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1978 - Dwyer, Chester - United States Patent 19
1978 - Dwyer, Chester - United States Patent 19
1978 - Dwyer, Chester - United States Patent 19
[54] MANUFACTURE OF E'I'HYL BENZENE 3,542,892 11/ 1970 Stoker et a1. .................. .. 260/671 R
_ 3,751,504 8/1973 Keown et a1. 260/671 R
[75] Inventon 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_ Gamz
N'Y Assistant ExaminerC. E. Spresser
[21] Appl, NQ; 767,855 Attorney, Agent, or FirmCharles A. Huggett; Michael
G. G'l
[22] Filed: Feb. 11, 1977 man- Raymon d W. B arel ay
[51] Int. 01.1 .............................................. .. c07c 3/52 [57] ABSTRACT
[52] U.S. Cl. ........................... .. 260/671 R; 260/671 C Benzene and dilute ethylene are reacted in vapor phase
[58] Field of Search ..... ............... .. 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 1 //
Dilute Ethylene>
/0
Ethylbenzene
Product
1
l3 l2 Ethyl- / /9
/4 | Benzene benzene
"" " /6 Recovery Recovery
REACTOR
2 Column / [8 Column / 20
/5/" 3 PE B_
Stripper
4
_. _. __ Fuel Gas
Flash
Drum /7
Residue
Alkyloroma?cs Recycle
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 According to the present invention, a reaction mix
are derived by dehydrogenation of ethyl benzene, 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 ethyl benzene is from alkyalation of benzene, 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 preferably only slightly above the boiling point of ben
possible to remove the heat of reaction by conventional 15 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 ?ow 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 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 sul?de, carbon dioxide and
water normally present in such tail gas are removable at In practising the present invention, ethylene is sup
little cost by caustic scrubbing to absorb the acidic gases plied in a diluted form, preferably as a mixture with
30 inert gaseous materials in which ethylene constitutes
hydrogen sul?de 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 re?neries 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 re?nery 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 sul?de
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-S 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-S for this purpose is fuel use. Water and hydrogen sul?de are tolerable if
provided in US. 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 sul?de 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 9 bons. Although they have unusually low alumina con
nitrogen 13 tents, i.e. high silica to alumina ratios, they are very
carbon monoxide 3
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 IO-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
Ef?uent from stage 4 of reactor 15 is cooled and of the tetrahedra. Brie?y, the preferred type zeolites
passed to a ?ash 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 ethyl benzene 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 alumina ratio of at least 12 are useful, it is preferred to
rejected as bottoms from stripper 20. The main stream use zeolites having higher ratios of at least about 30.
of bottoms from fractionator is returned by line 14 to Such zeolites, after activation, acquire an intracrystal
the inlet of reactor 15 where the polyethyl benzenes line sorption capacity for normal hexane which is
undergo transalkylation reactions with benzene. greater than that for water, i.e. they exhibit hydropho
The crude ethyl benzene product taken overhead bio properties. It is belived that this hydrophobic char
from fractionator 19 had the following composition: acter is advantageous in the present invention.
The type zeolites useful in this invention freely sorb
55 normal hexane and have a pore dimension greater than
C6 non-aromatics 0.005 wt. % about 5 Angstroms. In addition, the structure must pro
benzene 2.345 vide constrained access to larger molecules. It is some
toluene 0.254
ethyl benzene 97.166 times possible to judge from a known crystal structure
p-xylene 0.090 whether such constrained access exists. For example, if
m-xylene 0. 102 the only pore windows in a crystal are formed by 8
styrene 0.0l0
o~ aylene 0.016 membered rings of oxygen atoms, then access by mole
C, 0.0l2 cules of larger cross-section than normal hexane is ex
100.000 cluded and the zeolite is not of the desired type. Win
dows of IO-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-speci?ed 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 l to 12.
Rather than attempt to judge from crystal structure The class of zeolites de?ned herein is exempli?ed by
whether or not a zeolite possesses the necessary con ZSM-S, ZSM-l l, ZSM-l2, ZSM-35, ZSM-38 and other
strained access, a simple determination of the con similar materials. US. Pat. No. 3,702,886 describing and
straint index may be made by passing continuously a claiming ZSM-S is incorporated herein by reference.
mixture of an equal weight of normal hexane and 3
methylpentane over a small sample, approximately 1 ZSM-ll is more particularly described in U.S. Pat.
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-l2 is more particularly described in US. 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 rated herein by reference.
of air at 1000 F. for at least 15 minutes. The zeolite is ZSM-38 is more particularly described in US. appli
then flushed with helium and the temperature adjusted cation Ser. No. 528,060, ?led Nov. 29, 1974. This zeolite
between 550 F. and 950 F. to give an overall conver can be identi?ed, 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 20
volume of liquid hydrocarbon per volume of zeolite per (0.3-2.5)R20: (0-o.s)M,o = A1203: > s sio2
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 Z-(hydroxyalkyl) trialkylammonium
analyzed, most conveniently by gas chromotography, compound and M is an alkali metal cation, and is char
to determine the fraction remaining unchanged for each 25 acterized by a speci?ed 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
log", (fraction of n-hexane remaining) anhydrous state, as follows:
Constraint Index = 30
log") (fraction of 3-methylpentane remaining)
65