e d ep o s i t i o n o f bot h met al s fr om t he f eed
t o t he c at al y s t ( S) , t he aver age V/ Ni r at i o on t he c at al y s t must be
equal t o t hat i n t he f eed , but due t o t he t r an s f er o f vanadi um,
o l d er p ar t i c l es ar e l o s i n g vanadi um t o younger ones. Ev en t u al l y ,
i t appear s t hat t he o l d es t p ar t i c l es appr oach t he eq u i l i b r i u m
s i t u at i o n of l o s i n g vanadi um as f as t as t hey aq ui r e i t , and t h ei r
vanadi um c o nc ent r at i o n as y mp t o t i c al l y appr oaches a c onst ant whi l e
t h ei r n i c k el c o nc ent r at i o n r i s e s . Fi gur e 8 p r es ent s t he c al c u l at ed
cur v e and t he r es i d u al v al ues f o r vanadi um as a f un c t i o n o f t he
cube r oot o f n i c k e l . The f i t i s q ui t e r eas o nabl e, wi t h an R
2
o f
0. 70 and a f a i r l y even s c at t er of t he r es i d u al s .

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288
Sear c hi ng f o r t he next most c r i t i c a l d et er mi nant o f t he
vanadi um d i s t r i b u t i o n r ev eal ed a r el at i o n s h i p bet ween vanadi um and
t he q uant i t y o f z eo l i t e i n each p ar t i c l e, as measur ed us i ng t he
La+Ce i n t en s i t y v al u e.
Fi gur e 9 p r es ent s t h i s r el at i o n s h i p f o r t he measur ed vanadi um
v al ues (boxes), as wel l as f o r t he r es i d u al vanadi um v al ues (+)
af t er s u bt r ac t i o n o f t he c al c u l at ed c o n t r i b u t i o n s o f t he p a r t i c l e s '
age. Bot h s et s o f v al ues show a weak t r end f o r p ar t i c l es wi t h more
z eo l i t e t o c o nt ai n more vanadi um, an obs er v at i on made q u al i t at i v el y
e a r l i e r i n t h i s st ud y by v i ewi ng t he i n d i v i d u al p hases. I nc l ud i ng
a t er m i n our " f i t " t o account f o r t h i s r el at i o n s h i p i n t he for m of
V = A * ( Ni V3 ) + B*(La+Ce)
l ead s t o i mprovement of t he R
2
t er m t o 0. 79.
Fur t her i n s p ec t i o n o f t he d at a showed a t h i r d , but even more
t enuous, r el at i o n s h i p o f vanadi um wi t h t he Si / A l r at i o o f t he
p a r t i c l e s . Fi gur e 10 p l o t s t h i s r el at i o n s h i p f o r t he measur ed d at a
and f o r t he r es i d u al v al ues af t er s ubt r ac t i o n o f t he c al c u l at ed
ef f ec t s o f bot h age and z eo l i t e c o nt ent . Her e, c o r r ec t i o n f o r
t hese t er ms, p r i o r t o l o o k i ng f o r a r el at i o n s h i p , becomes even more
i mpor t ant due t o t he l ac k of i ndependence o f t he Si / A l r at i o s fr om
t he age and t he z eo l i t e l ev el s . From t he " measur ed" vanadi um
v al ues shown i n f i g . 10 i t can be seen t hat t he new c at al y s t t ype
p ar t i c l es have, i n g en er al , hi gher Si / A l r at i o s t han do t he o l d .
It i s v er y r easonabl e f o r them t o have l es s vanadi um mer el y because
t hey have been i n t he uni t f o r l es s t i me. A d d i t i o n al l y , s i n c e
z eo l i t e has a hi gher Si / A l r at i o t han do t he ot her phases i n t he
c at al y s t p ar t i c l es , some s o f t eni ng o f t he appar ent r el at i o n s h i p i s
l i k e l y due t o t he changes i n z eo l i t e cont ent (whi ch we have found
l ead s t o more vanadi um i n hi gher Si / A l c as es ) . Gi ven t hese l i mi t a -
t i o n s , t he r es i d u al v al ues do show a t end ency f o r t her e t o be
somewhat more vanadi um i n p ar t i c l es wi t h l ower Si / A l r at i o s . Th i s
i s p r obabl y an i n d i c at i o n o f t he " t r ap p i ng" ef f ec t o f al umi na i n
t he c at al y s t p ar t i c l es , as demonst r at ed e a r l i e r . I nc l ud i ng t h i s
t er m i n our f i t t o account f o r t h i s r el at i o n s h i p as
V = A * ( Ni V3 ) + B*(La+Ce) + C* ( Si / Al )
l ead s t o i mprovement of t he R
2
t er m t o 0. 84. The r el at i v e st and ar d
er r o r s o f t he A, B and C c ons t ant s ar e 5%, 18%, and 28%,
r es p ec t i v el y , whi ch ser v es as an i n d i c at i o n bot h o f t he q u al i t y o f
t he f i t as wel l as showi ng t he r el at i v e i mpor t ance o f each o f t he
par amet er s t o t he f i n al vanadi um d i s t r i b u t i o n . We have not
i nc l ud ed t he ac t ual v al ues f o r t he A, B, and C t er ms s i n c e t hey ar e
r el at ed onl y t o t he " gr ey l ev el " measur ement s, and we wi sh t o av oi d
any c o nf us i o n wi t h act ual c o nc ent r at i o n r el at ed emp i r i c al
r el at i o n s h i p s .
A p r es ent at i o n of t he f i n al c al c u l at ed " cur v e" f o r t he
vanadi um v al u es , p l o t t ed agai ns t n i c k el (age) i s shown i n Fi gur e
11. Al t hough we have ad mi t t ed l y t aken more l i b e r t i e s wi t h our
emp i r i c al f i t t han t he p r obabl e d at a q u al i t y p er mi t s , we have
i nt end ed an exampl e o f t he t yp es o f an al y s i s t hat become p o s s i b l e
us i ng t he combi nat i on o f modern i mage p r o c es s i ng t echni ques and

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292
i magi ng SIMS. In more c o n t r o l l ed (but per haps l es s r e a l i s t i c )
sampl e p r ep ar at i o ns done i n t he l ab o r at o r y , such an an al y s i s mi ght
be expect ed t o r ev eal more d epend abl e r el at i o n s h i p s .
REFERENCES
1. Jaras, S. , Appl. Cat al . , 2, 207 (1982).
2. Kugler, E. L. , and Leta, D. P., J . Cat al . , 109, 387 (1988).
3. Leta, D. P., and Kugler, E. L. , "Imaging SIMS in Cat al ysi s" ,
SIMS VI, Secondary Ion Mass Spectrometry, A. Beninghoven,
A. M. Huber, H. W. Werner, eds., 373 (1987).
4. Leta, D. P., and Kugler, E. L. , American Chemical Society
Symposium Series 411, " Characterization and Catalyst
Development," S. A. Bradley, M. J. Gattuso, R. J . Bert ol aci ni ,
Eds., ACS, Washington, D.C., 1989, pp. 354-364.
5. Leta, D. P., "Springer Series in Chemical Physics 44", A.
Benninghoven, R. J . Colton, D. S. Simons and H. W. Werner,
eds., Springer-Verlay, Berl i n, 1986, p. 232.
6. Mi l l s, G. A. , Ing. Eng. Chem. 42, 182 (1950).
7. Ri t t er, R. E. , Rheaume, L. , Welsh, W. A. , and Magee, J . S. ,
Oi l and Gas J., 103, (July 6, 1981).
8. Palmer J . L. , and E. B. Cornel ius, Journal of Applied
Cat al ysi s, vol . 35 (1987), pages 217-235.

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7
Chapter 18
Aluminum-Exchanged Sepiolite as a Component
of Fluid Cracking Catalysts
A. Corma, V. Forns, A. Mifsud, and J. Prez-Pariente
Instituto de Tecnologia Quimica, UPV-CSIC, Universidad Politcnica
de Valencia, Camino Vera S/N, 46022 Valencia, Spain
Sepiolite has been made exchangable by chemical
treatments and Mg
2+
at the border of the channels
has been substituted by Al
3+
. In this way
sepiolite with mild acidity, controlled mesopore,
and improved stability has been obtained. This
material is active for gasoil cracking, giving a
good bottom conversion, and light cycle oi l
products without excessive gas and coke
formation. Meanwhile, it is active for vanadium
passivation.
S e p i o l i t e i s a f i b r o u s magnesium s i l i c a t e , wh i c h i s formed
of t a l c - l i k e ri b b on s arran g ed i n s u c h a way t h a t t h e
t e t r a h e d r a l s h eet i s c on t i n u ou s b u t i n v e r t s a p i c a l
d i r e c t i o n s i n ad j ac en t ri b b on s (1) . I n t h i s way , c h an n el s
of 10.8 x 4.0 A i n a c r o s s -s e c t i o n p e r p e n d i c u l a r t o t h e
l e n g t h of t h e f i b r e (C ax i s ) are g en erat ed . The av erag e
f i b r e l en g t h of t h e mi n eral v a r i e s b etween 0.5 and 1.0 /xm,
and reag en t mol ec u l es have on l y ac c es s t o a s mal l p o r t i o n
of t h e i n t e r i o r of t h e c h an n el s . Na t u r a l ( 2 -4 ) , a c i d
l eac h ed (5) , and exc h an g ed s e p i o l i t e (6-8) h av e b een fou n d
u s e f u l f o r v an ad i u m p a s s i v a t i o n i n FCC c a t a l y s t s . However
a c l o s e r l ook t o t h e s t r u c t u r e and t e x t u r a l p r o p e r t i e s of
t h e s e p i o l i t e s t r o n g l y s u g g es t s t h a t t h i s m a t e r i a l ,
c o n v e n i e n t l y mod i fi ed , c ou l d p l a y a more e x t e n s i v e r o l e
i n FCC c a t a l y s t s . In d eed , t h e p r o p e r t i e s of t h e n a t u r a l
m a t e r i a l s u c h as s u r f a c e area and p ore volume c o u l d b e
ad eq u at e f o r u s e i n c a t a l y s i s . However, and more
s p e c i f i c a l l y f o r FCC c a t a l y s t s , s e p i o l i t e p res en t s a
l i m i t a t i o n d e r i v e d from i t s v ery low a c i d i t y .
Fu rt h ermore, i t b ecomes d i f f i c u l t t o i n t rod u c e
d i r e c t l y any a c i d i t y , due t o t h e v ery low i o n exc h an g e
c a p a c i t y of t h i s m a t e r i a l . The s t r u c t u r e of t h e
s e p i o l i t e g i v en i n Fi g u r e 1, shows t h a t t h e o c t a h e d r a l
0097-6156/91/0452-0293$06.00A)

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Si l i con
@ Magnesi um
O Oxygen
Hydroxyle
0 Crystal l ization Water
Figure 1. (001) projection of the unit cell of the sepiolite.

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18. CORMA ETAL. Aluminum-Exchanged Sepiolite
295
l a y e r i s composed mai n l y b y Mg i on s , 25% of wh i c h are
l o c a t e d a t t h e ed g es wh i c h form t h e "w a l l s " of t h e
c h an n el s , ru n n i n g al on g t h e f i b r e . T h es e Mg
2 +
, wh i c h are
c oord i n at ed wi t h fou r oxy g en s and two wat er mol ec u l es , are
mob i l e and c an , u n d er t h e h y d rot h ermal c o n d i t i o n s i n t h e
reg en erat or, mi g rat e t o t h e z e o l i t e component of t h e FCC,
and t o d ec reas e t h e s t a b i l i t y of t h e z e o l i t e . T h i s
phenomena h as b een ob s erv ed i n c ommerc i al s amp l es of FCC
c a t a l y s t s ( 5) . Nev ert h el es s , s e p i o l i t e h as b een p rov ed
t o b e an e x c e l l e n t v an ad i u m s c av en g er ( 4 ) .
I n ou r c as e, we have mod i fi ed t h e s e p i o l i t e i n ord er
t o i mp rov e t h e t e x t u r a l c h a r a c t e r i s t i c s , wh i l e remov i n g
t h e Mg
2 +
i on s of t h e b ord er and i n t r o d u c i n g ot h er c a t i o n s
wh i c h c an g i v e a c i d p r o p e r t i e s t o t h i s m a t e r i a l . I n t h e
p res en t work, t h e a c i d i t y , s t a b i l i t y and t e x t u r a l
p r o p e r t i e s of mod i fi ed s e p i o l i t e s are p res en t ed , and i t s
i m p l i c a t i o n s i n g a s o i l c r a c k i n g and v an ad i u m t r a p p i n g h av e
b een s t u d i e d .
E x p eri men t al
Ma t e r i a l s
S e p i o l i t e from V a l l e c a s ( S p ai n ) wi t h a c h emi c al
c omp os i t i on g i v en i n T ab l e I , was u s ed as s t a r t i n g
m a t e r i a l . Fol l owi n g t h e p roc ed u re d e s c r i b e d p r e v i o u s l y
( 8 ) , b etween 1.7 and 2 meq^.g'
1
of Na
+
, La
3 +
, A l , C r
3 +
and
H
+
were i n t rod u c ed i n t h e o c t a h e d r a l s h eet of t h e
s i l i c a t e , r e p l a c i n g t h e magnesium i on s l o c a t e d at t h e
ed g es of t h e f i b r e s i n n a t u r a l s e p i o l i t e ( Fi g u re 1 ) .
T ab l e I . C h emi c al c omp os i t i on of n a t u r a l V a l l e c a s -t y p e
s e p i o l i t e ( wt % ) .
S i 0
2
60.31
A1
2
0
3
1.88
Fe
2
0
3
0.48
CaO 0.27
MgO 25.48
Na
2
0 0.12
K
e
0 0.26
T i 0
2
0.22
Wei g h t l o s s on
c a l c i n a t i o n at 1000
f i
C 10.88
The c a t a l y s t s s t u d i e d were p rep ared b y d i s p e r s i n g 20
wt% of a USY z e o l i t e wi t h a 2.433 nm of u n i t c e l l s i z e i n
e i t h e r s i l i c a ( B as f ( D-l l -1 1 ) ) or a l u m i n i c s e p i o l i t e
( SA1 ) . The f i n a l c a t a l y s t was steamed a t 7 50
a
C i n a 100%
s t eam f o r 6 h ou rs .

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8
A c i d i t y Measurements
A c i d i t y measurements were c a r r i e d ou t f o l l o w i n g
a d s o r p t i o n / d e s o r p t i o n of p y r i d i n e a t d i f f e r e n t
t emp erat u res b y I.R. s p ec t ros c op y . Wafers of 10 mg.cm"'
of p u re sample were p r e t r e a t e d two h ou rs a t 10"
2
Pa and
t emp erat u res v a r y i n g b etween 100 and 4 50
a
C, i n a
g r e a s e l e s s c on v en t i on al p y rex IR c e l l . A f t e r t h a t , 6.10
2
Pa of p y r i d i n e were i n t rod u c ed i n t h e c e l l and d es orb ed
f o r 1 h a t 150, 300 and 4 50
a
C; a f t e r eac h t reat men t , t h e
I.R. s p ec t ru m was rec ord ed a t room t emp erat u re i n a P e r k i n
El mer 580 B s p ec t rop h ot omet er eq u i p p ed wi t h Dat a S t a t i o n .
From t h e i n t e n s i t y of t h e b ands of ad s orb ed p y r i d i n e
we c an measure t h e Lewi s (1450 cm"
1
) and B ron s t ed a c i d i t y
(1540 cm"
1
) ( 8 , 9 ) . When i n t e n s i t y of B ron s t ed I.R. b and
i s t oo low, we c an u s e t h e i n t e n s i t y of 1490 cm"
1
b and
as s i g n ed t o p y r i d i n e ad s orb ed on b ot h Lewi s and B ron s t ed
a c i d s i t e s . A f t e r Hughes and Wh i t e ( 1 0) , t h e ap p aren t
mol ar e x t i n c t i o n c o e f f i c i e n t r a t i o of t h e 1490 and 1450
cm"
1
b an d s of p y r i d i n e ad s orb ed on Lewi s s i t e s c an b e
es t i mat ed as e i
4 5 0
/
L
1 4 9 0
= 6. I n c on s eq u en c e we c an
c a l c u l a t e t h e c o n t r i b u t i o n of B ron s t ed s i t e s t o t h e
i n t e n s i t y of t h e 1490 cm"
1
b and from eq u at i on
l B
14 90
=
^ltoO "
l L
1 4 5 ( /
6
C
1
!
I n t h i s p ap er we w i l l c a l l "b " p aramet er t h e v al u es of
c a l c u l a t e d I
B
1 4 9 0
-
C a t a l y t i c exp eri men t s
The exp eri men t s were c a r r i e d ou t i n a fi x ed -b ed t u b u l a r
r e a c t o r , h eat ed b y an e l e c t r i c fu rn ac e d i v i d e d i n t o t h ree
h e a t i n g z on es . P r i o r t o eac h exp eri men t t h e c a t a l y s t was
s t r i p p e d wi t h N
2
at 482C ( r e a c t i o n t emp erat u re) f o r 20
mi n u t es . Then t h e r e a c t a n t ( wh i c h c h a r a c t e r i s t i c s are
g i v en i n T ab l e I I ) was c h arg ed a t t h e t op of t h e r e a c t o r
b y a c o n s t a n t -r a t e p o s i t i v e -d i s p l a c e m e n t pump. The
c a t a l y s t t o o i l r a t i o wi t h r e s p e c t t o t h e z e o l i t e c on t en t
was v a r i e d b etween 0.09 and 0.23 g.g"
1
b y c h an g i n g g a s o i l
feed (4.45-1.78 g) wh i l e keep i n g t h e wei g h t of z e o l i t e
c on s t an t (0.40 g ) .
I n a l l exp eri men t s t h e t i me on s t ream was kep t
c on s t an t a t 60 s ec on d s . Du ri n g t h e r e a c t i o n , t h e l i q u i d
p rod u c t s were c o l l e c t e d a f t e r p as s i n g t h rou g h a c on d en s er
l o c a t e d b el ow t h e r e a c t o r ; t h e g as eou s p rod u c t s were
t rap p ed downwards b y d i s p l ac emen t of wat er i n a g as
b u r e t t e . A t t h e end of eac h ru n , t h e r e a c t o r was p u rg ed
wi t h n i t r o g e n and t h e p u rg ed g as es were c o l l e c t e d f o r
a n a l y s i s i n t h e b u r e t t e . Fi n a l l y , t h e c a t a l y s t was
reg en erat ed "i n s i t u " b y b u rn i n g o f f t h e c oke wi t h a
s t ream (6 1 h'
1
) of a i r a t 530C f o r f i v e h ou rs .
The g as eou s p rod u c t s were an al y z ed b y g as
c h romat og rap h y wi t h a d ou b l e column of Poropak-Q and

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18. CORMA ETAL. Aluminum-Exchanged Sepiolite 297
S i l i c a , wh i l e t h e l i q u i d p rod u c t s were an al y z ed b y
s i mu l at ed d i s t i l l a t i o n . The amount of c oke was meas u red
from t h e wei g h t of wat er and c arb on d i o x i d e g en erat ed
d u r i n g reg en erat i on .
T ab l e I I . P r o p e r t i e s of t h e vacuum d i s t i l l a t e d g as
o i l .
API g r a v i t y a t 1 5
a
C 26.3
Con rad s on c arb on / wt 0.14
Hy drogen/ wt% 11.9
S u l fu r/ wt % 2.14
N
2
/ ppm 562
K-UOP 11.5
Fr e e z i n g p oi n t /
f l
C 24
P en s ky Mart en s /
a
C 130
V i s c o s i t y / C . S 4 0
a
C 11.54
D i s t i l l a t i o n c u rv e D-1160 (
a
C)
IBP 5 20 30 40 50 60 70 80 95 FBP
240 307 323 345 362 378 390 405 420 465 512
Re s u l t s and Di s c u s s i o n
The a c i d i t y of t h e d i f f e r e n t s e p i o l i t e s amp l es h as b een
compared a t 2 00
a
C of p ret reat men t t emp erat u re. I n T ab l es
I I I and IV , are g i v en t h e v al u es of t h e i n t e n s i t y of t h e
I.R. b an d s , c orres p on d i n g t o p y r i d i n e ad s orb ed on Lewi s
s i + t es ( c a t i o n s i n c l u d ed ) at 1450 cm"
1
, and on B ron s t ed
s i t e s c a l c u l a t e d as "b " p aramet er, from t h e i n t e n s i t y of
1490 and 1450 cm"
1
I.R. b an d s .
From t h e r e s u l t s p res en t ed , i t c an b e s een t h a t on l y
t h e s e p i o l i t e d e r i v a t i v e s whose exc h an g e c a t i o n s h av e h i g h
c h arg e/ rad i u m r a t i o , p res en t B ron s t ed a c i d i t y . I n f a c t ,
t h e o r i g i n of B ron s t ed a c i d i t y i n met al exc h an g ed c l a y s
(11) and i n s e p i o l i t e d e r i v a t i v e s i s t h e h i g h l y p o l a r i z e d
wat er mol ec u l es b onded t o t h e c a t i o n s s i t u a t e d a t t h e
i n t e r l a m e l l a r s p ac e and a t t h e ed g es of t h e o c t a h e d r a l
s h eet . C on s eq u en t l y , t h e h i g h er t h e p o l a r i z i n g power of
t h e c a t i o n , t h e h i g h er t h e a c i d i t y of t h e r e s u l t i n g
s e p i o l i t e d e r i v a t i v e i s . In d eed , on l y SA1, S Cr and SH
show B ron s t ed a c i d i t y (b p aramet er) , wh i l e SMg, SNa and
SLa do n ot . T h i s i s c on fi rmed b y t h e r e s u l t s p res en t ed
i n Fi g u r e 2, where we show t h e I.R. s p e c t r a i n t h e 1800-
1300 cm'
1
ran g e, of t h e ad s orb ed p y r i d i n e a f t e r
s u b s t r a c t i o n of s p e c t r a of t h e sample p r e t r e a t e d a t 2 00
a
C
and vacuum b efore ad s orb i n g p y r i d i n e . I t i s ev i d en t t h a t
on l y t h e A l
3 +
, C r
3 +
and H
+
s e p i o l i t e d e r i v a t i v e s show b ands
a t 1540 cm"
1
and 1640 cm"
1
c h a r a c t e r i s t i c of t h e p rot on at ed
p y r i d i n e .
By p l o t t i n g t h e B ron s t ed a c i d i t y (b p aramet er) v ers u s
d e s o r p t i o n t emp erat u re f o r t h es e t h ree s amp l es , one c an
o b t a i n a p i c t u r e of t h e s t r e n g t h d i s t r i b u t i o n f o r t h e

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T ab l e I I I . I n t e n s i t y of t h e I.R. b ands of p y r i d i n e
ad s orb ed on s e p i o l i t e d e r i v a t i v e s , b
p aramet er c a l c u l a t e d from eq u at i on 1, wi t h
an es t i mat ed e r r o r of 0.02.
PRETREAT.
!
1450 cm'
1 !
1490 cm"
1
b p aramet er
SAMPLE OC 150 300 450 150 300 450 150 300 450
100 - -
SMg 200 .43 .08 .03 .04 .01 -
300 .27 .05 .03 .02 -
450 .34 .03 .02 -
100 .07 .01 .01 -
SNa 200 .11 - - .01 -
300 .03 -
450 .04 -
SLa
100
200
300
450
.62
.25
.20
.13
.27 .17
.13 .06
.05 .01
.04 -
.05 .02 .01
.04 .01 -
.03 -
.02 -
T ab l e IV . I n t e n s i t y of t h e I.R. b ands of p y r i d i n e
ad s orb ed on s e p i o l i t e d e r i v a t i v e s , b
p aramet er c a l c u l a t e d from eq u at i on 1, wi t h
an es t i mat ed e r r o r of 0.02.
PRETREAT.
!
1450 cm"
1 !
1490 cm"
1
b p aramet er
SAMPLE oC 150 300 450 150 300 450 150 300 450
100 .61 .55 .20 .27 .16 .04 .17 .07
-
200 .90 .65 .22 .34 .17 .04 .19 .06
-
300 .67 .48 .50 .18 .10 .01 .07 .02
-
450 .30 .21 .20 .07 .03
-
.02
- -
100 1.40 .74 .08 .32 .12
_
.08

200 1.04 .66 .07 .24 .11
-
.07
- -
300 .62 .39 .03 .12 .06
-
.02
- -
450 .45 .23 .01 .06 .03
- - - -
100 1.20 .58 .06 .22 .11
-
.02 .01
-
200 .76 .47 .05 .16 .08
-
.04
- -
300 .42 .20 .02 .09 .03
-
.02
- -
450 .32 .12 .01 .05 .02
- - - -

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CORMA E T AL. Aluminum-Exchanged Sepiolite 299
-1613
1490
-1450
1490
1450
1598
1640.
1700
' (Cm"
1
)
1400 1700
/(Cm
1
)
1400
Fi g u r e 2. I.R. s p e c t r a of p y r i d i n e ad s orb ed on
d i f f e r e n t s e p i o l i t e d e r i v a t i v e s a f t e r d eg as s i n g a t
1 50
a
C and 10 Pa. a) Mg; b ) Na; c) La; d) p r o t o n i c ;
e) A l ; f) C r s e p i o l i t e s .

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300
p r o t o n i c a c i d i t y of t h e d i f f e r e n t s amp l es . Fi g u r e 3 shows
t h a t maximum i n B ron s t ed a c i d i t y c orres p on d s t o a c i d
c e n t e r s of medium s t r e n g t h ( 1 50
Q
C of d e s o r p t i o n
t emp erat u re ( T
d
) ) , and t h a t on l y t h e al u mi n i u m d e r i v a t i v e
h as some a c i d c e n t e r s of s t ron g a c i d i t y (T
d
=300
a
C) . S i t e s
wi t h v ery s t r o n g a c i d i t y ( T
d
> 4 00
B
C) h av e n ot b een fou n d
i n t h e s e p i o l i t e d e r i v a t i v e s . On a c omp arat i v e b a s i s we
h av e ob t ai n ed a "b " p aramet er of 0.10 f o r a c ommerc i al
amorphous s i l i c a - a l u m i n a (25% A 1
2
0
3
) , d eg as s ed a t 150
f i
C
and 10"
3
Pa.
I t i s known (12) t h a t , d ep en d i n g on t h e c a t i o n , t h e
p o s i t i o n of t h e 8a (1600-1625 cm"
1
) I.R. b an d as s i g n ed t o
p y r i d i n e c oord i n at ed t o c a t i o n s v a r i e s ( i . e . 1623 cm"
1
-
A l
3 +
; 1606 - La
3 +
; 1612 - Ni
2 +
; 1598 - Na
+
, e t c . ) . Then,
i f Lewi s a c i d i t y i s due t o t h e p res en c e of c a t i o n s a t t h e
ed g es of t h e c h an n el s , t h e s p e c t r a of t h e p y r i d i n e
c oord i n at ed t o Lewi s a c i d s i t e s w i l l c h an g e wi t h t h e
exc h an g ed c a t i o n . However, t h e s p e c t r a o f a l l t h e
s e p i o l i t e d e r i v a t i v e s show an b and a t 1613 cm"
1
. The
s od i u m d e r i v a t i v e of t h e s e p i o l i t e shows two 8a p y r i d i n e
b an d s , one a t 1613, and an ot h er ap p eari n g a t 1598 cm"
1
as s i g n ed t o [ Py : Na
+
] i n t e r a c t i o n , s h owi n g t h a t i n
s e p i o l i t e , b es i d es t h e Lewi s a c i d i t y a s s o c i a t e d t o t h e
c a t i o n s a t t h e b ord er (1598-1606 cm"
1
) t h e r e i s Lewi s
a c i d i t y due t o t h e p res en c e of "i n t r i n s i c " d e f e c t s i n t h e
s t r u c t u r e of t h e c l a y s i l i c a t e framework. I f t h i s i s s o,
t h e d i f f e r e n c e of i n t e n s i t y of t h e p y r i d i n e c oord i n at ed
I.R. b an d s must b e a s c r i b e d t o d i f f e r e n c e s i n
a c c e s s i b i l i t y t o p o t e n t i a l Lewi s s i t e c e n t e r s . I n f a c t ,
t reat men t s wi t h low pH s o l u t i o n s ( A l
3 +
, C r
3 +
, H
+
) i n c r e a s e s
t h e amount of a c c e s s i b l e Lewi s s i t e s wi t h r e s p e c t t o t h a t
of n a t u r a l s e p i o l i t e (SMg), wh i l e t reat men t s wi t h b a s i c
s o l u t i o n s b l o c k s t h e p o r o s i t y and c on s eq u en t l y t h e amount
of t h e ob s erv ed Lewi s s i t e s d ec reas es . T h i s b eh av i ou r,
wh i c h c an a l r e a d y b e s een i n Fi g u r e 2, i s more c l e a r l y
ob s erv ed i n Fi g u r e 4 where i n t e n s i t y of Lewi s b an d (1450
cm"
1
) f o r d i f f e r e n t s amp l es and a t d i f f e r e n t d e s o r p t i o n
t emp erat u re h as b een p res en t ed . A n ot h er p o s s i b l e
e x p l a n a t i o n f o r c h an g es i n Lewi s a c i d i t y c an b e r e l a t e d
wi t h t h e t h ermal s t a b i l i t y of t h e exc h an g ed s amp l es wi t h
r e s p e c t t o n a t u r a l s e p i o l i t e wh i c h p rev en t s t h e f o l d i n g
(13) of t h e s t r u c t u r e and c on s eq u en t l y t h e d ec reas e i n
s u r f a c e area ( 1 4 ) .
G a s o i l c r a c k i n g
A t t h i s p o i n t we have an aluminum t y p e s e p i o l i t e wh i c h
shows m i l d a c i d i t y and c o u l d b e u s ed as a component f o r
FCC c a t a l y s t s . Then, we have c h ec ked i f t h e al u mi n i u m
c o n t a i n i n g s e p i o l i t e c an a l s o p a s s i v a t e v an ad i u m. To do
t h a t , two FCC c a t a l y s t s c o n t a i n i n g 20% of a REHY z e o l i t e
i n e i t h e r 80% of a 23 wt% A1
2
0
3
c o n t a i n i n g s i l i c a - a l u m i n a ,
or 80% of a l u m i n i c s e p i o l i t e were p rep ared . B ot h s amp l es
where i mp reg n at ed t o i n c i p i e n t wet n es s wi t h a V
n ap h t h en at e/ xy l en e mi x t u re ( 1 5) , i n ord er t o i n t rod u c e
6000 ppm of vanadium. B ot h s amp l es were s t eam d e a c t i v a t e d

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18. CORMA ETAL . Aluminum-Exchanged Sepiolite 301
"b" factor
0.21
160 300 460
Fi g u r e 3. B ron s t ed a c i d i t y ("b" f a c t o r ) , as a
f u n c t i o n of t h e d e s o r p t i o n t emp erat u re f o r t h e
d i f f e r e n t s e p i o l i t e d e r i v a t i v e s . SA1, al u mi n i u m;
S Cr, chromium; SH p r o t o n i c , s e p i o l i t e s .
Intensity
1.2 i
150 300 460
Desorption Temperature *C
Fi g u r e 4. Lewi s a c i d i t y . I n t e n s i t y of t h e 1450 cm"
1
p y r i d i n e I.R. b and as a f u n c t i o n of t h e d e s o r p t i o n
t emp erat u re.

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a t 750
a
C f o r 12 ho u r s, and t he X-Ray d i f f r a ct o gr a ms a r e
gi ve n i n F i gu r e 5. It ca n be se e n t he r e t ha t whi le most
o f t he z e o l i t e c r y s t a l l i n i t y i n s i l i c a - a l u m i n a co nt a i ni ng
c a t a l y s t ( a) has been l o s t , t he c r y s t a l l i n i t y o f t he
z e o l i t e i n t he c a t a l y s t co nt a i ni ng a lu mi ni u m s e pi o l i t e ( b)
i s r e t a i n e d i n much hi ghe r d e gr e e . The r e f o r e , t hi s
s e p i o l i t i c m a t e r i a l i s a c t i ve f o r vanadium pa s s i va t i o n .
The hyd r o t he r ma l s t a b i l i t y o f t he SA1 sample has been
compared wi t h t ha t o f t he o r i gi n a l SMg i n F i gu r e 6. The
X-Ray d i f f r a c t i o n pa t t e r n o f an Al s e pi o l i t e be f o r e ( a)
and a f t e r ( b) st e a mi ng a t 700
a
C, 100% steam; and a n a t u r a l
s e pi o l i t e ( SMg) a l s o steamed a t 700
a
C ( c ) . The r e s u l t s
i n d i c a t e t ha t a f t e r t hi s t he r ma l t r e a t me nt an i mpo r t a nt
f r a c t i o n o f t he a lu mi ni c s e pi o l i t e r e ma i ns u na lt e r a t e d ,
whi le t he n a t u r a l sample i s co mple t e ly f o ld e d . The
f o l d i n g o f t he s e pi o l i t e i s shown by t he d i sa ppe a r a nce o f
t he ( 1,10) r e f l e x i o n a t 7.2, 2, and t he a ppe a r a nce o f
a new r e f l e x i o n a t 8.9, 2 ( 16). Mo reo ver, t he a d so r pt i o n
o f py r i d i n e shows t he pr e se nce o f a r e s i d u a l Brnsted
ac i d i t y i n the SA1 aft er the hy drothermal treatment which
i s approximately 30% of the untreated sample.
To study the g as oi l c rac ki n g b ehaviour of t h i s
mat eri al , two samples have b een prepared with 20% of a USY
z eol i t e embedded i n ei t h er s i l i c a , or SA1. These samples
were steamed at 750C, and the res u l t an t U.C. of the
z eol i t e was 24.31 . The g as oi l c rac ki n g res u l t s ob tained
with the two samples are given i n Fi g u res 7 and 8. The
i n t rod u c t i on of the al u mi n i c s e p i o l i t e i n the matrix i s
u s efu l , not only for vanadium p as s i v at i on as was shown
ab ove, b ut al s o introduces ad d i t i on al c rac ki n g a c t i v i t y
t o the c at al y s t ( Fi g . 7) . The SA1 does not produces a
s en s i b l e i n c reas e i n gases and coke, b ut i t s main c rac ki n g
b en efi t i s i n the b ottoms conversion, g i v i n g a s en s i b l e
i n c reas e i n the p rod u c t i on of d i es el ( Fi g . 8) . As can b e
seen i n Fi g u re 9, the i n c reas e i n d i es el g en erat i on due
t o the i n t rod u c t i on of S-Al occur at the expense of the
s l u rry o i l frac t i on .
Conclusions
I t i s p os s i b l e t o prepare, b y a c on v en t i on al
treatment, s ep i ol i t es i n which the magnesium at the
b orders of the channels has b een s u b s t i t u t ed b y A l
3 +
.
These samples show a much h i g h er ac i d i t y and
hy drothermal s t a b i l i t y than n at u ral s ep i ol i t es , most
of the ac i d i t y b eing i n the range of mi l d s t ren g t h s .
Al u mi n i c s ep i ol i t es while b eing good for vanadium
p as s i v at i on , do not present the inconvenience due t o
Mg mi g rat i on s t o the z eol i t e ( i f i n the same p art i c l e)
shown b y n at u ral s ep i ol i t e.
They present a good g as oi l c rac ki n g a c t i v i t y and
s e l e c t i v i t y , s p ec i al l y u s efu l for b ottoms conversion.

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18. CORMA ETAL. Aluminum-Exchanged Sepiolite 303
I 1 1 1 1
10 20 30 40 50 60
Fi g u r e 5. X-Ray d i f f r a c t i o n p a t t e r n of t h e c a t a l y s t
a f t e r s t eami n g i n t h e p res en c e of vanadium, a) REHY
+ s i l i c a - a l u m i n a ; b ) REHY + s e p i o l i t e .
20
Fi g u r e 6. X -ray d i f f r a c t i o n p a t t e r n of: n a t u r a l
s e p i o l i t e (a) ; al u mi n i u m exc h an g ed s e p i o l i t e a f t e r
s t eami n g a t 9 7 3 K (b ) ; n a t u r a l s e p i o l i t e a f t e r
s t eami n g a t 9 7 3 K ( c ) .

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Fi g u r e 7. G a s o i l c r a c k i n g c on v ers i on on USY + s i l i c a
( ) and USY + SA1 ( o ) c a t a l y s t s .

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18. CORMA ET A L . Aluminum-Exchanged Sepiolite 305
Fi g u r e 8. Y i e l d s of g a s o l i n e , d i e s e l , g as es and
c oke, a t d i f f e r e n t l e v e l s of c on v ers i on , on USY +
s i l i c a ( ) , and USY + SA1 ( O) c a t a l y s t .

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Fi g u r e 9. G a s o i l c on v ers i on ( g as es + c oke +
g as ol i n e) v ers u s s l u r r y o i l , ( ) USY + SA1, and
( O) USY + S i l i c a .

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18. CORMA ET AL. Aluminum-Exchanged Sepiolite 307
A l l these c h arac t eri s t i c s make aluminium s ep i ol i t es
mat eri al s worth t o b e t es t ed i n a l arg er s c al e for
c a t a l y t i c c rac ki n g of res i d u es .
Acknowl edcrmen t s
Fi n an c i al support b y the CICYT ( P roj ec t MAT 88-0147) i s
g rat efu l l y acknowledged.
Li t erat u re Ci t ed
1. Brauner K.; P rei n s i n g er, A. S t ru kt u r und Entstehung
des S ep i ol i t h s . Tschermaks Miner. U. Petrog. Mi t t .
1956, 6, 120.
2. Occelli, M.L.; Kennedy, J.V., U.S. Pat. 4 465 588,
1984.
3. Occelli, M.L.; Kennedy, J.V., U.S. Pat. 4 465 779,
1984.
4. Occelli, M.L. Fl u i d C at al y t i c Cracking Role in Modern
Refi n i n g , Oc c e l l i , M.L. ed., ACS Symp. Ser., 1988,
375,162.
5. de Jong, Jan Ide, Europ. Pat., 832018352, 1984.
6. Corma, A.; Mifsud, A.; Prez -Pariente, J. , SP Pat.
510013, 1982.
7. Corma, A.; Forns, V.; Mifsud, A.; Prez -Pariente, J.,
SP Pat. 527756, 1983.
8. Corma, A.; Mifsud A.; Prez -Pariente, J. , US Pat. 4
542 002, 1985.
9. B as i l a, M.R.; Kantner T.R.; Rhee, K.H. J. Phys. Chem.
1964, 68, 3197.
10. Hughes, T.R.; White, H.M. J. Phys. Chem. 1967, 71,
2192.
11. Farmer, V.C.; Mortland, M.M. J. Chem. Soc. (A) Inorg.
Phy s. Theor. 1966, 344.
12. Vz quez , M.I.; Corma, A.; Forns, V. Z eol i t es 1986, 6,
271.
13. Prez -Pariente, J.; Forns, V.; Corma, A.; Mifsud, A.
Appl . Clay . S c i . 1988, 3, 299.
14. Fernandez Al v arez , T.; R. Hisp. Belg. Min. Arcilla,
Madrid, 1970, p. 202.
15. Mi t c h el l , B.R. IEC PRD 1980, 19, 209.
16. P rei s i n g er, A. Clays and Clay Mi n eral s , Proc. 6th
Conf., Pergamon Press, Oxford, 1959, p. 61.

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Chapter 19
Long-Residue Processing in a Riser
Pilot Plant
Vida J. Stripinis
Oakville Research Centre, Shell Canada Limited, Oakville,
Ontario, Canada
P i l ot plants are often used for study ing the FCC
process. In order for res u l t s to be meaningful, it
i s necessary that p i l ot plant operation be
consistent with that of commercial u n i t s . When
processing feedstocks containing residue, t h i s
becomes even more important. Fai l u re to pay
attention to d et ai l s , such as feed/ cataly st
contacting, can lead to prob lems with data
i n t eg ri t y and with coke b uildup i n the equipment.
A ri s er p i l ot plant has been successfully used to
process heavy feedstocks with Conradson carb on
contents as high as 10%w.
A number of d i fferen t ty pes of lab oratory scale units have been
developed to simulate commercial c at al y t i c crackers. These
include fi xed b ed (MAT), fl u i d i z ed bed, and ri s er u n i t s . ( 1, 2 , 3 )
In p art i c u l ar, for simulating commercial ri s er FCC units which
process residue, a ri s er p i l ot plant i s the preferred choice.
The c at al y s t and o i l are i n plug flow and the contact time i s
short so that secondary reactions are avoided and c at al y s t
deactivation by coke formation i s properly simulated. The
res u l t i n g product s el ec t i v i t y , then, i s s i mi l ar to commercial
u n i t s . Experimental res u l t s from a lab oratory scale unit can
thus be translated to commercial u n i t s .
This paper describ es experience with residue processing i n
c at al y t i c cracking units i n the industry , b oth on a commercial
and p i l ot plant scale. S p ec i fi c changes which have been made to
the design and operating procedures of the Sh el l Canada Oakville
Research Centre (ORC) ri s er p i l ot plant are also discussed.
These have allowed processing of residues containing up to 9 . 9 %
Conradson Carbon Residue (CCR).
0097-6156/91/0452-0308$06.00y0

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19. STRIPINIS Long-Residue Processing
309
Commercial Exp eri en c e
A numb er of r e f i n e r s have p roc es s ed res i d u e c on t ai n i n g feed s t oc ks
i n commercial FCC u n i t s . Feeds wi t h as much as 5.1%w RCR (~6.5%w
CCR) and 85 ppm N i + V have b een p roc es s ed i n P h i l l i p s ' B org er
Refi n ery . ( 4 ) As h l an d has p roc es s ed feed s t oc ks of up t o 7.1%w RCR
(~8.5%w CCR) and 85 ppm Ni + V i n t h e i r RCC (Reduced Crude
Con v ers i on ) p roc es s . ( 5, 6 ) A commercial s c al e ART ( As p h al t
Res i d u al T reat i n g ) u n i t has p roc es s ed res i d u es c on t ai n i n g l e v e l s
of c on t ami n an t s as h i g h as 13.5%w RCR and 300 ppm N i + V (7,8) .
However, i n t y p i c a l day -to-day op erat i on of res i d u e c at c rac kers ,
feed s t oc k q u a l i t y i s not as extreme as t h os e i l l u s t r a t e d ab ove.
The ab ove d at a i n d i c at es t h at some commercial u n i t s can
al read y p roc es s l on g res i d u e from a numb er of a v a i l a b l e worl d
c ru d es . T h i s i s i l l u s t r a t e d i n Fi g u re 1 (9), a p l o t of met al s
v ers u s Conradson c arb on c on t en t f o r l on g res i d u es from v ari ou s
c ru d es . A b ox i s drawn i n d i c a t i n g t h e l i m i t a t i o n s of c u rren t FCC
t ec h n ol og y f o r h an d l i n g met al s and Conradson c arb on . A numb er of
l on g res i d u es f a l l wi t h i n t h i s b ox, al t h ou g h an even l a r g e r
numb er f a l l ou t s i d e i t . The c h al l en g e i s t o d ev el op FCC
t ec h n ol og y t o en ab l e ec on omi c al p roc es s i n g of p oorer q u a l i t y
feed s t oc ks .
P i l o t P l an t Exp eri en c e
Development of t ec h n ol og y i s g en eral l y done u s i n g l ab orat ory
s c al e u n i t s . Exp eri men t al d at a can b e ob t ai n ed wi t h l e s s expense
and wi t h more ac c u rac y and f l e x i b i l i t y t h an b y at t emp t i n g t o do
t h e same t e s t on a commercial s c al e. In t h e l ab orat ory , s mal l er
q u a n t i t i e s of feed s t oc k and c a t a l y s t are needed and lower
manpower and c a p i t a l c os t s are i n c u rred . By n ec es s i t y , b ench
s c al e u n i t s must p roc es s feed s t oc ks which are at l e a s t as
d i f f i c u l t as t h os e p roc es s ed c ommerc i al l y .
P roc es s i n g res i d u e on a l ab orat ory s c al e poses a numb er of
c h al l en g es . Res i d u e-c on t ai n i n g feed s t oc ks are more d i f f i c u l t t o
v ap ou ri z e and have a h i g h er coke formi n g t en d en c y t h an gas o i l s .
P a r t i c u l a r at t en t i on must b e p ai d t o p i l o t p l an t d es i g n and
op erat i n g p roc ed u res i n ord er t o av oi d coke format i on and
p l u g g i n g of t h e s mal l t u b i n g i n p i l o t p l an t s and t o en s u re
mean i n g fu l d at a.
Gu l f has rep ort ed prob lems c on d u c t i n g r e s i d c rac ki n g
s t u d i es i n p i l o t s c al e u n i t s . ( 1 0) The d i f f i c u l t i e s i n c l u d ed feed
i n j e c t o r p l u g g i n g and c a t a l y s t fl ow prob lems i n s mal l l i n e s i n
t h e i r 0.2 B/D g a s o i l c rac ki n g u n i t . They have b u i l t a somewhat
l arg er, 1.0 B/D p i l o t p l an t , s p e c i f i c a l l y f o r h i g h c arb on res i d u e
feed s t oc ks , and t h ey have p roc es s ed feed s t oc ks c on t ai n i n g up t o
7.66%w CCR. En g el h ard has op erat ed a mod i fi ed ARCO Lab u n i t wi t h
a feed s t oc k of 2.5% RCR (-3.5% CCR).(11) Kel l og g has a 1/3 B/D
u n i t u s ed f o r s t u d i es i n c on v en t i on al gas o i l FCC, HOC (Heavy Oi l
Crac ki n g ) and ART.(12) Nort h Sea res i d u e, c on t ai n i n g 3.9%w CCR,
has b een p roc es s ed i n t h e i r u n i t . ( 1 3 ) The ART p roc es s has, f o r
t h e most p art , b een d ev el op ed i n much l arg er u n i t s , namely , a 200

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B/D demonstration plant and a 10 , 0 0 0 B/D commercial unit which
have b oth processed poorer q u al i t y feedstocks.
Total ( 15 ) reports that operation of t h ei r p i l ot plant i s
not s at i s fac t ory for feedstocks with a v i s c os i t y greater than 8 0
cSt at 10 0 'C They state that thermal shock simulation and
feedstock atomiz ing and evaporation are unsatisfactory i n t h ei r
lab oratory scale u n i t .
Sh el l Canada's Oakville Research Centre has had a ri s er
p i l ot plant i n operation for about ten y ears. A s eri es of
modifications have been made to the unit over the y ears i n order
to improve i t s ab i l i t y to process heavier feedstocks. In s p i t e
of a rather low feedrate of 0 . 5 2 g/s (approximately 0 . 3 B/D),
poorer q u al i t y feedstocks have been processed than those
describ ed above. To date, feedstocks with Conradson carb on
contents up to 9. 9%w and v i s c os i t i es up to 12 0 cSt at 10 0 *C have
been successfully run i n the ORC p i l ot plant. Operating
experience with the p i l ot plant i s summarized i n Tab le I, and a
schematic i s shown i n Figure 2 .
Experience has shown that there are four key aspects of
design and operation of the p i l ot plant that must be considered
i n order for i t to operate successfully with residue-containing
feedstocks:
1) Feedstock atomiz ation and vaporiz ation
2 ) Feed/ cataly st mixing
3 ) Spent c at al y s t s t ri p p i n g
4) Product handling
These items wi l l each be discussed separately below. The
resolution of prob lems encountered i n the ORC lab oratory unit
while processing heavy feedstocks w i l l be describ ed.
Feedstock Atomiz ation and V aporiz ation
Feedstocks containing residue are more d i f f i c u l t to vapouriz e and
tend to coke more eas i l y . Atomiz ing the o i l feed to small
droplets res u l t s i n more surface area for heat t ran s fer and
q uicker vapouriz ation of the higher b oi l i n g materials i n i t . The
atomiz ing noz z le i n use on the ORC p i l ot plant achieves average
droplet siz es of less than 6 0 microns. This i s i l l u s t rat ed i n
Figure 3 , which i s a p l ot of Sauter mean diameter of the droplets
produced versus atomiz ing gas flow. The data was c ol l ec t ed at
conditions chosen to simulate p i l ot plant operation on a residue-
containing feedstock.
In c at al y t i c cracking, a large amount of heat needs to be
supplied at the reactor i n l et to vapouriz e the feed and provide
the heat of reaction. In commercial units, t h i s heat i s provided
by the hot c at al y s t rec i rc u l at ed from the regenerator. High heat
t ran s fer rates are achieved when the fl u i d i z ed c at al y s t i s mixed
with the feed. In some experimental units, feed and c at al y s t are
i n j ec t ed at reactor temperature. The heat of reaction must then
be supplied by an external heating element, at much slower rates
of heat t ran s fer. The product s el ec t i v i t y from such lab oratory
units cannot be expected to simulate that of commercial units

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STRIPINIS Long-Residue Processing
250
200
150
Ni + V, ppm
limit of current
t echnol ogy
4 6 8 10
Conr adson Car bon, %w
12 14
Figure 1 - Long Residue from Various Crudes
ri ser
reactor
vent
catal yst
hopper
cat al yst
st ri pper
N
2
condenser
r
liquid recei ver
gas
r N
2
feed
Figure 2 - Schematic of Riser P i l ot Plant

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312
T ab l e I. Ri s er P i l o t P l an t Op erat i on
Feed Rate 0.52 g/ s (approx 0.3 B/D)
C a t / Oi l Rat i o 2.5 t o 16 w/w
Reac t or Ou t l et Temp. up t o 540*C
Feed Temperature up t o 300*C
C at al y s t Temperature up t o 800*C
Feed CCR up t o 9.9%w
Feed V i s c o s i t y up t o 120 c S t @ 100*C
Reac t or P res s u re 1 b ar
Sauter Mean Diameter (microns)
70 p
60 -
50 -
40
30 -
20 -
10 -
0 1 2 3
Air Flow (nL/mi n)
Fi g u re 3 - At omi z i n g Noz z l e Performance

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313
very well. The preferred way to supply the heat req uired by the
process i s using hot c at al y s t , the same as i n a commercial u n i t .
Heating the feed to reactor temperature, usually greater
than 500*C, causes an ad d i t i on al prob lem. Coke i s formed by
thermal reactions of the feed i n the preheater and feed i n j ec t i on
system. The coking tendency i s more severe for heavy feedstocks
which have higher concentrations of coke precursors. This can be
avoided by l i mi t i n g the feed temperature to 300*C or l es s .
The p rac t i c e at ORC has been to preheat the feedstock to a
temperature s u ffi c i en t l y high to reduce i t s v i s c os i t y enough to
ensure good atomiz ation without causing coke formation i n the
feed system. The heat of vaporiz ation and reaction i s supplied
by the much hotter c at al y s t . Good simulation of commercial FCC
units has been achieved using t h i s operating strategy .
Feed/ Catalvst Mixing
Once the feedstock has been atomiz ed, i t must be mixed with the
c at al y s t i n a uniform way to ensure effi c i en t heat t ran s fer and
fas t vapouriz ation of the o i l . Oi l droplets must not be allowed
to h i t the wall of the reactor where they would deposit on the
wall and form coke. They must come i n contact with a c at al y s t
p art i c l e f i r s t . Coke formation on the wall can lead to flow
res t ri c t i on s i n the unit and an i n ab i l i t y to operate i t
successfully .
In the past, ORC experienced plugging from exactly t h i s
ty pe of phenomenon. When processing residue-containing
feedstocks, coke would b u i l d up j ust above the feed i n j ec t i on
noz z le causing the flow to the ri s er reactor to become
res t ri c t ed . As a res u l t , runs would have to be ended
prematurely . The coke b uild-up tended to be the worst at low
c at al y s t -t o-oi l rat i os when cataly st flow rates were also low.
It was thought that the density of the c at al y s t b eing supplied to
the mixing zone was not constant. During moments of low density ,
feed droplets would come i n contact with the wall and form coke
deposits. The cataly st i s supplied from.a hopper which i s
fl u i d i z ed with nitrogen. Bub b les of gas from the fl u i d i z ed b ed
were getting entrained with the cataly st to the mixing zone and
causing variations i n c at al y s t density .
The operation of the cataly st hopper was examined keeping
i n mind known facts about cataly st fl u i d i z at i on b ehavior. Figure
4 i l l u s t rat es the fl u i d i z at i on b ehavior of a t y p i c al FCC
c at al y s t . Cataly st b ed height i s p l ot t ed against s u p erfi c i al
v el oc i t y of the fl u i d i z i n g gas. At gas v el oc i t i es between z ero
and minimum fl u i d i z at i on v el oc i t y (Umf), the b ed height remains
unchanged. Once the minimum fl u i d i z at i on v el oc i t y i s reached,
the b ed s t art s to expand. When gas flow i s increased further,
the minimum b ub b ling v el oc i t y (Umb) i s reached. At t h i s point,
the gas s t art s to ri s e through the c at al y s t b ed i n the form of
b ub b les. The b ed height then s t art s to drop and slowly increases
again with increasing s u p erfi c i al v el oc i t y .
The c at al y s t hopper had, at times, been operated at gas
v el oc i t i es above the minimum b ub b ling v el oc i t y . This caused
b ub b les as well as c at al y s t to be c arri ed to the feed/ cataly st

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Bed Height
. cat al yst hopper
operati ng region
U
m
f U
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b
F i g u r e 4
Superfi ci al Vel oci t y
- FCC C a t a l y s t F l u i d i z a t i o n B e h a v i o u r

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19. STRIPINIS Long-Residue Processing 315
mi xi n g z one and r e s u l t e d i n v a r i a t i o n s i n c a t a l y s t d en s i t y and
t h e format i on of t h e coke d ep os i t s . To c orrec t t h i s , t h e gas
fl ow was red u c ed t o el i mi n at e b u b b l es from t h e c a t a l y s t b ei n g
s u p p l i ed t o t h e reac t or and t h e c a t a l y s t was i n s t ead s u p p l i ed i n
dense phase fl ow.
T h i s change i n c a t a l y s t hopper op erat i on v i r t u a l l y
el i mi n at ed t h e format i on of coke d ep os i t s i n t h e feed mi xi n g
z one. C a t a l y s t -t o -o i l r a t i o s as low as 2.5 have b een ac h i ev ed
even wi t h v ery heavy feed s t oc ks .
C at al y s t S t r i p p i n g
Good s t r i p p i n g i s i mp ort an t i n ord er t o mi n i mi z e coke format i on .
When c a t a l y s t i s s t r i p p e d e f f e c t i v e l y , h i g h er b o i l i n g mat eri al s
are rec ov ered as p rod u c t rat h er t h an b ei n g q u a n t i f i e d as q oke.
In ord er t o ac h i ev e t h i s , eq uipment t o s t r i p t h e s p en t c a t a l y s t
must b e c a r e f u l l y d es i g n ed . S t r i p p i n g n i t rog en and c a t a l y s t
res i d en c e time must t h en b e op t i mi z ed i n ord er t o ac h i ev e good
s t r i p p i n g . I f more n i t rog en i s u s ed t h an n ec es s ary , t h e p rod u c t
gas i s d i l u t e d , making ac c u rat e gas an al y s i s f o r y i e l d
d et ermi n at i on more d i f f i c u l t .
Such a s t u d y t o op t i mi z e spent c a t a l y s t s t r i p p i n g has b een
done f o r t h e ORC r i s e r p i l o t p l an t . A f t e r making changes t o t h e
d es i g n of t h e s t r i p p e r , a s e r i e s of t e s t s were done wi t h v ary i n g
s t r i p p i n g n i t rog en fl ow wh i l e keep i n g ot h er op erat i n g c on d i t i on s
c on s t an t t o d et ermi n e t h e optimum fl ow. The fl ow rat e chosen f o r
fu t u re op erat i on was one f o r which t h e ob s erv ed coke y i e l d had
reac h ed a minimum. The u n i t op erat es i n a b at c h mode wi t h t h e
c a t a l y s t b ei n g c o l l e c t e d and s t ri p p ed i n t h e same v e s s e l . As a
r e s u l t , an ot h er v a r i a b l e which a f f e c t s c a t a l y s t s t r i p p i n g i s t h e
l en g t h of time t h at t h e c a t a l y s t i s s t r i p p e d a f t e r t h e run i s
f i n i s h e d . A s t u d y was done t o op t i mi z e t h i s s t r i p p i n g t i me.
Ov e r a l l , t h e changes i n s t r i p p e r d es i g n and op erat i on r e s u l t e d i n
a coke y i e l d red u c t i on of 1.5%w at c on s t an t c on d i t i on s .
P rod u c t H an d l i n g
Res i d u e-c on t ai n i n g feed s t oc ks produce p rod u c t s t h at are h eav i er
and more v i s c ou s t h an normal. T h erefore, op erat i n g t emp erat u re
i n t h e p rod u c t condenser must b e chosen wi t h c are. I f t h e
t emp erat u re i s t oo low, t h e h i g h b o i l i n g , v i s c ou s p o r t i o n of t h e
p rod u c t d ep os i t s on t h e condenser tub e wal l s and g et s ret ai n ed i n
t h e condenser rat h er t h an b ei n g rec ov ered as p rod u c t . On t h e
ot h er hand, i f t h e temperature i s t oo h i g h , l i g h t l i q u i d s are not
condensed and g et c a r r i e d ov er i n t o t h e gas stream. I f t h e gas
sample i s al l owed t o c ool , t h es e l i g h t l i q u i d s can t h en condense
and not g et an al y z ed .
Exp eri en c e at ORC has shown t h at a condenser op erat i n g
t emp erat u re of 0*C i s t oo low when p roc es s i n g res i d u e-c on t ai n i n g
feed s t oc ks . The p rod u c t rec ov ery i s red u c ed b y 5% or more due t o
ret en t i on of heavy ends i n t h e condenser. A t emp erat u re of 38*C
i s s u f f i c i e n t l y h i g h t o av oi d t h i s prob lem. In ord er t o en s u re
t h at , i n s p i t e of t h i s , l i g h t l i q u i d s are condensed and not

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316
c arri ed over to the gas stream, the product receiver i s cooled to
- 2 4 *C and the gas stream knock-out pot also to - 2 4 *C.
Summary and Conclusions
By pay ing p art i c u l ar attention to FCC p i l ot plant design and
operating procedures, feedstocks containing s i g n i fi c an t amounts
of residue can be successfully processed i n a small-scale u n i t .
The c r i t i c a l aspects can be itemiz ed as follows:
o atomiz ation of o i l to small droplet s i z es ;
o feed temperature adequate to avoid coke formation i n the
feed system;
o use of hot c at al y s t to supply heat to the system, as i s
done i n commercial units;
o consistent c at al y s t flowrate to the feed/ cataly st mixing
zone by s el ec t i n g fl u i d i z i n g nitrogen flow rate to stay
below the minimum b ub b ling v el oc i t y of the c at al y s t ;
o uniform mixing of the feed and c at al y s t i n the b ottom of
the reactor to ensure quick vapouriz ation and avoid coke
formation i n the mixing zone;
o optimiz ed design and operation of the spent c at al y s t
s t ri p p er to ensure that coke y i el d s are minimiz ed without
d i l u t i n g the product gas more than necessary ; and
o proper s el ec t i on of condenser operating temperature i n
order to avoid retaining the heavy, viscous frac t i on of the
product on the condenser tub e walls.
By focussing on the above points, cat cracking experiments
can be performed i n lab oratory equipment with residue-containing
feedstocks. With proper choice of operating conditions, the
res u l t i n g product y i el d s and s el ec t i v i t y simulate those i n
commercial units q uite well.
Li t erat u re Cited
1) P. O'Connor and M.B. Hartkemp, "A Microscale Simulation
Test for FCC Development", ACS Los Angeles Meeting, Sept.
2 5 - 3 0 , 19 8 8 , pp. 6 5 6 - 6 6 2 .
2 ) J.E. Creighton, G.W. Young, "Fl u i d Cracking Cataly st
Evaluation: A Comparison of Testing Strategies", The
Cat al y s i s Society , 8t h North American Meeting, May 1- 4 ,
19 8 3 , Philadelphia, Pennsy lvania.
3 ) W.H. Humes, "ARCO's Updated Cat-Cracking P i l ot Unit", CEP,
Feb ruary 19 8 3 , 5 1- 5 4 .
4 ) J.B. Rush, P.V. Steed, "HDS + Cracking Ups Capacity ,
Yields", OGJ, May 2 8 , 19 8 4 , 9 6 - 10 3 .

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317
5) L.E. Busch, W.P. Hettinger, Jr. , Richard P. Krock, "Reduced
Crude Oil Conversion i n Commercial RCC and ART Process
Operations" (Paper No. AM-84-50), 1984 NPRA Annual Meeting,
March 25-27, 1984, San Antonio, Texas.
6) L.E. Busch, W.P. Hettinger, Jr. , R.P. Krock, "RCC Complex
Now Cornerstone of Ashland Refinery ", OGJ, December 10,
1984, 79-84.
7) D.B. B art h ol i c and R.P. Haseltine, "Development of
Engelhard's Art Process", API, 46th Mid-Year Meeting, May
11-14, 1981, Chicago, I l l i n o i s , pp. 335-339.
8) R.P. Haseltine, A.K. Logwinuk, D.L. Caldwell, The ART
Process Offers Increased Refinery Fl e x i b i l i t y " (Paper No.
AM-83-43), 1983 NPRA Annual Meeting, March 20-22, 1983, San
Francisco, C al i forn i a.
9) Oi l & Gas Data Book, 1986 ed. Pennwell Pub lishing Co.,
Tulsa, Oklahoma.
10) R.J. Campagna, A.S. Krishna, S.J. Yanik, "Research and
Development Directed at Resid Cracking", OGJ, Octob er 31,
1983, 128-134.
11) D.B. Bartholic, R.P. Haseltine, "Ut i l i z i n g Lab oratory
Equipment i n New Residual Oil Development" (Paper No. AM-
81-45), 1981 NPRA Annual Meeting, March 29-31, 1981, San
Antonio, Texas.
12) M. Schlossman et al, "Riser P i l ot Plant for Cat al y t i c
Cracking Studies", Kat al i s t i ks 7th Annual FCC Symposium,
Venice, It al y , May 12-13, 1986.
13) H. Torgaard, "North Sea Resid Tested as FCC Feedstock",
OGJ, January 10, 1983, 100-103.
14) D.F. Barger, C. B . Mi l l er, "Convert Resid for Fl ex i b i l i t y ",
Hydrocarb on Processing, May 1983, 68-70.
15) M. Denmar, A. T ri ki , J.P. Franck, "Advanced Analy ses
Improve Delta Coke Prediction for Resids", OGJ, Sept. 15,
1986.
RECEIVED J u n e 8, 19 9 0

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Chapter 20
Concepts for Future Residuum Catalyst
Development
P. O'Connor
1
, A. W. Gevers
1
, A. Humphries
2
, L. A. Gerritsen
3
,
and P. H. Desai
4
1
Akzo Chemicals BV, P.O. Box 975, 3800 AZ Amersfoort,
The Netherlands
2
Akzo Chemicals, Inc., 3250 East Washington Boulevard,
Los Angeles, CA 90023
3
Akzo Chemicals BV, P.O. Box 15, 1000 AA Amsterdam,
The Netherlands
4
Akzo Chemicals, Inc., 13000 Bay Park Road,
Pasadena, TX 77058
This paper reviews some main concepts for Resid Catalyst development.
In thearea of catalyst architecture, theeffect of an enhanced
accessibility of theactive sites by thelarger resid molecules,
can significantly improve both conversion and bottoms cracking.
Several generations of vanadiummetal catchers have been
developed (1, 2), leading to an improved activity retention at high
vanadiumlevels on catalyst. Therecent progress in nickel tolerance
with new nickel encapsulation technologies is just as dramatic.
The reduced coke, gas and hydrogen make of these types of catalysts
open theroad to asignificant increase in resid processing.
Developments in thezeolite field in terms of non-framework
alumina control, leading to super low delta coke zeolites and the
advent of enhanced surface activity zeolites, seempromising for
the resid cracking field (3).
R e s i d u p g r a d i n g i n t h e r e f i n i n g i n d u s t r y
S e v e r a l f o r e c a s t e r s ( 4 ) h a v e p r e d i c t e d t h a t t h e wo r l d ' s c r u d e
r e s e r v e s a r e we i g h t e d a b o u t t wo t o o n e i n f a v o r o f h e a v y v e r s u s l i g h t
c r u d e s . Co n s e q u e n t l y t h e i n e v i t a b l e t r e n d i s t h a t t h e a v e r a g e c r u d e
p r o c e s s e d wi l l b e c o me h e a v i e r . Ma r k e t f o r c e s , r e g i o n a l d e ma n d ,
e n v i r o n me n t a l c o n s i d e r a t i o n s a n d o t h e r f a c t o r s wi l l d e t e r mi n e t h e
e c o n o mi c s a n d j u s t i f i c a t i o n f o r h e a v y o i l c o n v e r s i o n . B u t i t i s
c l e a r t h a t i n t h e g l o b a l s c e n e , t h e r e wi l l b e a n i n c r e a s i n g s u p p l y ,
o f h e a v y o i l .
0097-6156y91A)452-0318$07.25/0

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20. O'CONNOR ETAL. Future Residuum Catalyst Development 319
On t h e o t h e r h a n d , a s t e a d y d e c l i n e i n f u e l o i l c o n s u mp t i o n
i n d i f f e r e n t r e g i o n s h a s b e e n r e p o r t e d (5, 6). I n c r e a s i n g s u p p l y ,
c o mb i n e d wi t h d e c r e a s i n g de man d f o r o i l , c h a l l e n g e s t h e r e f i n e r i e s
t o i n v e s t i g a t e c r e a t i v e s o l u t i o n s t o t h e r e s i d p r o b l e m. T h e ma i n
o b j e c t i v e i s t o c o n v e r t t h e h e a v y r e s i d t o d e s i r a b l e t r a n s p o r t a t i o n
f u e l s .
S e v e r a l h y d r o c a r b o n p r o c e s s e s a r e a v a i l a b l e f o r u p g r a d i n g
r e s i d : h y d r o t r e a t i n g , F l u i d C a t a l y t i c C r a c k i n g ( F C C ) , c o k i n g e t c . ,
s o me mo r e c a p i t a l i n t e n s i v e t h a n o t h e r s . T h e mo s t wi d e l y p r e v a l e n t
p r o c e s s i s t h e F CC p r o c e s s . T h e r e f o r e a n y a d v a n c e s i n p r o c e s s i n g
r e s i d i n F CC u n i t s w i l l h a v e wi d e a p p l i c a t i o n . T h i s p a p e r d e a l s
wi t h c o n c e p t s f o r d e v e l o p me n t s i n r e s i d c r a c k i n g , p a r t i c u l a r l y i n
r e s i d F CC d e v e l o p me n t , e v a l u a t i o n an d a p p l i c a t i o n .
Wh e r e as wo r l d wi d e de man d f o r g a s o l i n e i s e x p e c t e d t o r e ma i n
mo r e o r l e s s c o n s t a n t , de man d f o r mi d d l e d i s t i l l a t e s ( d i e s e l ,
k e r o s e n e , j e t f u e l ) i s e x p e c t e d t o i n c r e a s e . R e s i d c r a c k i n g t o y i e l d
g a s o l i n e d o e s n o t a l wa y s l e a d t o f a v o r a b l e e c o n o mi c s . Ma k i n g mi d -
d i s t i l l a t e s f r o m r e s i d h o we v e r , may o f f e r i n t e r e s t i n g o p p o r t u n i t i e s .
R e s i d P r o c e s s i n g
F r o m an F CC v i e wp o i n t , t h e r e i s n o t a c l e a r d e f i n i t i o n o f r e s i d
c r a c k i n g . I f we c o n s i d e r t h e o v e r a l l r e f i n e r y s c h e me , a l l ma t e r i a l s
n o t q u a l i f y i n g f o r g a s o i l t y p e s p e c i f i c a t i o n s a r e r e s i d , wh i c h
i n f a c t me an s t h a t t h e t r a d i t i o n a l F CC f e e d , V ac u u m Ga s o i l ( V GO) , i s
n e a r l y 10 0 % r e s i d , o r t o b e mo r e s p e c i f i c a f u e l o i l .
Th e f a c t t h a t a t r a d i t i o n a l VGO F CC u n i t i s a l s o a " f u e l o i l "
c r a c k e r , c a n b e i l l u s t r a t e d b y t h e f a c t t h a t p r o c e s s i n g o f VGO i n
a F CC u n i t i n a r e f i n e r y r u n n i n g o n Mi d d l e E a s t c r u d e , w i l l r e d u c e
t h e h e a v y f u e l o i l p r o d u c t i o n o f t h e r e f i n e r y b y a b o u t 10 % wt o n
c r u d e ( 7 ) .
F o r c o n v e n t i o n a l VGO c r a c k i n g t h e s h a r p n e s s o f t h e v ac u u m
s e p a r a t i o n b e t we e n t h e f l a s h e d d i s t i l l a t e a n d r e s i d u e i s n o t r e a l l y
i mp o r t a n t , p r o v i d e d t h a t t h e u n d e s i r a b l e n o n - v o l a t i l e a s p h a l t h e n e s
a n d me t a l c o mp o u n ds a r e l e f t i n t h e r e s i d u e .
E n t r a i n me n t i s k e p t a t a mi n i mu m b y a was h o i l s e c t i o n i n t h e
v ac u u m u n i t a n d c h e c k e d wi t h a c o l o u r s p e c i f i c a t i o n o n t h e F CC f e e d .
T h e " r e a l " F CC r e s i d c r a c k i n g s e e ms t o s t a r t , wh e n t h e was h o i l
s t r e a m i n t h e v ac u u m c o l u mn i s a l s o r o u t e d t o t h e F CC u n i t ,
o b v i o u s l y t h e c o l o u r o f t h e F CC f e e d w i l l d e t e r i o r a t e s t r o n g l y .
D e p e n d i n g o n t h e c r u d e o r i g i n , a l r e a d y t h e i n t r o d u c t i o n o f
d i r t y was h o i l c a n h a v e a s i g n i f i c a n t i mp a c t o n t h e me t a l c o n t e n t
o f t h e F CC f e e d a n d h e n c e t h e c a t a l y s t . S e v e r a l d e a s p h a l t i n g
p r o c e s s e s o p e n u p t h e p o s s i b i l i t y t o c u t d e e p e r , b u t a l s o mo r e
s e l e c t i v e i n t e r ms o f a s p h a l t h e n e a n d me t a l c o n t e n t i n t o t h e r e s i d .
Hi g h t e mp e r a t u r e d e e p f l a s h i n g a n d v ac u u m f l a s h i n g o f t h e r ma l l y
c r a c k e d d i s t i l l a t e a l s o c o n t r i b u t e s t o i n c r e a s i n g t h e p e r c e n t a g e o f
t h e c r u d e , wh i c h c a n b e r o u t e d t o t h e F CC u n i t .
I n t h e u l t i ma t e c a s e , d e p e n d i n g o n t h e f e e d s t o c k o r i g i n a n d t h e F CC
u n i t o p e r a t i o n a l c o n s t r a i n t , e v e n 10 0 % a t mo s p h e r i c r e s i d u e c a n
s o me t i me s b e p r o c e s s e d i n t h e F CC u n i t . ( T a b l e I . )

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T a b l e I . R e s i d C r a c k i n g i n F CC
- VGO C r a c k i n g - V ac u u m Ga s o i l
c l e a r , n o me t a l s
- V ac u u m F l a s h e d
d i s t i l l a t e f r o m
a t mo s p h e r i c r e s i d
- HVGO/ DAO - He av y VGO, Was h o i l s - C u t t i n g d e e p e r
- D e e p F l a s h e d VGO i n t o t h e b a r r e l ,
- F l a s h e d C r a c k e d r e s i d u e s wh i l e t r y i n g t o
- D e a s p h a l t e d O i l a v o i d e x c e s s i v e
a s p h a l t h e n e s a n d
me t a l s
- R e s i d C r a c k i n g - At mo s p h e r i c R e s i d u e ( AR) - Cr u d e s e l e c t i o n
t o a v o i d e x c e s s i v e
a s p h a l t h e n e s a n d
me t a l s
P r e t r e a t me n t t o
r e d u c e a s p h a l t h e n e s
an d me t a l s
P r o c e s s a b i l i t y o f r e s i d s i n F CC u n i t s
I t i s w e l l k n o wn t h a t t h e p r o c e s s i n g o f h e a v i e r , mo r e c o n t a mi n a t e d
f e e d s t o c k s ( me t a l s , a s p h a l t e n e s ) t e n d s t o i n c r e a s e t h e p r o d u c t i o n
o f c o k e an d g a s a n d d e a c t i v a t e s t h e c a t a l y s t . T h i s i s ma i n l y t h e
r e s u l t s o f ( 8 ) :
( 1 ) A l a r g e r f e e d f r a c t i o n t h a t d o e s n o t v a p o r i z e u n d e r c o n v e n t i o n a l
c r a c k i n g c o n d i t i o n s . F o r t h i s r e a s o n r e s i d i n F CC i s s o me t i me s
d e f i n e d a s t h e f r a c t i o n o f t h e f e e d b o i l i n g a b o v e an e f f e c t i v e
" o u t p o i n t " o f t h e f l a s h i n t h e b o t t o m o f t h e F CC r i s e r .
D e p e n d i n g o n t h e e x p e c t e d b o t t o m mi x t e mp e r a t u r e , c u t p o i n t s
o f 5 3 0 u p 5 6 0 C a r e me n t i o n e d i n t h e l i t e r a t u r e .
( 2 ) C o n t a mi n a t i o n b y h e a v y me t a l s ( V , N i ) . To ma i n t a i n t h e me t a l
c o n t e n t o n c a t a l y s t c o n s t a n t , u s u a l l y a l a r g e i n c r e a s e i n
c a t a l y s t c o n s u mp t i o n ( f r o m an a v e r a g e o f 0 . 15 l b / b b l u p t o a n d
a b o v e 0 . 5 l b / b b l ) i s r e q u i r e d . A l t e r n a t i v e l y s p e c i a l me t a l
r e s i s t a n t c a t a l y s t c a n b e a p p l i e d i n o r d e r t o mi n i mi z e c a t a l y s t
c o n s u mp t i o n . A r b i t r a r i l y a me t a l s c o n t e n t ( N i + V ) o f a b o v e
15 0 0 ppm o n c a t a l y s t i s s o me t i me s c o n s i d e r e d t o b e a me t a l s
c o n t a mi n a t e d r e s i d o p e r a t i o n .
( 3 ) A h i g h e r c o n c e n t r a t i o n o f b a s i c an d p o l a r mo l e c u l e s , i . e .
n i t r o g e n c o mp o u n ds t h a t a r e r e a d i l y a d s o r b e d o n t o t h e c a t a l y s t
a c i d i c s i t e s , l e a d i n g t o an i n s t a n t , b u t t e mp o r a r y d e a c t i v a t i o n .
P o l y c y c l i c a r o ma t i c s a l s o s t r o n g l y c o n t r i b u t e t o c o k e f o r ma t i o n .

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( A) Ot h e r p o i s o n s a s a l k a l i c o n t a mi n a n t s ( N a , K . . . . ) .
T h e h i g h e r c o k e p r o d u c t i o n o f r e s i d f e e d s t o c k s w i l l a l s o t e n d t o
i n c r e a s e t h e t e mp e r a t u r e o f t h e r e g e n e r a t o r an d h e n c e t h e
d e a c t i v a t i o n o f t h e c a t a l y s t .
F r o m t h e f o r e g o i n g i t b e c o me s o b v i o u s t h a t t h e F CC p r o c e s s a b i l -
i t y o f r e s i d f e e d s t o c k a n d t h e c h o i c e o f a p o s s i b l e F CC f e e d p r e -
t r e a t me n t ( f o r i n s t a n c e R e s i d Hy d r o p r o c e s s i n g ) w i l l d e p e n d o n t h e
f e e d q u a l i t y an d h e n c e i t s o r i g i n .
N a b e r e t a l ( 9 ) h a v e d e mo n s t r a t e d t h a t F CC s t i l l h a s a
c o n s i d e r a b l e p o t e n t i a l t o r e ma i n t h e ( r e s i d ) c o n v e r s i o n " wo r k h o r s e "
o f t h e o i l i n d u s t r y . At p r e s e n t a b o u t 4 5 % o f t h e wo r l d ' s c r u d e c a n
b e e n v i s i o n e d t o b e w i t h i n t h e f r o n t i e r s o f R e s i d F CC ( f i g u r e 1 ) .
Ap a r t f r o m t h e i mp o r t a n c e o f F CC f e e d p r e t r e a t me n t a n d F CC u n i t
d e s i g n , a l s o t h e i mp a c t o f F CC c a t a l y s t p e r f o r ma n c e i s c r u c i a l t o
a l l o w t h e p r o c e s s i n g o f h e a v i e r f e e d s .
T h e C a t a l y s t R o l e i n R e s i d F CC
R e v i e wi n g t h e ma i n c h a l l e n g e s i n R e s i d F CC, we c a n e s t a b l i s h t h e
a r e a s i n wh i c h F CC c a t a l y s t i mp r o v e me n t s c a n p l a y a r o l e i n
e n h a n c i n g t h e p r o c e s s a b i l i t y o f r e s i d s . ( s e e T a b l e I I . )
( a ) V a p o r i z a t i o n a n d c r a c k i n g o f l a r g e h y d r o c a r b o n s :
T h i s l e a d s t o a p o o r c o n v e r s i o n a n d h i g h e r c o k e an d f u e l g a s
y i e l d s . I n o r d e r t o i mp r o v e t h e c o n v e r s i o n o f l a r g e mo l e c u l e s ,
n e w mo d i f i c a t i o n s i n t h e F CC C a t a l y s t A r c h i t e c t u r e an d A c t i v e
S i t e A c c e s s i b i l i t y , a r e r e q u i r e d i n t e r ms o f P o r e S i z e a n d P o r e
A c i d i t y d i s t r i b u t i o n .
( b ) C o n t a mi n a t i o n b y h e a v y me t a l s ( V , N i ) :
S e v e r a l c a t a l y s t s o n t h e ma r k e t t o d a y c o n t a i n s p e c i a l v a n a d i u m
t r a p s o r v a n a d i u m s c a v e n g e r s i n o r d e r t o p r o t e c t t h e a c t i v e
i n g r e d i e n t s a g a i n s t p o i s o n i n g a n d / o r d e s t r u c t i o n b y V a n a d i u m.
T h e s e " Me t a l T r a p s " l i mi t t h e mo b i l i t y o f t h e v a n a d i u m p e n t o x i d e
c o mp o u n ds u n d e r F CC c o n d i t i o n s ( 2 , 1 0 ) . T h e n i c k e l p r o b l e m n e e d s
t o b e a p p r o a c h e d d i f f e r e n t l y : an d mo r e r e c e n t l y , p r o g r e s s h a s
b e e n made t o wa r d s r e d u c i n g t h e d e h y d r o g e n a t i o n a c t i v i t y o f n i c k e l
d i s p e r s e d o n F CC c a t a l y s t s ( 1 1 ) .
( c ) P o i s o n i n g a n d c o k e f o r ma t i o n b y b a s i c a n d p o l a r c o mp o u n ds :
Hi g h n i t r o g e n r e s i s t a n t c a t a l y s t s a n d / o r n i t r o g e n t r a p s a r e
a v a i l a b l e n o wa d a y s ; u n f o r t u n a t e l y , n o r e a l b r e a k t h r o u g h s h a v e
b e e n made i n r e d u c i n g t h e e f f e c t o f p o l y c y c l i c a r o ma t i c s
( Co n r a d s o n Ca r b o n C a t c h e r s ? ) . At p r e s e n t s u p e r l o w d e l t a c o k e
c a t a l y s t s a r e p r o d u c e d t o a l l o w f o r t h e a d d i t i o n a l c o k e p r o d u c e d
b y t h e s e p o l y c y c l i c a r o ma t i c s .
( d ) A c t i v e s i t e p o i s o n i n g b y S o d i u m, P o t a s s i u m; e t c
T h e S o d i u m r e s i s t a n c e o f t h e a c t i v e i n g r e d i e n t s i n F CC c a t a l y s t s
c a n a l s o b e t a c k l e d b y h i g h a c t i v i t y a n d s t a b i l i t y c a t a l y s t s .
( e ) S e v e r e Hy d r o t h e r ma l r e g e n e r a t i o n c o n d i t i o n s :
An i mp r o v e me n t i n c o k e s e l e c t i v i t y c a n h a v e a l a r g e i mp a c t o n

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F i g u r e 1 : R e s i d ( 3 7 0 C TB P +) p r o p e r t i e s i n r e l a t i o n t o F CC
p r o c e s s a b i l i t y ( s e e R e f . 9 ) . R e p r i n t e d wi t h
p e r mi s s i o n f r o m N a t i o n a l P e t r o l e u m R e f i n e r s
A s s o c i a t i o n p u b l i c a t i o n AM- 9 0 - 4 2 . C o p y r i g h t 19 9 0 .

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324
t h e a c t i v i t y s t a b i l i t y v i a t h e r e g e n e r a t o r t e mp e r a t u r e r e d u c t i o n .
Hi g h a c t i v i t y a n d s t a b i l i t y c a t a l y s t s a r e r e q u i r e d .
I t i s o b v i o u s t h a t d e p e n d i n g o n t h e t y p e a n d s e v e r i t y o f F CC f e e d
p r e t r e a t me n t ( C o k i n g , Hy d r o g e n a t i o n / D e me t a l l i z a t i o n ) an d t h e t y p e
o f F CC u n i t d e s i g n an d o p e r a t i n g p h i l o s o p h y t h e p r i o r i t y o f t h e
f o r e g o i n g a s p e c t s may d i f f e r c o n s i d e r a b l y . An i n t e r e s t i n g e x a mp l e
i s t h e c o mp a r i s o n b e t we e n t h e o p e r a t i o n o f F CC u n i t s wi t h an d
wi t h o u t h e a t r e mo v a l , ( T a b l e I I I . )
A l t h o u g h t h e t a b l e g i v e s a v e r y e x a g g e r a t e d c o mp a r i s o n b e t we e n t h e
t wo c a s e s , i t d o e s c l e a r l y d i s t i n g u i s h t h e i r p r i o r i t i e s .
I t i s a l s o c l e a r t h a t i n t h e c a s e o f F CC wi t h h e a t r e mo v a l ,
t h e f r o n t i e r o f r e s i d p r o c e s s a b i l i t y c a n a t a c e r t a i n mo me n t b e
d e t e r mi n e d b y t h e c o k e s e l e c t i v i t y o f t h e c a t a l y s t , wh i l e o n t h e
o t h e r h a n d t h e c o n v e r s i o n o f r e s i d i n a u n i t wi t h o u t h e a t r e mo v a l
may a l s o b e l i mi t e d b y t h e me t a l r e s i s t a n c e o f a c a t a l y s t .
C a t a l y s t A c c e s s i b i l i t y an d A r c h i t e c t u r e
i . D i f f u s i o n a n d a c t i v e s i t e a c c e s s i b i l i t y
T h e a c c e s s i b i l i t y o f a c t i v e s i t e s p l a y s an i mp o r t a n t r o l e i n t h e
a c t i v i t y an d s e l e c t i v i t y o f F CC. F o r r e s i d c r a c k i n g d i f f u s i o n a n d
a c c e s s i b i l i t y e f f e c t s c a n b e c o me o f p r i me i mp o r t a n c e .
I n a p r e v i o u s p a p e r ( 7 ) , we h a v e i l l u s t r a t e d t h a t d i f f u s i o n i n
F CC t a k e s p l a c e i n t h e n o n - s t e a d y r e g i me a n d t h a t t h i s e x p l a i n s t h e
f a i l u r e o f s e v e r a l a t t e mp t s t o r e l a t e l a b o r a t o r y me a s u r e me n t s o n F CC
c a t a l y s t s t o t h e o r i e s o n s t e a d y s t a t e d i f f u s i o n . A p a r t f r o m t h e
d i f f u s i o n a s p e c t s , N ac e ( 1 3 ) h a s a l s o i n d i c a t e d t h e l i mi t e d
a c c e s s i b i l i t y o f t h e z e o l i t e p o r t a l s u r f a c e a r e a b y c o mp a r i n g t h e
c r a c k i n g r a t e s o f v a r i o u s mo d e l c o mp o u n ds wi t h an i n c r e a s i n g n u mb e r
o f n a p h t h e n i c r i n g s o n z e o l i t e a n d amo r p h o u s F CC c a t a l y s t s , f i g u r e 2 .
Wi t h an i n c r e a s e i n t h e n u mb e r o f n a p h t h e n i c r i n g s , t h e c r a c k a -
b i l i t y o f t h e h y d r o c a r b o n mo l e c u l e i n c r e a s e s ( v i d e d a t a wi t h S i O^, -
Al Ô^ c a t a l y s t ) , wh i l e t h e r e l a t i v e c r a c k i n g r a t e b y z e o l i t e s
d r o p s o f f du e t o t h e l i mi t e d a c c e s s i b i l i t y o f t h e a c i d s i t e s i n t h e
z e o l i t e .
I t b e c o me s c l e a r t h a t s i g n i f i c a n t c o n v e r s i o n b e n e f i t s c a n b e
o b t a i n e d b y i n c r e a s i n g t h e a c t i v i t y c o n t r i b u t i o n i n t h e me s o p o r e
r a n g e ( a b o u t 2 0 t o 2 0 0 An g s t r o m d i a me t e r ) i n a c a t a l y s t , T a b l e I V .
R e s u l t s o b t a i n e d f r o m t e s t i n g v a r i o u s c a t a l y s t s wi t h V ac u u m g a s o i l
( VGO) a n d At mo s p h e r i c R e s i d u e ( AR) c o n f i r m t h a t i n d i c a t e d i mp r o v e -
me n t o f F CC c o n v e r s i o n .

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T a b l e I V . I mp a c t o f e n h a n c e d a c c e s s i b i l i t y o n c o n v e r s i o n
C a t a l y s t Me s o p o r e Me s o p o r e C o n v e r s i o n i n
S u r f a c e a r e a a c t i v i t y MS T t e s t , wt %
VGO AR D e l t a
A l o w l o w 6 3 6 3 0
B h i g h h i g h 6 3 6 5 + 2
C me di u m me di u m 6 2 6 4 + 2
D h i g h me di u m 6 8 7 4 + 6
D e v e l o p me n t me di u m me di u m 6 6 7 4 + 8
MS T = Mi c r o S i mu l a t i o n T e s t ( 1 4 ) ;
Hi g h T e mp e r a t u r e , S h o r t c o n t a c t T i me MAT ( 5 6 0 C, 15 s e c o n d s )
VGO = K u wa i t
AR = N o r t h S e a
C a t a l y s t D e a c t i v a t i o n : 5 h r s 7 8 8 C, 10 0 % s t e a m, 15 0 0 ppmN i
A l t h o u g h an i n c r e a s e i n me s o p o r e s u r f a c e a r e a an d a c t i v i t y w i l l
r e s u l t i n an i n c r e a s e i n c o n v e r s i o n an d r e s i d c o n v e r s i o n , T a b l e I V
a l s o s h o ws t h a t t h e r e i s n o s i mp l e c o r r e l a t i o n b e t we e n t h e o b s e r v e d
c a t a l y s t p r o p e r t i e s a n d t h e s e r e s u l t s . A p p a r e n t l y o t h e r a s p e c t s
s u c h a s p o r e s i z e d i s t r i b u t i o n a n d p o r e c h e mi s t r y a l s o p l a y an
i mp o r t a n t r o l e .
An o t h e r a s p e c t wh i c h n e e d s t o b e c o n s i d e r e d i s t h e e f f e c t o f
c a t a l y s t t o o i l r a t i o . I n a c o mme r c i a l u n i t t h e e f f e c t i v e me s o p o r e
a c t i v i t y w i l l b e a f u n c t i o n o f t h e me s o p o r e a c t i v i t y o f t h e
c a t a l y s t a n d o f t h e c a t a l y s t t o o i l r a t i o ( CT O) :
E f f e c t i v e me s o p o r o s i t y = Me s o p o r o s i t y x CTO
Me s o p o r o s i t y i s e x p r e s s e d i n t e r ms o f s u r f a c e a r e a a s me a s u r e d b y
Hg a d s o r p t i o n i n t h e 2 0 t o 10 0 An g s t r o m r a n g e . F i g u r e 3 i n d i c a t e s
h o w t h e e f f e c t i v e me s o p o r e a c t i v i t y h a s a s t r o n g e f f e c t o n
c o n v e r s i o n o f b o t t o ms i n t h e c a s e o f At mo s p h e r i c R e s i d u e , wh i l e t h i s
e f f e c t i s mu c h l e s s p r o n o u n c e d i n t h e c a s e o f VGO f e e d s t o c k .
F o r a c o mme r c i a l u n i t t h i s i mp l i e s t h a t we n e e d t o e n h a n c e t h e me s o
p o r e a c t i v i t y wh i l e a v o i d i n g a d r o p i n CTO du e t o ( f o r i n s t a n c e ) a
h i g h e r d e l t a c o k e o f t h e c a t a l y s t .
i i . P o r e S i z e A c i d i t y D i s t r i b u t i o n
I n an i d e a l i z e d s i t u a t i o n o n e c a n o p t i mi z e s e v e r a l s t a g e s i n t h e
c r a c k i n g o f a r e s i d mo l e c u l e :
S t a g e o n e : C a t a l y s t s o r b s n o n v o l a t i l e o r p a r t i a l l y v o l a t i l e r e s i d .
L a r g e a s p h a l t h e n e s c r a c k an d d e c o mp o s e n e a r l y i n s t a n t a n -
e o u s l y , a n d me t a l s a r e d e p o s i t e d o n t h e c a t a l y s t s u r f a c e .

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20. O'CONNOR ET AL. Future Residuum Catalyst Development 327
k / ko
4
\ Acces s i bi l i ty
\ Li mi tati on
Si 02- A1203
Zeol i te
k =Cracking rate
ko =Cracking rate of C16
i i i i . i i i J - u -
'0 1 2 3 4 5
Naphthenic ri ngs
16 12 13 14 16
Carbon number
F i g u r e 2 : A c t i v e S i t e a c c e s s i b i l i t y ( 1 3 ) .
Bottoms, wt%
15
VGO
ATM.RESID
CTO * PV-Meso (20-100 Ad)
MST at 70 wt% convers i on
F i g u r e 3 : E f f e c t i v e Me s o p o r o s i t y c o n c e p t .

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S t a g e t wo : L a r g e h y d r o c a r b o n mo l e c u l e s p r e c r a c k i n me s o p o r e s .
S t a g e t h r e e : Hy d r o c a r b o n c r a c k i n g o n s u r f a c e o f a n d i n z e o l i t e p o r e s .
He t t i n g e r e t a l ( 7 ) h a v e p r e s e n t e d t h i s s t a g e d c r a c k i n g c o n c e p t a s
a u s e f u l mo d e l f o r F CC r e s i d c a t a l y s t d e s i g n ( f i g u r e 4 ) . B a s e d o n
t h i s mo d e l we c a n e n v i s i o n a v e r y s p e c i f i c P o r e S i z e A c i d i t y
D i s t r i b u t i o n ( f i g u r e 5 ) , wh i c h wo u l d b e n e c e s s a r y t o a c h i e v e an i mp r o v e -
me n t i n r e s i d c o n v e r s i o n .
We h a v e n o t e d t h a t r e g a r d i n g t h e n e c e s s i t y o f s p e c i a l l a r g e
" L i q u i d c a t c h i n g " ( L C) p o r e s , t h e r e i s a v e r y s i g n i f i c a n t i mp a c t o n
c o k e a n d f u e l g a s s e l e c t i v i t y .
F i g u r e 6 s h o ws an e x a mp l e o f t h e c o k e s e l e c t i v i t y i n t h e MS T
u n i t wi t h a n o r ma l VGO f e e d s t o c k .
An o t h e r i n t e r e s t i n g f e a t u r e i s t h a t t h e s e L C p o r e s r e s u l t i n an
i n c r e a s e i n t h e o v e r a l c o n v e r s i o n . T h i s e f f e c t i s mo s t p r o n o u n c e d
wh e n t h e c a t a l y s t i s i mp r e g n a t e d wi t h N i c e l ( 15 0 0 ppmN i c k e l i n MS T)
a n d a t h i g h c o k e y i e l d s . F r o m t h i s i t s e e ms o b v i o u s t h a t p o r e mo u t h
b l o c k i n g i s a l s o a f a c t o r i n R e s i d F CC, an d t h a t t h e p r e s e n c e o f
L C p o r e s c a n b e b e n e f i c i a l i n t h i s r e s p e c t . Me s o p o r e s , a r e e s s e n t i a l
f o r r e d u c t i o n o f t h e b o t t o ms y i e l d wi t h a r o ma t i c a n d / o r n a p h t h e n i c
f e e d s t o c k s . ( T a b l e V. )
T a b l e V. I mp a c t o f me s o p o r e a c t i v i t y
B o t t o ms y i e l d i n t h e MS T a t 4 wt % c o k e '
*)
A r o ma t i c / N a p t h e n i c
F e e d s t o c k
P a r a f f i n i c
F e e d s t o c k
C a t .
C a t .
C a t .
A
B
C
h i g h z e o l i t e
a c t i v i t y
l o w me s o p o r e
a c t i v i t y
me di u m z e o l i t e
a c t i v i t y
h i g h me s o p o r e
a c t i v i t y
me di u m z e o l i t e
a c t i v i t y
h i g h me s o p o r e
a c t i v i t y
14 . 5
12 . 0
11. 0
13 . 2
11. 5
10 . 5
* MS T t e s t wi t h 15 0 0 ppmN i , c a t a l y s t d e a c t i v a t e d 5 h o u r s a t 7 8 8 C.

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L i q u i d a s p h a l t e n e
No n -A c i d i c l a r g e p ores
1
A c i d i c Ma t r i x
H+ H+
\//////////////////////////A
i C4 . C5=, C3= e t c .
Z e o l i t e P o r t a l S u r f a c e A rea
F i g u r e 4 : S t a g e d C r a c k i n g Mo d e l ( 1 5 ) .
S u r f a c e
A r e a
Smal l Pores
< 20 Ad
Meso Pores
30 - 100 Ad
"Li qui d
catchi ng"
Large Pores
> 100 Ad
J L_J I I I I I I I 1 i 1 I I I L
P ore Di a m e t e r
Rel ati ve
Acti vi ty
F i g u r e 5 : P o r e s i z e A c i d i t y D i s t r i b u t i o n .

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330
T a b l e 5 i n d i c a t e d t h e l a r g e e f f e c t o f me s o p o r e a c t i v i t y o n t h e
r e d u c t i o n o f b o t t o ms y i e l d wi t h Ar o ma t i c / N a p h t h e n i c f e e d s t o c k s .
F o r t h e p a r a f f i n i c f e e d s t o c k s t e s t e d , t h e i mp a c t o f t h e z e o l i t e
a c t i v i t y i s mu c h mo r e p r o n o u n c e d , an d t h e c a t a l y s t wi t h t h e h i g h e s t
z e o l i t e a c t i v i t y a n d l o we s t me s o p o r e a c t i v i t y g e n e r a t e s t h e l o we s t
b o t t o ms y i e l d .
T h e s e r e s u l t s s e e m t o c o r r e l a t e w e l l wi t h t h e " c o n c e p t u a l
p i c t u r e " o f s t a g e d c r a c k i n g a s p r e s e n t e d b y He t t i n g e r ( f i g u r e 5 ) a n d
t h e i n f l u e n c e o f mo l e c u l a r s t r u c t u r e ( l a r g e n u mb e r o f r i n g s v s l o w
n u mb e r o f r i n g s ) o n t h e e f f e c t i v e n e s s o f t h e z e o l i t e a c t i v i t y a s
i n d i c a t e d b y N a c e ( f i g u r e 2 ) . A s a l i e n t p o i n t o f t a b l e 5 i s t h e
f u r t h e r r e d u c t i o n o f b o t t o ms y i e l d s o b t a i n e d wi t h a s p e c i a l
t e c h n o l o g y h i g h me s o p o r e a c t i v i t y c a t a l y s t ( C a t . C ) .
F i g u r e 7 i l l u s t r a t e s t h a t t h e r e i s an e s s e n t a i l d i f f e r e n c e i n
t h e p o r e s i z e a r c h i t e c t u r e b e t we e n c a t a l y s t s p r o d u c e d wi t h t h i s
t e c h n o l o g y ( C a t . C) a n d t h o s e p r o d u c e d w i t h t h e o t h e r ma n u f a c t u r i n g
t e c h n o l o g i e s ( C a t . A, B ) . Wi t h t h e C a t . C T e c h n o l o g y ( h i g h me s o p o r e
a c t i v i t y c a t a l y s t s ) t h e r e i s a s h i f t t o wa r d s mo r e p o r e s i n t h e
" l a r g e r " me s o p o r e a r e a ( T a b l e I V . )
C a t a l y s t R e s i s t a n c e t o D e a c t i v a t i o n b y Me t a l s
i . S t r a t e g i e s t o r e d u c e v a n a d i u m e f f e c t s
T h e r e a r e s e v e r a l g o o d r e v i e w a r t i c l e s wh i c h c o v e r t h e r e s e a r c h o f
t h e me c h a n i s m o f v a n a d i u m d e a c t i v a t i o n o f F CC c a t a l y s t s ( s e e 2 ,
8 ) . B a s i c a l l y t h e v a n a d i u m p r e s e n t i n t h e l a r g e me t a l p o r p h o r i n
mo l e c u l e s i s d e p o s i t e d o n t h e o u t e r s u r f a c e o f t h e c a t a l y s t , du e
t o t h e f a s t d e c o mp o s i t i o n o f t h e s e mo l e c u l e s .
A t h i g h t e mp e r a t u r e s a n d i n t h e p r e s e n c e o f s t e a m, v a n a d i u m
b e c o me s mo b i l e an d mo v e s i n t o o t h e r p a r t s o f t h e c a t a l y s t . I n a F CC
u n i t t h i s t a k e s p l a c e d u r i n g t h e r e g e n e r a t i o n p h a s e ( a v e r a g e 7 0 0 C
an d 5 - 2 5 % s t e a m a t mo s p h e r e ) . V a n a d i u m o x i d e VÔ^ f o r me d d u r i n g
r e g e n e r a t i o n c a n r e a c t wi t h t h e z e o l i t e , RE Ô^, Na a n d AÔ- *
p r o mo t i n g d e s t a b i l i z a t i o n a n d c o l l a p s e o f t n e z e o l i t e s t r u c t u r e
( 1 6 , 1 7 ) . E v e n i n t h e c a s e t h a t a v e r y s t a b l e z e o l i t e i s a b l e t o
wi t h s t a n d t h i s a t t a c k , a c t i v i t y l o s s e s c a n o c c u r du e t o n e u t r a l i -
z a t i o n o f t h e z e o l i t e an d ma t r i x a c i d s i t e s .
F CC c a t a l y s t d e v e l o p me n t t o r e d u c e t h e e f f e c t o f v a n a d i u m h a s
b e e n a i me d a t r e d u c t i o n o f v a n a d i u m mo b i l i t y : t h e a p p l i c a t i o n o f
s p e c i a l i n g r e d i e n t s i n t h e c a t a l y s t wh i c h f u n c t i o n a s me t a l
s c a v e n g e r s o r me t a l c a t c h e r s . I n t h e p a s t ( 2 , 10 ) t r a n s p o r t e x p e r i -
me n t s we r e u s e d t o s h o w t h a t d u r i n g s t e a m- a g i n g , i n t r a p a r t i c l e
t r a n s f e r o f v a n a d i u m o c c u r s an d t h a t mi g r a t i n g v a n a d i u m c a n b e
i r r e v e r s i b l y s o r b e d b y a me t a l t r a p s u c h a s s e p i o l i t e ( 2 ) i n t h e
f o r m o f a h e a t s t a b l e v a n a d a t e .
A s i mp l e v a n a d i u m mo b i l i t y t e s t c a n b e s e t u p , i n wh i c h t h e
v a n a d i u m wh i c h mi g r a t e s f r o m v a n a d i u m- l o a d e d c a t a l y s t t o wa r d s
n o n - v a n a d i u m l o a d e d c a t a l y s t c a n b e me a s u r e d u n d e r c a t a l y s t a g i n g
( u s u a l l y s t e a mi n g ) c o n d i t i o n s ( 2 ) .
T h e me t h o d we a p p l i e d i s a s f o l l o w s : T h e c a t a l y s t i s s i e v e d i n t o
a c o a r s e a n d a f i n e f r a c t i o n . T h e c o a r s e f r a c t i o n o f t h e c a t a l y s t
( P S D >7 5 yum) i s i mp r e g n a t e d h o mo g e n e o u s l y wi t h a b o u t 4 0 0 0 ppm
v a n a d i u m f ey a t r a d i t i o n a l p o r e v o l u me i mp r e g n a t i o n me t h o d .

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O'CONNOR ET AL. Future Residuum Catalyst Development 331
1
58 60 62 64 66 68 70 72
CONVERSION, WT%
F i g u r e 6 : S e l e c t i v i t y b e n e f i t o f i mp r o v e d p o r e a r c h i t e c t u r e .

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A f t e r t h i s b o t h f r a c t i o n s a r e mi x e d t o g e t h e r a g a i n , a n d t h e mi x t u r e
i s s t e a me d i n a f i x e d b e d f o r 5 h o u r s a t 7 8 8 o r 8 3 0 C, wi t h 10 0 %
s t e a m. T h e s t e a me d mi x t u r e i s t h e n s i e v e d a g a i n an d t h e v a n a d i u m
c o n t e n t o f t h e c o a r s e f r a c t i o n ( P S D >7 5 yum) i s me a s u r e d .
T h i s a p p r o a c h mi n i mi z e s t h e e f f e c t s o f c a t a l y s t a t t r i t i o n p h e n o me n a
o n t h e v a n a d i u m mo b i l i t y d e t e r mi n a t i o n .
T h e v a n a d i u m mo b i l i t y ( VM) i s t h e n d e f i n e d a s f o l l o w s :
V V
C- s t a r t - C- e n d
VM ( %>=_ : *
1 0 0
V
s t a r t
^C^ s t a r t = V a n a d i u m l e v e l o f c o a r s e f r a c t i o n ( > 7 5 y u m) , b e f o r e
mi x i n g an d s t e a mi n g ( p p mwt )
^C^ e n d = V a n a d i u m l e v e l o f c o a r s e f r a c t i o n ( > 7 5 yum) a f t e r
mi x i n g a n d s t e a mi n g ( p p mwt )
T h e f o l l o w i n g t a b l e ( Tab l e VI . ) , s h o ws an e x a mp l e o f v a n a d i u m mo b i l i t y
an d i t s d e p e n d e n c e o n c a t a l y s t c o mp o s i t i o n .
T a b l e V I . R e d u c t i o n o f v a n a d i u m mo b i l i t y
C a t a l y s t V a n a d i u m mo b i l i t y
( % V mi g r a t i o n )
US Y 6 1. 5
L
2 3
L 0
L
2
U
3
US Y + A c t i v e A1
?
0 5 2 . 7
US Y + A c t i v e kUO* + MTT* ) 3 3 . 0
* ) MTT = A me t a l t r a p , a s d e s c r i b e d i n R e f e r e n c e ( 1 8 ) .
I n F CC u n i t s wh i c h e x h i b i t a h i g h t e n d e n c y t o v a n a d i u m mi g r a t i o n ,
t h e a p p l i c a t i o n o f me t a l t r a p s c a n b e v e r y b e n e f i c i a l .
F a c t o r s t h a t i n f l u e n c e v a n a d i u m mo b i l i t y i n c o mme r c i a l F CC u n i t s a r e :
1. T h e o x i d a t i o n s t a t e o f t h e v a n a d i u m ( s e e a l s o 2 )
2 . R e g e n e r a t o r t e mp e r a t u r e ; i t h a s b e e n o b s e r v e d t h a t t h e v a n a d i u m
mo b i l i t y c a n d o u b l e wi t h A0 C r e g e n e r a t o r t e mp e r a t u r e ( s e e
f i g u r e 8 ) .
3 . T h e p r e s e n c e o f s t e a m a n d c a r b o n o n c a t a l y s t .
4 . T h e v a n a d i u m l e v e l an d t h e c a t a l y s t r e p l a c e me n t o n i n v e n t o r y .

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F i g u r e 8 i l l u s t r a t e s t h e e f f e c t o f t e mp e r a t u r e o n v a n a d i u m mo b i l i t y
( me a s u r e d o n e q u i l i b r i u m c a t a l y s t s f r o m t h r e e F CC u n i t s ) a n d t h e
l a r g e i mp a c t o f c e r t a i n u n i t v a r i a b l e s . F o r t h e s e me a s u r e me n t s t h e
c o a r s e e q u i l i b r i u m c a t a l y s t was t e s t e d i n a mo b i l i t y t e s t u s i n g t h e
me t h o d d e s c r i b e d a b o v e b y s u b s t i t u t i n g s i e v e d c o a r s e e q u i l i b r i u m
c a t a l y s t f o r v a n a d i u m i mp r e g n a t e d c a t a l y s t .
I n c a s e o f a r e l a t i v e l y l o w v a n a d i u m mo b i l i t y , t h e d e a c t i v a t i o n
b y v a n a d i u m w i l l b e l e s s , an d s o w i l l b e t h e e f f e c t o f i n c o r p o r a t i n g
a me t a l t r a p . S t i l l i t a l s o a p p e a r s t o b e i mp o r t a n t t o a d d r e s s t h e
s t r a t e g y t o c o mb at v a n a d i u m i n t h i s c a s e . I f v a n a d i u m i s o n l y p r e s e n t
o n t h e o u t e r l a y e r an d i n t h e l a r g e r p o r e s o f a c a t a l y s t , t h e e f f e c t
o n z e o l i t e d e a c t i v a t i o n mi g h t b e d e c r e a s e d . Ho we v e r o wi n g t o d e a c t i -
v a t i o n o f a c i d s i t e s i n t h e s e me s o p o r e s , t h e b o t t o ms c r a c k i n g
p o t e n t i a l o f t h e c a t a l y s t s w i l l b e s t r o n g l y a f f e c t e d . T h u s t h e
p r e s e n c e o f v a n a d i u m c a t c h i n g c a p a b i l i t y i n t h e s e l a r g e r p o r e
r e g i o n s b e c o me s e s s e n t i a l . T h i s i s c l e a r l y v i s i b l e w i t h mo r e r e s i d
i n t h e f e e s t o c k .
S i n c e t h e me t h o d o f me t a l i mp r e g n a t i o n w i l l a l s o h a v e a l a r g e i mp a c t
o n t h e p r o f i l e o f v a n a d i u m d e p o s i t i o n o f t h e c a t a l y s t , we c l e a r l y
n e e d t o r e v i e w t h i s a s p e c t o f c a t a l y s t t e s t i n g . V i a c y c l i c me t a l
i mp r e g n a t i o n a n d c a t a l y s t d e a c t i v a t i o n , we c a n a p p r o a c h " R e a l - Wo r l d "
c o n d i t i o n s f a r b e t t e r . (Table VII.)
T a b l e V I I . E f f e c t o f a c c e s s i b i l i t y
C o n v e r s i o n i n MS T, % wt
C a t a l y s t A
C a t a l y s t B
" A c c e s s i b l e " v a n a d i u m c a t c h e r
10 0 % VGO 6 0 % VGO/
4 0 % N o r t h S e a AR
6 6 6 6
6 8 7 1
* ) 5 0 0 0 ppm V me t a l l e v e l , i mp r e g n a t i o n b y a c y c l i c d e a c t i v a t i o n
me t h o d .
T h e r o u t e o f c a t a l y s t d e a c t i v a t i o n v i a a c y c l i c me t a l i mp r e g n a t i o n
an d d e a c t i v a t i o n me t h o d h a s p r o d u c e d s i g n i f i c a n t i mp r o v e me n t s i n
a p p r o a c h i n g r e a l i s t i c v a n a d i u m an d n i c k e l p r o f i l e s o v e r t h e c a t a l y s t
p a r t i c l e s . F r o m e l e c t r o n mi c r o p r o b e a n a l y s e s o f N i a n d V l o a d e d
c a t a l y s t i t h a s b e e n e s t a b l i s h e d t h a t a f t e r p o r e v o l u me s a t u r a t i o n ,
N i a n d V a r e r a t h e r h o mo g e n e o u s l y d i s t r i b u t e d o v e r t h e c a t a l y s t .
I n c y c l i c i mp r e g n a t e d c a t a l y s t s , N i i s ma i n l y p r e s e n t o n t h e
c a t a l y s t s u r f a c e . I n c o n t r a s t a v a n a d i u m p r o f i l e o v e r t h e p a r t i c l e i s
f o u n d . I n t h e c a s e t h a t n o s t e a m i s a p p l i e d i n t h e r e g e n e r a t i o n
s t a g e o f t h e c y c l i c d e a c t i v a t i o n p r o c e d u r e , t h e V r e ma i n s ma i n l y
c o n c e n t r a t e d a t t h e s u r f a c e o f t h e c a t a l y s t p a r t i c l e s . Ot h e r me t h o d s
a s i ma g i n g S I MS ( 1 9 ) a n d L u mi n e s c e n c e ( 2 0 ) a r e a l s o b e i n g a p p l i e d
t o mo n i t o r a n d c o mp ar e t h e N i an d V d i s t r i b u t i o n o f d e a c t i v a t e d

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c a t a l y s t s v e r s u s c o mme r c i a l l y d e a c t i v a t e d e q u i l i b r i u m c a t a l y s t s .
C a r e f u l s e l e c t i o n o f t h e d e a c t i v a t i o n c o n d i t i o n s ( me t a l s p e r
c y c l e , r e g e n e r a t o r t e mp e a t u r e , % wt s t e a m i n c a n a l s o
a l l o w u s t o d i s t i n g u i s h b e t we e n c a t a l y s t d e a c t i v a t i o n b y me t a l s a n d
b y h y d r o t h e r ma l e f f e c t s . ( T a b l e V I I I . )
T a b l e V I I I . Me t a l s t o l e r a n c e b y c y c l i c d e a c t i v a t i o n
C o n v e r s i o n l o s s ( wt % i n MS T)
C a t a l y s t Z e o l i t e L o w me t a l s Hi g h me t a l s
c y c l e s c y c l e s
g Z - 14 US 2 . 8 5 . 5
K L Z - 2 10 2 . 4 4 . 8
Ak z o AD Z - 4 0 2 . 3 3 . 5
Ak z o AD Z - 4 1 2 . 6 3 . 0
L o w me t a l s : 10 0 0 ppm V, 5 0 0 ppm N i
Hi g h me t a l s : 3 0 0 0 ppm V, l OOOppm N i
I t c a n b e o b s e r v e d t h a t t h e ma g n i t u d e o f c o n v e r s i o n l o s s o f 1 t o
2 p o i n t s MS T p e r 10 0 0 ppm V c o r r e s p o n d s q u i t e w e l l w i t h c o mme r i c a l
d a t a . N o t e t h a t t h i s i s o n l y t r u e f o r V l e v e l s b e l o w 5 0 0 0 ppm t h a t
i s , a t r e l a t i v e l y l o w V l e v e l s .
i i . N i c k e l e f f e c t s an d e n c a p s u l a t i o n
I n t h e e i g h t i e s , mo r e a n d mo r e F CC u n i t s p r o c e s s e d n i c k e l r i c h
f e e d s t o c k s , e s p e c i a l l y n i c k e l r i c h p a r a f f i n i c a t mo s p h e r i c r e s i d s
f r o m t h e N o r t h S e a a n d A s i a P a c i f i c s o u r c e s .
A l t h o u g h n i c k e l h a s o n l y a ma r g i n a l e f f e c t o n c a t a l y s t
d e a c t i v a t i o n , n i c k e l i t s e l f i s a c t i v a t e d e s p e c i a l l y o n a l u mi n a
s u r f a c e s a n d wo r k s a s a d e h y d r o g e n a t i o n a g e n t c a t a l y z i n g t h e
r e a c t i o n s f o r mi n g c o k e , g a s a n d e s p e c i a l l y h y d r o g e n ( 2 ) . A l s o
a s a c o n s e q u e n c e o f t h e h i g h e r l o c a l i z e d c o k e f o r ma t i o n , b l o c k i n g
o f t h e p o r e s w i l l t a k e p l a c e , r e s u l t i n g i n a l o s s o f a c t i v i t y .
A p a r t f r o m t h e u s e o f S b o r B i p a s s i v a t o r s o n t h e c a t a l y s t s i d e , u p
t o v e r y r e c e n t l y t h e o n l y a p p r o a c h h a s b e e n t o mi n i mi z e t h e a c t i v e
a l u mi n a s u r f a c e i n t h e c a t a l y s t a n d c o n s e q u e n t l y s a c r i f i c e b o t t o ms
c o n v e r s i o n f o r n i c k e l r e s i s t a n c e .
A n e w t e c h n o l o g y o f c a t a l y s t p r o d u c t i o n ( 1 1 ) i s c a p a b l e o f
g e n e r a t i n g ma t e r i a l s i n wh i c h t h e n i c k e l a c t i v i t y a s d e h y d r o g e n a t i o n
a g e n t h a s b e e n s t o p p e d b y a mu l t i - s t e p s t r a t e g y . ( T a b l e I X. )

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O'CONNOR ET AL. Future Residuum Catalyst Development 335
Mo b i l i t y
35
30
25
20
15
10
-Un i t A
S i m i l a r C a t a l y s t s
-
Un i t C
- A -
A
-
A
-
i i i
Un i t B
1 i 1 i 1 i 1 i
A 5h 788 St
A 5h 830 St
Un i t A:
High T, Low Inv
Un i t B. C:
Low T, H i g h Inv
0 2000 4000 6000
V anadium on c at , ppm.wt
F i g u r e 8 : V a n a d i u m M o b i l i t y o n F CC c a t a l y s t s .

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T a b l e I X. S t r a t e g y t o c o mb at N i c k e l
S i l i c a R i c h S u r f a c e F o r ma t i o n o f l a r g e c r y s t a l l i t e s a n d
s t a b l e i n e r t N i - s i l i c a t e s
Al u mi n a r i c h S u r f a c e E n c a p s u l a t i o n o f n i c k e l i n n o n - a c t i v e
a l u mi n a t e t r a h e d r a l s t r u c t u r e s
Z e o l i t e N o n - f r a me wo r k Al u mi n a C o n t r o l ( AD Z )
F i g u r e 9 d e mo n s t r a t e s t h e c l e a r b e n e f i t o f n i c k e l e n c a p s u l a t i o n i n
r e d u c i n g t h e a c t i v i t y f o r h y d r o g e n p r o d u c t i o n . T h e o b s e r v e d R l Ô^
e f f e c t o n h y d r o g e n p r o d u c t i o n , i s r e l a t e d t o t h e f o r ma t i o n o f
z e o l i t e s u r f a c e n o n - f r a me wo r k a l u mi n a . P r o g r e s s i n n i c k e l t o l e r a n c e
o f F CC c a t a l y s t wi t h t h e s e n e w t e c h n o l o g i e s i s a t l e a s t a s d r a ma t i c
a s i n v a n a d i u m t o l e r a n c e ( 2 ) .
Co mme r c i a l F CC o p e r a t i o n s wi t h n i c k e l o n e q u i l i b r i u m c a t a l y s t
( a b o v e 2 0 0 0 ppm) wi t h o u t t h e u s e o f p a s s i v a t o r , h a v e b e c o me f e a s i b l e .
T h i s n e w t e c h n o l o g y a l s o a l l o ws f u r t h e r o p t i mi z a t i o n o f t h e me s o p o r e
a c t i v i t y , t h e c o n c e p t u a l f i g u r e 10 i l l u s t r a t e s t h i s p o i n t , wh i c h n o w
h a s b e e n c o n f i r me d i n c o mme r c i a l F CC o p e r a t i o n s ( 2 1 ) .
As wi t h v a n a d i u m u n d e r r e l a t i v e l y l o w mo b i l i t y c o n d i t i o n s , n i c k e l
r e ma i n s ma i n l y d e p o s i t e d i n t h e l a r g e r p o r e s o f t h e c a t a l y s t .
He n c e t o i n v e s t i g a t e n i c k e l e f f e c t s a s r e a l i s t i c a l l y a s p o s s i b l e ,
C y c l i c D e a c t i v a t i o n ( CD ) me t h o d s a r e r e c o mme n de d.
T a b l e X: d e mo n s t r a t e s t h i s , s h o wi n g h o w t h e c a t a l y s t r a n k i n g c a n b e
i n f l u e n c e d b y t h e d e a c t i v a t i o n p r o c e d u r e u s e d .
T a b l e X. I n f l u e n c e o f c a t a l y s t r a n k i n g b y t y p e o f d e a c t i v a t i o n
p r o c e d u r e .
Me t h o d p o r e v o l u me c y c l i c
i mp r e g n a t i o n d e a c t i v a t i o n
C a t a l y s t * ) L CMR E S L CMR E S
MS T y i e l d 7 0 % wt
C o n v e r s i o n
H
2
0 . 16 0 . 2 2 0 . 17 0 . 15
D r y g a s 3 . 1 3 . 1 3 . 0 2 . 5
Ga s o l i n e 4 4 . 2 4 4 . 0 4 4 . 0 4 5 . 2
B o t t o ms 13 . 1 12 . 2 14 . 2 12 . 6
Co k e 3 . 4 3 . 8 4 . 2 3 . 7
C
4
=/ C
4
t o t 0 . 6 3 0 . 7 0 0 . 6 0 0 . 6 5

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* ) C a t a l y s t C h a r a c t e r i s t i c s :
L CMR : Mi n i mu m me s o p o r e a c t i v i t y wi t h MR me t a l t r a p
E S : Hi g h me s o p o r e a c t i v i t y wi t h ADVANCE t e c h n o l o g y
C a t a l y s t R e s i s t a n c e t o D e a c t i v a t i o n b y Ot h e r P o i s o n s
Ot h e r c a t a l y s t p o i s o n s b e s i d e s n i c k e l an d v a n a d i u ma r e :
1. P o i s o n s wh i c h n e u t r a l i z e o r d e s t r o y a c i d s i t e s , a s f o r i n s t a n c e
s o d i u m, p o t a s s i u m, n i t r o g e n .
2. P o i s o n s ( s u c h a s b a s i c a n d p o l a r c o mp o u n ds i n t h e f e e d ) wh i c h
p r i ma r i l y e n h a n c e t h e f o r ma t i o n o f c o k e an d h e n c e i n d i r e c t l y
a l s o c a u s e t h e d e a c t i v a t i o n o f t h e c a t a l y s t .
F o r t h e f i r s t t y p e o f p o i s o n s , we c a n e i t h e r t r y t o a p p l y t h e s ame
a p p r o a c h a s wi t h v a n a d i u m; me a n i n g s p e c i f i c c a t c h e r s o r o f f e r a
s u f f i c i e n t e x c e s s o f a c i d s i t e s : s a c r i f i c i a l s i t e s i n o r d e r t o
r e d u c e t h e r e l a t i v e i mp a c t o f t h e p o i s o n i n g . F o r i n s t a n c e , i n t h e
c a s e o f a n i t r o g e n r e s i s t a n t c a t a l y s t , u s u a l l y t h e c a t a l y s t d e s i g n
w i l l i n v o l v e a r e l a t i v e l y h i g h r a r e - e a r t h an d h i g h z e o l i t e c o n t e n t
c a t a l y s t wi t h t h e o p t i o n o f a d d i t i o n a l s a c r i f i c i a l s i t e s i n t h e
f o r m o f a c t i v e a l u mi n a (12).
O b v i o u s l y s u c h a t y p e o f f o r mu l a t i o n c o u l d h a v e s o me n e g a t i v e
c o n s e q u e n c e s f o r t h e c a t a l y s t : p r i ma r i l y a h i g h e r c o k e mak e a n d
p r o b a b l y a l s o s o me o c t a n e p e n a l t y .
Wi t h r e g a r d s t o s o d i u m we a l s o n e e d t o c o n s i d e r t h e s t a b i l i t y
r e s i s t a n c e o f t h e z e o l i t e . F o r t u n a t e l y , s o me o f t h e n e we r z e o l i t e s
a r e a b l e t o ma i n t a i n t h e i r s t r u c t u r a l i n t e g r i t y , i n t h e p r e s e n c e o f
h i g h s o d i u m l e v e l s . Ho we v e r , t h e a c i d s i t e s p r e s e n t r e ma i n s t i l l
v e r y s u s c e p t i b l e t o n e u t r a l i z a t i o n b y s o d i u m.
We c a n a l s o d i s t i n g u i s h a f e w l i n e s o f a p p r o a c h r e g a r d i n g
c a t a l y s t p o i s o n s wh i c h d e a c t i v a t e t h e c a t a l y s t b y c o k e f o r ma t i o n ,
t h a t i s b y b l o c k i n g o f p o r e s a n d t h e c a t a l y s t a c t i v e s i t e s ,
1. C o n v e r s i o n o f t h e s e c o k e p r e c u r s o r s p r i o r t o t h e f o r ma t i o n o f
t h e c o k e . I t i s t o s o me e x t e n t d e b a t a b l e wh e t h e r t h i s c a n b e
d o n e . S o me i mp r o v e me n t s a r e p o s s i b l e u s i n g an i mp r o v e d c a t a l y s t
p o r e a r c h i t e c t u r e a n d a c i d i t y d i s t r i b u t i o n .
2. Ad a p t c a t a l y s t d e s i g n t o mi n i mi z e t h e e f f e c t o f c o k e o n c a t a l y s t .
T h i s i s an a s p e c t wh i c h c l e a r l y d e s e r v e s a t t e n t i o n , a s we mi g h t
e x p e c t s i g n i f i c a n t d e p o s i t i o n o f c o k e i n t h e v e r y b e g i n n i n g o f
t h e r i s e r wh e n p r o c e s s i n g r e s i d s .
3. Re d u c e t h e c a t a l y t i c c o k e f o r ma t i o n o f t h e c a t a l y s t i n o r d e r t o
a l l o w s o me r o o m f o r t h e a d d i t i o n a l c o k e f o r me d b y t h e s e p o i s o n s .
I n t h i s a p p r o a c h we a c c e p t t h a t t h e e x t r a c o k e f o r me d i s u n -
a v o i d a b l e , an d t h a t we n e e d t o c o mp e n s a t e b y i mp r o v i n g t h e c o k e
s e l e c t i v i t y o f t h e c a t a l y s t .
T h e ma i n s t r a t e g i e s f o r a d d r e s s i n g t h e s e t y p e s o f c a t a l y s t p o i s o n s
a r e s u mma r i z e d i n T a b l e X I .

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"Ni -Ac t i v at i n g "
Ni -En c ap s u l at i on "
_ J i I i I i L_
O A c t i v e A1203
No A1203
A c t i v e A1203
i n c l u d i n g
ADVANCE T ec h n ol og y
0 2 4 6 8
RE203, %wt on Y
MST at 70%wt Conversion
1500 ppm Ni, 5h 788 100%St
F i g u r e 9 : Hy d r o g e n p r o d u c t i o n v s C a t a l y s t d e s i g n .
COKE
Tradi ti onal
- Optimum
LCS Where ?
MESOPORE ACTIVITY
--- Ac t i v e A1203
Ac t i v e A1203
Advance Technology
MST Test
1500 ppm Ni
5h 788 St.
Kuwait VGO
F i g u r e 10 : Co k e s e l e c t i v i t y v s Me s o p o r e a c t i v i t y .

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T a b l e X I . S t r a t e g i e s f o r a d d r e s s i n g c a t a l y s t p o i s o n s
T y p e o f P o i s o n E x a mp l e s S t r a t e g y Re mar k s
P o i s o n s wh i c h
n e u t r a l i z e o r
d e s t r o y a c i d
s i t e s
N a, K ,
n i t r o g e n
s p e c i f i c p o i s o n
c a t c h e r s
s a c r i f i c i a l
s i t e s : h i g h
n o t s u c c e s s f u l
y e t
n e e d t o c o mp e n -
s a t e f o r c o k e -
s e l e c t i v i t y
P o i s o n s wh i c h
d e a c t i v a t e
s i t e s an d b l o c k
p o r e s b y e x t r a
c o k e f o r ma t i o n
b a s i c an d
p o l a r
c o mp o u n ds
c o n v e r t c o k e
p r e c u r s o r s
mi n . e f f e c t
o f c o k e o n
c a t a l y s t
r e d u c e c a t a -
l y t i c c o k e
f o r ma t i o n
s p e c i a l p o r e
a c i d i t y d i s t r .
n e e d t o c o mp e n -
s a t e f o r c o k e
s e l e c t i v i t y
We c a n c o n c l u d e t h a t an i mp r o v e me n t i n c o k e s e l e c t i v i t y p l a y s an
i mp o r t a n t r o l e i n t h e s t r a t e g i e s t o c o p e wi t h b o t h t y p e o f p o i s o n s .
C a t a l y s t S e l e c t i v i t y a n d S t a b i l i t y
As d i s c u s s e d i n t h e p r e v i o u s s e c t i o n s an y i mp r o v e me n t s i n c o k e
s e l e c t i v i t y c a n b e u t i l i z e d t o e x t e n d t h e f r o n t i e r s o f r e s i d
p r o c e s s i n g a s s e v e r a l t y p e s o f p o i s o n s i n t h e r e s i d f e e d , mo s t o f
a l l t h e p o l a r h y d r o c a r b o n s w i l l i n c r e a s e t h e c o k e f o r me d . A l s o f o r
f u e l g a s we c a n o b s e r v e t h a t n o n - o p t i ma l v a p o r i z a t i o n an d c r a c k i n g
c o n d i t i o n s w i t h r e s i d w i l l s t r o n g l y e n h a n c e g a s f o r ma t i o n . A l o w
c o k e a n d g a s c a t a l y s t i s h e n c e a b i g p l u s f o r r e s i d p r o c e s s i n g .
( T a b l e X I I . )
T a b l e X I I . L o w c o k e a n d g a s c a t a l y s t
Z e o l i t e N o n - f r a me wo r k c o n t r o l (3), a l s o l o w c o k e wi t h
me d i u m/ h i g h RE Ô^ l e v e l s .
F u e l g a s d e c r e a s e s wi t h h i g h e r RE Ô^ l e v e l s
A c t i v e Al Ô^ Mo d i f i e d s u r f a c e c h e mi s t r y t o r e d u c e c o k e a n d
g a s f o r ma t i o n (11, 20)
C a t a l y s t S p e c i a l p o r e s i z e A c i d i t y D i s t r i b u t i o n
A r c h i t e c t u r e r e d u c e s c o k e a n d g a s f o r ma t i o n

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B a s e d o n t h e " i d e a l i z e d o b j e c t i v e s " o u t l i n e d i n T a b l e X I I L , we c a n
a r r i v e a t t h e f o l l o w i n g c a t a l y s t c h a r a c t e r i s t i c s f o r o p t i mu m c o k e
an d g a s r e d u c t i o n
RE S I D - 1 Mi n i mu m g a s Me di u m r a r e e a r t h z e o l i t e wi t h
me di u m t o h i g h me s o p o r e a c t i v i t y .
RE S I D - 2 Mi n i mu m c o k e L o w r a r e e a r t h z e o l i t e wi t h l o w
me s o p o r e a c t i v i t y .
T h e p r o g r e s s i n c o k e s e l e c t i v i t y a n d b o t t o ms o r r e s i d c r a c k i n g i s
i l l u s t r a t e d i n T a b l e X I I I b e l o w:
T a b l e X I I I . R e s i d c o n v e r s i o n a t c o n s t a n t c o k e
RC, R e s i d c o n v e r s i o n = 1 0 0 - b o t t o ms - c o k e , i n MS T
RC D e l t a RC
B a s e 7 9 . 3
ADVANCE 8 0 . 6 1. 3
D E V - 1* ) 8 2 . 8 3 . 5
D E V - 2 * ) 8 3 . 8 4 . 5
RE - US Y c a t a l y s t wi t h me di u m me s o p o r e a c t i v i t y , d e a c t i v a t e d 5 h o u r s
a t 7 8 8 C, 10 0 % s t e a m a n d 15 0 0 ppmN i .
* ) E x p e r i me n t a l l a b o r a t o r y s a mp l e s
I t i s c l e a r t h a t t h e z e o l i t e d e l t a c o k e w i l l h a v e a s t r o n g e f f e c t
o n t h e r e g e n e r a t o r t e mp e r a t u r e a n d h e n c e o n t h e c a t a l y s t d e a c t i -
v a t i o n . D e p e n d i n g o n t h e t r e n d i n F CC r e g e n e r a t o r t e mp e r a t u r e s ,
t h e a s p e c t o f h y d r o t h e r ma l s t a b i l i t y mi g h t b e c o me o f g r e a t e r
i mp o r t a n c e .
I t h a s b e e n o b s e r v e d t h a t , t h e i n d i r e c t e f f e c t o f d e l t a c o k e
o n c a t a l y s t d e a c t i v a t i o n , an d t h e d i r e c t e f f e c t o f d e l t a c o k e o n
t h e b l o c k i n g o f a c i d s i t e s ( e a r l y ) i n t h e r i s e r s e e ms t o b e a
p r i me f a c t o r , wh i c h d o mi n a t e s c o n v e r s i o n an d s e l e c t i v i t y e f f e c t s i n
a r e s i d t y p e o f o p e r a t i o n .
F u t u r e P e r s p e c t i v e s
F r o m t h e f o r e g o i n g c h a p t e r s i t s h o u l d b e c l e a r t h a t t h e d e v e l o p me n t
o f a s u c c e s s f u l F CC r e s i d c a t a l y s t d e p e n d s o n s e v e r a l a s p e c t s t h e
r e l a t i v e p r i o r i t i e s o f wh i c h w i l l b e d e t e r mi n e d b y t h e r e f i n e r y
o b j e c t i v e s , f e e d s t o c k , F CC u n i t c o n f i g u r a t i o n an d l i mi t a t i o n s . S t i l l ,
i t i s wo r t h wh i l e t o d i s t i n g u i s h c e r t a i n " i d e a l i z e d o b j e c t i v e s " i n
o r d e r t o f o c u s t h e c a t a l y s t d e v e l o p me n t i n t h i s f i e l d . T h e a d v a n c e s
i n r e s i d F CC c a t a l y s t d e v e l o p me n t u p t o n o w h a v e b e e n ma i n l y i n t h e
f i e l d o f me t a l t o l e r a n c e ( me t a l t r a p s ) , wh i l e a l s o p r o g r e s s h a s

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0
b e e n made i n c r a c k i n g t h e l a r g e r h y d r o c a r b o n mo l e c u l e s .
F o r t h e f u t u r e we n e e d t o a d d r e s s s o me o t h e r c r i t i c a l p o i n t s t o u c h e d
u p o n i n t h i s r e v i e w a s ( T a b l e XI V . )
T a b l e XI V . S o me f u t u r e c h a l l e n g e s
- Ho w t o r e d u c e t h e f o r ma t i o n a n d t h e d e t r i me n t a l e f f e c t o f t h e
f e e d c o k e o r c o k e f o r me d b y p o l a r c o mp o u n ds
- D e v e l o p me n t o f t r a p s f o r p o i s o n s , wi t h o u t n e g a t i v e l y a f f e c t i n g
t h e c a t a l y s t s e l e c t i v i t y
- A c c e s s i b i l i t y a n d e f f e c t i v e n e s s o f v a n a d i u m t r a p p i n g
- F u r t h e r r e d u c t i o n o f " c a t a l y t i c " c o k e a n d f u e l g a s p r o d u c t i o n i n
o r d e r t o a l l o w mo r e r o o m f o r r e s i d p r o c e s s i n g
- C r a c k i n g o f c e r t a i n " d i f f i c u l t " mo l e c u l e s
I t i s a l s o c l e a r t h a t a g o o d u n d e r s t a n d i n g o f t h e F CC p r o c e s s
o b j e c t i v e s , l i mi t a t i o n s a n d c o n f i g u r a t i o n w i l l b e o f c r u c i a l
i mp o r t a n c e f o r t h e d e v e l o p me n t o f an o p t i mi z e d r e s i d F CC c a t a l y s t
f o r mu l a t i o n .
RE F E RE NCE S
1. S ee f o r exampl e:
( a) M. L. Oc c e l l i an d J . V. Ken n edy i n GB 2. 116. 062 A ( 198 3 )
( b ) M. L. Oc c e l l i an d J . V. Ken n edy i n US 4. 465. 588 ( 198 4 )
( c ) M. L. Oc c e l l i an d H. E. S wi f t i n US 4. 466. 884 ( 198 4 )
( d) M. L. Oc c e l l i i n US 4. 615. 996 ( 198 6 )
( e ) J . I . de J o n g i n US 4. 519. 897 ( 198 5 )
2. M. L. Oc c e l l i i n " F l u i d Cat al y s t Cr ac k i n g : Ro l e i n Mo der n
Re f i n i n g " , ACS S ympo s i umS e r i e s , v o l 375,
M. L. Oc c e l l i , E d. ACS Was h i n gt o n D. C. , p 162 ( 19 8 9 ) .
( a) J . S c h e r z e r i n " Ca t a l y t i c Mat e r i al s : Re l at i o n s h i p b et ween
s t r u c t u r e an d r e a c t i v i t y , ACS S ympo s i umS e r i e s , v o l 248
T. E. , Whyt e, R. A. D. B e t t a, E. G. Der o uan e an d R. T. K. Bak e r ,
E d i t o r s , ACS Was h i n gt o n D. C. , p 157 ( 198 3 )
( b ) R. J . P e l l e t , C. S . B l ac k we l l an d J . A. r ab o ; J . Cat al y s i s 114,
71- 89 ( 198 8 )
( c ) B. de K r o e s , C. J . Gr o en en b o o man d P. O' Co n n o r ;
" New Z e o l i t e s i n FCC" , Akz o Cat al y s t S ympo s i um1986,
May 25- 28, The Ne t h e r l an ds .
H. Th. Ri j n t e n , an d H. J . L o v i n k e d i t o r s .
G. J . Tho mps o n, R. H. Hen s en , C. N. Cab r e r a an d E . J . Ho ude;
" P r o c e s s i n g r e qu i r e me n t s an d ec o n o mi c an al y s i s o f Heavy Oi l an d
s yn c r ude r e f i n i n g " , i n t h e 12 t h Wo r l d P e t r o l e u m Co n gr e s ,
Ho us t o n 1987, J o h n Wi l e y & S o n s l t d.

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0
5. C. Carter; NPRA Annual meeting 1986, AM-84-27
6. J .A. Dudley; AIChe 1989, Spring National Meeting, Houston
7. P. O'Connor and F.W. van Houtert; "The role of diffusion in
bottoms conversion", Akzo Catalyst Symposium1986, May 25-28,
The Netherlands. H.Th. Rijnten and H.J Lovink editors.
8. J .L. Mauleon and J .B. Sigaud; "Characterization and selection
of heavy feeds for upgrading through fluid catalytic cracking
process" in the 12th world PetroleumCongress, Houston 1987,
Hohn Wiley & sons Ltd.
9. J .E. Naber, P.H. Barnes and M. Akbar; J .P.I . PetroleumRefining
conference, Tokyo - Japan, October 1988.
10. M.L. Occelli and J .M. Stengel in "Fluid Catalytic Cracking:
Role in Modern Refining", ACS SymposiumSeries, vol 375,
M.L. Occelli, Ed. ACS Washington D.C., p 195 (1989).
11. C. Lam, P. O'Connor and C. P. Smit; "The Advance Catalyst Series",
Akzo Catalyst Symposium1988, May 29-June 1, The Netherlands,
H.J . Lovink editor.
12. J. Scherzer and d.P. McArthur; "Catalytic Cracking of High
Nitrogen PetroleumFeedstocks: Effect of Catalyst Composition
and Properties", I nd. Eng. Chem. Res. 1988, 27, p 1571-1576.
13. D.M. Nace; I nd. Eng. Chem. 9 (2), 203, 1970.
14. P. O'Connor and M.B. Hartkamp in "Characterization and Catalyst
Development", ACS Symposiumseries, vol 411, S.A. Bradley,
M.J . Gatturo and R.J . Bertolacini, editors ACS Washington DC,
p 135 (1989).
15. P. Hettinger in "Fluid Catalytic Cracking: Role in Modern
Refining", ACS SymposiumSeries, Vol 375, M.L. Occelli, editor
ACS Washington DC, p 308 (1989).
16. M.L. Occelli and J .M. Stencel in "Zeolite as Catalysts, sorbents
and Detergent Builders" H.G. Karge and J . Weitkamp, editors
Elsevier, p 127 (1989).
17. M.L. Occelli and J .M. Stencel in "Zeolites, Facts, Figures,
Future", P.A. Jacobs, P.A. Vanjarter, editor Elsevier, part B
p 1311, 1989.
18. C. Groenenboomin "Zeolites as Catalysts, Sorbents and Detergent
Builders", H.G. Karge, editor Elsevier, p 199, 1989.
19. D.P. Leta and E.L. Kugler; "Secondary Ion Mass Spectranetry Proc.
I nt. Conf.", 6th 1987, p 373 (1988).
20. MM.L. Occelli; J ournal of Catalysis, 96, 1985, 2, p 363-370.
21. A.W. Gevers, P. O'Connor and E. Brevoord; "Advance: an
exceptional FCC Catalyst desing", Akzo Catalysts South American
Catalyst Seminar, 1989, October 19-20, 1989, H.J . Lovink editor.
RECEIVED October 5, 1990

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Chapter 21
Metal-Resistant Fluid Cracking Catalysts
Thirty Years of Research
M. L. Occelli
Although the deleterious effects of metals such as V, Cu, Ni
and Fe have been known for well over forty years (1-19), the
study of metal resistant fluidized cracking catalysts (FCC)
became an area of intense research in industrial and academic
laboratories only in the early seventies when the Arab Oil
embargo induced nearly a four-fold increase in crude prices
and greatly reduced overseas crude availability (2).
Metal levels (Ni+V) on equilibrium catalysts from U.S.
refineries have been monotonically increasing with time since
the early sixties (20). This trend continued during the 1980-
1986 period (Figure 1) when crude prices decreased to about
$25/bbl from $38/bbl, Figure 2. Following the 1986 oil price
collapse (crudes sold for $9.35/bbl in August 1986), V level
started to decrease somewhat, probably because of the refiners
selection of more paraffinic crudes. However, Ni levels on
equilibrium catalysts has remained unchanged. Thus, the
importance of processing metals contaminated feeds has not
significantly changed through the years and it has been
projected that by 1995, 25% to 30% of the world's FCC units
will be partially operating as resid crackers (21).
It is the purpose of this paper to review the progress made in
understanding and designing zeolite-containing fluidized
cracking catalysts capable of negating the deleterious effects
of metals such as nickel and vanadium.
The development of metal resistant FCC requires extensive experimentation and
rapid testing. Pilot-plant evaluation and screening of experimental FCC
formulations (although more realistic) are not practical because they are time
consuming and therefore costly. Thus, the investigation of metal containing FCC
as well as the design of metal resistant FCC has been performed in industrial
laboratories (perhaps at the cost of accuracy) using bench-scale microreactors
similar to the one developed by Ciapetta and Anderson (22).
0097-6156/91/0452-0343$06.00A)

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A spectroscopic study of 23 domestic crude oils has revealed the presence of 28
elements (23). Representative metal types and levels usually found in petroleum
are shown in Table 1; Ni and V are, in general, the most abundant metals found.
TABLE 1. Metal Contaminants (W M) Levels in Petroleum
Equilibrium FCC from a refinery contains these metals at levels that are usually
below the limit of detection of most spectroscopic techniques of catalyst
characterization. Furthermore, the simultaneous presence of several elements and
coke further complicate the study of the effects that individual metals may have
on catalyst performance.
Although several metal-containing heterocyclic compounds (such as porphyrins,
phthalocyanines, naphthenates) are present in oil fractions most of the bench-scale
research has been based on relatively rapid Ni, V, or Ni/V deposition procedures
in which experimental FCC formulations have been artificially metal contaminated
with solutions of Ni and/or V naphthenate dissolved in benzene (or toluene) (24).
Metal levels in these novel FCC are usually above 0.5%; that is well above the
concentration that today exist on equilibrium FCC, see Figure 1. High metal
concentration facilitate the study and characterization of Ni and V effects by
modern characterization techniques such as X-ray photoelectron spectroscopy
(XPS), Laser Raman spectroscopy (LRS), X-ray diffraction (XRD), electron
microscopy, secondary ion mass spectrometry (SIMS), and
51
V nuclear magnetic
resonance (NMR).
Nickel-Containing Cracking Catalyst
The role of metals in catalyzing the nonselective cracking of gas oils has been well
documented in the literature for several types of fluidized cracking catalysts (1-29).
During the cracking process, Ni and V-containing porphyrins and porphyrins-like
complexes decompose, leaving metal contaminants on the catalyst surface (15).
Metals such as Ni (and to a lesser extent Fe) have little effect on cracking activity
(and surface area), but change product distributions and increase coke, hydrogen,
and light gas yields at the expense of the (more valuable) gasoline fraction (13,18,
25,26), Figure 3. In metals-tolerant FCC, it is believed that inactive metal silicates
or even aluminates are formed on the catalyst surface (27). Metals-surface
interactions, that is metals passivation, strongly depend on the composition of the
cracking catalyst surface.
Fe
As
Cr
Co
Cu
Mn
Mo
Ni
Se
V
Pb
0.1
0.5
0.001
0.03
0.14
0.50
0.008
50.0
0.020
4.0
0.10
5.0
1.0
0.01
13.0
7.0
2.5
0.05
350.0
2.0
300.0
0.40

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OCCELLI Metal-Resistant FCCs 345
0 NICKEL
VANADIUM
1980 81 82 83 84 85 86 87 88 89 1990
CAL ENDAR YEAR
Figure 1. Metal level trends in equilibrium fluid cracking catalysts (FCC). Data
based on Davison analysis of samples from 96% of fluid units in the USA and
Canada.

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21. OCCELLI Metal-Resistant FCCs
347
WT % METALS) WT % METALS
F i g u r e 3 . Me t a l e f f e c t s o n : ( A) c o n v e r s i o n , ( B ) g a s o l i n e , ( C) L CGO
an d S O, ( D) h y d r o g e n an d ( E ) c a r b o n g e n e r a t i o n . P a r t i a l l y a d a p t e d
f r o m R e f . 2 5 .

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1
i. The Effects of Catalyst Composition. A study of the interaction of Ni with
typical components (the gel, clay and the zeolite) of a fluid cracking catalyst (FCC)
has shown that after calcination, Ni is present mainly as an easily reducible NiO-
like phase on all the supports tested (27). However, after steam-aging, Ni interacts
with the clay and the gel to form a NiAl
2
0
4
surface specie. In a FCC, steaming
causes Si to migrate to the surface where, in the presence of Ni, it can form inert
NiSi0
3
-like compounds (27). The ability of a matrix to minimize Ni dispersion and
of the matrix components to form chemically inert Ni-compounds will control the
activity of this metal for catalyzing those secondary cracking reactions during gas
oil conversion that generates light gases and coke at the expense of gasoline make
(10,18,27,28,31). Recently, it has been reported that the deleterious effects of Ni
can be reduced by FCC whose matrix consists of a partially dealuminated kaolin
mineral embedded in a SiO
z
-rich support (16,18).
Nickel tolerance in FCC can also be induced by addition of particles (such as
sepiolite, attapulgite, crysotile) which can irreversibly sorb and passivate metals (29-
31). The excellent agreement between the Raman spectrum of natural garnierite
(an hydrous magnesium-nickelsilicate) and the spectra of calcined or steam aged
Spanish sepiolite loaded with 5% Ni has confirmed the presence of NiSi0
3
-like
structures (such as Ni crysotile) resulting from Ni-sepiolite interactions induced by
the various heat treatments used to age the catalyst (28). It is believed that clays,
in addition to improving the FCC physical properties, can interact with metal
contaminants like Ni and form surface compounds (such as Ni-aluminates or Ni-
silicates) which are less deleterious to the cracking process than supported NiO-
like species. Thus, a Ni-resistant cracking catalyst should contain a clay and a
matrix capable of minimizing metals dispersion while forming inert Ni-compounds
(27).
ii. Nickel Passivation. Resistance to metal poisoning in a cracking catalyst can
be achieved by adding to the feed metals [such as Sb(32), Bi (33), Sn (34), Sn-Sb
combinations (35), Ba (36), P and B (37)], thought capable of forming inert
residues on the catalyst surface. Initially the bulk of the successful work, was
performed by researchers at Phillips (32, 36, 38-42) using artificially impregnated
as well as equilibrium FCC evaluated at microactivity test (MAT) conditions. It
was reported that when using an equilibrium FCC with 0.31% Ni and 0.45% V,
addition of 0.5% Sb increase (at 75% conversion) the gasoline make by 12%; coke
and hydrogen decreased by 15% and 55% respectively (43). An organo-antimony
compound (Phil-Ad
(R)
CA) was used as the Sb-loading agent in bench scale, pilot
plant as well as in the commercial testing conducted at the Phillips Borger refinery
in Texas. The equilibrium FCC from this refinery contained high (0.22-3.0% Ni
and 0.48-0.90% V) metal levels. Nonetheless, Sb injection to the feed increased
(at a certain reactor T) gasoline make by 6.1% while hydrogen, dry gas and coke
decreased by 44.6%, 27.5%, and 15.3%, respectively (43). As a result of improved
selectivities, a net increase in product value of 41 cents/barrel of oil converted was
obtained (43).
Antimony, although effective in reducing the dehydrogenation activity of Ni can
be volatile, thus capable of contaminating a FCC unit internals and generate
products on the EPA list of hazardous material. Bi-based passivators may offer the
benefit of Sb-based technology without the concern that volatile Sb-compounds

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21. OCCELLI Metal-Resistant FCCs 349
pose to refiners (46). Metals passivation with Bi has been demonstrated in five
commercial units during the 1986-87 period (46). However, Bi may not be as
effective as Sb in passivating Ni contaminants in a FCC unit (47). Recently, it has
been suggested that Sb volatity could be reduced by introducing into a FCCU
diluents, such as aluminas and clays, loaded with Sb (30). The controlled release
of Sb from the diluent surface to the host catalyst particle and to the gas phase,
would then moderate the dehydrogenation activity of Ni contaminants in the feed
and on the catalyst surface.
Other methods of metal passivation reported in the patent literature have
proposed the use of H
2
S (48,49), steam and methane gas (50-52). With H
2
S,
Nickel is converted to a sulfide and then oxidized to a washable sulfate that can
be recovered.
iii. Characterization of Ni Containing FCC. Overcracking by nickel can be
diminished by a variety of passivating agents. The most commonly used agent is
Phillips Petroleum's Phil-Ad CA which consists of an organic antimony compound
(32,53). However, the study of these systems has been conducted mainly on
supported binary mixtures of Sb and Ni. Parks and co-workers have used XPS to
show that nickel and antimony form an alloy in which nickel is covered by
antimony (39,40). Nickel (II) antimonates formation was later suggested also by
Woltermann and Magee (54).
Polycrystalline Ni-Sb alloys, unsupported Sb-loaded Ni powders, artificially
contaminated as well as equilibrium FCC (from a heavy oil cracker) have been
studied using X-ray diffraction (XRD), Auger spectroscopy and x-ray
photoelectron spectroscopy (XPS) by workers at Phillips in what was one of the
first examples of a multi-characterization technique approach to FCC study (39,40).
XPS results have indicated that in an equilibrium FCC, 50 to 80% of the surface
Sb and 30% to 50% of the surface Ni could be reduced to metal. This XPS data
suggested that Ni and Sb were present on at least two different sites (that can be
differentiated by their reducibility at 500C/H
2
) and that reduction caused a twofold
increase in the Ni/Sb ratio due to greater Ni dispersion.
At the higher metal level (2.0-4.5% Ni with up to 2% Sb) used to study artificially
contaminated materials, XRD results have shown the formation of Ni-Sb alloys
(NiSb x<0.08) whereas XPS data have indicated that a non-reducible antimony
oxide, a well dispersed reducible Sb phase together with reducible Sb (that form
an alloy with reducible Ni), were present. Selective chemisorption data for
unsupported Ni-powders, showed that one surface structure can effectively
passivate 2-3 Ni atoms with respect to H
2
chemisorption. XPS examination
confirmed that Sb segregates at the surface of Ni particles where it can drastically
affect the electron properties of neighboring Ni atoms thus reducing their activity.
Transmission electron micrographs and XPS results have been used to show that
a catalyst, with a high silica content in the matrix, prevents nickel dispersion
(16,18). In fact, in a FCC with a Si-rich (Si/Al = 4.3) surface, XPS data has
indicated that calcination and steaming cause nickel (and vanadium) migration to
the cracking catalyst surface where nickel sinters. As a result, nickel crystallites 50

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to 70A in size have been observed by transmission electron microscopy (TEM),
Figure 4. The Si0
2
-rich matrix prevents good Ni distribution on the surface; large
Ni crystallites and inert NiSi0
3
formation are believed responsible for the catalyst's
low carbon and hydrogen generation during gas oil cracking at MAT conditions
(16,18). XRD, scanning transmission electron microscopy (STEM), and x-ray
fluorescence have also been used to observe nickel crystallites formation on a
catalyst surface (55). Formation of these type of silicates on amorphous supports
have also been proposed by Meisenheimer (8).
XPS has been used also to show that Ni may be present as Ni
+ 2
or as Ni
+ 3
on the
surface of regenerated FCC (56). Initially, Ni was found to be homogeneously
distributed on the catalyst surface; then as Ni levels increased above 2%, surface
enrichment of Ni occurred (56). Ni migration can be correlated with the
luminescence quenching of the rare-earths (RE) containing Y-zeolite (REY)
present in the FCC matrix (16). Steaming induced Ni migration from the
luminescence centers (REY crystals) and partial restoration of band intensity was
observed (16). XPS and TEM data have indicated that Ni can move to the catalyst
surface were sintering occures, see Figure 4. Nickel distribution has also been
investigated using secondary ion mass spectrometry (SIMS) (12). Nickel and
vanadium effects can be additive (56,57).
Vanadium-Containing Cracking Catalysts
Vanadium is present in crudes mainly in the +4 state (58). In fact, up to 50% of
the total vanadium in crude oil can be found as V0
2+
in organometallic compounds
such as porphyrins and naphthenates (59-63). During the cracking reaction in a
FCCU, these compounds deposit V (probably in the form of VO
+ 2
cations) on the
catalyst surface. Then, after steam-stripping and catalyst regeneration, formation
of V
+ s
surface phases occur. The effects of vanadium on FCC properties are more
severe than any of the other metals present in petroleum feedstocks. In fact,
vanadium causes an irreversible loss of cracking activity which is the result of a
decrease in crystallinity, pore volume and surface area of the catalyst, Figure 5.
i. Characterization of V-Containing FCC. The ever increasing availability and
application of modern spectroscopic techniques of catalyst characterization have
provided invaluable guidance to the study of vanadium effects and interaction in
cracking catalysts. Thermogravimetric (TGA) and differential thermal analysis
(DTA) data have shown that vanadium naphthenates and porphyrins readily
decompose exothermally under reactor (reduction) conditions. In air, vanadium
compounds are less stable and fully decompose below 500C forming V
2
O
s
. This
oxide has also been observed in RE-free materials using luminescence (13), Laser
Raman spectroscopy (28) and XPS (27) measurements.
SIMS (61,64,86), microscopy (65), XPS (56), electron microprobe techniques
(14,66), electron paramagnetic resonance (EPR) (67) and luminescence
experiments (68) have been successfully employed to probe and study V mobility
and reactivity on a catalyst surface. TEM, STEM and energy dispersive X-ray
emission (EDX) measurements have indicated that V interaction with REY-
crystals induced vanadate clusters formation (65). Vanadium was also found
capable of reacting with rare-earths outside the zeolite cavities to form LaV0
4

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OCCELLI Metal-Resistant FCCs 351
Figure 4. Transmissions electron micrographs of 2% Ni on catalyst (A) before
and (B) after steaming. Steam-aging has little effect on Ni distribution and
crystallite size stays unchanged at 50-70& .

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oH 1 1 1 1 1 1
0 0.5 1 1.5 2 2.5 3
WT % METAL ON CATALYST
F i g u r e 5 . Th e e f f e c t s o f V l e v e l s o n an F CC s u r f a c e a r e a a f t e r
h e a t i n g f o r 10 h a t : A) 5 4 0 C i n a i r , B ) 7 3 0 C i n a i r an d C)
7 3 0 C w i l l 9 5 % s t e a m. R e p r i n t e d wi t h p e r mi s s i o n f r o m R e f . 13 .
( C o p y r i g h t 19 8 5 Ac a d e mi c P r e s s )

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(65). Radial electron diffraction patterns (65), XRD and Laser Raman
spectroscopy (69) have confirmed the formation of REV0
4
type phases.
X-ray absorption spectroscopy has indicated that, after deposition, vanadium is in
the +4 state and converts to the +5 state after regeneration (70). Similar
conclusion has been reported from XPS measurements (56). Owing to the polar
nature of vanadium porphyrin complexes, vanadium is initially deposited on the
catalyst outer surface, where during regeneration in air, forms V
2
O
s
. Then vanadia,
at regeneration condition, becomes a highly mobile fluid capable of migrating into
the FCC macroporous structure where it interacts with and degrades zeolite
crystallinity (56).
Analysis of vanadium-loaded model materials (such as EuY, amorphous
aluminosilicate gels and EuY-gel mixtures) by electron paramagnetic resonance
(EPR) has provided information concerning metal oxidation state and
stereochemistry (67). EPR data has indicated that when vanadyl cations are
introduced in the form of vanadyl naphthenate, they were stabilized in a zeolite
with the faujasite structure as pseudo-octahedral V0
2+
even after calcination at
540C. Upon steaming, these V0
2+
cations were then converted almost entirely
to V
+ 5
species (67). The formation of EuV0
4
was verified but the concentration
of this vanadate was never proportional to the total rare-earth content of the
zeolite. In EuY-gel mixtures the gel preferentially sorbed vanadium where it was
stabilized mainly in the form of V
2
O
s
.
Luminescence experiments (68) have shown that vanadium after being
preferentially sorbed by the gel, did not migrate during calcination but did migrate
between the zeolite and the matrix during steaming. After heating in air at 575C,
vanadium was found to be in the form of V0
2+
cations on the zeolite and primarily
in the form of V
2
O
s
on the gel matrix. The environment of Eu
3+
cations is very
sensitive to heat treatment; these cations can react with V during steaming to form
EuV0
4
(68).
ii. Mechanisms of Vanadium-FCC Interactions. It has been proposed that V-REY
interactions generate RE-V
2
O
s
eutectics that, because of their low (630C) melting
points can flow (during regeneration) into the FCC macroscape where they can
limit (or inhibit) the availability of the cracking centers to the diffusing
hydrocarbons molecules (5,57,71). The formation of RE-V
2
O
s
eutectics has been
proposed also by other authors (61,62). However, Wormsbecker et al (14) have
shown experimentally that by heating at 760C in air V-loaded catalysts (containing
less then 5%V) deactivation did not occur and disputed the importance of rare-
earth eutectics formation during catalyst regeneration.
DTA/TGA studies have shown an endothermic melting point of pure V
2
O
s
indicating a reaction between the zeolite and V
2
O
s
before V
2
O
s
liquefaction.
(57,72) Analysis of the mixture by XRD has shown the formation of a tetragonal
REV0
4
thought to be the product of a reaction between V
2
0
5
and the rare-earth
cations present in the zeolite. Pompe et al (72) further proposed that since
vanadate formation requires more oxygen than V
2
O
s
can supply, oxygens were
removed from the zeolite lattice
"2Z(0)
15
RE
M
+ V
2
O
s
= 2REVO,

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during vanadate formation, causing the collapse of the crystal structure. Sodium
in the system lowers the melting point of the REV0
4
eutectic, thus promoting the
ease of zeolite destruction (72). This mechanism of REY collapse by V has been
rejected by Mauge and co-workers (65).
Mauge et al (65) have proposed a mechanism of REV0
4
generation that did not
require the removal of framework oxygen atoms since it involve a reaction between
V
2
O
s
and the La-(OH)-La linkages present in the zeolite sodalite cages (65). The
presence of steam was not necessary for this reaction to occur; LaV0
4
was
observed after calcinationat 600 C/air of V-loaded LaY crystals (65). Formation
of LaV0
4
after calcination at 760C/5h in air has been observed also by LRS (69).
Speronello and Reagan (26) have proposed that vanadium migrates along the
catalyst matrix and then, during regeneration, reacts with the zeolite.
Wormsbecher et al (14) have attributed vanadium mobility to vanadic acid
formation during steam aging (87):
V
2
0
5(
.) + H. O^ = 2H
3
V0
4( V)
.
At the V-levels used, it was observed that only after steam-aging V contaminants
were found capable to decrease zeolite crystallinity. Vanadic acid was believed
capable of leaching Al from the zeolite framework in the form of A1V0
4
thus
causing reduction in crystallinity and therefore cracking activity (14). However,
experimental evidence for A1V0
4
formation could not be obtained by XRD, LRS
(28,73,74) or by
51
V NMR (75,76). This vanadate is not thermally stable at test
conditions. In fact, the DTA profile of a reference (unsupported) A1V0
4
has
indicated that this compound begins to decompose at about 650C (74).
Losses in cracking activity in a FCCU can be minimized by prudent unit design.
In fact, Hettinger (77) has reported that by maintaining a small amount of coke
on regenerated FCC it is possible to minimize the oxidation of V contaminants to
(mobile and reactive) V
2
O
s
and keep most of the V as V
2
0
4
. Lower valence
vanadium oxides melt at temperatures much higher than those encountered in a
FCCU regenerator. The properties of these oxides are described below in
Table 2 (88).
Table 2. Some physicochemical properties of vanadium oxides.
VA VO, VA
VO
Color Orange Blue Gray- Gray
Black
Melting Point (C) 658 1640 1970 950
Density (g/cc) 3.34 4.34 4.84 5.55
AH
f
(kcal/mole) 373 342 296 117
structure Trig. Rutile Corundum NaCl
Bipy.

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Lower valences of V can also be obtained by exposing V-contaminated FCC to a
reducing atmosphere. Vanadia can be reduced to V
2
0
4
under relatively mild
conditions (AG = -33.5 kcal/mol); reduction of V
2
0
4
to V
2
0
3
is more difficult (A = -
17.4 kcal/mol).
Catalyst deactivation could also result from blockage of the zeolite and FCC
microporous structure by the presence of Vanadia and debris generated by V-
zeolite interactions (78). It has been claimed that, by removing these type of
contaminants, part of the catalyst's original activity can be restored (78).
w
Si and
27
A1 MASNMR spectroscopy has been used to show that on calcination,
cracking components such as HY, Si-enriched HY, REHY and CREY, undergo
dealumination and that steam aging increases the presence of extra framework Al
in these zeolites; dealumination was more severe in HY type materials (73,74).
Faujasite crystals (with or without RE-ions) are thermally stable at 760C/5h in air
for V loading up to 4%. When the V on catalyst levels are raised to 5%, the
crystal structure collapses indicating that, at this V concentration and temperature,
the presence of steam is not required to promote zeolite destruction (73,74).
However, when the same thermal treatment is repeated in the presence of steam
(at 1 atm), the ease with which V destroys the zeolite crystallinity greatly increases;
CREY crystals (containing a 3.5% Na
2
0) collapse with only 0.4% V (73,74). The
zeolite V-resistance seems to decrease when RE-ions are present and increases
with increasing extra framework Al in the following order:
HY (Linde's LZ-210) > HY (Linde's LZY-82) > REHY > CREY
Extra framework Al in HY-type zeolites (generated during calcination and
steaming) could directly react with VO
+ 2
cations and form stable complexes thus
increasing the crystal tolerance to V.
HY-type crystals as well as X-ray amorphous aluminosilicate gels (AAA alumina),
form mullite (Al
6
Si
2
0
13
) when heated at 1200C in air. In the presence of V, these
materials form mullite at lower temperatures (760C) indicating that V acts as a
mineralizing agent (69). In addition to mullite and tridymite, an X-ray amorphous
V
2
O
s
phase is formed. At the high temperatures used for FCC regeneration,
oxycations of vanadium (V0
2
+
or VO
+ 2
) could attack the Al-0 bond in HY causing
dealumination and lattice collapse. The amorphous product re-crystallizes then
into a vanadium-containing mullite phase and the excess silica and vanadium form
tridymite and a supported V
2
O
s
phase (69). In the presence of steam, hydroxy
vanadyl ions and other protonated species resulting from the interaction of V
compounds (such as V
2
O
s
) with steam, could accelerate Al-removal from the
faujasite structure thus increasing the ease of mullite formation.
In REHY and in calcined rare earths exchanged Y-zeolites (CREY) containing
about 7.6% Ce
2
0
3
, 4.0% La
2
0
3
, 2.8% Nd
2
0
3
and 0.9 Pr
2
0
3
crystals, it is believed that
Ce
+ 4
ions, present as an oxycerium complex, undergo a redox reaction with
oxyvanadyl cations (VO
+2
) and form a stable orthovanadate (74):
A
[Ce Ce]
+4
+ 2VO
+ 2
+ 4 H
2
0 = 2 CeV0
4
+ 8H
+

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Vanadate formation (LaV0
4
) occur also in LaY crystals (69). Removal of other
charge compensating cations (such as Na
+
ions) in the form of vanadates further
destabilize the crystal lattice thus promoting and enhancing zeolite destruction.
iii. Vanadium Passivation. Addition of antimony organics to cracking catalysts can
drastically reduce the dehydrogeneration activity of Ni contaminants. However,
vanadium passivation has not been as successful, although tin has been reported
capable of reducing the deleterious effects of V impurities (79-80). In fact, tin
concentrations between 0.2 wt% and 2.50 wt% have been shown effective in
preventing the breakdown of the zeolite structure (82).
The effects of Sn on V-contaminated model catalysts have been recently studied
using luminescence experiments (68), EPR (67) and Mossbauer spectroscopy (83).
Luminescence experiments have provided useful information on the environment
of the rare-earth cations present in the zeolite and were used to monitor V-
migration between the zeolite and the catalyst matrix even in the presence of Sn.
Tin-119 Mossbauer spectroscopy has indicated that Sn-V interactions take place
only during steam-aging forming Sn
4+
-0-V
5+
complexes; V-Sn alloys were not
observed (88). EPR data has shown that tin promotes the oxidation of VO
+ 2
to
V
+ s
during steam aging with formation of Sn
4+
-0-V
+s
complexes. It is believed
that these complexes inhibit V-zeolite interactions thus helping in preserving
zeolite crystallinity and cracking activity when fluidized cracking catalysts are
contaminated with V-compounds. The presence of excess tin seems to minimize
oxidation to V
+ 5
and promotes the formation of EuV0
4
; thus excess tin is to be
avoided (67). The deleterious effects of V on a FCC are best negated (at MAT
conditions) by the use of V-scavengers.
Although vanadium mobility on a FCC surface has been recognized by several
researchers, intraparticle transport of vanadium has been observed (at MAT
conditions) only a few years ago (66). It has been reported in the patent literature
that vanadium (and nickel) resistance in a FCC can be significantly enhanced by
the addition of certain diluents capable of acting as metal scavangers (29-31). In
fact, addition of alumina and alumina-containing materials with (30) or without
(29) passivating agents (such as Sn or Sb) or addition of natural layered
magnesium silicates as well as addition of certain natural zeolites (31) can inhibit
the deleterious effects that metal contaminants (like Ni and V) in gas oils have on
the cracking activity and selectivity of commercial fluid cracking catalysts.
Specifically, sepiolite addition to a high activity commercial FCC, can generate
dual-functional cracking catalyst (DFCC) mixtures that, even when metal
contaminated with as much as 1.5 wt% vanadium, have been found capable of
retaining useful cracking activity (70% conversion ) when cracking a light gas oil
(with an API gravity of 29.6) at microactivity test (MAT) conditions, see Figures
6,7. Improved coke and hydrogen selectivity were also observed.
Investigation of nickel and vanadium mobility under hydrothermal conditions has
been studied by analyzing surfaces of the steamed materials by electron microprobe
(66). Probe analysis of two DFCC containing 2% vanadium alternatively on the
host catalyst and on the diluent (sepiolite or alumina particles) has indicated that
heating in air at 540C does not induce any significant migration of vanadium from
particle to particle. However, when heating was performed in a fluidized bed in
the presence of 100% steam, vanadium was found to migrate from the FCC to the

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5
2
.
c
h
0
2
1
0.5
_L_
1.0 1.5
VANADIUM (WT%)
2.0
F i g u r e 6. R e t e n t i o n o f c r a c k i n g a c t i v i t y i n t h e p r e s e n c e o f V
b e f o r e A) an d a f t e r B ) a d d i t i o n o f S e p i o l i t e . Re p r o d u c e d wi t h
p e r mi s s i o n f r o m R e f . 6 6 . ( C o p y r i g h t 19 8 9 Ame r i c a n C h e mi c a l S o c i e t y )
90
80
70
2? 60
>
UJ
z
50
O
W
<
40
30
20
DFCC
O FCC
1.0 1.5
VANADIUM (WT%)
F i g u r e 7. R e t e n t i o n o f g a s o l i n e mak e i n t h e p r e s e n c e o f V b e f o r e
A) an d a f t e r B ) a d d i t i o n o f S e p i o l i t e . Re p r o d u c e d wi t h p e r mi s s i o n
f r o m R e f . 6 6 . ( C o p y r i g h t 19 8 9 Ame r i c a n C h e mi c a l S o c i e t y )

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-
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5
2
.
c
h
0
2
1
F i g u r e 8. C r o s s s e c t i o n s o f e q u i l i b r i u m F CC c o n t a i n i n g a l u mi n a
p a r t i c l e s . I o n i ma g e s s h o w A) s i l i c o n , B ) a l u mi n u m, C) v a n a d i u m,
an d D) n i c k e l . Th e a l u mi n u m an d v a n a d i u m i o n i mag e a r e a l mo s t
i d e n t i c a l , t h u s s h o wi n g V a c c u mu l a t i o n o n a l u mi n a . Re p r o d u c e d
wi t h p e r mi s s i o n f r o m R e f . 8 6 . ( C o p y r i g h t 19 8 8 Ac a d e mi c P r e s s )

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sepiolite or alumina granules surface but not vice versa. Analysis of two nickel-
containing DFCC revealed that neither heating in air or in steam induced
intraparticle transfer of nickel at the thermal and hydrothermal conditions used to
age the fresh catalysts (66) prior to microactivity testing.
LRS characterization of DFCC system tested at MAT conditions, have indicated
that in steam aged catalysts containing more than 1% V, [V
2
0
7
] units are formed
lending support to the experimental work of Glemser and Muller (84) in which the
reaction: V
2
0
5( 8>1)
+ 2H
2
0(g) = H
4
V
2
0
7( g )
was reported. Thus it is believed that
H
4
V
2
0
7
is one of the volatile V-compounds that can be generated in the steam-
stripping zone of a FCC unit. Yannopoulos (87) has proposed that vanadia react
with steam to form vanadic acid. Experimental evidence of H
3
V0
4
formation in
V-loaded FCC has not (to date) been presented.
Vanadium mobility has also been observed at pilot plant test conditions (85).
Furthermore, Kugler and Leta (86) using data from imaging secondary ion mass
spectrometry (SIMS) have observed recently that an equilibrium FCC containing
alumina granules accumulates V preferentially on the alumina particulates thus
supporting laboratory and pilot plant results (85) that have indicated that V-
contaminated surfaces can react with steam and form volatile compounds capable
of migrating from particle-to-particle, Figure 8. In summary, transport experiments
at MAT conditions, together with pilot plant results (85) have indicated that the
DFCC enhanced vanadium resistance can be attributed to the gas phase transport
of this metal from the host catalyst to the diluent (sepiolite) where it is sorbed and
passivated.
DFCC systems appear to have the necessary metals tolerance to process residual
oils and the abundant, cheaper, but heavily vanadium-contaminated, Venezuelan
and Mexican crudes (66). Therefore, the dual function fluid cracking catalyst
(DFCC) concept could lead to the generation of important catalysts for U.S.
refineries should Middle East politics cause another sudden escalation in crude oil
prices and availability. The concept is practical and easily implementable and it
may offer a cost advantage over conventional commercial cracking catalysts (66).
Acknowled gments
The skilled assistance received from Mr. B. McCormick in evaluating experimental
cracking catalysts during the 1979-1985 period is gratefully acknowledged. Other
aspects of catalysts characterization and testing was made possible by the support
and cooperation received from Dr. S. L. Suib (University of Connecticut), Dr. J .
M. Stencel (University of Kentucky), Dr. E. Goldish, and Dr. P. Ritz (Unocal).
Special thanks are due to Dr. D. Leta (Exxon) for providing the micrographs
shown in Figure 8. Finally, I would like to thank Ms. Seneti Kongaika for typing
this manuscript.

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58. Saveceno, A. J.; Fanale, D. T.; Coggeshal, N. D. Anal. Chem., 1961,33,500.
59. Skinner, D. A., Ind. Eng. Chem., 44, 1159, 1952.
60. Sundararaman, P. Anal. Chem., 57, 2204, 1985.
61. Jaras, S. App. Catal., 1982, 2, 207.
62. Jaras, S., First Katalistiks FCC Symposium, Bordeaux, France, Oct. 1980.
63. Fish, R. H.; Komlenic, J. J., Anal. Chem., 1984, 56, 510.
64. Upson, L.; Jaras, S.; Dalin, I. Oil & Gas J., 1982, 135.
65. Mauge, F.; Courcelle, J. C.; Engelhard, Ph.; Gallezot, P.; Grosmanging, J.
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J. W. eds (1986).
66. Occelli M. L. in "Fluid Catalytic Cracking: Role in Modern Refining, ACS
Symposium Series, Vol. 375: M. L. Occelli, E., ACS, Washington, D. C., p.
162 (1989).

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67. Anderson, M. W., Occelli, M. L. and Suib, S. L., J. Catal, 112, 2, p. 375
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68. Anderson, M. W., S. L. Suib, and Occelli, M. L., J. Catal., 118, 31 (1989).
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71. Murphy, J. R., Katalistiks 3rd FCC Symposium, Amsterdam, May 1982.
72. Pompe, R.; Jaras, S.; Vanneberg, N. -G. App. Catal. 1984, 13, 171.
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82. English, A. R., Kowalczyk, D. C. Oil and Gas J. 127, July 16, 1984.
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Author Index
Beyerlein, R. A., 109
Bohmer, Robert W., 183
Cheng, W-C, 198
Corella, J., 165
Corma, A., 12,79,293
Desai, P. H.,318
Disko, M. M., 269
Doremieux-Morin, C, 212
Dwyer, J., 56
Eckert, H., 242
Feng, Y., 27
Fornes, V., 12,79,293
Fraissard, J., 212
Frances, E., 165
Franco, M. J., 79
Fyfe, C. A., 27
Gerritsen, L. A., 318
Gevers, A. W., 318
Grondey, H., 27
Gruia, M., 212
Hall, J. B., 109
Hsieh, C. R., 96
Huggins, B. J., 109
Humphries, A., 318
Iyer, P. S., 242
Knopp, Kelly G., 183
Kokotailo, G. T., 27
Kugler, E. L., 269
Kurihara, L. K., 224
Lamberti, W. A., 269
Leib, T. M., 144
Leta, D. P., 269
Lunsford, Jack H., 1
Marchal, C, 212
Marshall, C. L., 109
McKay, DwightL., 183
Meyers, B. L., 109
Mifsud, A., 293
Miller, S. J., 96
Mocholf, F. A., 12,79
Monton, J. B., 12
Occelli, M. L., 224,242,252,343
O'Connor, P., 318
Pappal, D. A., 45
Perez-Pariente, J., 79,293
Rajagopalan, K., 198
Rawlence, D. J., 56
Rey,F., 12
Sapre, A. V., 144
Schipper, P. H., 45
Stencel, J. M., 242,252
Stripinis, Vida J., 308
Suib, S. L., 224
Tamborski, G. A., 109
Thoret, J., 212
Varady, W. A., 269
Affiliation Index
Akzo Chemicals, 318
Amoco Corporation, 109
Chevron Research and Technology
Company, 96
Crosfield Catalysts, 56
Exxon Research and Engineering
Company, 269
Mobil Research and Development Corporation,
45,144
Phillips Petroleum Company, 183
Shell Canada Limited, 308
Texas A&M University, 1
Universidad Politecnica de Valencia (Spain),
12,79,293
University Pierre et Marie Curie, 212
University of British Columbia, 27
University of CaliforniaSanta Barbara, 242
University of ConnecticutStorrs, 224
University of KentuckyLexington, 242252
University of Manchester Institute of Science
and Technology, 56
University of Zaragoza (Spain), 165
Unocal Corporation, 224,242,252,343
W. R. Grace and Company-Conn., 198
364

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INDEX
365
Subject Index
A
Activity, cracking 14,16-20
Aluminum atoms, distribution of types in
faujasites, 1,2/
Aluminum-exchanged sepiolite as components
of fluid catalysis cracking catalysts
acidity measurement procedure, 296
Bronsted acidity vs. desorption
temperature, 297,300,301/
catalytic experimental procedure, 296,297*
experimental materials, 295*
gas-oil conversion vs. slurry oil, 302,306/
gas-oil cracking, 300,302,303-306/
gas-oil cracking conversion on
ultrastable Y zeolite catalysts, 302,304/
Lewis acidity, 300,301/
natural Vallecas-type sepiolite,
chemical composition, 295f
pyridine adsorbed on derivatives
intensity of IR bands, 297,298*
IR spectra, 297,299/
vacuum-distilled gas oil, properties, 296,297*
X-ray diffraction pattern
catalyst, 300,302,303/
sepiolite forms, 302,303/
yields of gasoline, diesel, gases, and
coke, 302,305/
Amorphous silica-alumina cracking catalysts,
replacement with synthetic faujasites, 27
Amorphous silica-alumina matrix
role in resid feed cracking, 198
selectivity, 199-210
Antimony metals passivation process
applications, 183,187
development, 183
B
p zeolites, effect on octane enhancement, 79-80
C
Carbenium ion, isomerization, 105,106/
Catalyst accessibility and architecture,
future development, 324-331
Catalyst composition, effect on nickel
tolerance in FCC, 348
Catalyst deactivation
effect of Ni, 335,336*,337/,338
resistance to poisons, 338,339*
simulation methods, 109-110
Catalyst density
carbon, effect on catalyst, 140
estimation of contribution by
factors, 139
excluded volume, effect on change,
141-142
factors contributing to change, 139-142
incremental addition of heteroatom
species, effect on change, 139-141
metals, effect on catalyst, 140-141
Catalyst pore architecture, 330,331/
Catalyst selectivity and stability,
improvements, 339-340*
Catalytic cracking, octane enhancement
with high-silica zeolites, 96-108
Cation mobility, synthetic faujasite, 31,34/
Chemical extraction of Al, synthesis of
dealuminated synthetic faujasites, 35
Coke-conversion kinetics
effect of feedstock quality and oil
partial pressure on coking, 147
reaction(s), 146
reaction rate per unit volume for
gas-oil cracking, 147-148
Coke-conversion selectivity,
definition, 149
Commercial fluid cracking catalysts,
composition, 198
Commercial metals passivation systems,
examples, 192
Crackability, definition, 149
Cracking activity
influencing factors, 14,16-20
SAPO-37, 88,90,91/92,93/
Cracking selectivity, influencing factors,
2021-24/
Crude oil, 1980-1990 prices, 343,346/
Cumene dealkylation, effect of framework
Al concentration on activity, 3-4,5/
Cyclic metal impregnation and
deactivation, advantages for catalyst
deactivation, 334,335*

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366
D
Dealuminated synthetic faujasite
advantages, 31
27
Al magic angle spinning NMR spectra
WgWyoûminatedY zeolite samples, 40,41/
hydrothermally treated samples, 35,37/38
hydroxyl group concentration determination, 40
relationship of Si/Al ratio to unit cell
dimension, 31,35
29
Si magic angle spinning NMR spectra
highly dealuminated Y zeolite samples, 40,41/
hydrothermally treated samples, 35,36/38
synthesis, 3541
Dealuminated Y zeolites, origin of strong
acidity, 1-10
Dealumination, effect on zeolite activity, 3
Dealumination process, effect on Al
distribution in framework, 3
Dempsey-Mikovsky-Marshall model of acid
strength, relationship of Al distribution
in framework to acid strength, 1,3
Density separation of precoked catalyst,
description, 110-111
Divalent exchange, synthetic faujasite, 29-33
Durabead 5, replacement of amorphous
silica-alumina cracking catalysts, 27
Dynamic activity, definition, 149
E
Effective mesoporosity, definition, 326
Equilibrium catalyst separation, monitoring of
FCC catalyst deactivation profile, 109-142
Equilibrium cracking catalyst, density
separation, 110-111
Excluded volume, effect on charge-density
change, 141-142
Extensive zeolite crystallites, analytical electron
microscopic investigation, 131,132-134/
Extraframework aluminum
catalytic role during gas-oil cracking, 13
effect on superacid site formation, 13
elimination, effect on gas-oil cracking
behavior, 13-20
method and conditions of formation,
effect on catalytic role, 13
role in strong acidity of Y zeolites, evidence,
7,8/9
F
Faujasite, framework structure, 28,3Qf
Feedstock quality, effect on metals
passivation, 193,194^,195
Fixed-bed microactivity tests
comparison of conversion for catalysts
with that of fixed-fluid-bed reactor
experiments, 144,145/146
problems with conversion to riser
reactor performance, 146
Fixed-bed test, description, 97
Fixed-fluid-bed reactor
estimates of model parameters, 162,163*
model, 148-149
operating conditions, 148,149*
Fixed-fluid-bed reactor experiments
conversion for catalysts, comparison
with that of fixed-bed microactivity
tests, 144,145/146
conversion to riser reactor
performance, problems, 146
Fluid catalytic cracking (FCC)
application, 224
modeling of riser reactor, 165-178
process, 224
Fluid catalytic cracking catalyses)
aluminum-exchanged sepiolite as
components, 295-306
factors affecting laboratory
evaluation, 109-110
metal level trends, 344,345/
Fluid catalytic cracking catalyst
deactivation profile monitoring by
equilibrium catalyst separation
activity profile for increasingly severe
laboratory deactivations, 129,130/131
analytical electron microscopic
investigations of equilibrium
catalyst fractions, 131-137
catalyst age, 112-113
catalyst history, 111112r,113
coking of equilibrium catalyst
procedure, 113
cumene cracking activity, 116,118*
deactivation profile, 128-129,13Qf,l 31
density of steam-deactivated vs. fresh
catalyst, 121,123*
density variations for heaviest
fractions, 127-128

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INDEX 367
deactivation profile monitoring by
equilibrium catalyst separation
Continued
digisorb analyses of coked and
regenerated equilibrium catalyst
fractions, 114,117*
distribution of catalyst fractions,
114,115/,116
equilibrium catalyst fraction
properties, correlation with fraction
density-age, 114-123
excluded volume, effect on solvent
accessibility, 123-128
experimental procedure, 113-114,115/
factors leading to density variation, 125
feedstock contaminant metal material
balance on catalyst, 111,112*
fraction analytical procedure, 114
gravimetric reactor used in cumene
cracking studies, 114,115/
laboratory steam deactivations,
comparison, 128-129
laboratory-steamed catalyst,
comparison with equilibrium
fractions, 121,122*
metal content of catalyst, 111*
metal deposition vs. catalyst age, 118-119,12Qf
micropore structure vs. solvent
accessibility, 123,124/125
properties of equilibrium catalyst
fractions, 114,116*
properties of fresh and steam-
deactivated catalyst, 121-122*
quantitative estimates of density
variations, 125,126*,127
rare earth material balance catalyst, 111,112*
rate of dealumination compared with rate
of zeolite destruction, 128
separation method, 113-114
surface area-micropore volume loss for
equilibrium catalyst,
117*,119,120/,121-122*
testing of cumene cracking reactions on
separated fractions, 114,115/
Fluid catalytic cracking catalyst design,
objective, 79
gasoline, effect of ZSM-5 zeolite
addition, 56-77
Fluid catalytic cracking catalyst metals
passivation
antimony
effect of maintenance on optimization
concentration, 190,194/
effect of type on optimization, 190,192
effect on CO combustion promoters and
SO* catalysts, 186-187
passivation effects on charge rate,
187,188*,189
case studies, 187,188*
catalyst V/Ni ratio effects on hydrogen
generation, 189-190,191/
commercial application, 186
commercial systems, 192
effect on environment, industrial
hygiene, and metallurgy, 186
effectiveness of elements for hydrogen
yield reduction, 184,185*
evaluation results for 75 vol %
conversion, 184,185/
future application and development, 192-193
hydrogen reduction vs. metal levels,
187,188/
industry-wide acceptance, 187-191
mechanism, 186
modeling of effects, 193,194*,195
optimization of benefits, 190,192
research and development,
184,185*/,186
technology transfer to commercial use,
190,191/
Huidized-bed tests, description, 97
Gas-oil cracking
effect of ZSM-5 zeolite, 58,59*,60
superacid sites, effect in ultrastable
Y zeolites, 13-20
Gasoline cracking
effect of Y zeolite, 60,62*,63,64*
effect of ZSM-5 zeolite, 60,62*,63,64*
Hexadecane cracking, effect of total Al
content, 39

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Hexagonal prism atom distribution,
stereoscopic view, 31,32/
Hexane cracking
effect of framework Al concentration on
activity, 3
effect of framework Al content, 7,8/9
High-silica zeolites, octane enhancement
in catalytic cracking, 96-108
Hydrogen generation, effect of catalyst
V/Ni ratio, 189-190,191/
Hydrogen transfer index test
description, 97,100
procedure, 97
values for catalysts vs. linear hexane
conversion, 100,102/
Hydrothermal stability, SAPO-37, 82-89
Hydrothermal treatment, synthesis of
dealuminated synthetic faujasite,
35-41
Hydroxyl groups in dealuminated synthetic
faujasite, determination of total
concentration, 40
Hydroxyl IR bands of Y zeolites, effect of
sodium, 4,6/7
H-Y zeolite, effect of dealumination on
activity for acid-catalyzed reactions, 1
Intimate mixture of crystalline and collapsed
zeolite, analytical electron microscopic
investigation, 131,135/136,137/
Isoolefins, effect of zeolite addition on
reactions in gasoline, 63,70-73
L
Laboratory steam deactivations,
disadvantages for equilibrium catalyst
simulation, 110
Laser Raman spectroscopy, characterization
of vanadium-contaminated components of
FCC, 252-262
Linde X zeolite
replacement of amorphous silica-alumina
cracking catalysts, 27
synthesis, 28
Linde Y zeolite, synthesis, 28
Long residue, metals vs. Conradson carbon
content, 308
Long residue processing in riser pilot
plant
atomizing nozzle performance, 310,312/
catalyst stripping, 315
commercial experience, 309,311/
FCC catalyst fluidization behavior,
313,314/
feed-catalyst mixing, 313,314/315
feedstock atomization, 310,312/
feedstock vaporization, 310,313
operating conditions of plant, 310,312*
pilot plant experience, 30^-310,311/,312*
problems with laboratory-scale
processing, 309-310
product handling, 315-316
requirements, 316
schematic representation of plant,
310,311/
Luminescence as probe of metal effects in
fluid catalytic cracking catalysts
calcination, effect on vanadyl
porphyrin spectra, 227,232/238
catalyst preparation, 225
excitation wavelength, effect on vanadyl
phthalocyanine, 233,235/239
laser Raman spectra of steam-aged LaHY
crystals, 227,229/237
LaV04, spectra, 233,236f,239
luminescence lifetime data, 227,228/
LaY, 233*,240
Sn-passivated sample, 233,237*,240
luminescence procedure, 225
organic precursors used, 225226/
single photon counting nanosecond
fluorometer, schematic diagram, 227,228/
steam-aged LaHY crystals, X-ray
diffractograms, 227,225^,237
steam-aged LaY crystals, spectra,
233,236/239
tin addition
effect on vanadyl naphthenate
spectra, 227,23(^,238
effect on vanadyl phthalocyanine
spectra, 233,235/239
effect on vanadyl porphyrin spectra,
227,231/238
tin-loaded LaY impregnated with vanadyl
porphyrin, spectra, 227,233,234/238

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INDEX 369
Luminescence as probe of metal effects in
fluid catalytic cracking catalysts
Continued
treatments
effect on vanadyl naphthenate
spectra, 227,23Qf,237
effect on vanadyl phthalocyanine
spectra, 233,234/,238-239
effect on vanadyl porphyrin spectra,
227,231/,238
wavelength, effect on vanadyl porphyrin
spectra, 227,232/,238
M
Mesopore, impact of activity, 328*,330
Metal contaminants
effect on product distributions and
yields, 344,347/
levels in petroleum, 344*
Metal effects in fluid catalytic cracking
catalysts
avoidance techniques, 224-225
use of luminescence as probe, 225-240
Metal-resistant fluid catalytic cracking
catalysts
developmental problems, 343-345
nickel-containing cracking catalyst,
344-351
vanadium-containing cracking catalysts,
350-359
Metals passivation
advantages, 183-184
development and application for FCC
catalysts, 184-195
integration into overall refining
optimization models, 183
modeling effects, 193,194*,195
Methanol dehydration, effect of framework
Al concentration on activity, 3
Microactivity fixed bed
estimates of model parameters,
162,163*
model, 150-151
operating conditions, 149*
Model for strong acidity
description, 9-10
validity, 10
Modified zeolites, advantages, 212
Molar expansion parameter, definition, 162
Motor octane increase using ZSM-5 in
catalytic cracking
C5 and C6 olefin composition vs.
catalyst, 49,51*
effect of ZSM-5 zeolite on gasoline
composition, 53,54*
experimental procedure, 46,47-48*
FCC gasoline composition, 49,50*
iso/normal paraffin ratios for C5-C9 for
catalysts with and without ZSM-5
zeolite, 53/
isoparaffin yields for C 5-C 9 for
zeolite, 51,52/53
octane yields at 70 vol % conversion,
46,48*,49
olefin yields for C 5-C 9 for catalysts
with and without ZSM-5 zeolite,
51,52/
paraffin-olefin-N-catalyst A
composition of gasolines at 70 vol
% conversion, 49*
Na2<3, effect on framework
dealumination, 39
Nickel, effect on catalyst deactivation,
335,336*,337/,338
Nickel-containing cracking catalyst
characterization, 349-350,351/
effect of catalyst composition, 348
nickel passivation, 348-349
role of nickel, 344,347/
Nickel passivation, procedure, 348-349
NMR-invisible Al, characterization method,
39-40
Nonselective adsorption, effect on charge-
density change, 142
Numerical method, description, 151
Octane enhancement
effect of SAPO-37,79-94
effect of ZSM-5 zeolite addition to
FCC catalysts, 56-77

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370
Octane enhancement in catalytic cracking
with high-silica zeolites
additives
effect on iso/normal paraffin
composition, 100,101/
effect on selected hydrocarbon types, 97,100*
C 4 olefinicity vs. Si/Al ratio, 97,98-99/
catalyst preparation, 96-97
fixed-bed tests, 97
fluidized-bed tests, 97
hydrogen transfer index test, 97,100,102/
isomerization of normal carbenium ion,
105,106/
oligomerization of olefins, 105,107,108/
pilot plant test, 103*,104/,105*,106/
selectivity, 108
selectivity to C 5 plus vs. Si/Al ratio,
97,98-99/
Petroleum, metal contaminant levels, 344*
Petroleum cracking catalyst character-
ization via secondary ion MS imaging
advantages, 269-270
binary-phase masks of equilibrium V
gas-oil catalyst images, 275,277/278
calculated curve and residual values for
V vs. Nil/ 3, 285,287/
calculated curve and residual values vs.
Ni
1
^, zeolite concentration, and
Si/Al ratio, 288,291/292
distributions from particle to particle, 281-292
image processing, 271
ion images of equilibrium resid-type
catalyst particles, 279,28Qf
ion images of equilibrium V gas-oil
catalyst particles, 275,276/
low-magnification ion images of equilib-
rium catalyst particles sampled 4 weeks
into catalyst-type change, 281,282/
multiparticle analysis
qualitative, 281,282/
quantitative, 281,283-292
nickel and vanadium distribution between
phases, 273-280
phase distributions for vanadium and
nickel vs. catalyst, 278*,279
Petroleum cracking catalyst character-
ization via secondary ion MS imaging
Continued
Si/Al ratio images, 271,272/273
signal formation in SIMS, mechanism, 274
SIMS instrumentation, 270-271
V vs. Ni concentration 4 weeks into
catalyst-type change, 283,284/285
V vs. Ni concentration 8 weeks into
catalyst-type change, 285,286/
V vs. Si/Al ratios, 288,29Qf
V vs. zeolite concentrations, 288,289/
Pilot plant test
gasoline composition vs. additive, 105*
incremental measured octane differences,
103,104/
incremental octane yield differences,
103,104/
product inspections, 103*
relative carbon number yields vs. base
case, 105,106/
Poisoning studies of Y zeolites
effect of sodium on hexane cracking, 4,5/
mechanisms for effectiveness, 4
Pore-size acidity
distribution, 326,328*,329/
selectivity, 328,331/
Rare earth form of Y zeolite, replacement
of amorphous silica-alumina cracking
catalysts, 27-28
Refining industry, resid upgrading, 318-319
Resid catalyst development, future
catalyst resistance to deactivation
metals, 330,332-338
poisons, 338,339*
catalyst role in resid FCC,
321,323*,324,325*
catalyst selectivity and stability,
339^-340*
concepts for the future, 318-341
diffusion and active site accessibility,
324,325-326*,327/
future challenges, 340,341*
mesoporosity concept, effective, 326,327/
nickel, effect on catalyst deactivation,
335,336*,337/,338

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INDEX
371
Resid catalyst development, futureContinued
pore-size acidity distribution, 326,328-331
processability of resids in FCC units,
320-321,322/
resid processing, 319,320*
resid upgrading in refining industry, 318-319
vanadium effects, reduction strategies,
330,332*,333/,334-335*
Resid cracking
definition, 319
description, 319,320*
model, 328,329/
stages, 326,328
Resid fluid catalytic cracking, improvements in
catalyst role, 321,323*,324,325*
Resids in fluid catalytic cracking catalyst units,
processability, 320-321,322/
Riser pilot plant
advantages, 308
long residue processing, 308-316
Riser pilot plant composition analyses of
motor octanes
C 5 and C6 olefin composition vs.
catalyst, 49,51*
catalyst properties, 46,47*
catalyst steaming conditions, 46,47*
experimental procedure, 46,47-48*
FCC gasoline composition, 49,50*
feedstock properties, 46,48*
iso/normal paraffin ratios for C 5-C 9 for
zeolite, 53/
isoparaffin yields for C 5-C 9 for
zeolite, 51,52/53
octane yields at 70 vol % conversion,
46,48*,49
olefin yields for C 5-C 9 for catalysts
with and without ZSM-5 zeolite, 51,52/
paraffin-olefin-N-catalyst A composition
of gasolines at 70 vol % conversion, 49*
ZSM-5 zeolite, effect on gasoline
composition, 53,54*
Riser reactor(s)
estimates of model parameters, 162-163
model, 151
operating conditions, 149*
Riser reactor of fluid catalytic cracking unit
assumptions of model, 167-168
calculation of product distribution, 172
Riser reactor of fluid catalytic cracking unit
Continued
data input to program or model, 177
deactivation kinetics, 172
description, 165
five-lump model, 168,170
flow rate
in riser inlet, 172
vs. riser height, 169,17Qf
mean molecular weight of feedstock, 169,171
model(s)
examples, 177-178,180*,f
output, 178,180*
previous models, 166-167
modeling, 173-174,175/
nomenclature, 174,175/
operating conditions, 165-166
procedure, 174,176-177
product distribution at exit, 177
residence time of catalyst in riser, 171
temperature along riser height, 171
total pressure, effect, 178,18Qf
volumetric flow rate, 169
weight fraction of feedstock at inlet, 173
SAPO-37
activation temperature, effect on
crystallinity, 88,89/
chemical composition, 81*
cracking activity, 88,90-93
experimental procedure, 81*,82
hydrothermal stability, 82-89
IR spectra
sample treated at several conditions,
85,86-87/88
sample treated in vacuum at
increasing temperatures, 83,84/85
selectivity, 92,93/
silicon concentration, effect on
cracking activity, 88,90,91/
synthesis, 80-81
thermal stability, 82-89
Secondary ion MS (SIMS) imaging, petroleum
cracking catalyst characterization,
269-292
Selective sorption, effect on charge-density
change, 142

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Selectivity, cracking 20,21-24/
Selectivity of silica-alumina matrices
activity and selectivity of hydrothermally
pretreated catalysts, 208,209/
activity per unit surface area for gas-
oil cracking, 205,206/
27
A1-NMR characterization of catalysts,
200,202f,204*
composition and pretreatment
effect on coke selectivity, 205,207/
effect on H2 selectivity, 205,206/
experimental materials, 199
experimental procedure, 199-200
tight hydrocarbon selectivity of hydrothermally
retreated catalysts, 208,21Qf
pretreatment time, effect on catalyst
surface area, 200,201/
product distribution vs. composition,
208,209-21Qf
properties of catalysts, 199*
properties of sour, imported heavy gas
oil, 200*
29
Si-NMR characterization of catalysts,
200,203f,204
XPS characterization, 200,204*
Sepiolite
applications, 293
description, 293
effect on vanadium-containing cracking
catalysts, 356,357/359
modification for use in FCC catalysts,
295-306
structure, 293,294/295
Silica-alumina matrix, amorphous, See
Amorphous silica-alumina matrix
Silicon, effect of amount of SAPO-37
cracking activity, 88,90,91/
Slip velocity, definition, 165
Sodalite cage atom distribution,
Sodalite cage complex, stereoscopic view, 29,3Qf
Sodium, effect on hydroxyl IR bands of Y
zeolites, 4,6/7
Sodium poisoning, effect on hexane
cracking of Y zeolites, 4,5/
Solid-solid reaction between Y zeolite and
vanadium pentoxide
adsorption isotherms, 214,218/219
electron paramagnetic resonance
spectrum, 219,22(^,221
Solid-solid reaction between Y zeolite and
vanadium pentoxideContinued
experimental materials, 213
exrjerimental procedure, 213-214
2
^Si-NMR spectrum, 214
transmission electron microscopic
results, 221
l
2
9Xe-NMR spectrum, 219
129
Xe chemical shift vs. number of
adsorbed Xe atoms, 219,22Qf
X-ray data, 214,216-217*
X-ray spectra vs. V/(A1 + Si), 214,215/
Solid-state NMR of quadrupolar nuclei, use
in probing structure of metal oxide
surface species on catalysts, 243
Solid-state reactions between zeolites and salts
analytical techniques, 212-213
examples, 212-213
Strong acidity origin in dealuminated Y
zeolites
extraframework Al, role, 7,8/9
framework Al concentration, effect, 3-4,5/
hydroxyl IR bands, 4,6/7
model, 9-10
poisoning studies, 4,5/
Superacid site effects on gas-oil cracking
in ultrastable Y zeolites
acidity measurements vs. degassing
temperatures, 14,16*
cracking activity, 14,16-20
cracking selectivity, 20,21-24/
effect on cracking selectivity
levels of conversion, 20,21/
(NH4)
2
SiF
6
,20,23/
unit cell size, 20,22/
zeolite, 20,24/
gas-oil cracking activity, 14,16,17/
n-heptane cracking activity, 18,19/20
physicochemical characteristics of
samples, 14,15*
Synthetic faujasite
cation mobility, 31,34/
chemical extraction of Al, 35
divalent exchange, 29,31
hexagonal prism atom distribution,
hydrothermal treatment, 35-41
replacement of amorphous silica-alumina
cracking catalysts, 27-28

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INDEX 373
Synthetic faujasiteContinued
site designations, 29
sodalite cage atom distribution,
sodalite cage complex, stereoscopic
view, 29,3Qf
trivalent exchange, 29
X-ray diffraction patterns, 31,34/
T
Thermal stability, SAPO-37,82-89
Translation of laboratory fluid catalytic
cracking catalyst characterization
tests to riser reactors
catalyst deactivation functions for RE Y
zeolite and ultrastable Y zeolite catalysts,
schematic representation, 155,156/
catalyst deactivation rate, impact on
predicted conversions, 155,157/
heat of reaction, impact on conversions,
155,157/
model parameters, estimates, 162,163*
parametric studies, 153,154*
potential erroneous ranking of
catalysts, 151,152*
predicted coke-conversion selectivity vs.
catalyst activity
RE Y zeolite catalysts, 154,156/
ultrastable Y zeolite catalysts, 155,158,16(y
predicted product selectivities vs.
conversion, 159,16(y
quantitative predictions, 152,153*
reaction network for gas-oil cracking,
158-159
RE Y zeolite catalysts, 154-155,156/
ultrastable Y zeolite catalysts,
155,156-157/,158,16Qf
Trivalent exchange, synthetic faujasite,
29,30f,31
U
Ultrastable Y zeolite
effect of superacid on gas-oil cracking,
13-20
formation techniques, 12-13
mechanism of octane enhancement, 31
V
V2O 5 /1H2O gels, vibrational
characteristics, 252-253
Vacuum gas oil, characteristics, 81*,82
Vanadium, strategies to reduce effects on
FCC catalysts, 330,332*,333/,334-335*
Vanadium-51 NMR characterization of
vanadium-contaminated aluminas and
aluminosilicate gels
y-aluminas, 244,245/246
aluminosilicate gels, 246,247/248,249/
effect of nuclear electric quadruple
moment-electrostatic field gradient
interaction, 244
experimental materials, 243-244
experimental procedure, 243
pseudoboehmite alumina, 244,245/246,247/
pulse length, effect on spectra of
aluminosilicate gels, 248,249/
sensitivity of spectra to hydration state
aluminosilicate gels, 248,249/
pseudoboehmite, 246,247/
Vanadium-containing cracking catalysts
alumina particles, effect, 358/359
characterization, 350,353
sepiolite addition, effect, 356,357/359
V levels, effects on FCC surface area
after heating, 350,352/
V-FCC interactions, mechanisms,
353,354*,355-356
vanadium passivation, 356,357-358/359
Vanadium-contaminated aluminas and
aluminosilicate gels, vanadium-51 NMR
characterization, 243-250
Vanadium-contaminated components of
fluid catalytic cracking catalyst
characterization
27
A1 magic angle spinning NMR
spectrum of parent aluminosilicate
gel, 255,257/
aluminosilicate gel loaded with V,
laser Raman spectra, 258,260*,261/262
catalyst characterization procedure
Raman spectroscopy, 254
XPS measurements, 253-254
effect of steaming on surface area, 255,256*
percent distribution of V
5 +
and V
4 +
after steaming, 262

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Vanadium-contaminated components of
fluid catalytic cracking catalyst
characterizationContinued
percent distribution of V
5
+, V
4
+ and
V
3
+ after reduction, 262,263/
pseudoboehmite aluminas loaded with
V, laser Raman spectra, 255-256,258f,259f
reducibility in H2 to V
4
+ and V
3 +
,
262,264f,265
steam-aged aluminosilicate gels loaded
with V, X-ray diffractograms, 255,257/
surface properties, 255,256r,257/
surface V/Al and V/(Si + Al) ratios before
and after reduction, 262,264/265
V-loaded aluminosilicate gels and aluminas,
XPS, 262,263-264/265
Vanadium mobility
definition, 332
dependence on catalyst composition, 332f
effect of accessibility, 334r
influencing factors, 332,333/334
Vanadium naphthenate, effect on cracking
activity, 242-243
Vanadium on alumina and titania supports,
trends, 248,250
Vanadium oxides, physicochemical
properties, 354r
Vanadium pentoxide, solid-state reaction
with Y zeolite, 213-221
X
X-ray photoelectron spectroscopy (XPS),
characterization of vanadium-
contaminated components of FCC,
252-255,262-265
Y
Y zeolite
effect on cyclic structure reactions, 72,74-78
effect on gasoline cracking,
60,62f,63,64r
effect on isoolefin distribution, 63,68/
effect on olefin reactions, 63,71r,72,73/
effect on /i-olefin distribution, 63,69/
effect on total hydrocarbon
distribution, 63,65/
effect on total olefin distribution, 63,67/
effect on total paraffin distribution, 63,66/
intergrowth occurrence, 28-29
solid-state reaction with vanadium
pentoxide, 213-221
ultrastabilization techniques, 12-13
Z
Zeolites, effect on reactions in gasoline
cyclic structures, 72,74-77
cycloolefins, 72,74/75-77
cycloparaffins, 72,75-77
ZSM-2 zeolite
framework structure, 28
synthesis, 28
ZSM-3 zeolite
synthesis, 28
ZSM-5 zeolite
applications, 45
effect on octane enhancement in
catalytic cracking, 96-108
increase of motor octane, 46-54
shape-selective behavior, 45-46
use in catalytic cracking applications, 45
ZSM-5 zeolite addition to fluid catalytic
cracking catalysts
description, 56
effect on cyclic structure reactions, 72,74-78
effect on gas-oil cracking, 58,59r,60
effect on gasoline cracking,
60,62/,63,64f
effect on isoolefin distribution, 63,68/
effect on olefin reactions,
63,7U,72,73/
effect on n-olefin distribution, 63,69f
effect on total hydrocarbon
distribution, 63,65/
effect on total olefin distribution, 63,67/
effect on total paraffin distribution, 63,66/
parent gasoline composition, 60,6If
role, 57
ZSM-20 zeolite
effect on octane enhancement, 79-80
intergrowth occurrence, 28-29
synthesis, 28

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(FCC) Symposium Volume 452) Mario L. Occelli (Eds.) - Fluid Catalytic Cracking II. Concepts in Catalyst Design-American Chemical Society (1991)

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(FCC) Symposium Volume 452) Mario L. Occelli (Eds.) - Fluid Catalytic Cracking II. Concepts in Catalyst Design-American Chemical Society (1991)

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ACS SYMPOSIUM SERIES 452

Fluid Catalytic Cracking II

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