USOO5959168A

United States Patent (19) 11 Patent Number: 5,959,168

Van der Aalst et al. (45) Date of Patent: Sep. 28, 1999

54) ZEOLITE-BASED ETHYLABENZENE 4,992,606 2/1991 Kushnerick et al. ................... 585/467

PROCESS ADAPTABLE TO AN ALUMINUM 5,004,841 4/1991 Lee et al. ................................ 568/678
CHLORIDE-BASED ETHYLBENZENE 5,081,323 1/1992 Innes et al. . 585/449
PLANT 5,145,817 9/1992 Sherrod ---- ---------- -- - 502/6S

5,149,894 9/1992 Holtermann et al. ................... 585/467

75 Inventors: Matheus J. M. van der Aalst; E. 3.
2----- Y-2
Casci et al. ...............................585/467
/1993 Lee et al. ........
208/46
Mohammed S. U. Samson, both of 5,236,575 8/1993 Bennett et al. ........................... 208/46
Terneuzen, Netherlands, Garmt R. 5,243,116 9/1993 Lee et al. ................................ 585/467
Meima, Midland, Mich.; Michael O. de 5,258.565 11/1993 Kresge et al. .......................... 585/467
Steenwinkel, Philippine, Netherlands 5,430.211 7/1995 Pogue et al. ............................ 585/323
5,453,554 9/1995 Cheng et al. ........................... 585/467
73 Assignee: The Dow Chemical Company, 5,600,048 2/1997 Cheng et al. ........................... 585/449
Midland, Mich. FOREIGN PATENT DOCUMENTS
21 Appl. No.: 08/945,595 0366515 A1 5/1990 European Pat. Off..
1.-1. 0537389 A1 4/1993 European Pat. Off..
22 PCT Filed: Oct. 1, 1997 0432814 B1 9/1995 European Pat. Off..
86 PCT No.: PCT/US97/17844 WO 94/29245 12/1994 WIPO.
WO95/11196 4/1995 WIPO.
371 Date: Feb. 17, 1998
S C eD. If, OTHER PUBLICATIONS
S 102(e) Date: Feb. 17, 1998 K. Weissermel and H.-J. Arpe, Industrial Organic Chemis
87 PCT Pub. No.: WO98/14417 try, 2nd ed., VCH Verlagsgesellschaft, Weinheim, Germany,
1993, pp. 333-336.
PCT Pub. Date:Apr 9, 1998
Primary Examiner-Glenn Caldarola
Related U.S. Application Data Assistant Examiner Thuan D. Dang
Attorney, Agent, or Firm Marie F. Zuckerman
63 Continuation-in-part of application No. 08/724,748, Oct. 2,
1996, abandoned. 57 ABSTRACT
51) Int. Cl. ............................... C07C 1/00; CO7C 2/64; A zeolite-based ethylbenzene process which is suitable for
C07C 2/68; C07C 5/22 retrofitting aluminum chloride-based ethylbenzene plants.
52 U.S. Cl. .......................... 585/323:585/313; 585/316; The process involves alkylating benzene with ethylene in an
585/450; 585/467; 585/475 alkylation Zone in the presence of Zeolite beta or Y or an
58 Field of Search ..................................... 585/323,312 MCM Zeolite so as to produce an alkylation product mixture
585/316, 450 467 475 containing benzene, ethylbenzene, and polyethylbenzenes
s s s which can be separated in the aromatics recovery
56) References Cited (distillation) stage of an aluminum chloride-based plant. The
polyethylbenzenes are Subsequently contacted with benzene
U.S. PATENT DOCUMENTS in a transalkylation Zone using Zeolite beta or mordenite or
4,358.362 11/1982 Smith et al. .............................. 2080, YSO as to produce a transalkylation product mixture which
4.459.426 7/1984 Inwood et al. ... ... 585/323 is also separable in the aromatics recovery stage of an
4,665,255 5/1987 Chang et al. ... ... 585/467 aluminum chloride-based plant.
4,798.816 1/1989 Ratcliffe et al. . ... 502/62
4,891,458 1/1990 Innes et al. ............................. 585/323 19 Claims, 1 Drawing Sheet

(NEW) REACTION STAGE (EXISTING) AROMATICRECOVERY STAGE

BENIENE
STMiO SMFO

STMIHO

2. SMIHO

4.
S,
8
". 9
l i RESIDE
MBE SINGLE BED BENZENE EHYBENIENE PEB
ALKYATOR RASALKYLATOR RECOVERY RECOVERY RECOVERY
U.S. Patent Sep. 28, 1999 5,959,168

| | |
 5,959,168
1 2
ZEOLITE-BASED ETHYLABENZENE disclosed for alkylation, including mordenite, ZSM-5, ZSM
PROCESS ADAPTABLE TO AN ALUMINUM 11, ZSM-12, Y, omega, EU-1, NU-87, beta, MCM-22,
CHLORIDE-BASED ETHYLBENZENE MCM-36, MCM-49, MCM-56, MCM-58, and SSZ-25. With
PLANT regard to the use of dealuminated acid mordenite Zeolite in
the ethylation of benzene, reference is made, for example, to
CROSS REFERENCE TO RELATED U.S. Pat. Nos. 5,004,841, 5,198,595, and 5,243,116. With
APPLICATIONS regard to the use of Zeolite ZSM-5, reference is made to U.S.
This application claims the benefit of international appli Pat. No. 4,665,255. For alkylations with zeolites ZSM-11
cation no. PCT/US97/17844, filed Oct. 1, 1997, which and ZSM-12, reference is made to U.S. Pat. No. 4,358,362.
claims the benefit and is a continuation-in-part of application With regard to the use of Zeolite EU-1, reference is made for
Ser. No. 08/724,748, now abandoned, filed Oct. 2, 1996. example to EP-A1-0,537,389; for Zeolite NU-87 to U.S. Pat.
This invention relates to a process of alkylating benzene No. 5,178,748; for Zeolite beta, reference is made, for
with ethylene in the presence of a catalytic Zeolite to form example, to U.S. Pat. No. 4,891,458 and to U.S. Pat. No.
ethylbenzene. 5,081,323; for Zeolite Y to U.S. Pat. No. 4,459,426 and to
Ethylbenzene is used to prepare Styrene from which 15 U.S. Pat. No. 4,798,816 and to U.S. Pat. No. 4876,408; for
polystyrene is prepared. Zeolite MCM-22 to U.S. Pat. No. 4,992,606; for Zeolite
Historically, ethylbenzene is commercially manufactured MCM-36 to U.S. Pat. No. 5,258,565; for Zeolite MCM-49 to
by the liquid phase alkylation of benzene with ethylene in U.S. Pat. No. 5,236,575 and PCT publication WO94/29245;
for MCM-56 to U.S. Pat. No. 5.453,554; for MCM-58 to
the presence of a Friedel-Crafts catalyst, most typically WO95/11196; and for SSZ-25 to U.S. Pat. No. 5,149,894.
aluminum chloride. Hydrogen chloride may be required as Zeolites offer Several advantages over aluminum chloride;
a co-catalyst. (See, for example, K. Weissermel and H.-J. most notably, Zeolites are environmentally harmless and
Arpe, Industrial Organic Chemistry, 2" ed., VCH Press, non-corrosive. Additionally, alkylations with Zeolite cata
Weinheim, Germany, 1993, pp. 333-336.) An aluminum lysts do not require catalyst preparation and neutralization
chloride ethylbenzene plant typically comprises a benzene 25 Stages. Even more advantageously, the waste problems
drying Stage, a catalyst preparation Stage, an alkylation
Stage, a transalkylation Stage, a neutralization and catalyst asSociated with aluminum chloride-based ethylbenzene
disposal Stage, and an aromatic product recovery plants are eliminated.
(distillation) stage. On the other hand, Zeolite catalysts may possess different
AS regards the alkylation Stage, the Selectivity to ethyl energy and feed composition requirements and may produce
benzene is enhanced by using a high benzene/ethylene molar different isomeric and by-product mixtures from an alumi
ratio, typically around 3:1. Nevertheless, the product mix num chloride catalyst. For example, the gas phase alkylation
ture obtained from the alkylation contains benzene, of benzene to ethylbenzene over Zeolite ZSM-5 produces
ethylbenzene, and polyethylbenzenes including Xylenes as undesirable by-products. Moreover, gas phase
diethylbenzenes, triethylbenzenes, tetraethylbenzenes, and 35
processes typically possess higher energy levels than an
optionally higher polyethyl-benzenes. The alkylation prod aluminum chloride-based process. AS another disadvantage,
uct mixture is fed to a transalkylation reactor and contacted Zeolite-based ethylbenzene plants are generally grass-roots
with a transalkylation catalyst, Such as an aluminum chlo designs which customize the benzene alkylation,
ride complex. A transalkylation product mixture is obtained transalkylation, and product recovery Stages to the activity
having a composition close to that expected for thermody 40
and Selectivity of the Zeolite employed. Such plants require
namic equilibrium, which provides the maximum attainable a significant expenditure of capital.
ethylbenzene. The product mixture from the transalkylator, It would be advantageous from an environmental and
after neutralization, is separated in the aromatics recovery economic point of View, if an aluminum chloride-based
Stage of the plant which typically comprises a three column ethylbenzene plant could be retrofitted with Solid acid alky
distillation train. The first column recovers benzene which 45 lation and transalkylation catalysts, So as to convert the plant
may then be recycled to the alkylation reactor or to the into a Zeolite-based facility. In order to obtain the increased
transalkylation reactor. The Second column recovers the economic advantages of a retrofit design, however, the
desired ethylbenzene end-product. The third column recov pre-existing aromatics recovery (distillation) stage of the
erS diethylbenzenes and triethylbenzenes, and if present, aluminum chloride-based plant must be essentially unmodi
higher polyethylbenzenes. 50 fied. This can best be accomplished, if the product mixture
An aluminum chloride-based ethylbenzene plant has Sev derived from the Zeolite-based process is a close match to
eral disadvantages, among them, the corrosiveness of the the product mixture derived from the aluminum chloride
alkylation catalyst and proceSS Streams. Accordingly, high based plant. Such a Successful conversion of an aluminum
investment and maintenance costs are incurred to ensure that chloride-based ethylbenzene plant into a Zeolite-based eth
numerous parts of the plant are corrosion resistant. In 55 ylbenzene plant would provide the multiple benefits of
addition, the aluminum chloride catalyst, which is dissolved Zeolite catalysis at Significantly reduced capital investment.
or Suspended in the reaction mixture, must be removed from SUMMARY OF THE INVENTION
the product Stream and disposed. Removal is effected by
neutralization via an elaborate Series of aqueous and caustic This invention is a Zeolite-based ethylbenzene process
washes. Increased expenditures are required for the catalyst 60 which is suitable for retrofitting an aluminum chloride-based
preparation and neutralization Stages of the plant. AS a ethylbenzene plant. The proceSS broadly comprises three
further disadvantage, an aluminum-containing waste is Stages. In the first Stage, which is conducted in an alkylation
obtained whose disposal can create Significant environmen Zone, benzene is contacted with ethylene in at least a partial
tal problems. liquid phase at a total benzene/ethylene molar ratio between
It is known that the alkylation of benzene with ethylene to 65 1.5:1 and 3.0:1 in the presence of a catalytic amount of an
form ethylbenzene can be catalyzed by a Solid acid, alkylation catalyst Selected from acidic Zeolites beta, Y,
Specifically, an acidic Zeolite. Many Zeolites have been MCM-22, MCM-36, MCM-49, and MCM-56. The contact
 5,959,168
3 4
ing is conducted under proceSS conditions Sufficient to corrosive, therefore plant maintenance costs are lower.
prepare an alkylation product mixture comprising benzene, Moreover, Zeolite-based plants do not require the elaborate
ethylbenzene, and polyethylbenzenes, including and expensive neutralization and waste disposal Stages of
diethylbenzenes, and higher molecular weight residues. aluminum chloride-based plants. Additionally, retrofitting an
Under the contacting conditions described herein the existing plant expends significantly leSS capital than install
diethylbenzenes/ethylbenzene weight ratio in the alkylation ing a new plant from a grass-roots design. As a further
product mixture ranges from 1:2.5 to 1:8.0. advantage, the liquid phase Zeolite-based process of this
In the Second Stage of the novel retrofit process of this invention requires less energy input than other Zeolite-based
invention, the alkylation product mixture is Separated in an processes, and beneficially produces little or no unwanted
aromatics recovery Stage designed for an aluminum Xylenes. Finally, in the alternative embodiment of this
chloride-based plant. Specifically, the alkylation product invention wherein the heat generated from the alkylation
mixture is passed into a three-column distillation train. Stage is used to operate the distillation Stage and preheat the
Benzene is recovered in the first column. Thereafter, the alkylation and transalkylation Stages, the process of this
bottoms from the first distillation column comprising invention advantageously requires essentially Zero-energy
ethylbenzene, polyethylbenzenes, and higher molecular 15 input. Such a reduction in energy input translates into further
weight residues are passed into a Second distillation column economic Savings.
to recover ethylbenzene. Thereafter, the bottoms from the BRIEF DESCRIPTION OF THE DRAWING
Second distillation column comprising polyethylbenzenes
and higher molecular weight residues are passed into a third The FIGURE is a drawing of a zeolite-based ethylbenzene
distillation column to recover polyethylbenzenes including plant which is Suitable for retrofitting an aluminum chloride
diethylbenzenes. based ethylbenzene plant.
In the third stage of the novel retrofit process of this DETAILED DESCRIPTION OF THE
invention, the polyethylbenzenes which are recovered from INVENTION
the third distillation column are passed into a transalkylator 25
wherein the polyethylbenzenes are contacted with benzene The novel invention described herein is a zeolite-based
in the liquid phase at a molar ratio of total moles of benzene process for producing ethylbenzene which is particularly
groups on the benzene and polyethylbenzenes to total moles well adapted for retrofitting an aluminum chloride-based
of ethyl groups on the polyethylbenzenes ranging from 1.5:1 ethylbenzene plant. The proceSS involves three Stages. More
to 3.0:1. The contacting occurs in the presence of a catalytic particularly, the process involves the Selection of Specific
amount of a transalkylation catalyst Selected from acidic alkylation and transalkylation catalysts and Specific molar
Zeolites mordenite, beta, and Y. The contacting is conducted ratioS of reactants So as to produce alkylation and transalky
under reaction conditions Sufficient to produce a transalky lation product Streams which closely match the product
lation product mixture containing benzene, ethylbenzene, Streams obtained from an aluminum chloride-based process.
and polyethylbenzenes, including diethylbenzenes Such that 35 The product Streams are matched with respect to chemical
the weight ratio of the diethylbenzenes to ethylbenzene composition and with respect to the relative amounts of
ranges from 1:2.5 to 1:8.0. components. As a consequence, the alkylation and transalky
Finally, the transalkylation product mixture is passed into lation product Streams derived from the process of this
the aforementioned distillation train, and thereafter the tran invention can be readily Separated in the pre-existing aro
Salkylation product mixture is separated in the three distil 40 matics recovery stage of an aluminum chloride-based eth
lation columns mentioned hereinbefore to recover benzene, ylbenzene plant.
ethylbenzene, and polyethylbenzenes. In the first stage of the novel retrofit process of this
In an additional embodiment of this invention, the heat invention, fresh benzene (Feed 2, FIG. 1) or recycle benzene
generated from the alkylation Stage is used to operate the (Feed3, FIG. 1) is contacted with ethylene (Feed 1, FIG. 1)
distillation Stages and/or preheat the feedstreams of the 45 in at least a partial liquid phase in an alkylation Zone at a
alkylation and transalkylation Stages. total benzene/ethylene molar ratio between 1.5:1 and 3.0:1
The unique Selection in this invention of Specific Solid and in the presence of a catalytic amount of a Zeolitic
acid alkylation catalysts with Specific molar ratioS of alky alkylation catalyst. Preferably, the total benzene/ethylene
lation reactants produces an alkylation product mixture molar ratio varies between 1.7:1 and 2.5:1. The catalyst is
having a diethylbenzenes/ethylbenzene weight ratio 50 Selected from acidic zeolites beta, Y, MCM-22, MCM-36,
between 1:2.5 and 1:8.0. Significantly, an alkylation product MCM-49, and MCM-56. The alkylation process conditions,
mixture of this composition is readily Separated in the described in detail hereinbelow, are Sufficient to prepare an
pre-existing distillation columns of an aluminum chloride alkylation product mixture containing benzene,
based ethylbenzene plant. Essentially no modification of the ethylbenzene, and polyethylbenzenes including
distillation Stage is required. Likewise, the Selection in this 55 diethylbenzenes, triethylbenzenes, and optionally tetra,
invention of specific transalkylation Solid acid catalysts with penta, and hexaethylbenzenes, as well as, a higher molecular
Specific molar ratioS of transalkylation reactants gives rise to weight residue. Under the conditions described herein, the
a transalkylation product mixture having a diethylbenzenes/ diethylbenzenes/ethylbenzene weight ratio in the product
ethylbenzene weight ratio between 1:2.5 and 1:8.0. Here too, mixture ranges from 1:2.5 to 1:8.0, preferably, from 1:4.0 to
the Separation of the transalkylation product mixture is 60 1:7.0 Additionally, under the process conditions described
readily adapted to the pre-existing distillation Stages of an herein the benzene/ethylbenzene weight ratio in the alkyla
aluminum chloride-based ethylbenzene plant. tion product typically varies from 1:1 to 2:1.
In view of the above, the process of this invention is The alkylation reactor in which the benzene is contacted
usefully employed to convert an aluminum chloride-based with the ethylene is suitably a continuous flow reactor
ethylbenzene plant into a Zeolite-based ethylbenzene plant. 65 wherein the catalyst may occupy a fixed-bed, slurry bed, or
Zeolite catalysts eliminate the many disadvantages of an fluidized bed. Preferably, the catalyst is loaded into a fixed
aluminum chloride catalyst. For example, Zeolites are not bed. The alkylation reactor is beneficially designed to con
 5,959,168
S 6
trol the temperature close to isothermal conditions. purpose of increasing the catalyst's Strength and attrition
Accordingly, the heat obtained from the exothermic alkyla resistance. Suitable Supports include aluminas, Silicas,
tion reaction is removed directly by use of a shell and tube aluminosilicates, titania, and clayS. Preferably, the Support is
reactor design or indirectly by use of external heat eXchang an alumina or Silica.
CS. For a continuous mode of operation, any weight hourly
Benzene and ethylene are required for the alkylation Space Velocity of the total feed with respect to the catalyst is
proceSS and may be obtained from any commercial Source. beneficially employed which gives rise to a final alkylation
Optionally, the benzene may be dried before use, preferably, product Stream wherein the diethylbenzenes/ethylbenzene
by azeotropic distillation. Alternatively, the benzene may be weight ratio ranges from 1:2.5 to 1:8.0. The exact weight
dried over any Suitable Solid drying agent Selected, for hourly Space Velocity to be applied will depend on the
example, from aluminas, Silicas, Silica-aluminas, and Zeo intrinsic activity of the Zeolite under consideration. The
lites. Preferred drying agents include LTA Zeolites, Such as more active the Zeolite, the shorter the residence times that
3A, 4A, and 5A, as well as Linde brand zeolite 13X and
can be used. Typically, the weight hourly Space Velocity of
SELEXSORB(R) brand activated alumina (Alcoa Industrial the total feed comprising benzene and ethylene over the total
15 alkylation catalyst ranges from 5 grams total feed per gram
Chemicals). After drying, the water concentration in the catalyst per hour, or simply hr', to 100 hr', and preferably,
benzene feed is preferably reduced to a value less than 300 from 10 hr' to 20 hr'.
parts per million (ppm) by weight, and preferably, less than The alkylation Stage of this invention is carried out at any
200 ppm. temperature and pressure which give rise to a final alkylation
Optionally, the benzene feed may be pretreated before use product Stream wherein the diethylbenzenes/ethylbenzene
to remove oxygen which is capable of inhibiting the alky weight ratio ranges from 1:2.5 to 1:8.0. In addition, the
lation catalyst. A typical pretreatment procedure involves reaction conditions should be Sufficient to maintain at least
Sparging the liquid benzene feed with an oxygen-free Sparge one of the reactants or product compounds in at least partial
gas or passing the benzene over a reduced copper bed, as liquid phase, or alternatively in full liquid phase, in order to
described in U.S. Pat. No. 5,300,722. 25 retard catalyst fouling. Typically, benzene is introduced in
Benzene and ethylene may be introduced into the alky the liquid phase. Ethylene is then Supplied into each reaction
lation Zone as Separate feeds or as a combined feed. Further, Zone in Such a way that it dissolves into the benzene and/or
the benzene may be introduced to the alkylation Zone as a other product compounds. Typically, the contacting tem
Single feed Stream or Split into a plurality of feedstreams perature ranges between 100° C. and 300° C., preferably,
which are introduced into the reactor at different locations. between 200° C. and 265 C. The pressure should be
Ethylene, on the other hand, is beneficially split into a Sufficient to keep the alkylating agent Substantially in
plurality of feedstreams which are introduced into the reac Solution, but not So high as to accelerate catalyst deactiva
tor at different locations. A preferred design comprises a tion. Pressures between 10 bargauge (barg) (1,000 kPa) and
plurality of catalyst-containing reaction Zones in fluid con 50 barg (5,000 kPa), and preferably, between 25 barg (2,500
nection in Series. In this design, the entire benzene feed is 35 kPa) and 35 barg (3,500 kPa), are suitably employed.
delivered to the first reaction Zone, while a Series of fractions If the alkylation Stage is designed and run as described
of ethylene is delivered respectively to the first reaction Zone hereinabove with a total benzene/ethylene molar ratio of
and between each pair of contiguous reaction Zones. The between 1.5:1 and 3.0:1, then ethylbenzene is typically
reaction Zones may be operated with the same or different produced in at least 65 percent Selectivity. For the purposes
alkylation catalysts and at the same or different temperatures 40 of this invention, the ethylbenzene selectivity is defined as
and Space Velocities. More preferably, three to twenty the mole percentage of converted benzene which forms
catalyst-containing reaction Zones are used and a corre ethylbenzene. Diethylbenzenes are also produced, primarily
sponding number of alkylating agent Streams. Increasing the as the para and meta isomers. Triethylbenzenes and option
number of catalyst beds augments the ethylbenzene ally tetraethylbenzenes, pentaethylbenzenes, and hexaethyl
Selectivity, as compared with Supplying the whole of the 45 benzenes may also be produced. A total Selectivity to mono-,
alkylating agent to the first reaction Zone. Furthermore, by di-, and triethylbenzenes of at least 95 mole percent, and
feeding the alkylating agent as a Series of fractions, a better preferably, at least 99.0 mole percent is achieved. These
control of the reaction temperature is possible for this selectivities compare favorably with the selectivities found
exothermic reaction. in an aluminum chloride-based ethylbenzene process.
The catalyst required for the alkylation Stage is Selected 50 In the Second Stage of the retrofit process of this invention,
from acidic crystalline aluminosilicates beta, Y, MCM-22, the alkylation product mixture is separated into its constitu
MCM-36, MCM-49, and MCM-56. Zeolite beta is originally ent parts. Separation is effected by distillation in an aromat
described in U.S. Pat. No. 3,308,069 and U.S. Re 28,341, ics recovery Zone which is designed for an aluminum
and later described in U.S. Pat. Nos. 4,891,458 and 5,081, chloride-based ethylbenzene plant. In the distillation
323. Zeolite Y is described in U.S. Pat. No. 3,130,007, and 55 Sequence, the alkylation product stream (Feed 4, FIG. 1) is
modified forms thereof are described in U.S. Pat. No. fed into a first distillation column wherein benzene (Stream
4,459,426 and 4,798,816. Zeolite MCM-22 is described in 3, FIG. 1) is recovered. The recovered benzene may be, in
U.S. Pat. No. 4,992,606. Zeolite MCM-36 is fully described whole or in part, recycled to the alkylation Stage or fed into
in U.S. Pat. No. 5,258.565. A description of MCM-49 is the transalkylation stage. Thereafter, the bottoms (Stream 7,
found in WO 94/29245, and MCM-56 is found in U.S. Pat. 60 FIG. 1) from the first distillation column comprising
No. 5,453,554. Modified forms of the aforementioned ethylbenzene, polyethylbenzenes, and higher molecular
Zeolites, including these Zeolites as modified by acid, Steam, weight residues are passed into a Second distillation column
or heat treatments or by ion-exchange or impregnation with wherein substantially pure ethylbenzene (Stream 11, FIG. 1)
metal ions, may also be employed. Preferably, the alkylation is recovered. Subsequently, the bottoms (Stream 8, FIG. 1)
catalyst is acidic zeolite beta, MCM-22, or Y. 65 from the Second distillation column comprising polyethyl
Optionally, the alkylation catalyst may be bound to, benzenes and higher molecular weight residues are passed
Supported on, or extruded with any Support material for the into a third distillation column wherein diethylbenzenes, and
 5,959,168
7 8
optionally triethylbenzenes and tetraethylbenzenes are Steam, or other treatments known to those skilled in the art
recovered. This third fraction (Stream 10, FIG. 1), prefer may also be employed.
ably containing little or essentially no higher molecular The transalkylation Zone is generally conceived as a
weight residues, is fed to the transalkylation reactor. A Single catalyst bed, preferably a fixed-bed design, which
residue (Stream 9, FIG. 1) is also recovered as bottoms from operates in a continuous mode with a liquid phase reactant
the third distillation column. stream (Stream 6, FIG. 1). The polyethylbenzenes are fed
The above-described distillation train should also possess into the transalkylation Zone typically without any pretreat
conventional design features and operational parameters ment. If the benzene is obtained from the distillation Stage,
suitable for the distillation of a product stream obtained from then no pretreatment of the benzene is required.
an aluminum chloride-based ethylbenzene plant. Design Alternatively, if the benzene is obtained from a fresh com
features include, for example, the Size of the columns and mercial Source, then it may be desirable to pretreat the
the number of plates in each column. Operational parameters benzene as mentioned hereinabove in connection with the
include, for example, column temperature, column pressure, alkylation process. The benzene and polyethylbenzenes may
and liquid and vapor flow rates. A variety of well-known be fed as a combined feed or a split feed.
heat Sources can be used to drive the distillations, including 15 Any transalkylation process conditions can be employed
Steam, hot oils, and furnaces. Since the heat Source influ in the transalkylation Zone provided that the transalkylation
ences the operating conditions of the distillation column, it product mixture contains benzene, ethylbenzene and dieth
is difficult to render a detailed description of all of the ylbetzenes in a diethylbenzenes/ethylbenzene weight ratio
process conditions which may be operable. Generally between 1:2.5 and 1:8.0, and preferably, between 1:4.0 and
Speaking, any temperature and pressure can be employed in 1:7.0. For example, the ratio of total moles of benzene
the distillations provided that the desired component of the groups in the benzene and polyethylbenzenes to total moles
product Stream is Separated and recovered. As a general of ethyl groups on the polyethylbenzenes should vary from
guideline, the first distillation column which Separates ben 1.5:1 to 3.0:1. Typically, the temperature ranges from 150
Zene typically operates at atmospheric pressure and at a C. to 270° C., and preferably, from 225°C. to 250° C. Below
temperature between 130 C. and 170° C. Typically, the 25 150 C. the catalyst activity may be too low, and the catalyst
Second distillation column which Separates ethylbenzene lifetime may be adversely affected. Above 270° C. the
operates at a pressure of greater than 1 barg (100 kPa) up to overall selectivity to ethylbenzene may decrease. Sufficient
3 barg (300 kPa) and at a temperature between 180° C. and preSSure is employed to keep the reactants in the liquid
240 C. Typically, the third distillation column operates at a phase. Normally, the pressure ranges between 20 barg (2,000
temperature between 180° C. and 240° C. and under kPa) and 40 barg (4,000 kPa), and preferably, between 25
Vacuum. The aforementioned distillation conditions are barg (2,500 kPa) and 35 barg (3,500 kPa). In order to reach
purely exemplary of the many conditions which one skilled an acceptable level of polyethylbenzenes conversion of from
in the art may use to separate the desired end-products. 40 to 60 weight percent, the residence time of the overall
Accordingly, the process of this invention should not be transalkylation feedstream in the transalkylation Zone is high
limited solely to the distillation conditions mentioned 35 resulting in a weight hourly Space Velocity ranging between
herein, So long as the conditions are Suitable for a product 0.5 hr' and 10 hr', and preferably, between 1 hr' and 3
stream obtained from an aluminum chloride-based ethylben hr.
Zene plant. The product composition from the transalkylation Stage is
In the third Stage of the retrofit process of this invention, Similar to that of the alkylation Stage, both in chemical
at least a portion of the polyethylbenzenes (Stream 10, FIG. 40 composition and relative amounts of components.
1) Separated in the aromatics recovery stage is fed into a Accordingly, the transalkylation product stream (Stream 5,
transalkylation Zone wherein they are contacted with fresh FIG. 1) is fed together with the alkylation product stream
benzene (Stream 2, FIG. 1) or alternatively recycle benzene into the aromatics recovery Stage, described hereinabove,
(Stream 3, FIG. 1) from the benzene recovery stage in the which is designed for an aluminum chloride-based ethyl
presence of a catalytic amount of a transalkylation catalyst. 45 benzene plant. Specifically, the transalkylation product mix
The catalyst is Selected from acid Zeolites mordenite, beta, ture is fed into the first distillation column where benzene is
and Y. Zeolite mordenite is described by R. Szostak in recovered. The bottoms from the first distillation column
Handbook of Molecular Sieves. Structure, Synthesis, and containing ethylbenzene and polyethylbenzenes are fed into
Properties, Chapman & Hall, New York, N.Y., 1992. A the Second distillation column where ethylbenzene is recov
preferred form of mordenite Zeolite is set forth in U.S. Pat. 50 ered; and the bottoms from the second distillation column
No. 5,004.841 and related U.S. Pat. Nos. 5,175,135, and are fed into the third distillation column wherein polyeth
5,198,595. This preferred mordenite is an acidic mordenite ylbenzenes are recovered.
having a Silica/alumina molar ratio of at least 30:1 and a It is noted that the distillation Stages and the preheating of
Symmetry Index, as determined by X-ray diffraction, of at the alkylation and transalkylation Stages of the process of
least 1.0. The Symmetry Index is defined as the sum of the 55 this invention require a Source of heat, whereas the alkyla
peak heights of the 111 (13.45, 20) and 241 (23.17, 20) tion Stage, which involves an exothermic reaction, produces
reflections divided by the peak height of the 350 (26.25, heat. Accordingly, in an alternative embodiment of this
20) reflection. This preferred mordenite is prepared by (1) invention, the design of this proceSS can incorporate a means
heating a mordenite having a Silica/alumina molar ratio of for transferring the heat produced from the alkylation Stage
less than 30:1 and a Symmetry Index of between 0.5 and 1.0, 60 to the distillation Stages and/or the preheating of the alky
and thereafter (2) treating the heated mordenite with Strong lation and transalkylation Stages, including for example,
acid So as to remove an amount of alumina Sufficient to Steam generation or conventional heat transfer fluids or a
provide a Silica/alumina molar ratio of at least 30:1, and (3) shell and tube reactor design. When the heat from the
optionally, repeating the heating and Strong acid treatments alkylation Stage is used to drive the distillation Stages of this
to remove additional alumina. Citations for Zeolites beta and 65 process and preheat the feedstreams of the alkylation and
Y were set forth hereinbefore with respect to the alkylation transalkylation Stages of this process, and when the three
catalysts. Beta, mordenite, and Y Zeolites modified by acid, Stages of the process are run in accordance with the preferred
 5,959,168
9 10
reaction conditions described hereinabove, then the retrofit EXAMPLE 1.
process of this invention advantageously requires essentially
Zero-energy input. Only Small amounts of energy may be Alkylation with Zeolite Beta Catalyst
needed to run peripheral machinery, Such as the compressors Benzene was alkylated with ethylene in the presence of
and pumps. acidic zeolite beta to ethylbenzene. The beta Zeolite (10g,
This invention will be further clarified by a consideration PQ Zeolites B.V., CP861 DL-25) having a SiO/Al2O
of the following examples which are intended to be purely molar ratio of 24 and bound with alumina (20 percent) was
exemplary of the use of the invention. Other embodiments loaded into a continuous flow, fixed-bed tubular reactor (90
of the invention will be apparent to those skilled in the art cm lengthx18.9 mm internal diameter) with benzene and
from a consideration of this specification and from the split ethylene feeds (15 splits). The reactor was filled with
practice of the invention as disclosed herein. Unless other carborundum (SiC) at the bottom and top, with catalyst (25
wise noted, all percentages are given on a weight percent g) located in-between the carborundum layers. The benzene
basis. feedstock was dried over activated alumina (30 g SELEX
COMPARATIVE EXPERIMENT 1. 15 SORB(R) CDO brand, Alcoa) and thereafter passed over a
reduced copper bed (140 g, Cu-filter R-311, BASF) to
Alkylation with Aluminum Chloride Catalyst remove oxygen. A variety of benzene/ethylene molar ratioS
was tested between 1.5:1 and 2.5:1, as shown in Table I.
For comparative purposes with the examples, the alkyla Liquid phase reaction conditions were maintained. Products
tion of benzene with ethylene was conducted under conven were analyzed by on-line gas chromatography. The reaction
tional conditions with an aluminum chloride catalyst. A conditions, product distribution, and diethylbenzenes/
homogeneous alkylator was used at 170° C. and 6 barg (600 ethylbenzene weight ratio are set forth in Table I. Product
kPa) pressure. Catalyst provided 200 ppm aluminum to the Selectivities are set forth in Table II.
reaction. Benzene was dried in an azeotropic distillation When the results of Example 1 are compared with the
Section, but not treated further. Process conditions and results of Comparative Experiment 1, it is seen that the
results are set forth in Tables I and II. Zeolite beta catalyst produces an alkylation product Stream

TABLE I
Alkylation of Benzene with Ethylene as a Function of Catalyst and Benzene/Ethylene Molar Ratio
Ex.: CE 1 Ex2 Ex 1
Catalyst: AICI MCM-22 Beta
BZ/Etha 2.O 2.4 1.9 1.5 1.9 2.O 2.2 2.4 2.5
T (C.) 170 170 225 225 225 225 225 225 225
P bar 6 6 47 47 47 47 47 47 47
(kPa) 6OO 6OO 47OO 47OO 47OO 47OO 47OO 47OO 47OO
WHSV (hr) 5 5 5 5 5 5 5
BZP 48.5 56.7 46.3 37.3 47.3 49.2 53.1 55.0 57.2
EBP 40.2 32.8 42.4 45.O 40.9 40.O 37.9 36.7 35.4
DEBP 9.9 9.2 9.8 14.8 10.2 9.4 8.0 7.3 6.6
TEBb 0.5 O.8 1.1 2.O 1.2 1.O O.8 O.7 O6
Others 0.5 O.2 O.1 O.3 O.1 O1 O.O O.O O.O
Heavies 0.5 O.3 O.2 0.5 O.3 O.2 O.2 O.2 O.2
DEB/EBP 1:41 1:36 1:43 1:30 1:4.O 1f4.3 1f4.7 1/5.O 1/5.4

BZ/Eth = benzene/ethylene molar ratio.

Weight percentage in product stream: Bz = benzene: EB = ethylbenzene: DEB = diethylbenzenes; TEB =
triethylbenzenes; Others = Balance other products, excluding heavies. DEB/EB = weight ratio of diethylbenzenes
to ethylbenzene.

The product Selectivities, calculated as mole percentages, which is closely similar to the product Stream produced by
are set forth in Table II. 50 the aluminum chloride catalyst. Accordingly, the alkylation
product Stream from the beta-based proceSS can be separated
TABLE II in the aromatics recovery (distillation) stage of the alumi
num chloride-based plant without modification of the recov
Product Selectivities as a Function of Catalyst ery Stage.
55
Sel. CE 1 Ex. 1 Ex. 2 EXAMPLE 2
(mole %) AICI Beta MCM-22
Alkylation with Zeolite MCM-22 Catalyst
EB 82.2 82.8 82.9
DEB 16.O 15.4 15.3 The alkylation of benzene with ethylene was conducted as
TEB O6 1.4 1.4 60 described in Example 1 with the exception that acid Zeolite
Total EB + 98.8 99.6 99.6 MCM-22 (10 g) was used in place of Zeolite beta. MCM-22
PolyEB's was prepared according to the method described in U.S. Pat.
Product selectivities as mole percentages based on data in Table 1 for BZ/Eth
No. 5,334,795. Alkylation results are set forth in Tables I and
ratio of 2.0 (1.9 for MCM-22). II. When these results were compared with the results of
EB = ethylbenzene: DEB = diethylbenzenes; TEB = triethylbenzenes; 65 Comparative Experiment 1, it was seen that Zeolite MCM
PolyEB's = polyethylbenzenes. 22 produced an alkylation product Stream which was closely
Similar to the product Stream produced by the aluminum
 5,959,168
11 12
chloride catalyst. Accordingly, the alkylation product Stream sition obtained with aluminum chloride, Such that the
from the MCM-22-based process could be separated in the mordenite-based product can be separated in the aromatics
aromatics recovery (distillation) stage of the aluminum recovery Stage of an aluminum chloride-based plant.
chloride-based plant without modification of the plant.
EXAMPLE 4
COMPARATIVE EXPERIMENT 2.
Transalkylation with Beta Catalyst
Transalkylation with Aluminum Chloride Catalyst
Benzene was transalkylated with diethylbenzenes accord
The transalkylation of polyethylbenzenes with benzene ing to the procedure of Example 3, with the exception that
was conducted under conventional conditions with an exceSS the transalkylation catalyst was Zeolite beta having an SiO/
of aluminum chloride complex at 60° C. and atmospheric Al-O molar ratio of 24 (PQ Zeolite B.V., CP861 DL-25).
preSSure. A heterogeneous transalkylator was used with a The beta Zeolite was extruded with an alumina binder (20
Separate aluminum chloride complex phase. The polyethyl percent, based on weight of beta) into particles of 1.6 mm
benzenes feedstock containing mainly diethylbenzenes was diameter having a surface area of 441 m/g. Process condi
obtained from the alkylation of benzene with ethylene over 15 tions and results are set forth in Table III. When the results
a Zeolite beta catalyst. Benzene feedstock was dried in an of Comparative Experiment CE 2 were compared with the
azeotropic distillation section, but not treated further. Prod results of Example 4, it was concluded that the beta-based
uct distribution obtained was close to 95 percent of equi transalkylation produced a product composition Similar to
librium. Process conditions and results are set forth in Table the composition obtained with aluminum chloride, Such that
III the beta-based product could be separated in the aromatics
recovery Stage of an aluminum chloride-based plant.
TABLE III We claim:
Product Distribution in Transalkylation of 1. A Zeolite-based proceSS for producing ethylbenzene
Benzene with Diethylbenzenes which is suitable for retrofitting an aluminum chloride-based
25 ethylbenzene plant comprising:
Ex. 3 Ex. 4
Feedstream CE 2 Mordenite Beta (A) contacting benzene with ethylene in at least a partial
Composition AICI (100 g) (40 g) liquid phase in an alkylation reactor at a total benzene/
Bze 66.4 54.4 54.8 54.8
ethylene molar ratio between 1.5:1 and 3.0:1 in the
EBC 2.1 37.4 32.4 32.4
presence of a catalytic amount of an alkylation catalyst
DEB 30.6 8.5 11.5 11.5 Selected from acidic zeolites beta, Y, MCM-22, MCM
TEB O.O O.3 O.2 0.4 36, MCM-49, and MCM-56, the alkylation process
Others O.9 0.4 1.1 O.9 conditions being Sufficient to prepare an alkylation
DEB/EB 1:4.4 1:2.8 1:2.8 product mixture containing benzene, ethylbenzene,
DEB Conv 72.2 62.4 62.4
35
polyethylbenzenes including diethylbenzenes, and
aT = 245° C.: P = 35 bar (3,500 kPa); WHSV = 2 hr'; Bz/Eth = 2.3. higher molecular weight residues, the diethylbenzeneS/
T = 220° C.: P = 35 bar (3,500 kPa), WHSV = 2 hr'; Bz/Eth = 2.3. ethylbenzene weight ratio ranging from 1:2.5 to 1:8.0;
Weight percentage of component in stream: Bz = benzene; EB = ethylben
Zene; DEB = diethylbenzenes; TEB = triethylbenzenes; Others =Balance of (B) passing the alkylation product mixture into a distil
products. DEB/EB = diethylbenzenes?-ethylbenzene weight ratio. lation train designed for an aluminum-chloride based
Diethylbenzenes conversion given as mole percentage. 40 ethylbenzene plant wherein benzene is recovered in a
first distillation column; thereafter passing the bottoms
EXAMPLE 3 from the first distillation column comprising
ethylbenzene, polyethylbenzenes, and higher molecu
Transalkylation with Zeolite Mordenite Catalyst lar weight residues into a Second distillation column to
Mordenite Zeolite was evaluated as a catalyst in the 45 recover ethylbenzene, and thereafter passing the bot
transalkylation of benzene with diethylbenzenes. The tran toms from the Second distillation column comprising
Salkylation reactor was a continuous flow, fixed bed, tubular polyethylbenzenes and higher molecular weight resi
reactor (90 cm length by 18.9 mm internal diameter) oper dues into a third distillation column to recover poly
ating in an upflow mode. The reactor was filled with ethylbenzenes including diethylbenzenes,
carborundum (SiC) at the bottom and top with catalyst 50 (C) passing at least a portion of the polyethylbenzenes
located in-between the carborundum layers. An acidic recovered from the third distillation column into a
mordenite Zeolite having a SiO/Al2O molar ratio of 81 was transalkylator wherein the polyethylbenzenes are con
prepared according to the procedure described in U.S. Pat. tacted with benzene in the liquid phase at a molar ratio
No. 5,175,135 and then bound with silica (20 percent, based of total moles of benzenes in the benzene and polyeth
on weight of mordenite). The bound catalyst was in the form 55 ylbenzenes to total moles of ethyl groups on the poly
of extrudates (3 mm) having a surface area of 355 m /g. The ethylbenzenes ranging from 1.5:1 to 3.0:1 in the pres
polyethylbenzenes feedstock containing mainly diethylben ence of a catalytic amount of a transalkylation catalyst
Zenes was obtained from the alkylation of benzene with Selected from acid Zeolites mordenite, beta, and Y, the
ethylene over a Zeolite beta catalyst. The benzene feedstock contacting being conducted under reaction conditions
was dried over activated alumina (30 g Selexsorb CDO 60 Sufficient to produce a transalkylation product mixture
brand, Alcoa) and pretreated over a reduced copper bed (140 containing benzene, ethylbenzene, and polyethylben
g, Cu-filter R-311, BASF) to remove oxygen. Process Zenes including diethylbenzenes, the diethylbenzeneS/
conditions, feedstock and product compositions are Set forth ethylbenzene weight ratio ranging from 1:2.5 to 1:8.0;
in Table III. When the results of Comparative Experiment and
CE 2 are compared with the results of Example 3, it is 65 (D) passing the transalkylation product mixture into the
concluded that the mordenite-based transalkylation pro aforementioned distillation train wherein the transalky
duces a product composition similar enough to the compo lation product mixture is separated in the three distil
 5,959,168
13 14
lation columns mentioned hereinbefore to recover (A) contacting benzene with ethylene in at least a partial
benzene, ethylbenzene, and polyethylbenzenes. liquid phase in an alkylation Zone at a total benzene/
2. The process of claim 1 wherein the alkylation is ethylene molar ratio between 1.7:1 and 2.5:1 in the
conducted at a temperature ranging from 100° C. to 300° C. presence of an alkylation catalyst Selected from acidic
3. The process of claim 1 wherein the alkylation is Zeolites beta, Y, MCM-22, MCM-36, MCM-49, and
conducted at a pressure between 10 barg (1,000 kPa) and 50 MCM-56, the process being conducted at a temperature
barg (5,000 kPa). between 200° C. and 265 C., a pressure between 25
4. The process of claim 1 wherein the alkylation is barg (2,500 kPa) and 35 barg (3,500 kPa), and a weight
conducted at a weight hourly Space Velocity of the total hourly Space Velocity of the total feed containing
alkylation feed containing benzene and ethylene over total 1O
benzene and ethylene Over total alkylation catalyst of
alkylation catalyst ranging from 5 hr' to 100 hr'. from 10 hr' to 20 hr', so as to prepare an alkylation
5. The process of claim 1 wherein the total benzene to product mixture containing benzene, ethylbenzene, and
ethylene molar ratio ranges from 1.7:1 to 2.5:1. polyethylbenzenes including diethylbenzenes, and
6. The process of claim 1 wherein the alkylation catalyst
is zeolite beta or Zeolite MCM-22. 15 higher molecular weight residues, the diethylbenzeneS/
7. The process of claim 1 wherein the alkylation catalyst ethylbenzene weight ratio ranging from 1:2.5 to 1:8.0;
is Supported on Silica or alumina. (B) passing the alkylation product stream into a distilla
8. The process of claim 1 wherein a plurality of catalyst tion train designed for an aluminum chloride-based
containing reaction Zones in fluid connection in Series is ethylbenzene plant, wherein benzene is recovered in a
employed as the alkylation Zone, wherein the whole of the first distillation column; thereafter passing the bottoms
benzene is delivered to a first reaction Zone, and a Series of from the first distillation column comprising
fractions of ethylene are delivered respectively to the first ethylbenzene, polyethylbenzenes, and higher molecu
reaction Zone and between each pair of contiguous reaction lar weight residues into a Second distillation column to
ZOCS.
recover ethylbenzene, and thereafter passing the bot
9. The process of claim 8 wherein 3 to 20 catalyst 25
toms from the Second distillation column comprising
containing reaction Zones are used with a corresponding polyethylbenzenes and higher molecular weight resi
number of alkylating agent Streams. dues into a third distillation column to recover poly
10. The process of claim 1 wherein benzene is recovered ethylbenzenes,
from a distillation column operating at atmospheric pressure
and at a temperature between 130 C. and 170° C. (C) passing the polyethylbenzenes recovered from the
11. The process of claim 1 wherein ethylbenzene is third distillation column into a transalkylator wherein
recovered from a distillation column operating at a tempera the polyethylbenzenes are contacted with benzene in
ture between 180° C. and 240° C. and at a pressure of 1 barg the liquid phase at a molar ratio of total moles of
(100 kPa) to 3 barg (300 kPa). benzenes in the benzene and polyethylbenzenes to total
12. The process of claim 1 wherein polyethylbenzenes are 35 moles of ethyl groups on the polyethylbenzenes rang
recovered in a distillation column operating under Vacuum at ing from 1.5:1 to 3.0:1 in the presence of a transalky
a temperature between 180° C. and 240 C. lation catalyst Selected from acidic Zeolites mordenite,
13. The process of claim 1 wherein the transalkylation is beta, and Y, the contacting being conducted at a tem
conducted at a temperature ranging from 150° C. to 270° C. perature between 225 C. and 250 C., a pressure
14. The process of claim 1 wherein the transalkylation is 40
between 25 barg (2,500 kPa) and 35 barg (3,500 kPa),
conducted at a pressure ranging from 20 barg (2,000 kPa) to and a weight hourly Space Velocity of the total feed
40 barg (4,000 kPa). containing benzene and polyethylbenzenes over tran
15. The process of claim 1 wherein the transalkylation is salkylation catalyst of between 1 hr' and 3 hr', so as
conducted at a weight hourly Space Velocity of the total to produce a transalkylation product mixture of
transalkylation feedstream containing benzene and polyeth 45
benzene, ethylbenzene, and polyethylbenzenes includ
ylbenzenes over the transalkylation catalyst from 0.5 hr' to ing diethylbenzenes, wherein the weight ratio of dieth
10 hr.
16. The process of claim 1 wherein the transalkylation ylbenzenes to ethylbenzene ranges from 1:2.5 to 1:8.0;
catalyst is Zeolite beta. (D) feeding the transalkylation product mixture into the
17. The process of claim 1 wherein the heat generated 50 aforementioned distillation train wherein the transalky
from the alkylation Stage is used to operate the distillation lation product mixture is separated in the three distil
Stages and/or preheat the feedstreams of the alkylation and lation columns mentioned hereinbefore to recover
transalkylation Stages. benzene, ethylbenzene, and polyethylbenzenes, and
18. The process of claim 1 wherein the benzene to (E) optionally, using the heat generated in the alkylation
ethylbenzene weight ratio in the alkylation product mixture 55 reactor to operate the distillation Stages and preheat the
ranges from 1:1 to 2:1. feedstreams of the alkylation and transalkylation
19. A Zeolite-based process for producing ethylbenzene Stages.
which is suitable for retrofitting an aluminum chloride-based
ethylbenzene plant comprising: