United States Patent 19 11 4,107,224

Dwyer 45) Aug. 15, 1978

(54) MANUFACTURE OF ETHYL BENZENE 3,542,892 11/1970 Stoker et al. .................... 260/671 R
3,751,504 8/1973 Keown et al. ................... 260/671 R
75) Inventor: Francis G. Dwyer, West Chester, Pa. 4,016,218 4/1977 Haag................................ 260/671 R
73) Assignee: Mobil Oil Corporation, New York, Primary Examiner-Delbert E. Gantz
N.Y. Assistant Examiner-C. E. Spresser
21 Appl. No.: 767,855 Attorney, Agent, or Firm-Charles A. Huggett; Michael
G. Gilman; Raymond W. Barclay
22 Filed: Feb. 11, 1977
57 ABSTRACT
51) Int. Cl.' ................................................ C07C3/52
52 U.S. Cl. .................. ... 260/671 R; 260/671 C Benzene and dilute ethylene are reacted in vapor phase
58) Field of Search .......is esses see so so so so 260/671 R, 671 C over solid porous catalyst such as zeolite ZSM-5 in a
56 References Cited series of reaction zones with intermediate injection of
cold reactants and diluent to control temperature.
U.S. PATENT DOCUMENTS
3,436,432 4/ 1969 Mitsche ............................ 260/671 R 4 Claims, 1 Drawing Figure

Benzene. //
Dilute Ethylene
Ethylbenzene
Product
Ethyl
benzene
Recovery
Column 2O

/5 PE B
Stripper

Alkylaromatics Recycle
U.S. Patent Aug. 15, 1978 4,107,224

027

iauazuaq

//

G/
 4,107,224
1. 2
in which nitrogen is added in an amount equal to 0.5
MANUFACTURE OF ETHYL BENZENE mole per mole of ethylene.
BACKGROUND OF THE INVENTION SUMMARY OF THE INVENTION
The large quantities of sytrene required by industry 5 According to the present invention, a reaction mix
are derived by dehydrogenation of ethylbenzene, sup ture of benzene and ethylene is charged to a series of
plied in part by fractional distillation of hydrocarbon alkylation reactors containing catalyst such as acid zeo
fractions of eight carbon atom aromatics such as those lite ZSM-5. In addition to the excess of benzene over
separated from catalytic reformates. The other primary the stoichiometric value for reaction with ethylene
source of ethylbenzene is from alkyalation of benzene, 10 content of the charge, the ethylene is diluted by inert
usually with ethylene. The commercial alkylation hydrocarbons in an amount greater than equi-molar
plants presently in operation employ catalysts of the quantity. Cooling between stages is accomplished by
Friedel-Crafts type, usually aluminum chloride. The injection of the charge mixture at low temperature,
liquid catalyst of that type in a stirred reactor makes it 15 preferably only slightly above the boiling point of ben
possible to remove the heat of reaction by conventional zene at the partial pressure of benzene in the charge
techniques. mixture as introduced. Activity of the catalyst as mea
The Friedel-Crafts catalysts are highly corrosive and sured by conversion of ethylene is very high, catalyst
require that reactors, heat exchangers and other auxilia life is prolonged and selectivity to ethyl benzene plus
ries by fabricated from expensive corrosion-resistant diethyl benzene is excellent under these conditions.
materials. The spent catalyst and other waste from such 20 DESCRIPTION OF THE DRAWING
plants present a troublesome pollution problem. In addi
tion, the reactants must be very pure to avoid undesir A suitable flow diagram for accomplishing the stated
able by-products. In an adaptation of Friedel-Crafts objects of the invention is set out in the single FIGURE
catalyst to the use of catalytic cracking tail gas as source 25 of the annexed drawing.
of ethylene for alkylation of benzene, all possibly reac DESCRIPTION OF PREFERRED
tive components other than ethylene must be scrupu EMBODIMENTS
lously excluded. Hydrogen sulfide, carbon dioxide and In practising the present invention, ethylene is sup
water normally present in such tail gas are removable at plied in a diluted form, preferably as a mixture with
little cost by caustic scrubbing to absorb the acidic gases 30 inert gaseous materials in which ethylene constitutes
hydrogen sulfide and carbon dioxide and by condensa about 15 to 20 weight percent. A convenient source of
tion of the water contained in the tail gas or picked up such dilute ethylene exists in many oil refineries as tail
during scrubbing. Carbon monoxide requires much gas from many units, for example from Fluid Catalytic
more expensive technique, but obviously must be re Cracking (FCC). Typically such tail gases are used as
moved before the gas is brought into contact with a 35 refinery fuel after treating to remove hydrocarbons
Friedel-Crafts catalyst. saleable as components of premium products such as
It will be immediately apparent that much of the bottled gas (LPG), gasoline or as charge for such pro
disadvantage of Friedel-Crafts catalyst will be avoided cess units as alkylation. In addition, the fuel gas is
by the use of a solid heterogeneous catalyst. Many solid treated to remove the acidic gases hydrogen sulfide
porous catalysts having acid character have been which causes pollution of stack gases and carbon diox
shown to be active for the reaction of ethylene with ide which has no fuel value. It is a particularly valuable
benzene to synthesize ethyl benzene. Typically, the feature of the present invention that unreacted inert
charge to such reaction will be a mixture in which the components of the ethylene diluting medium are fuel
mole ratio of benzene to ethylene is high enough to gas and may be easily separated from the crude product.
suppress the formation of polyethyl benzenes and such 45 The dilute ethylene stream for practice of the present
amounts of these by-products as may be formed are invention requires only the same pretreatment as does
subjected to transalkylation with benzene, either in the fuel gas, whereby the pretreatment of the gas for prac
alkylation reactor or in a separate vessel. The acid cata tice of the invention also prepares the gas to the extent
lysts are effective for promotion of polymerization. needed for fuel gas use. Note particularly that removal
Some alkyl benzenes having larger side chains than 50 of carbon monoxide, a valuable fuel component, is un
ethyl can be found in the product. In addition the activ necessary and this gas may be used in the process as
ity of the catalyst declines very rapidly, possibly due to diluent and then passed on for fuel use.
formation of high molecular weight compounds which The principal diluents are the hydrocarbons methane
remain on the catalytic surfaces. and ethane, which will be present in an aggregate
It has been shown that zeolites in the nature of zeolite 55 amount greater than the quantity of ethylene. Other
ZSM-5 show high activity and selectivity for alkylation diluents include hydrogen, nitrogen and carbon monox
of benzene with ethylene and that catalysts of this type ide. Carbon dioxide is also a diluent and may be retained
in the acid form remain active for unusually long peri in the stream if desired, however it is readily removed
ods between regenerations to burn off carbonaceous with treatment to remove hydrogen sulfide and is pref.
deposits which render the catalyst ineffective. Good erably taken out to upgrade off-gas from the process for
discussion of acid zeolite ZSM-5 for this purpose is fuel use. Water and hydrogen sulfide are tolerable if
provided in U.S. Pat. No. 3,751,506, granted Aug. 7, more rapid aging of the catalyst is acceptable, but these
1973 on an application of George T. Burress. That pa are moderately detrimental in the process and must be
tent proposes control of the exothermic heat of reaction removed in any event before supply of the off-gas to
by conducting the reaction is a series of reactors with 65 furnaces and the like.
intermediate cooling and addition of ethylene between A suitable dilute ethylene stream for use in process is
stages. Note is there made that the course of the reac prepared by Scrubbing tail gas from the usual gas plant
tion may be affected by diluents and examples are given of an FCC Unit with aqueous caustic to remove hydro
 4,107,224 4.
3
gen sulfide and carbon dioxide. The washed gas is consumed is 99.5% by weight at weight hourly space
cooled to condense water and any residual hydrocar velocity (based on ethylene) of 5.
bons of more than two carbon atoms. The treated gas The zeolite catalysts utilized are members of a novel
had the following composition. class of zeolites exhibiting some unusual properties. The
zeolites induce profound transformations of aliphatic
hydrocarbons to aromatic hydrocarbons in commer
methane 37 vol% cially desirable yields and are generally highly effective
ethane 19
ethylene 19 in conversion reactions involving aromatic hydrocar
hydrogen
nitrogen
9
13
bons. Although they have unusually low alumina con
carbon monoxide -3- 10 tents, i.e. high silica to alumina ratios, they are very
100 active even when the silica to alumina ratio exceeds 30.
The activity is surprising since catalytic activity is gen
erally attributed to framework aluminum atoms and
The said dilute ethylene stream was supplied by line cations associated with these aluminum atoms. These
10 to apparatus shown diagramatically in the drawing. 15 zeolites retain their crystallinity for long periods in spite
Fresh benzene entered the system at line 11 to mix with of the presence of steam at high temperatures which
recycle benzene from line 12 and provide a blended induces irreversible collapse of the framework of other
stream of benzene in line 13. One portion of the dilute zeolites, e.g. of the X and A type. Furthermore, carbo
ethylene stream is mixed with polyalkyl aromatics recy naceous deposits, when formed, may be removed by
cled by line 14 and the blend is mixed with a portion of 20 burning at higher than usual temperatures to restore
the benzene from line 13 to provide an aromatics to activity. In many environments the zeolites of this class
ethylene ratio by weight of 70. That mixture is admitted exhibit very low coke forming capability, conducive to
to stage 1 of a reactor 15 at 260 pounds per square inch very long times on stream between burning regenera
gauge (psig) and 785 F. tions.
The reactor 15 is provided with four beds of HZSM 25 An important characteristic of the crystal structure of
5, each designated as a "stage' with plenum chambers this class of zeolites is that it provides constrained ac
between the beds for introduction of cool reactants. cess to, and egress from the intracrystalline free space
The balance of the dilute ethylene from line 10 and by virtue of having a pore dimension greater than about
the balance of the benzene from line 13 are mixed in 5 Angstroms and pore windows of about a size such as
pipe 16 and supplied in three portions to the plenum 30 would be provided by 10-membered rings of oxygen
chambers following stages 1, 2 and 3 to cool effluent atoms. It is to be understood, of course, that these rings
from the preceding stage to about 785 F. and supply are those formed by the regular disposition of the tetra
fresh reactants. In each stage the temperature rises to hedra making up the anionic framework of the crystal
about 820 F. due to the exothermic nature of the reac line aluminosilicate, the oxygen atoms themselves being
tion. 35 bonded to the silicon or aluminum atoms at the centers
Effluent from stage 4 of reactor 15 is cooled and of the tetrahedra. Briefly, the preferred type zeolites
passed to a flash drum 16 from which unreacted diluent useful in this invention possess, in combination: a silica
is withdrawn to be used as fuel. Condensate from drum to alumina mole ratio of at least about 12; and a struc
16 is then passed by line 17 to a benzene recovery frac ture providing constrained access to the crystalline free
tionator 18 from which unreacted benzene is taken space.
overhead to line 12 for recycle as described. Bottoms The silica to alumina ratio referred to may be deter
from fractionator 18 are transferred to fractionator 19 mined by conventional analysis. This ratio is meant to
from which ethylbenzene is taken overhead as product represent, as closely as possible, the ratio in the rigid
at line 20. The bottoms from fractionator 19 are trans anionic framewrok of the zeolite crystal and to exclude
ferred in part to a stripper 20 from which polyethyl 45 aluminum in the binder or in cationic or other form
benzenes are taken overhead and returned to fraction within the channels. Although zeolites with a silica to
ator 19. Materials heavier than polyethyl benzene are use alumina ratio of at least 12 are useful, it is preferred to
rejected as bottoms from stripper 20. The main stream zeolites having higher ratios of at least about 30.
of bottoms from fractionator is returned by line 14 to 50 Suchline
zeolites, after activation, acquire an intracrystal
sorption capacity for normal hexane which is
the inlet of reactor 15 where the polyethyl benzenes greater than that for water, i.e. they exhibit "hydropho
undergo transalkylation reactions with benzene. bic' properties. It is belived that this hydrophobic char
The crude ethyl benzene product taken overhead acter is advantageous in the present invention.
from fractionator 19 had the following composition: The type Zeolites useful in this invention freely sorb
55 normal hexane and have a pore dimension greater than
C non-aromatics
benzene
0.005 wt.%
2.345
about 5 Angstroms. In addition, the structure must pro
toluene 0.254 vide constrained access to larger molecules. It is some
ethylbenzene 97.66 times possible to judge from a known crystal structure
p-xylene
m-xylene
0.090
0.102 whether such constrained access exists. For example, if
styrene 0.00 the only pore windows in a crystal are formed by 8
Ow tylene
C
0,016
0.02
membered rings of oxygen atoms, then access by mole
100,000
cules of larger cross-section than normal hexane is ex
cluded and the zeolite is not of the desired type. Win
dows of 10-membered rings are preferred, although, in
It will be readily apparent to those skilled in the art 65 some instances, excessive puckering or pore blockage
that benzene and toluene can be reduced to very low may render these zeolites ineffective. Twelve-mem
levels by redistillation to provide ethyl benzene at bet bered rings do not generally appear to offer sufficient
ter than 99.5% purity. The yield, based on ethylene constraint to produce the advantageous conversions,
 4,107,224
5 6
although puckered structures exist such as TMA offre However, in all instances, at a temperature within the
tite which is a known effective zeolite. Also, structures above-specified range of 550 F. to 950 F., the con
can be conceived, due to pore blockage or other cause, straint index will have a value for any given zeolite of
that may be operative. interest herein within the approximate range of 1 to 12.
Rather than attempt to judge from crystal structure The class of zeolites defined herein is exemplified by
whether or not a zeolite possesses the necessary con ZSM-5, ZSM-11, ZSM-12, ZSM-35, ZSM-38 and other
strained access, a simple determination of the “con similar materials. U.S. Pat. No. 3,702,886 describing and
straint index' may be made by passing continuously a claiming ZSM-5 is incorporated herein by reference.
mixture of an equal weight of normal hexane and 3 ZSM-11 is more particularly described in U.S. Pat.
methylpentane over a small sample, approximately 1 O
gram or less, of catalyst at atmospheric pressure accord No. 3,709,979, the entire contents of which are incorpo
ing to the following procedure. A sample of the zeolite, rated herein by reference.
in the form of pellets or extrudate, is crushed to a parti ZSM-12 is more particularly described in U.S. Pat.
cle size about that of coarse sand and mounted in a glass No. 3,832,449, the entire contents of which are incorpo
tube. Prior to testing, the zeolite is treated with a stream 15 rated herein by reference.
of air at 1000' F. for at least 15 minutes. The Zeolite is ZSM-38 is more particularly described in U.S. appli
then flushed with helium and the temperature adjusted cation Ser. No. 528,060, filed Nov. 29, 1974. This zeolite
between 550 F. and 950 F. to give an overall conver can be identified, in terms of mole ratios of oxides and in
sion between 10% and 60%. The mixture of hydrocar the anhydrous state, as follows:
bons is passed at 1 liquid hourly space velocity (i.e., 1
volume of liquid hydrocarbon per volume of zeolite per (0.3–2.5)RO: (0-0.8)MO: AlO: > 8 SiO,
hour) over the zeolite with a helium dilution to give a
helium to total hydrocarbon mole ratio of 4:1. After 20 wherein R is an organic nitrogen-containing cation
minutes on stream, a sample of the effluent is taken and derived from a 2-(hydroxyalkyl) trialkylammonium
analyzed, most conveniently by gas chromotography, 25
compound and M is an alkali metal cation, and is char
to determine the fraction remaining unchanged for each acterized by a specified X-ray powder diffraction pat
of the two hydrocarbons. tern.
The "constraint index' is calculated as follows: In a preferred synthesized form, the zeolite has a
formula, in terms of mole ratios of oxides and in the
logo (fraction of n-hexane remaining) 30
anhydrous state, as follows:
Constraint Index = logo (fraction of 3-methylpentane remaining)
(0.4-2.5)RO: (0-0.6)MO: AlO: xSiO,
The constraint index approximates the ratio of the wherein R is an organic nitrogen-containing cation
cracking rate constants for the two hydrocarbons. Zeo derived from a 2-hydroxyalkyl) trialkylammonium
lites suitable for the present invention are those having 35 compound, wherein alkyl is methyl, ethyl or a combina
a constraint index in the approximate range of to 12.
Constraint Index (CI) values for some typical zeolites tion thereof, M is an alkali metal, especially sodium, and
are: x is from greater than 8 to about 50.
The synthetic ZSM-38 zeolite possesses a definite
CAS C
distinguishing crystalline structure whose X-ray diffrac
tion pattern shows substantially the significant lines set
ZSM-5 forth in Table I. It is observed that this X-ray diffraction
ZSM-1
ZSM-12 pattern (significant lines) is similar to that of natural
ZSM-38 ferrierite with a notable exception being that natural
ZSM-35
TMA Offretite
Beta 45
ferrierite patterns exhibit a significant line at 11.33A.
ZSM-4 TABLE I
H-Zeolon d (A) IAIo
REY
Amorphous Silica-Alumina Strong
Erionite Medium
50 Weak
Medium
It is to be realized that the above constraint index Medium
Weak
values typically characterize the specified zeolites but Weak
that such as the cumulative result of several variables Weak
used in determination and calculation thereof. Thus, for Very Strong
a given zeolite depending on the temperature employed 55 Very Strong
Medium
within the aforenoted range of 550 F. to 950 F., with Very Strong
accompanying conversion between 10% and 60%, the Very Strong
Medium
constraint index may vary within the indicated approxi Strong
mate range of 1 to 12. Likewise, other variables such as Medium
Weak
the crystal size of the zeolite, the presence of possible 60 Mediun
occluded contaminants and binders intimately com
bined with the zeolite may affect the constraint index. It
will accordingly be understood by those skilled in the 9
i Weak
Weak
Weak
Weak
art that the constraint index, as utilized herein, while
affording a highly useful means for characterizing the 65
zeolites of interest is approximate, taking into consider A further characteristic of ZSM-38 is its sorptive
ation the manner of its determination, with probability, capacity providing said zeolite to have increased capac
in some instances, of compounding variable extremes. ity for 2-methylpentane (with respect to n-hexane sorp
 4,107,224 8
7
tion by the ratio n-hexane/2-methyl-pentane) when being that natural ferrierite patterns exhibit a significant
compared with a hydrogen form of natural ferrierite line at 11.33A. Close examination of some individual
resulting from calcination of an ammonium exchanged samples of ZSM-35 may show a very weak line at
form. The characteristic sorption ratio n-hexane/2- 11.3-11.5A. This very weak line, however, is deter
methylpentane for ZSM-38 (after calcination at 600 L 5 mined not to be a significant line for ZSM-35.
C.) is less than 10, whereas that ratio for the natural TABLE II
ferrierite is substantially greater than 10, for example, as d (A) I/Io
high as 34 or higher. Very Strong
Zeolite ZSM-38 can be suitably prepared by prepar 0. 2
ing a solution containing sources of an alkali metal ox- 10
ide, preferably sodium oxide, an organic nitrogen-con
taining oxide, an oxide of aluminum, an oxide of silicon
and water and having a composition, in terms of mole
ratios of oxides, falling within the following ranges:
s Very Very Strong
Medium
Medium
Medium
Weak
Weak
Weak
Weak
15 Strong
R-- Broad Preferred Medium Strong
Medium
R-- -- M-- 0.2 - 1.0 0.3 - 0.9 Strong
OH/SiO, 0.05 - 0.5 0.07 - 0.49 Weak
HO/OH 41 - 500 100 - 250 Medium
SiO/Al2O, 8.8 - 200 12 - 60 Very Strong
20 Very Strong
Weak
wherein R is an organic nitrogen-containing cation Weak Medium
Weak Medium
derived from a 2-(hydroxyalkyl) trialkylammonium Weak
compound and M is an alkali metalion, and maintaining Weak
Weak
the mixture until crystals of the zeolite are formed. (The 25 Weak
quantity of OH is calculated only from the inorganic Weak
sources of alkali without any organic base contribu
tion). Thereafter, the crystals are separated from the
liquid and recovered. Typical reaction conditions con
sist of heating the foregoing reaction mixture to a tem 30
: O
Weak
Weak
Weak

perature of from about 90° C. to about 400 C. for a A further characteristic of ZSM-35 is its sorptive
period of time of from about 6 hours to about 100 days. capacity proving said zeolite to have increased capacity
A more preferred temperature range is from about 150 for 2-methylpentane (with respect to n-hexane sorption
C. to about 400° C. with the amount of time at a temper by the ratio n-hexane/2-methylpentane) when com
ature in such range being from about 6 hours to about 80 35 pared with a hydrogen form of natural ferrierite result
days. ing from calcination of an ammonium exchanged form.
The digestion of the gel particles is carried out until The characteristic sorption ration-hexane/2-methylpen
crystals form. The solid product is separated from the tane for ZSM-35 (after calcination at 600° C.) is less
reaction medium, as by cooling the whole to room than 10, whereas that ratio for the natural ferrierite is
temperature, filtering and water washing. The crystal substantially greater than 10, for example, as high as 34
line product is thereafter dried, e.g. at 230 F. for from or higher.
about 8 to 24 hours. Zeolite ZSM-35 can be suitably prepared by prepar
ZSM-35 is more particularly described in U.S. appli ing a solution containing sources of an alkali metal ox
cation Ser. No. 528,061, filed Nov. 29, 1974. This zeolite ide, preferably sodium oxide, and organic nitrogen-con
can be identified, in terms of mole ratios of oxides and in 45 taining oxide, an oxide of aluminum, an oxide of silicon
the anhydrous state, as follows: and water and having a composition, in terms of mole
ratios of oxides, falling within the following ranges:
(0.3–2.5)RO: (0–0.8)MO: AlO: > 8 SiO,
wherein R is an organic nitrogen-containing cation R- Broad Preferred
derived from ethylenediamine or pyrrolidine and M is 50 R- -- M -- 0.2 - 1.0 0.3 - 0.9
an alkali metal cation, and is characterized by a speci OH/SiO, 0.05 - 0.5 0.07 - 0.49
HO/OH 41 - 500 100 - 250
fied X-ray powder diffraction pattern. SiO/Al2O, 8.8 - 200 12 - 60
In a preferred synthesized form the zeolite has a for
mula, in terms of mole ratios of oxides and in the anhy wherein R is an organic nitrogen-containing cation
drous state, as follows: 55
derived from pyrrolidine or ethylenediamine and M is
(0.4-2.5)RO : (0,0.6)MO: A1,O: xSiO, an alkali metal ion, and maintaining the mixture until
crystals of the zeolite are formed. (The quantity of
wherein R is an organic nitrogen-containing cation OH is calculated only from the inorganic sources of
derived from ethylenediamine or pyrrolidine, M is an alkali without any organic base contribution). Thereaf
alkali metal, especially sodium, and x is from greater ter, the crystals are separated from the liquid and recov
than 8 to about 50. ered. Typical reaction conditions consist of heating the
The synthetic ZSM-35 zeolite possesses a definite foregoing reaction mixture to a temperature of from
distinguishing crystalline structure whose X-ray diffrac about 90° C. to about 400° C. for a period of time of
tion pattern shows substantially the significant lines set 65 from about 6 hours to about 100 days. A more preferred
forth in Table II. It is observed that this X-ray diffrac temperature range is from about 150° C. to about 400
tion pattern (with respect to significant lines) is similar C. with the amount of time at a temperature in such
to that of natural ferrierite with a notable exception range being from about 6 hours to about 80 days.
 4,107,224
10
The digestion of the gel particles is carried out until
crystals form. The solid product is separated from the Void Framework
reaction medium, as by cooling the whole to room Zeolite Volume Density
temperature, filtering and water washing. The crystal Ferrierite 0.28 cc/cc 1.76 g/cc
line product is dried, e.g. at 230 F., for from about 8 to Mordenite
ZSM-5,-11
28
29
1.7
.79
24 hours. Dachiardite 32 1.72
The specific zeolites described, when prepared in the L
Clinoptilolite .34
32
1.71
1.61
presence of organic cations, are catalytically inactive, Laumontite .34 1.77
possibly because the intracrystalline free space is occu 10 ZSM-4 (Omega) 38 1.65
pied by organic cations from the forming solution. They Heulandite 39 1.69
P .41 1.57
may be activated by heating in an inert atmosphere at Offretite 40 1.55
1000 F. for one hour, for example, followed by base Levynite 40 1.54
Erionite 35 1.51
exchange with ammonium salts followed by calcination Gmelinite 44 1.46
at 1000 F. in air. The presence of organic cations in the 15 A.Chabazite 47
.5
1.45
1.3
forming solution may not be absolutely essential to the Y 48 1.27
formation of this type zeolite; however, the presence of
these cations does appear to favor the formation of this When synthesized in the alkali metal form, the zeolite
special type of zeolite. More generally, it is desirable to is conveniently converted to the hydrogen form, gener
activate this type catalyst by base exchange with ammo 20 ally by intermediate formation of the ammonium form
nium salts followed by calcination in air at about 1000 as a result of ammonium ion exchange and calcination
F. for from about 15 minutes to about 24 hours. of the ammonium form to yield the hydrogen form. In
Natural zeolites may sometimes be converted to this addition to the hydrogen form, other forms of the zeo
type zeolite catalyst by various activation procedures lite wherein the original alkali metal has been reduced
and other treatments such as base exchange, steaming, 25 to less than about 1.5 percent by weight may be used.
alumina extraction and calcination, in combinations. Thus, the original alkali metal of the zeolite may be
Natural minerals which may be so treated include ferri replaced by ion exchange with other suitable ions of
erite, brewsterite, stilbite, dachiardite, epistilbite, heu Groups IB to VIII of the Period Table, including, by
landite, and clinoptilolite. The preferred crystalline way of example, nickel, copper, zinc, palladium, cal
aluminosilicates are ZSM-5, ZSM-11, ZSM-12, ZSM-38 30 cium or rare earth metals.
and ZSM-35, with ZSM-5, particularly preferred. In practicing the desired conversion process, it may
In a preferred aspect of this invention, the zeolites be desirable to incorporate the above described crystal
hereof are selected as those having a crystal framework line aluminosilicate zeolite in another material resistant
density, in the dry hydrogen form, of not substantially to the temperature and other conditions employed in
below about 1.6 grams per cubic centimeter. It has been 35 the process. Such matrix materials include synthetic or
found that zeolites which satisfy all three of these crite naturally occurring substances as well as inorganic ma
ria are most desired because they tend to maximize the terials such as clay, silica and/or metal oxides. The
production of gasoline boiling range hydrocarbon prod latter may be either naturally occurring or in the form
ucts. Therefore, the preferred zeolites of this invention of gelantinous precipitates or gels including mixtures of
are those having a constraint index as defined above of 40 silica and metal oxides. Naturally occurring clays which
about 1 to about 12, a silica to alumina ratio of at least can be composited with the zeolite include those of the
about 12 and a dried crystal density of not less than montmorillonite and kaolin families, which families
about 1.6 grams per cubic centimeter. The dry density include the sub-bentonites and the kaolins commonly
for known structures may be calculated from the num 45 known as Dixie, McNamee-Georgia and Florida clays
ber of silicon plus aluminum atoms per 1000 cubic Ang or others in which the main mineral constituent is hal
stroms, as given, e.g., on Page 19 of the article on Zeo loysite, kaolinite, dickite, nacrite or anauxite. Such clays
lite Structure by W. M. Meier. This paper, the entire can be used in the raw state as originally mined or ini
contents of which are incorporated herein by reference, tially subjected to calcination, acid treatment or chemi
cal modification.
is included in "Proceedings of the Conference on Mo 50 In addition to the foregoing materials, the zeolites
lecular Sieves, London, April 1967,' published by the employed herein may be composited with a porous
Society of Chemical Industry, London, 1968. When the matrix material, such as alumina, silica-alumina, silica
crystal structure is unknown, the crystal framework magnesia, silica-zirconia, silica-thoria, silica-berylia,
density may be determined by classical pyknometer silica-titania as well as ternary compositions, such as
techniques. For example, it may be determined by im 55 silica-alumina-thoria, silica-alumina-zirconia, silica
mersing the dry hydrogen form of the Zeolite in an alumina-magnesia and silica-magnesia-zirconia. The
organic solvent which is not sorbed by the crystal. It is matrix may be in the form of a cogel. The relative pro
possible that the unusual sustained activity and stability portions of Zeolite component and inorganic oxide gel
of this class of zeolites is associated with its high crystal matrix may vary widely with the zeolite content rang
anionic framework density of not less than about 1.6 60 ing from between about 1 to about 99% by weight and
grams per cubic centimeter. This high density, of more usually in the range of about 5 to about 80% by
course, must be associated with a relatively small weight of the composite.
amount of free space within the crystal, which might be Indications are that the catalyst will show very slow
expected to result in more stable structures. This free aging in this configuration. This conclusion is based on
space, however, is important as the locus of catalytic 65 semi-commercial scale comparisons among adiabatic
activity. runs comparing alkylation of benzene over HZSM-5
Crystal framework densities of some typical zeolites with pure (polymer grade) ethylene and with ethylene
ac diluted in the manner described above. Temperature
 4,107,224 12
11
probes in the adiabatic semicommercial reactor report a ating agent, e.g. ethylene. The alkylating agent WHSV
migration of the zone of maximum temperature down to each of any alkylation reactor stages is maintained
ward through the down-flow reactor when charging between about 1 and about 10 lb. alkylating agent/hr-lb.
polymer grade ethylene. The zone of maximum temper crystalline aluminosilicate. The most desirable ethylene
ature is considered to be the zone of maximum (exother WHSV is within the range of about 2 to about 6 lb.
mic) reaction and it is concluded that catalyst ages as ethylene/hr-lb. crystalline aluminosilicate. When the
the zone moves downward. That effect is seen to a ethylene WHSV is maintained within the above limits,
much lesser degree when charging the above-described an economical cycle between regenerations of catalyst
dilute ethylene to the adiabatic reactor. Instead, the exists.
zone of maximum temperature in the catalyst bed re 10 Operating in the manner described, run lengths of up
mains quasi-stationary with a much lower rate of move to 29 days have been achieved, all terminated for rea
ment. This can lead logically to the conclusion that the sons other than deactivation of the catalyst. It will be
catalyst is aging at a far less rapid rate. clear immediately that dilution of ethylene in the degree
The process of this invention is conducted such that described increases the heat capacity of the system with
alkylation of the aromatic hydrocarbon compound, 15 resultant lower temperature rise across each catalyst
benzene, with ethylene, is carried out in the vapor bed. Also achieved is reduction in partial pressure of
phase by contact in a reaction zone under alkylation ethylene thus reducing polymerization of that olefin and
effective conditions, said catalyst being characterized as subsequent formation of by-products such as butylben
above zeolite which has been hydrogen exchanged such zene. The inert hydrocarbons increase the partial pres
that a predominate portion of its exchangeable cations 20 sure driving force to desorb coke precursors from the
are hydrogen ions. In general, it is contemplated that catalyst surface and thus reduce aging rate.
more than 50% and preferably more than 75% of the I claim:
cationic sites of the ZSM-5 zeolite will be occupied by 1. In a process for effecting ethylation of an alkylata
hydrogen ions. The alkylatable aromatic compound and ble aromatic hydrocarbon compound by contacting said
alkylating agent are desirably fed to a first stage at an 25 compound with ethylene under conversion conditions
appropriate mole ratio of one to the other. The feed to of 250 to 600 C., a pressure between about 0.1 and
such first stage is heated. After reaction takes place, the about 100 atmospheres, a feed weight hourly space
effluent of the first stage is cooled to remove heat of velocity between about 0.1 and about 100 and a molar
reaction by addition of reactants. A plurality of reaction feed ratio of said compound to ethylene between about
stages are possible for the process of this invention. It is 30 1 and about 30 in the presence of a crystalline alumino
generally desirable to provide cooling between reactor silicate zeolite having a silica to alumina ratio of at least
stages by addition of cool reactant. about 12 and a constraint index within the approximate
In vapor-phase alkylation of benzene with ethylene, range of 1 to 12 in a series of beds of said zeolite wherein
the first stage mole ratio of benzene to ethylene may be effluent of each such bed except the last is admixed with
in the range of about 1:1 to about 30:1. The first stage 35
fresh reactant supplied at a temperature lower than that
feed is heated to a reactor inlet temperature within the of said effluent and the so-quenched reaction mixture is
range of about 650 F to about 900 F at a pressure passed to the next such bed; the improvement comprises
within the range of about atmospheric to about 3000 supplying charge to the first said bed and fresh reactants
p.s.i.g. Preferred inlet temperatures fall within the range to said effluents as a mixture consisting essentially of
of about 700 F to about 850 F and preferred pressures said alkylatable aromatic hydrocarbon compound and
fall within the range of about 25 p.s.i.g. to about 450 ethylene admixed with at least an equi-molar amount of
p.s.i.g. The repeating of reaction staging is carried out inert hydrocarbon diluent consisting essentially of
while maintaining an overall aromatic hydrocarbon,
e.g. benzene, to alkylating agent, e.g. ethylene, mole methane, ethane or a mixture of the same whereby to
ratio of about 1:1 to about 30:1, with a preferred range 45 increase the partial pressure driving force to desorb
of about 2.5:1 to about 25:1. As the reaction proceeds coke precursors from the catalyst surface.
through the stages, the aromatic:alkylating agent mole 2. The process of claim 1 wherein said alkylatable
ratio is held constant by changes in the ratio in the fresh hydrocarbon is benzene.
interstage feed. 3. The process of claim 1 wherein said crystalline
It is noted that extremely high total feed space veloci 50 aluminosilicate zeolite is ZSM-5.
ties are possible in the process of this invention, i.e. up 4. The process of claim 1 wherein said crystalline
to 800 lb. total feed/hr-lb. crystalline aluminosilicate. aluminosilicate zeolite is admixed with a binder there
An important factor in the present process is, however, for. ak : k k sk
the weight hourly space velocity (WHSV) of the alkyl
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