United States Patent (19) (11) 4,150,061

Feinstein et al. (45) Apr. 17, 1979

54 PROCESS FOR CONVERTNG PYROLYSIS (56) References Cited
GASOLINE TO BENZENE AND U.S. PATENT DOCUMENTS
ETHYLBENZENE-LEAN XYLENES
3,720,726 3/1973 Mitsche et al.................. 260/672 T
75 Inventors: Allen I. Feinstein, Wheaton; Un K. Primary Examiner-C. Davis
Im, Naperville, both of Ill. Attorney, Agent, or Firm-William C. Clarke; Arthur G.
Gilkes; William T. McClain
73 Assignee: Standard Oil Company (Indiana), 57 ABSTRACT
Chicago, Ill. Fractionated pyrolysis gasoline containing toluene,
xylenes, ethylbenzenes, C7-C9 paraffins, olefins and
(21) Appl. No.: 849,606 naphthenes are selectively hydrodealkylated and tran
salkylated to give ethylbenzene-lean xylenes and ben
Zene in the presence of a catalyst comprising a tung
22 Filed: Nov. 8, 1977 sten/molybdenum component of WO3 and MoC)3 and
an acidic component of 60 (wt)% of mordenite and 40
(51) Int. Cl’................................................ CO7C 3/62 (wt)% of catalytically active alumina.
(52) ... 260/672 T; 260/672 R
(58) Field of Search ........................ 260/672 T, 672 R 10 Claims, 1 Drawing Figure

MAKE UP 2 10a
HYDROGEN

C - Cs
PARAFFNS
RACTION
ZONE
2
BENZENE
s
TOLUENES

XYENES

A. TRMETHYLeeNZENES
U.S. Patent 4,150,061

NSLEJZW3EI9N?T_ALH
Z/
 4,150,061 2
the stream and desulfurized to remove the sulfur. The
PROCESS FOR CONVERTNG PYROLYSS. stream is thereupon distilled in an aromatics recovery
GASOLINE TO BENZENE AND - unit to remove the benzene, toluene and C8-C9 frac
ETHYLBENZENE-LEAN XYLENES tions. The C8-C9 fraction which includes C8 aromatics
that contain 42-44% ethylbenzene are generally re
BACKGROUND OF THE INVENTION turned to the refinery to be used in gasoline blending at
This process relates to a method for the selective a lower economic value than the other products of the
hydrodealkylation and transalkylation of aromatic hy olefins plant.
drocarbons and the cracking of paraffins. Alkyl aro In the prior art, a number of processes are peripheral
matic compounds have long been produced from hy 10 to the instant invention of a process for producing ben
drocarbon fractions relatively rich in such materials. Zene and ethylbenzene-lean xylenes from pyrolysis gas
Early sources were liquids from coking or other distilla oline, but no processes are directly related to the instant
tion of coals. More recently, these products have been invention.
derived from fractions obtained in refining of petro There is no process utilizing hydrodealkylation and
leum. An important source in recent years has been the 15 /or transalkylation in the prior art wherein toluene
aromatic liquid naphthas known as pyrolysis gasoline yields benzene, and xylenes, ethylbenzene yields ben
resulting from the thermal cracking of gases, naphthas, Zene, high boiling C7-C9 paraffins and olefins, yield
and gas oils to produce olefins. C1-C5 paraffins and xylenes are left unchanged simulta
However derived, these aromatic-ring streams have neously with a single catalyst, without side-reactions
usually been distilled and otherwise separated (e.g. sol 20 producing undesired products by hydrodemethylation
vent extraction) to obtain the desired product compo thus destroying the desired products namely, the xy
nents. The purpose of these operations typically has lenes.
been to obtain C8 aromatics and benzene which are now For example, U.S. Pat. No. 3,478,120 relates to a
used in huge quantities in the manufacture of tereph process and catalyst for the dealkylation of hydrocar
thalic acid and other chemical products. The separated 25 bons which comprises contacting the said hydrocarbons
streams usually resulting from the above separation by with a catalyst comprising iron group metals and cal
distillation or other means consist of product streams of cium aluminate. A stream comprising ethylbenzene and
benzene, toluene, C8 aromatics containing xylenes and a xylenes can be subjected to dealkylating conditions
bottoms product of C9 and C10+ aromatics. The pyrol whereby the ethylbenzene and xylenes are selectively
ysis gasoline stream yields a C7-C9 fraction which is 30 dealkylated to methane, ethane, toluene and benzene.
usually blended into automotive gasoline. In another example, U.S. Pat. No. 3,919,339, discloses
This invention accordingly relates to a conversion a process for selective hydrodealkylation of ethylben
process for the hydrodealkylation and transalkylation zene to toluene and benzene in a hydrocarbon feedstock
of fractionated pyrolysis gasoline containing ethylben comprising ethylbenzene and xylenes, and for simulta
zene into more useful compounds. More specifically, 35 neous isomerization of the xylenes top-xylene. The U.S.
this invention is concerned with a conversion process Pat. No. 3,919,339 process comprises contacting the
for the concurrent transalkylation and hydrodealkyla
tion of a fractionated pyrolysis gasoline stream contain feedstock with a catalyst comprising a cobalt or nickel
ing toluene, ethylbenzene and xylenes into ethylben component on an acidic inorganic refractory oxide
zene-lean xylenes and benzene utilizing a catalyst com support at a temperature between 650-950 F., a pres
prising a tungsten/molybdenum component of WO3 sure below 300 psig and a hydrogen-to-hydrocarbon
and MoO3 and an acidic catalyst of 60 (wt)% mordenite feed ratio between 1:1 and 20:1. Preferably, the catalyst
and 40 (wt)% catalytically active alumina. used is cobalt on silica:alumina.
The C8 aromatics found in pyrolysis gasoline gener U.S. Pat. No. 3,957,621 discloses a method for the
ally contain approximately 44% ethylbenzene. The 45 preparation of alkyl aromatic hydrocarbons by the pro
presence of ethylbenzene in mixed xylenes is detrimen cessing of a fraction of heavy reformate, those from
tal to process yields and process economics when these which benzene and lighter components have been
xylenes are utilized in the production of p-xylene. Frac largely removed by distillation. The fraction is hydro
tional distillation to remove ethylbenzene from mixed cracked over a zeolite catalyst associated with a hy
xylenes is not economically practical because of the 50 drogenation/dehydrogenation component. Ethylben
closeness of their boiling points. Ethylbenzene can be zene is selectively removed from the charge stock
removed from xylenes by repeated recrystallizations which occurs in part by dealkylation of the side chain
but this is economically very expensive and is techni and in part by disproportionation to benzene and C9--
cally difficult. alkylbenzenes such as ethyltoluene and diethylbenzene
Pyrolysis gasoline is produced in an olefins plant by a 55 instead of benzene and xylenes as in the instant applica
steam cracking process which optimizes olefin produc tion.
tion of carbon chain length of from C2 to C4. The com Alkyl aromatics such as toluene or ethylbenzene can
position of pyrolysis gasoline depends upon various be disproportionated to benzene and polymethylben
factors, i.e., kind offeedstock, type of cracking unit and zenes, and benzene and polyethylbenzenes, respec
cracking conditions. All pyrolysis gasolines generally tively, as is disclosed in U.S. Pat. No. 3,578,723 by use
contain considerable amounts of aromatics, normally of the crystalline zeolite catalyst ZSM-4. U.S. Pat. No.
40-80% benzene, toluene and xylenes, together with 3,578,723 does not teach dealkylation of ethylbenzene
paraffins, naphthenes, olefins and diolefins. Pyrolysis to benzene and ethane.
gasoline is generally unstable and must be stabilized by In another approach, ethylbenzene in a hydrocarbon
selective hydrogenation immediately upon production 65 stream can be dehydrogenated to styrene according to
in the olefins plant. U.S. Pat. No. 3,720,726 using a zeolite catalyst having a
In the prior art, a pyrolysis gasoline stream from an mordenite crystal structure containing alumina fixed in
olefins plant is hydrotreated with hydrogen to stabilize combination therewith.
 4,150,061
3 4.
Accordingly, in the prior art there are a number of vaporized before being introduced into the reaction
processes to dealkylate alkyl aromatics to benzene and One, . . . . . . : .
polymethylbenzenes. Also, processes are in the prior art The feedstock is contacted in the reaction zone with
to dehydrogenate ethylbenzene to styrene. However, the hereinafter described catalyst in the presence of
the prior art has not disclosed the process utilizing a 5 hydrogen-affording gas. Advantageously, a hydrogen
catalyst composition comprising a tungsten/molyb to-hydrocarbon mole ratio of at least 1:1 is employed,
denum component of WO3 and MoC)3 and an acidic and the hydrogen-to-hydrocarbon mole ratio can range
component of 60 (wt)% of mordenite and 40 (wt)% of up to 50:1. Preferably, the hydrogen-to-hydrocarbon
catalytically active alumina whereby a heavy aromatics mole ratio can range between 4:1 to about 10:1 at ap
fraction of pyrolysis gasoline containing toluene, ethyl 10 proximately 465 psig. The contact time is of the range of
benzene, xylenes and sizeable amounts of non-aromatics 1. to 20 seconds, preferably 3 to 10 seconds, wherein
selectively hydrodealkylated and transalkylated to eth contact time is defined as bulk volume of the catalyst
ylbenzene-lean xylenes and benzene. divided by volumetric flow rate of reactants and hydro
gen. Other operating conditions comprise an elevated
SUMMARY OF THE INVENTION 15 temperature of about 600' F. to about 1000 F., prefera
This invention comprises a hydrodealkylation/tran bly about 750 F. to about 950 F.; an elevated pressure
salkylation process for selectively hydrodealkylating of about 100 psig to about 1,000 psig, preferably about
and transalkylating a heavy aromatics fraction from 150 psig to about 500 psig; and a space velocity
pyrolysis gasoline within the boiling point range of 0 (WHSV) of about 0.1 to about 20 weights of hydrocar
from about 230 to 340 F., which contains toluene, 2 bon per hour per weight of catalyst, preferably about 1
C7-C9 paraffins, ethylbenzene, xylenes and quantities of to about 10 weights of hydrocarbon per hour per
C9 aromatics to ethylbenzene-lean xylenes and benzene, weight of catalyst.
and hydrocracking high-boiling paraffins and naph Side reactions such as hydrogenation of the aromatic
thenes to C1-C5 paraffins which process comprises con ring are controlled by the sulfiding of the catalyst to the
tacting the feedstock with a catalyst comprising tung 25 sulfided form with sulfur compounds, such as hydrogen
sten/molybdenum components on a mordenite, base sulfide and carbon disulfide, either prior to or at the
suspended in a matrix of a refractory inorganic oxide at start of the hydrodealkylation/transalkylation reaction.
a temperature in the range from about 600 to 1000 F. If hydrogen sulfide is used, the catalyst. is advanta
geously subjected to the hydrogen sulfide prior to its
and a pressure of from about 100 to 1000 psig. 30 use as a catalyst for hydrodealkylation/transalkylation.
DETAILED INVENTION
DESCRIPTION OF THE If carbon disulfide is employed, it may be added to the
hydrocarbon feed during the initial stages of the run.
The present invention selectively hydrodealkylates The catalytic composition of the process of this in
vention comprises a hydrogenation component dis
and transalkylates the C7-C9 aromatic components of 35
the pyrolysis gasoline stream to produce ethylbenzene posed upon a solid acidic cracking support. The hydro
genation component comprises two members selected
lean xylenes and benzene. High boiling C7-C9 paraffins from the group consisting of the oxides of metals of
and olefins in the stream are concurrently cracked to Group VIb of the Periodic Table of Elements and mix
C1-C5 paraffins which are a valuable feed for the olefins tures thereof. The pertinent Periodic Table of Elements
plant. Particularly, it is a process for the hydrodealkyla may be found on the inside of the back cover of
tion and transalkylation of pyrolysis gasoline containing HANDBOOK OF CHEMISTRY AND PHYSICS,
alkyl aromatic hydrocarbons wherein ethyl groups are 45th edition, Robert C. Weast, editor, Chemical Rubber
dealkylated and alkyl groups of one carbon are trans Company, Cleveland, Ohio (1964). The preferred
ferred from one molecule to another. Group VIb metals are tungsten and molybdenum. Mo
The success of this hydrodealkylation/transalkyla 45 lybdenum is present in an amount within the range of
tion process is due primarily to the use of particular about 1.0 to about 20 weight percent, expressed as
catalytic compositions which are employed therein and MoO3 and based upon the weight of the catalytic com
the operating conditions that are used. position, while tungsten is present in an amount within
Typical feedstocks of the present invention are hy the range of about 1 to about 10 weight percent, ex
drocarbon streams which contain single-ring aromatic 50 pressed as WO3 and based upon the weight of the cata
hydrocarbons which boil within the range from about lytic composition.
230 to 340 F. and contain predominantly 7 to 8 carbon The solid acidic cracking support of the catalyst em
atoms and a small quantity of hydrocarbons containing ployed in the process of the present invention comprises
9 carbon atoms. Such aromatic hydrocarbon streams a mordenite-type, large-pore crystalline aluminosilicate
are usually a hydrocarbon fraction derived from the 55 material and a suitable refractory inorganic oxide. Pref.
pyrolysis gasoline stream from an olefins plant. Accord erably, the mordenite-type, large-pore crystalline alu
ingly, the feedstock of this invention can contain ethyl minosilicate material is suspended in and distributed
benzene, xylenes, toluene and paraffins, olefins: and throughout the matrix of the refractory inorganic oxide.
naphthenes of 6-9 carbon atom chain length and small The mordenite-type, large-pore crystalline aluminosili
quantities of C9 aromatics. A preferred fresh feedstock 60 cate material is present in an amount within the range of
is one containing a toluene/Cs aromatic mole ratio about 5 to about 95 weight percent, based upon the
greater than 1.4:1. . . . . .. . . . . . . . weight of the support.
Typically the C7-C9 fraction of hydrogenated pyrol The refractory inorganic oxide component of the
ysis gasoline is mixed with a hydrogen-containing gas support of the catalyst that is employed in the process of
and preheated to a suitable temperature, and then-trans- 65 the present invention may be an oxide of a single metal,
ferred to the hydrodealkylation/transalkylation reac or it may be a mixture of the oxides of two or more
tion zone, which may contain one or more reactors. metals of Groups. III and IV of the Periodic Table of
Advantageously, the feed is substantially completely Elements. For example, the refractory inorganic oxide
 4,150,061
5 6
component may be catalytically active alumina, or it form containing exchangeable sodium and/or calcium
may be a mixture of silica and alumina, or it may be a ions, or other alkali metal or alkaline earth metal ions.
mixture of boria, titania, gallia, and alumina. The pre Preferably, the alkali metal cations, such as sodium ions,
ferred refractory inorganic oxide is a catalytically ac may be replaced or cation-exchanged with a member
tive alumina. 5 selected from the group consisting of an alkaline earth
An example of the refractory inorganic oxide compo metal, a rare earth metal, hydrogen, and a hydrogen
ment that is employed in the catalyst of this invenion is precursor to provide an alkali metal content in the mor
PHF or Aero-1000 Alumina manufactured by Ameri denite that is less than 1 weight percent, calculated as
can Cyanamid Corp. It is described as high-purity gam the metal. Ammonium ions comprise a hydrogen pre
ma-alumina, the inspection data being: surface area 206 10 cursor and may be employed to cation-exchange the
p?/g, pore volume 0.6 cc/g, average pore diameter 90 alkalimetal of the mordenite. Heat is employed to drive
A (Angstroms), sodium content 0.1 wt.%, silicon con off ammonia leaving the mordenite in the hydrogen
tent 0.02 wt.%, iron content 0.025 wt.%. form. Mordenite differs from other aluminosilicates in
The aluminosilicate material that is a component of that substantially all the exchangeable metal cations
the support of the catalytic composition that is em 15 may be replaced with hydrogen ions without causing
ployed in the process of the present invention is a destruction of the characteristic crystal structure of the
mordenite-type, large-pore crystalling aluminosilicate mordenite.
material. It is sometimes hereinafter referred to as "mor The porous refractory inorganic oxide that is em
denite aluminosilicate material.” By large pore material ployed in the catalytic composition of the present in
is meant a material that has pores which are sufficiently 20 vention may be a catalytically active alumina, silica
large to permit the passage thereinto of benzene mole alumina, silica-magnesia, titania-alumina, zinc-oxide
cules and larger molecules, and the passage therefrom alumina, gallium oxide-alumina and the like. Catalyti
of reaction products. For use in catalysts that are em cally active alumina, such as gamma-alumina and eta
ployed in petroleum hydrocarbon conversion pro alumina, is the preferred refractory inorganic oxide.
cesses, it is preferred to employ a large-pore crystalline 25 Such alumina should have a pore diameter of about 70
aluminosilicate material having a pore size of at least 6 Angstroms to about 200 Angstroms and a surface area
to 10 Angstrom units (A). The mordenite aluminosili of at least 100 square meters per gram. Suitably, the
cate material of the catalyst of the present invention surface area should be within the range of about 200
possesses a pore size of 6-9 A. square meters per gram to about 500 square meters per
A preferred mordenite-type aluminosilicate material 30 gram.
is the synthetic Zeolon manufactured by the Norton The co-catalytic composition of the present invention
Chemical Company. Zeolon-His the hydrogen form of may be prepared in various ways. For example, finely
this synthetic mordenite. Mordenite is characterized by divided mordenite-type aluminosilicate material may be
its high silica-to-alumina ratio and its crystal structure. stirred into a solor gel of the refractory inorganic oxide
The mordenite may have a silica-to-aluminaratio within 35 and soluble compounds of the Group VIb metals added
the range of about 6 to about 100. The composition of to the sol or gel, followed by the cogelling of the solor
mordenite is given in Kirk-Othmer, "Encyclopedia of gel mixture by the addition of dilute ammonia. The
Chemical Technology,' first edition, Volume 12, page resulting cogelled material is then dried and calcined. In
297 (1954), as (Ca, Na2)Al2SigO22.6H2O. The proposed another method of preparation, the finely divided mor
structure is one in which the basic building block is a denite is mixed into a sol or gel of the refractory inor
tetrahedron consisting of 1 silicon or aluminum atom ganic oxide, the sol or gel mixture is cogelled by the
surrounded by four oxygen atoms. The crystal structure addition of dilute ammonia and the resulting gel is sub
is made up of 4- or 5-membered rings of these tetrahe sequently dried, pelleted, calcined, cooled, and impreg
dra. These 4- and 5-membered rings are believed to give nated with a solution or solutions of the Group VIb
the structure its stability. The chains are linked together 45 metals. As an alternate method of preparation, a hydro
to form a network having a system of large parallel gel of the refractory inorganic oxide is blended with
channels interconnected by small cross channels. Rings finely divided aluminosilicate material, and a solution or
of 12 tetrahedra form the large channels. Other syn solutions of soluble compounds of the Group VIb met
thetic zeolites also have such 12-membered rings, but als are added to this blend, and the resulting mixture is
they have interconnected cages, whereas the mordenite 50 thoroughly blended. The blended mixture is then dried,
has parallel channels of uniform diameter. For example, pelleted, and calcined. Suitable drying conditions for
synthetic faujasite, which has the formula Na3Al3 use in the above-described metal manufacturing meth
SiO14, is characterized by a 3-dimensignal array of ods comprise a temperature in the range of about 200
pores which consist of 12-13 Angstrom (A) cages inter F. to about 400 F. and a drying time of about 5 to 30
connected through 6-9 A windows. 55 hours. Suitable calcination conditions comprise a tem
The mordenite aluminosilicate material that is pre perature in the range of about 900 to 1400" F. and a
ferred, the Zeolon manufactured by the Norton Chemi calcination time of about 2 to about 20 hours. Preferred
cal Company, with its high ratio of silica to alumina drying and calcination conditions are a temperature of
exhibits the ability to undergo complete acid exchange about 250 F. for about 16 hours and a temperature of
from the original sodium form to the hydrogen form. about 1000' F. for about 6 hours, respectively.
The theoretical silica-to-alumina ratio is about 10 to 1 The catalytic composition that is employed in the
and the effective pore diameter in Angstroms (A) is process of the present invention can be prepared in
within the range of 6 to 9A. The surface area in square several other ways. For example, the mordenite-type,
meters/gram is within the range of 400-450m/g and its large-pore crystalline aluminosilicate material can be
static water capacity in weight percent is within the 65 pulverized into a finely-divided state and then physi
range of 10-11%. cally admixed with a finely-divided powder of the se
The mordenite in the catalytic composition of the lected refractory inorganic oxide component. After a
present invention may be in the unexchanged cation thorough blending of the two solid components, the
 4,150,061
7 8
resulting mixture may be co-pelleted, and impregnated a co-catalytic support comprising 60 percent by weight
with one or more solutions of the metals of the hydroge H-mordenite, large-pore crystalline aluminosilicate ma
nation component, i.e., the metals of Group VIb. The terial suspended in a matrix of catalytically active alu
resulting composition is thoroughly mixed to form a mina. Operating conditions in reaction zone 5 comprise
blended composition, which is subsequently dried to a a pressure of 150 psig to 500 psig, a temperature of
moisture content ranging from about 20 to 40 weight about 750 F. to about 950 F., a space velocity
percent, based upon the total weight of the composi (WHSV) within the range of about 1.0 to about 10
tion. The dried material is then calcined at a tempera weights of hydrocarbon per hour per weight of catalyst,
ture within the range of about 900 to about 1100 F. and a hydrogen-to-hydrocarbon ratio that does not
The following is another method of preparation. The 10 exceed 10:1 at a pressure of approximately 465 psig.
mordenite-type, large-pore crystallization aluminosili The effluent from reaction zone 5 is passed through
cate material in a finely-divided state may be added to a line 7 to high pressure separator 8 wherein the light
hydrosol or a hydrogel of the refractory inorganic gases containing hydrogen are separated therefrom.
oxide component and blended therein to form a homog The separated hydrogen-containing gas is passed
enous mixture. The hydrogenation component, i.e., the 15 through line 9 to fractionator 10 to separate low-boiling
metals of Group VIb, are added in the form of heat C1-C5 paraffins. The hydrogen-containing gas is recy
decomposable components to this homogenous mixture. cled to reaction zone 5. Make-up hydrogen is added to
These heat-decomposable components may be added in this hydrogen-containing gas after the fractionation by
a single solution or in several solutions. The resulting way of line 2joining line 10a. The separated low-boiling
composition is then thoroughly mixed, dried, and cal hydrocarbons consisting mainly of C1-C5 paraffins are
cined, as described above. sent to the front end of the olefins plant as a valuable
Alternatively, the homogenous mixture of the above feedstock. The liquid effluent from high pressure sepa
paragraph may be dried and pelleted, or dried, and the rator 8 is passed through line 11 to control valve 12,
resulting material may be impregnated with the hydro which permits the pressure to be reduced prior to the
genation component, followed by drying and calcining, 25 passage of the liquid effluent through line 13 to fraction
as described above. ation zone 14. In fractionation zone 14, the liquid is
The invention comprises a process for the hy separated into benzene, toluene, xylenes, and some tri
drodealkylation/transalkylation of alkylaromatics methylbenzenes. Each of these streams is separated
which process consists essentially of contacting an al from one another in the fractionation zone. Benzene is
kylaromatic stream in a reaction Zone under hy 30 removed by way of line 16, while toluene is taken from
drodealkylation/transalkylation conditions and in the line 17 and the xylenes are removed by way of line 18.
presence of a catalyst to furnish a product containing Trimethylbenzenes are removed from fractionation
hydrodealkylated/transalkylated aromatics, said cata zone 14 by way of line 19 and sent to the gasoline pool.
lyst comprising a hydrogenation component which The toluene in line 17 joins the fresh feedstock from
comprises two Group VIb metals deposed upon a solid 35 line 1 to be sent to reaction zone 5.
support of a co-catalytic component comprising H Reaction conditions in general are as follows: reac
mordenite and a porous refractory inorganic oxide, said tion temperatures can range between 600 and 1000 F.,
refractory inorganic oxide being selected from the preferably between 700-850 F. The reaction can be
group consisting of catalytically active alumina or sili conducted at a pressure of from about 100 to about 1000
ca-alumina, silica, zirconia, gallium oxide, titania and psig, preferably 150 to 500 psig, Hydrogen to hydrocar
mixtures thereof, and said Group VIb metals being bon mole ratios can be within the range of 1:1 to 50:1,
present as members selected from the group consisting preferably 4:1 to 10:1 at approximately 465 psig Space
of (1) the elements, (2) their oxides, (3) their sulfides, velocities can be within the range of from about 0.1 to
and (4) mixtures thereof. When the refractory inorganic about 20 unit weights of hydrocarbon charge per
oxide is alumina, the catalyst co-support contains at 45 weight of catalyst per hour (WHSV), preferably about
least 5 weight % alumina, preferably 80 weight % alu 1:1 to 1:10. Feedstock concentrations can be varied. A
13.
preferred fresh feedstock is one containing a tolue
PROCESS DESCRIPTION ne/Cs aromatic mole ratio of greater than 1.4:1. Contact
times can vary from approximately 1 to 20 seconds.
A simplified process flow scheme for this embodi 50 Preferred contact time is 3 to 10 seconds.
ment is depicted in FIG.1. Auxiliary equipment, such as Embodiments of the process of the present invention
pumps and heat exchangers, is not shown in the draw may be found in the following examples. These embodi
ing. Such auxiliary equipment is well-known to those ments and examples are presented for purposes of illus
skilled in the art and the uses and locations of this equip tration only and are not intended to limit the scope of
ment in this particular process system will be recog 55 the invention.
nized easily by those having ordinary skill in the art.
Fresh feedstock comprising a C7-C9 fraction of hy EXAMPLE I-III
drogenated pyrolysis gasoline is introduced into the Feedstocks of the composition shown in Table I sim
process system by way of line 1. The fraction contains ulating actual reactor feeds were used in the following
C7-C8 aromatics, C7-C9 paraffins, olefins and naph 60 examples.
thene and overhead Co- aromatics. Hydrogen-contain Table I
ing gas is combined with the reactant stream by way of Typical Composition of a
line 3. Carbon disulfide is added by way of line 3a. The Simulated Pyrolysis Gasoline Reactor Feed
resulting mixture with recycle toluene from line 17 is Wt. 2%
passed through line 4 into reaction zone 5. Reaction 65
Touene 65.1
zone 5 contains a catalyst bed or catalyst beds 6. The Xylenes 14.7
catalyst in this reaction zone comprises 3.0 percent by Ethylbenzene 10.3
weight WO3 and 5 weight percent by weight MoC3 on C9 Aromatics 1.6
 4,150,061 10
Table I-continued TABLE II-continued
Typical Composition of a - Conversion of Pyrolysis Gasoline Fraction to
Simulated Pyrolysis Gasoline Reactor Feed Benzene and Xylenes: Effect of Temperature
Wit. 2 Ethylbenzene 10.3 1.3 0.7 0.6
Benzene 2.7 Xylenes 14.7 22.2 21.1 20.1
C7-C9 Paraffins 5.6 C9. Aromatics 1.6 6.4 5.7 4.7
C10 Aromatics 0.5 0.4 0.6
Total 100.0
Toluene Conversion, wt.% 39.3 43.0 44.1
Ethylbenzene Conversion, wt.% 87.4 93.4 94.6
The catalyst used in Examples I-III consisted of 5%
MoO3/3% WO3 on a gamma-alumina matrix containing
C7-C9 Paraffin Conversion, wt.%
Ethylbenzene Concentration in
99.4 100.0 100.0
C8 Aromatics, wt.% 5.5 3.1 2.7
60% mordenite-H. The catalyst was crushed and used (The C-C, paraffins in the feed consisted of (wt.%); 2.8% n-heptane, 2.7%
in a -20 to +40 mesh (U.S. Sieve) granular form. The n-octane, and 0.1% n-nonane.
B.E.T. surface area of the catalyst was 371 m/g.
Preparation of the catalyst was accomplished as fol- 15 The examples cited on Table II show a net produc
lows: 2298.9 g of American Cyanamid sol, 9.5% Al2O3, tion of benzene and xylenes at the expense of ethylben
was blended with 333.4 g of Norton Zeolon-H pow zene and toluene, and illustrate that ethylbenzene con
dered mordenite sieve, in a Waring blender. The blend version can be increased to as high as 95% by raising
was gelled with 100 ml of a 50% NH4OH solution and the reaction temperature from 800 to 900 F.
dried overnight at 250 F. The dried material was then 20 EXAMPLE IV AND V
ground 20/40 mesh and calcined 3 hours at 1000 F.
460 g of the 20/40 mesh base was impregnated with a The conditions of Examples I-III were repeated at a
solution made by dissolving 30.3 g ammonium molyb temperature of 850 F. and different contact times. The
date and 16.3 g ammonium metatungstate dissolved in results appear in Table III.
400 ml of distilled water. The sample was dried at 250 25 TABLE III
F. for 5 hours and calcined in air at 1000 F. for 3 hours. Conversion of Pyrolysis Gasoline Fraction to
It was made to contain 5% MoO3/3% WO3 supported Benzene and Xylenes: Effect of Contact Time
on 60% mordenite-H/40%. Al2O3. Catalyst: 5% Moos, 3% WO3, 60% H-Zeolon/40% Al2O3
Prior to use, the catalyst was sulfided with hydrogen Example IV V
sulfide. 30 Conditions:
The reactor consisted of a tubular stainless steel pipe, Temperature, 20 F. 850 850
17 inches long, having an inner diameter (I.D.) of 0.5 Pressure, psig 465 465
inches. The reactor was heated by a constant tempera WHSW 17.4 3.5
ture salt bath and the internal reactor temperature was Contact Time, sec. 3.1 14.8
H2/HC Mole Ratio 6.1 6.3
measured by a movable thermocouple located in a ther 35 Product Analysis Yield, wt.%
mowell along the reactor axis. Feed
Hydrogen and the hydrocarbon feed were preheated C1 to C6 Paraffins 5.7 14.7
and metered into the reactor system. The liquid and Methane 0.1 0.6
gaseous product streams were separated in a high pres Ethane 1.5 5.5
sure separator under system pressure. The liquid prod 40 Propanes
Butanes
2.1
1.5
5.9
2.2
uct was continuously withdrawn and collected under 3 Pentanes 0.4 0.5
psig pressure. The gaseous products were depressurized Hexanes 0.1
to 3 psig and sent directly to an on-line gas chromato C7 to C9 Paraffins() 5.6 1.7 o
graph. Benzene
Toluene
2.7
65.
6.7
44.7
20.3
37.7
Product samples were collected at intervals of at least 45 Ethylbenzene 0.3 2.5 0.7
24 hours and analyzed by gas chromatography. The Xylenes 14.7 2. 21.1
data resulting are summarized in Table II. Cg Aromatics 1.6 7.0 5.7
TABLE II C10 Aromatics 0.6 0.4
Conversion of Pyrolysis Gasoline Fraction to Toluene Conversion, wt.% 3.3 43.0
Benzene and Xylenes: Effect of Temperature 50 Ethylbenzene Conversion, wt.% 75.3 93.4
C7-C9 Paraffin Conversion, wt.% 70,3 100
catalyst 5% Moos, 3% WO3, 60% H-Mordenite/40% Al2O3 Ethylbenzene Concentration in
Example I II III C8 Aromatics, wt.% 0.7 3.1
Conditions (The C-C, paraffins in the feed consisted of (wt %); 2.8% n-heptane, (2.7
n-octane, and 0.1% n-nonane.
Temperature, F. 800 850 900
Pressure, psig 465 465 465 55
WHSV 3.8 3.5 3.6 The examples cited in Table III illustrate that the
Contact Time, sec. 14.0 4.8 14.8 conversion of ethylbenzene can be significantly in
H2/HC Mole ratio 6.4 6.3 5.8 creased by increasing the contact time. The increase in
Product Analysis, wt.% Yield, wt.% ethylbenzene conversion is accompanied by a corre
Feed sponding increase in benzene and ethane yield indicat
C1-C6 Paraffins
Methane
9.9
0.3
14.7
0.6
16.8
1.7
ing that the ethylbenzene is undergoing hydrodeethyla
Ethane 2.9 5.5 8.4 tion. A marked increase in C7-C9 paraffin conversion is
Propane 3.5 5.9 4.8 also achieved by increasing the contact time.
Butanes 2.5 2.2 6
Pentanes 0.6 0.5 0.3 65 EXAMPLES VI AND VII
Hexanes 0. a
C7-C8 Paraffins() 5.6 ---
The conditions of Examples IV and V were repeated
Benzene 2.7 20.2 20.3 20.8 but with an increased hydrogen to hydrocarbon mole
Toluene 65. 39.4 37. 36.4 ratio. The results appear in Table IV.
 4, 150,061
11 12
TABLE IV temperature within the range of from 600 to about
Conversion of Pyrolysis Gasoline Fraction to 1000 F., a pressure in the range of from about 100 to
Xylenes and Benzene: Effect of H2:HC Ratio 1000 psig, a hydrogen to hydrocarbon mole ratio of
Catalyst. 5% Moo3, 3% WO3, 60% H-Zeolon/40% Al2O3 from about 1:1 to 50:1, a contact time within the range
Example VI VII of between 1 to 20 seconds and a catalyst composition
Conditions: comprising a tungsten/molybdenum component of
Temperature, F. 850 850 WO3 and MoC)3 with an acidic component of mordenite
Pressure, psig 465 465 on a high surface area alumina support.
WHSV 254 12.2 2. The process of claim 1 wherein the said tungsten/-
Contact Time, sec,
H2/HC Mole Ratio
3.1
3.9
3.1
9.
10 molybdenum component comprises tungsten being
Product Analysis Yield, wt.% present in an amount within the range of from about 1 to
Feed 10 (wt) 7% expressed as WO3 and molybdenum being
C to C6 Paraffins - 4.1 9.2
present in an amount within the range of from about 1 to
Methane 0. 0.2 20 (wt) %, expressed as MoO3 and based upon the
Ethane 0.9 2.7 15 weight of the catalytic composition.
Propanes 1.5 2.9 3. The process of claim 1 wherein the said acidic
Butanes 1.3 2.
Pentanes 0.2 0.7 component of mordenite and high surface area alumina
Hexanes 0. comprises the said mordenite being present in an
C7 to C9 Paraffins() 6.0 .2 0.3
20
amount within the range of from 5 to about 95 (wt) %
Benzene
Toluene
2.9
64.6
13.6
49.0
18.9
42.4
and the catalytically active alumina being present in an
Ethylbenzene 10.8 3.7 1.5 amount within the range of from 95 to 5 (wt) %.
Xylenes 13.9 20.1 21.6 4. The process of claim 1 wherein the said catalyst
C9. Aromatics 1.8 7.4 5.8 composition comprises a tungsten/molybdenum com
C10 Aromatics O.7 0.6
25
ponent of 3 (wt) 9% WO3 and 5 (wt) 9%. MoO3 of total
Toluene Conversion, wt.% 24.1 34.4 weight of said catalytic composition and an acidic com
Ethylbenzene Conversion, wt.% 65.2 91.9 ponent comprising 60 (wt) 9% mordenite and 40 (wt) 9%
C7-C9 Paraffin Conversion, wt.% 86.8 95.8 catalytically active alumina of total weight of said
Ethylbenzene Concentration in
C8 Aromatics, wt.% 15.7 6.3 acidic cracking component.
(The C-C paraffins in the feed consisted of (wt.%); 2.4% n-heptane, 3.5% 30 5. The process of claim 4 wherein the said mordenite
n-octane, and 0.1% n-nonane. is in the hydrogen form and the said alumina is gamma
alumina.
The examples cited in Table IV show that ethylben 6. The process of claim 1 wherein said catalyst com
zene conversion to benzene and ethane, as well as the position comprises the sulfided form.
conversion of C7-C9 paraffins can be increased by in 35
7. The process of claim 1 wherein the said reaction
creasing the H2/HC mole ratio in the feed. products are separated from unreacted feedstocks.
What is claimed is: 8. The process of claim 1 wherein the said hydrogen
1. A process for producing ethylbenzene-lean xylenes to hydrocarbon mole ratio is from about 4:1 to 10:1 at
and benzene wherein a fractionated pyrolysis gasoline approximately 465 psig.
aromatics stream which boils within a range from about 9. The process of claim 1 wherein the said contact
230 to 340 F., comprising toluene, C7-C9 paraffins, time is from 3 to 10 seconds.
olefins, naphthenes, ethylbenzene and xylenes is mixed 10. The process of claim 1 wherein the said tempera
with hydrogen, and subjected to a hydrodealkylation/- ture is within the range from about 750 to 950 F.
transalkylation reaction under conditions including a : s k

45

50

55

65
 UNITED STATES PATENT OFFICE
CERTFHCATE OF CORRECTION
Patent No. 4150 06 Dated April 17, 1979 --
Inventor(s) Allen I. Feinstein and Un K. In
It is certified that error appears in the above-identified patent
and that said Letters Patent are hereby corrected as shown below:
Patent
Colum Line
1. 19 'aromatic-ring" should be --aromatic-rich--
3 11-12 "non-aromatics selectively' should be
--non-aromatics is selectively.--
O 31 "Temperature, 20°F" should be --Temperature, °F--
O 53 '' (2.7 n-octane," should be - -2.7% n-octane--
l 9 "254" should be - -25. 4.--
Table IW Entries for "Methane' are shifted one space to
the left
eigned and Sealed this
Twelfth Da y of August 1980
SEAL
Attest:

SDNEY A. DAMOND
Attesting Officer Commissioner of Patents and Trademarks