ake selectivity is a term that The Concept of Delta Coke

Charles C. Wear
C often means d ifferent thing s
to d ifferent peop le. So to lead
off our d iscu ssion, let's focus on a
The concept of delta co ke is neither
novel nor compl icated. It is simply
def inition: Coke selectivity is the rela- the diff erenc e between co ke on
tive coke -making tende ncy of any spen t catalyst (at stripper outlet)
given cracking c atalyst. In the vernac - and co ke on regene rated cata lyst.
ular, a catalyst that has "good coke expresse d as a weight perc ent of
se lectivity" mea ns it prod uces lower catalyst.
co ke co mpa red to some referenc e
catalyst. This is usually co nside red a More co rrec tly, delta coke c an be
favorable cha racter istic , since liquid thought of as the amount of co ke
yields are preferred . formed on the catalyst for a single
pass of the catalyst through the
That seems fairly straightforward. but reactor wh ich, in the continuous
the often misunde rstood part is just steady -state ope ration of a com-
w hat the phrase "coke-making ten- mercial FCCU, is also equal to the
dency" really means. Many times it is amou nt of coke burned off the cat-
co nfused with coke yield as alyst in the regenerato r,
expressed in say, weight percent of
fresh feed . However, the coking ten- Della coke also has kinetic signifi-
dency of a catalyst in the context of ca nce , especially on the reactor-
"co ke selectivity" is actua lly its ten- side of the process where it formed.
dency to prod uce deita coke. The coke on cata lyst per pass is a

Cat a la gra m 106 Fall 2009 I3

funct ion of many variables , includ- Figure 1
ing but not limited to: feed quality Simplified Overall Energy Balance
and dispersion at the nozzle, reac-
tor tempe rature and pressure, cata-
lyst activ ity and contact time, and
last but not least. cata lyst coke
selectivity. Reactor Vapors

Therefore, when all other variables

affecting de lta coke are more or
less consta nt, a catalyst that pos- Losses
sesses "coke select ivity" wil l exhibit Heat of
Reacti on , ,- - -- Flue Gas
lower delta co ke at any given activ i-
ty.

A "co ke balance" around the regen-

erator results in a useful exp ression
for delta coke. The coke yield must Strip ping
equa l the d ifferenc e in coke enter- Stream - - - --,
ing and leaving the regeneratoc
Therefore,
Co k e Yie ld = CIO (CSC-CRC)
or
eSC -e RC = Co ke Yield = Delt a Coke
CIO
where: Re CYCle ~ - - - Air
Coke Yield is wt.% Feed
CIO is Cat Cir cul ation ,
lb. Ca Ulb. Feed
e Re is Co ke on Spen t Cata lyst,
Fresh Feed t
wt. % Catalyst
eR G is Co ke on Regenerated Catalys t,
wt.% Cata lyst
ENERGY IN ENERGY OUT
Fre sh Fe ed Reactor Vapors
Recycle Flue Gas
Note that co ke yield and cat/oi l must A ir Misc. Lo sses
be expressed on the same feed Stripping Stream
basis, fresh or fresh plus recycle, to
yield a meaningfu l number
energy to heat the fresh feed, recycle The princi ple of energy balance
Since co ke yield and cat/oi l are feed and stripping steam to react or holds for the ind ividual reactor and
related to d elta co ke in the above- outlet temperature, to heat the air to regenerator as well as the overall
mentioned manner, it follows that a flue gas temperature, to supply the process, as shown in Figure 2.
coke "selective" cata lyst can endothe rmic heat of reaction and any Table I lists the simpl ified co mpo -
decrease coke "yield", but not nec- losses to the atmosphe re--all of this nents to balanc e eac h vessel. By
essarily Fo r instance , in many must co me from the coke 's heat of equating the regenerator heat pro-
cases, coke select ive catalysts will co mbustion. A portion of the feed- duct ion 10 the heat transferred by
operate with hig her cat/oi l ralios stock is therefore "co nsumed" to sup- catalyst, a useful relationship can
with little or no change in coke yield. ply the energy requirements of the be derived:
An understand ing of this req uires proce ss. Heat of Coke Co mbustion + Other Term s
examination of the FCC U heat bal- = Heat Tran sferr ed by Catalyst
ance and the interac tion of proc ess One co nsequence is that the coke
Coke Yield (.6.Hc)
ope rating variables. yield as weight percent feed is deter-
~ CIO C pC' l (T~_ - TRx)
mined by the sum of these energy
Heat Ba lance Effects requirements, not by the cata lyst co ke Del ta Coke =
selectivity (or feed coki ng tende ncy Coke Yield = ~ (T -T)
A comme rcia l unit, like all steady- for that matter). This is the key concept C/O dHc Regen fb

state processes, must be in energy that d istinguishes delta coke, w hich is

balanc e. This means that the total cata lyst and feed related , to coke Noti ng that the cata lyst heat
energy coming into the process yield, which is not. We will return to capacity (epCat) is constant for
must equal the energy leaving the this concept in a moment. any particula r c ase, along with the
process, as shown in Figure 1. The coke's specific heat of combus -

4 I www.e-cata lysts.com
 Figure 2
Energy Balance of Reactor and Regenerator Involves Catalyst Circulation Rate

1-- - - Reactor Vapor s

Losses

Heat of
Reaction r::::J---~- Flu e Gas

Losses
Stripping
Stream - - --'1
- Spent Ca t -
Heat of
Co mbust ion -:
-Regen Cat -

ReCYCle ~ ' - -- Air

Fresh Feed t REACTOR

HEAT BALANCE
REGENERATOR
HEAT BALANCE

Figure 3
tion (He) w hen hydrogen in coke Typical Effect of Delta Coke on FCC Operation
and degree of CO comb ustion are
cons tant, the following proportional- 1400
ity holds: 1380

Delta Coke cx:; {T Regen - T Rx} 1360

!'"
This implies that a coke selec tive
ca talyst w ill, for a co nstant reactor
..'"
l!!
1340 Regen Temp, ·F

tempe rature, red uc e regenerator

temperature. This is exac tly w hat is
'"e
C
1320

1300
observed co mmercially. Cons ider
the unit in full co mbustion that has 1280 Example:
changed to a catalyst with d ifferent
Rea ctor Tem perature 980 'F
co ke select ivity. Depend ing on the 1260
Feed Tempe rature 4 50' F
shift in delta coke, the changes No Recycle
Full Comb ustion
shown in Figure 3 occ ur. 9.0 2 mol.% O 2 in Flue Gas

Of cou rse, unit response to coke §

~
selective catalysts is not limited to 0 8.0
regene rator tem pe rature redu c- "0
Qi
tions. Consider the unit in partial CO
combustion, where a drop in reg en- .
;;::
'"
0
7.0
erator temperature cou ld possibly U
result in a undesirable increase in ~ 6.0 Coke Yield, wt,%
regenerated cata lyst carbon level.
For this case, it would be wise for ~
the operator to intervene--via 5.0
increased promoter additions 0 .60 0.70 0.80 0.90 1.00
and/or air rate-to burn more CO to
Delta Coke, wt.%
Catalagram 106 Fall 2009 I5
 Table I A Check on Data Consistency
Energy Balance Relationship
The fact that del ta coke can be
measured di rectly by co mpa ring
the difference in co ke levels
between spen t and regenerated
+ Heat of Coke
cata lyst samples was di scu ssed
+ Heat of Reaction
C ombustion earlier; Delta coke determined in
this manner, versus the calculations
+ Heat Up Feed - Heat UpAir
of de lta coke from the unit heat bal-
+ Heat Up Recycle - Heat Up Coke
(C/O ) c, cat (TRegen-TRX)
anc e, can be a useful tool to check
+ Heat Up Strip St rea m - Heat Up Rx
data cons istency.
Entrainments

+ Account for Losses - Account for Most process engineers will calcu-
Losses
late coke yield using air rate and
- Heat from Regen flue gas composition, and then ca l-
Entrainments culate catalyst ci rculation rate by
heat balance. These coke yield and
cat/oil results can then be used to
CO 2 and thus return the dense bed have seen operators use Davison calcu late a delta coke. If this "heat
to origina l temperature. co ke selective catalys ts to their fullest balance method" to obtain d elta
extent, and thus alleviate ope rating coke differs substantia lly from the
In this examp le, these "externa l constraints and improve refinery prof- direct sampling method , it co uld
stimuli" from the operator directly itab ility: mean one or more of the following:
affect the overall heat balance by • Increase reactor temperature to
inc reasin g the heat release pe r produce maximum gasoline • Incorrect flu e gas analysis or
pound of coke bur ned (hig her octane. air rate (the most co mmon
CO/CO) . It therefore takes the co m- problem).
• Increase cat circulation for
bustion of less coke to satisfy the • Nonrepresentative catalyst
increased conversion .
energy demand of the process . So,
• Increase resi d content for addi- samples (also a co mmon
for this partial co mbustion c ase,
tional bottoms destruct ion, problem).
coke yield wil l d rop at the same or
nearly the same reacto rlregenerator • Increase feed rate to satisfy • Error in heat balance
temperatures (and therefore cat/oil). increased product demand. method, data or assump-
It has to, bec ause the catalyst tions.
• Increase CO,ICO for lower
cause d a reduction in the delta • Excessive entrainment of
coke , and by defi nition coke yield co ke yield,
interstitial hydroca rbons
must be lower if delta coke dr ops at through the stripper
constant caUoi l! As with many things in life, "more" cat-
alyst co ke selectivity in all cases does
Types of Delta Coke
Remember earlier in this discussion not nec essarily mean "better". A thor-
it was stated that catal yst (and feed ough review of the base operation,
It is convenient to define compo-
qua lity) have a d irect effect on delta inc lud ing goals and cons train ts
nents of delta co ke as to source,
coke, but that the unit heat balanc e should be perfor med before any cata-
and several propo sed breakd owns
determines coke yield. As the pre- Iyst change is co nside red . For exam-
have been published. A sampling is
ce di ng example showed , some - ple, some ope rations are preclud ed
listed in Table II. The three compo-
times it's d ifficult to sepa rate what from the use of incremental catalyst
nents of delta co ke def ined below
changes were caused directly by co ke selectivity. Consid er the unit in
can be influenced by pro p er c ata-
ca talyst (or feed) as opposed to full co mbustion, at maximum catalyst
lyst design :
heat balance cha nges made by the circulation and feed temperature, that
operato r: cannot "he avy-up" the feed nor
1.Catalytic-the co ke deposit
accept a lower reactor temperature.
formed whe n hydrocarbon is
In reality, the dif ference is not very This obviously is not a unit that would
cracked via ac id site cata ly-
importan t in many cases . The profit from cata lyst coke selectivity. it is
sis.
impo rtant point is that coke selec- a unit, however, which cou ld g reatly
2.Cat/Oil-adso rbed/u nstripped
tive catalysts will, in more cases benefit by removing these limitations,
hydrocarbons entrained by
than not, allow an ope rator to have and many have do ne exac tly that via
catalyst flowing throug h the
more flexibility in running his plant. revamps.
stripper
Below are some of the ways we

6 I www.e-catalysts.com
 3.Contam inant-coke produced as Table II
byp roduct of conta minant Typical Delta Coke Breakdowns 1' , 2)
metal (V, Ni, Cu, Fe) dehydro-
ge nation act ivity.

Catalytic Delta Coke Zeolite -High Metals

.. .
Most crac king catalysts have two
sou rces of ac id sites, and therefore
two types of activity-zeoli te and
, . ..
matrix. Zeoli te is crys talline 0.52 65 0.40 29
silica/a lumina with a specific struc - 0.10 14
0.12 15
ture. In the usual case it is whe re
most of the overall ca talyst activity 0.12 5 0.40 29
resides.
.. : 0.04 15 0.50 28
The balanc e of the ca talyst particle 0.80 100 1.40 100
is defined as the matrix. it may be
similar to the zeo lite in com pos ition
(silica/alumina), but does not have Diffe rences in zeo lite type also affect tec hnology behind Davison's cu r-
the partic ular crysta lline struct ure co ke selec tivity. The key issue is the rent octane ca talyst p rod uct line.
uniqu e to zeo lites. Many of today's c hemica l co mposi tion (Si/AI ratio) of The coke select ive pro pe rties of
matrices resemb le the amorphous the equilibrated zeoli te, wh ich is these octane catalysts have b een
ca talysts of the 1950's and 60's.t measured by X-ray as the unit ce ll thoro ug hly treated in ea rlier
size. Zeo lites that eq uilib rate with high Cata/agrams(Numbers 73 and 74) .
The act ivity assoc iated with the zeo- Si/AI ratios (low ce ll sizes) exhib it
lite and the matrix have very differ - retard ed hyd roge n transfe r rates Cat/Oil Coke
ent selectivity pattern s, especially in whic h, among othe r things (such as
rega rd to co ke. This is illustrated in inc reasing gasoline octane), reduc e Cat/oil co ke is perhap s the most
Figure 4. A s matrix act ivity relative catalytic coke make. Davison's expe ri- insidious co mpone nt of de lta coke
to zeolite is minimized, de lta co ke at ence with these zeo lites, g enerica lly because 1 it is totally inde pende nt of
co nsta nt ac tiv ity d ec reases--the refer red to as "ultrastable" or USY any b eneficia l c hem ica l reaction
ca talys t b ecomes more "coke types, is unmatch ed in the industry. taking plac e, suc h as making gaso -
select ive". The pr emium form of USY, patented line, and 2 it has the hig hest heat of
by Davison as "Z-14US", is the co re co mb ustion (highest hydro gen co n-
tent) w hich leads to high intraparti-
Figure 4 c le temperatures during regene ra-
Effect of Zeolite/Matrix Activity on Catalyst Coke Selectivity tion.
1.4
A properly des igned and operated
1.3
cata lyst strip per will minimize the
1.2 Pilot Plant Data
amount of hydrocarbons that flow
930 ' F Reactor Tempe rature into the reg enerator along with the
1.1 75 Sec . Contact Time
c irculating spent c atalyst. Strip p ing
~

""o0 1.0
steam rates of at least two lb. per
1000 lb. of catalyst c ircu lated are
.'!l 0.9 typ ically reco mmend ed. Inc reasing
a;
0 catalyst level (resid ence time) in the
~ 0.8
stripp er can also be effecti ve in min-
ia; 0.7 imiz ing carry-ove r. The co mmon
'" 0.6
co mmerc ial practice is to increase
steam rate and/or strippe r level until
0.5 no fur ther reduction in regenerator
temper ature is obse rved, p roviding ,
0.4 of course, reactor-side ca ta lyst
0.0 1.0 2.0 3.0 4.0 5.0 losses do not inc rease.
Relative ZeolitelMatrix Activity Ratio

tin the 1980's most high matrix catalysts were neither selective nor metals tolerant. tooays high MSA MIDAS' catalysts have been shown to improve coke selectivity
by eliminating and cracking coke precursors.

Catalagram 106 Fall 2009 I7

Steam injection dis places hydroca r- Table III
bon vapo r between cata lyst par ti- Effect of Surface Area on Hydrocarbon Stripping
cles -it is not very effec tive in revers-
ing surface adsorption or pore con -
densation. In some cases , higher Surface Area, M 2 /g 439 389 105
react or (strip per) temperatures have .. 0.89 1.8 1.14
bee n found to redu ce cat/o il co ke.
The mechanis m may involve volatiz-
ing and/or further cr ackin g of des -
.... 72 184 436

orbed materiaJ.3 Unstripped Coke (Wt.% FF) Afte r 1 Minute

Cat/o il co ke is a lso influenc ed by 17.3 17.7 6.4

catalyst matrix pore size and sur-
2.0 1.7 1.3
face area . Cata lyst "strippab ility"
can be measured in the la b by sub- Unstripped Coke (Wt.% FF) After 15 Minutes
jectin g an inert porous material to 1.5 1.3 1.1
heavy oil. followed by nitrog en str ip-
pin g at typi cal reac tor operating 1.7 0.9 0.8
con d itions. The results is shown in
Table III as a function of stripp ing Conditions : MAT REACTOR: 5 gm. Charge , 16 WHSV, 3 C/O,
time and te mperature. WEST COAS T FEED, N, STRIP PING AT 30 SCCM ,

Volume Avg. Pore Diameter : 40, 000 (pore Volume)

High intra p artic le te mpe ratu res
associated with adso rbe d hyd roca r- . Surface Area
bon have been the subjec t of sever-
al studie s.4 .5 wh ic h showed that To summarize. cata lysts desig ned to Contaminan t Delta Coke
hig h surface ar ea (hence. more minimize the cat/oil compone nt of d elta
adsorpt ive) cata lyst pa rtic les a re coke should have low surface area. The hyd rog en-p roduc ing effec t of
pron e to d eactivate rap idl y w hen larg e average po re diameter matric es feed metals-parti cular ly tha t of nick-
regenerated . Partic le temp eratur es to discourag e hyd rocarbon adso rption el. co p per, and vanad ium-de posi t-
seve ra l hund red d eg rees hig her and enhance "st rippab ility". ed on the c rac king catalyst is we ll
than average regenerator bed tem- known . Coke is a co mpanion p rod-
p eratures we re ca lculated. uc t of d ehydrog enation , and from
Tabl e II it is c lear that con taminant
Table IV
co ke can be a subst antial perc ent-
Metal Aging Study Results'1O) age of the overall delta co ke for
500 ppm Ni (Im pregnated After
500 ppm Ni + Sb
metals-lad en catalysts.
Steam Deact ivation1)

Fresh Age d 2 Aged 2 The pa ssivation of nicke l byantimo-

ny (licen sed by Phillips Petroleum
Co.) and of vanad ium by tin addi-
68.5 69.5 69.0 tives is being practiced com mer-
0.21 0.08 0.075 c ially.! Claims of a 50% red uction in
2.6 2.5 2.45
hyd roge n and coke pro d uce d by
contam inant metals have been pub -
70.0 68.0 69.5 lished .6.7.8.9
0.42 0.38 0.145
4.15 4.2 2.8
We have found that the level of
hyd roge n and co ke p roduc tion du e
79.0 78.0 77.0 to contaminant meta ls is also a
0.45 0.35 0.14 funct ion of cata lyst ma trix co mposi-
4.0 3.9 3.8 tion. Matrices with low alumina con -
tent and low surface areas are more
1 Deactivat ion Conditions : 1350'F, 100% Steam, 15 psig , 8 Hrs .
2Aged 13 Cycles in Cy clic Fixed -Fluid Bed Pilot Units; 40 WHSV, 3 clo, 1000' F effect ive in minimizing conta minant
Reaction /1100'F Reg enerati on meta l dispersio n and d ehyd rog ena-
"Typical Matrix Surfa ce Area tion ac tivity' (Table IV).

fT in passivatio n is no longer practiced in the ind ustry. Integral vanadium traps. such as those in IMPACT, are much more effective for selectiv ity preservation in hig h
metals operations.
.,JSee note on page 7.

8 I www.e-catalysts .com
Cok e Selec tive Cata lyst Davison has used these principles for 4. Bond i, A., Miller, R.S., and Sch laffer, w. G.;
Properties years to design a wide range of cata- Ind. Eng. Chern. Process Des. Dell. 1(3); 962:
p.196.
lysts. Curr ent examp les are members
As can be seen from the prec eding of the Oc tacat. GXO, and Nova fami- 5. Wilson, W.B.. Good . G.M.. Deahl, t J.,
d iscussion. catal yst design has a lies that have led the industry in coke Brewer. C.P. . and App leby, W.G.: Ind. Eng.
direct bearing on the formation of selectivity, as well as octane enhance - Cre m; 48(11), November 1956: p. 1982.
various co mponents of the overall ment. Davison R&D is focused on a 6. Joh nson , M.M. and Tabler, D.C.: US No.
"delta coke". Certain c atalyst prop- co ntinuous program of impro ving 3,7 11,422.
er ties . associa ted wit h the true these produ cts . as well as on the
"co ke selec tive" cata lyst system. act design of new coke select ive grades 7. Dale, G.H. and Mc Kay, D.L.: Hydrocarbon
Processing ; Septe m ber 1977: p. 97.
to minimize delta co ke for any given suc h as the DXB family.
activity level. The essential ing redi- 8. English. A.R. and Kow alczyk, D.C.:
ents are 1 a zeolite that will equili- References O&CJ, July 16, 1984 : p. 127.
brate at low unit c ell size. w hile
9. Barlow, R.C.: "C cm mercia t Applic at ion of
retaining the ap pro priate ac tivity 1. Cimbalo, R.N., Foster, R.L.. and Wachtel.
Vanadium Passivation Tec hnology", NPRA
S.J.: O&GJ ; May 15.1 972: p. 112.
level to do minate that of the matrix Spri ng Meeting , 1986.
and/ a matrix of con trolled surface 2. Mauleon, J.L., and Courceue. J.e.: O&CJ:
10 . Ritter, R.E.: Catalagram No. 73: 1985: p.
area with large pores to maximize Octobe r 21. 1985: p. 64.
14.
strippability and control dispersion
3. Sch uurm ans, H.A.J.; Ind. Eng. Chern.
and d ehyd rog enation activity of Process Des. Dell. : 19(2): 1980 : p.267.
con taminant metals.

Gatte Named North American General Manager

Bob Galle has been appointed General Manager - North America. Refining
Technologies. In his new role, Bob will have overall responsibility for the
North Americ an business activ ities in support of the g lobal Refining
Technolog ies strategy, Bob will also be a member of the Refining
Technologies g lobal management team.

Bob has worked in key roles at Grac e for the last 21 years, He has previous -
ly held positions as the Vice President Sustainab ility and New Ventures; Vice
President and General Manag er of the Discovery Sciences business,
Ge neral Manager Grace Catalyst AB in Stenungsund, Sweden, and Vice President and COO
of e-Catalysts, Inc. In the earlier part of his career, Bob held positions as Technical Sales
Manager for FCC, and a Manage r of Business Development for Davison Catalysts,

Bob has a PH.D in Chemical Eng ineering from the Pennsylvania State University and a
Bache lor of Science in Chemica l Engineering from Rensselaer Polytechnic Institute.

Catalagram 106 Fall 2009 I9