United States Patent 0 "P1C6 seats

Patented Dec. 27, 1966

1 2
tion of {an organic phase, since styrene in the liquid phase
3,294,856 polymerizes rapidly, and, especially in the reboilers, the
PROCESS FOR PREPARATIGN AND Pl presence of polymer leads to deposits and sharply lower
CATIUN 0F STYRENE heat transfer e?iciency.
Harold A. Huckins, Jr., New Canaan, Conn, assignor to 5 In the absence of a su?icient amount of water vapor,
Haicon International Inc., a corporation of Delaware
Filed Feb. 4, 1964, Ser. No. 343,193 the reactor effluent cannot be employed as a heat source,
4 Claims. (Cl. 260-669) since a low water content increases the likelihood of the
formation of an organic phase and the fouling of the
This application is a continuation-in-part of my co reboilers. At least 50% by weight of the e?luent must
pending application, serial number 119,148, ?led June 23, 10 be water vapor prior to introduction to the reboiler,
1961, now abandoned. preferably 65%.
This invention relates to the production of styrene. As stated above, it is desirable to have large amounts
More particularly, this invention relates to an improved of water in the feed to the dehydrogenation. General
method for producing styrene by the dehydrogenation of ly, sufficient water is added to the feed to yield a reactor
ethyl benzene. 15 e?luent having suliicient water vapor for introduction
It is well known in the art to produce systene by the into the reboilers. If, however, su?icient water is not
dehydrogenation of ethyl benzene. Presently the vast present, or it is desirable to have even greater quantities
majority of the styrene commercially produced is pre of water vapor in the eiiiuent, additional water can be
pared by this dehydrogenation technique. added to the e?luent. Since it is desirable to rapidly
In processes involving the dehydrogenation reaction of 20 cool the e?luent to avoid side reactions, such as dealkyla
ethyl benzene the styrene, the dehydrogenation is normal tion, the addition of water directly into the e?luent serves
ly carried out employing steam in admixture with the ethyl a two-fold purpose. The reactor e?iuent vapor is rapidly
benzene feed to the reactor in order to maintain low cooled from its exit temperature of over 600 C. to just
styrene partial pressure and also to supply the heat re above its dew point, e.g., about 105 C. It is preferably
quired for this endothermic reaction. 25 at this temperature of incipient condensation that the
The more steam present, the more favorable the equi reactor e?luent is passed to the reboilers. The advan
librium for the production of styrene at a given total tages of the invention, however, can be achieved so long
pressure. Depsite the advantages of high steam ratios, as the e?iuent is cooled within 50 C. of the dew point,
the amount of steam used has been limited by economic preferably 10 C. Again a two-fold bene?t is secured.
factors, e.g., the cost of the heat for vaporizing large 30 Not only does the rapid cooling prevent side reactions
quantities of steam. Though the dehydrogenation re of the eilluent itself, but it also reduces the tendency to
actor e?luent mixture has conventionally been used to polymerize the liquid styrene in the distillation columns.
preheat reactor feed gases, the heat expended in vaporiz The dehydrogenation can be carried out at tempera
ing the steam has hitherto been considered unrecover tures of the order of about 500 C. to 750 C., using
able. Furthermore, since the reactor eflluent has to be 35 about 1 to 10 pounds of steam per pound of ethyl
condensed, normally in a water cooled tubular heat ex benzene, and dehydrogenation catalysts such as zinc,
changer or scrubbing tower, further expenses are in chromium, iron, or magnesium oxide, on activated char
curred by using high steam ratios. coals, aluminas, or bauxites, with conversions of 30
In order to produce satisfactorily pure styrene, the 70% of ethyl benzene.
condensed reactor effluent, after separation of the water, 40 The reactor e?luent comprises ethyl benzene, styrene,
must be subjected to a series of distillations to remove steam, and associated hydrocarbon materials.
impurities including benzene and toluene, ethyl benzene The attached drawing is a schematic ?ow sheet of a
and tars and polymers. practice of the invention and illustrates the invention.
It is an object of the present invention to provide an Referring to the accompanying drawing, in a partic
improved method for producing styrene. 45 ular practice of the invention about 100 parts by weight
It is a particular object of the invention to produce of fresh ethyl :benzene feed is charged to vaporizer 1
styrene by the dehydrogenation of ethyl benzene. through lines 2 and 3. About 40 par-ts of steam or water
It is a special object of the invention to provide an is combined with fresh ethyl benzene feed and charged
improved process for the separation of styrene from im to the vaporizer through lines 4 and 3. The ethyl ben
purities associated therewith while achieving very high 50 zene~water mixture is vaporized in vaporizer 1 by in
process economies. direct heat exchange with eliluent from the ethyl benzene
Other objects of the invention will be apparent from dehydrogenation reactor. The vaporized feed mixture is
the following description: passed by means of line 5 to preheater 6 wherein the
In accordance with the instant invention, it has been temperature of the feed mixture is increased to about
discovered that, if sufficient water vapor is present, the 530 C. by indirect heat transfer with the reactor ef?uent
e?luent can be employed in an economical and advan The preheated feed mixture passes from heat exchanger
tageous manner for supplying heat for the distillation 6 through lines 7 and 8 to reactor 9 wherein the ethyl ben
steps essential for the puri?cation of the styrene. zene is dehydrogenated to styrene. About 220 parts of
Brie?y, a portion of the reactor e?luent vapor is passed 60 steam is superheated in superheater 10 and combined
to the reboiler or reboilers of the distillation columns to with the ethyl benzene-steam charge to the reactor by
supply all or at least part of the heat requirements. A means of lines 11 and 8. The combined gaseous charge
su?icient amount of the effluent is passed to the column mixture to the dehydrogenator is at a temperature of
so that only the water vapor need condense to supply the about 630 C.
required heat input. As a matter of fact, it is mandatory 65 In the dehydrogenation reactor 9, ethyl benzene is
that the condensation of any substantial amount of or catalytically dehydrogenated to styrene using a ?xed bed
ganic material be prevented, so as to avoid the forma iron oxide-based catalyst. About 40% of the ethyl ben
 3,294,856 -
3 4
zene is converted to styrene. As a result of the endo cipally hydrogen produced during the course of dehy
thermic nature of the reaction, the gaseous e?luent which drogenation reaction together with small quantities of
is vremoved from reactor 9 by the means of line 12 is C0, C02 and methane is separated and removed through
at a temperature of about 580 C. line 31. The organic phase which contains the product
The reactor e?iuent passes by means of line 12 to pre styrene is removed by line 32 and is passed by means
heater 6 wherein it is used to preheat fresh feed to the not shown to the distillation column 25 wherein benzene
reactor 9. and toluene are separated, then to column, 22 wherein
The reactor e?iuent passes from preheater 6 at about ethyl benzene is separated, and ?nally to column 19
440 C. and is transferred by means of line 13 to ya wherein highly pure styrene is obtained as product over
porizer 1 wherein it is employed to vaporize ethyl ben 10 head distillate.
zene-water feed to the reactor 9. At about 250 C. the The temperature and pressures employed in the distil
reactor e?iuent is removed from the vaporizer 1 through lation columns 25, 22 and 19 are such as are known in
line 14 and is sent to cooler 15 wherein water is sprayed the art.
into the e?iuent thereby cooling the e?luent to about The crude styrene illustratively has a composition by
"105 C. 15 weight of about 37% styrene, 61% ethyl benzene, 1%
The reactor effluent is removed from cooler 15 and toluene, 0.7% benzene, and 0.3% tar. Inhibitor is added
While still in the vapor state, is then employed to provide at appropriate locations in the distillation columns to
the distillation heat to one or more of the reboilers on prevent polymerization of the styrene, i.e., to the column
the columns needed for the separation and puri?cation re?ux streams.
of the product styrene. 20 In column 2.5, at 157 mm. of mercury pressure, ben
In this preferred embodiment of the invention as illus zene and toluene in amount of about 2 parts distill over
trated in the accompanying drawing, the cooled reactor head :at a head temperature of about 57 C. The bot
effluent vapor is used to provide the distillation heat to toms containing styrene, ethyl benzene, and tar at about
all three of the distillation columns which are normally 90 C. passes to column 22. Column 22 is operated at
used to purify the reactor e?iuent styrene. The order 25 35 1mm. of mercury pressure and with a bottoms temper
of separating out the impurities in styrene can be ar ature of 90 C. Ethyl benzene in amount of about 61
ranged as shown or, alternatively, in the ?rst column parts is distilled overhead and can be recycled to the
benzene, toluene and ethyl benzene could be separated dehydrogenation reactor.
as an overhead product, in rthe second column styrene The bottoms comprising styrene and tar is passed to
could be separated from the residue, polymer and tar, column 19 wherein by appropriate lowering of the oper
and in the third column benzene-toluene could be sep ating pressure substantially pure styrene is distilled over
arated from the ethyl benzene. head in amount of about 37 parts and thus separated
The cooled reactor e?iuent vapor from cooler 15 is from the bottoms tar. A suitable operating pressure for
passed through 'line 16 and then divided into a plurality this distillation column is 20 mm. of mercury pressure.
of portions, three of which are used in reboilers associ 35 By the above described process, it is apparent that
ated with the styrene puri?cation columns. outstanding economies of operation are achieved.
One portion comprising about 6% of the e?duent is It will be apparent to those skilled in the art that nu
passed by means of lines 16 and 17 to reboiler 18 which merous departures can be made from the preferred em
is associated with distillation column 19 wherein styrene bodiment of the invention as described above. Thus, de
is separated from higher boiling tar and polymer. An 40 sirably, the water vapor in the reactor e?duent can be
other portion comprising about 50% of the e?zluent is employed to provide distillation heat to less than all
sent through lines 16 and 20 to reboiler 21 which is asso of the three columns formerly used for the puri?cation
ciated with column 22 wherein ethyl benzene is frac of the product styrene. However, in its most desirable
tionally distilled overhead ?rom a bottom styrene frac aspects, the invention is practiced whereby the water ,
tion. A third portion of the cooled reactor ef?uent com 45 vapor provides distillation heat to all of the columns as
prising :about 6% of the e?iuent passes through lines above described. In some cases where the benzene and
16 and 23 to reboiler 24 which is used to provide distil toluene mixture from this distillation are separated from
lation heat to distillation column 25. In distillation col each other, this heat source could also be used for this
umn 25, a benzene-tolene fraction is fractionally dis separation.
tilled overhead from a bottoms ethyl benzene-styrene 50 In view of the foregoing disclosures, variations and
containing fraction. modi?cations thereof will be apparent to those skilled in
About 38% of the cooled e?iuent is not required to the art, and it is intended to include within the invention
provide distillation heat to the said distillation columns all such variations and modi?cations except as do not
19, 22 and 25 and passes through lines 16 and 26 and is come within the scope of the appended claims.
condensed in condenser 27 by indirect heat exchange with 55 I claim:
cooling water. At times of startup, shutdown or for con 1. In a process for the production of styrene by the
trol purposes some steam could be added together with dehydrogenation of ethyl benzene in the presence of
the reactor e?iuent going to the reboiler-condensers. steam wherein the reactor effluent contains steam and
The reboilers 18, 21 and 24 are reboiler condensers organic material including styrene, and wherein the
wherein by indirect heat exchange the reactor e?iuent 60 styrene is separated from the reactor e?iuen-t by distilla~
from cooler 115 is further cooled and partially condensed tion, the improvement which comprises: indirectly con
and liquid from the base of the respective distillation tacting at least portion of the gaseous reactor e?luen't
column is heated and vaporized. In this way, the heat with a liquid stream from said distillation so as to con
of condensation of the water vapor in the reactor e?iuent dense the steam, but not a substantial amount of said
is economically employed to provide the necessary dis organic material, in said reactor e?luent, thereby pro
tillation heat for the separation of product styrene from viding distillation heat for said distillation.
other materials associated therewith. Care is taken to 2. In a process for the production of styrene by the
distribute isu?icient amount of vapor to the distillation dehydrogenation of ethylbenzene in the presence of steam
columns so as to prevent condensation of styrene. wherein the gaseous reactor e?iuent contains steam and
The partially condensed reactor e?luent is combined organic material including styrene, and wherein the sty
by means of lines 28, 29 and 30 with any eiiiuent that rene is separated from the reactor effluent by distillation,
bypasses the reboilers, passed through condenser 27, and the improvement which comprises: indirectly contacting
sent by means of line 28 to separator 29. In the separa a water-containing portion of the gaseous reactor effluent
tor, the mixture is decanted and a lower aqueous layer with a cooler portion of said gaseous reactor e?iuent
is removed by means of line 30. Vent gas which is prin 75 from which an aqueous phase has been separated, and
 3,294,856
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condensing 65m in the water-containing portion of the which distillation heat is provided by the water-contain
gaseous reactor ef?uent to provide distillation heat for in-g portion of the gaseous reactor ef?uent.
said portion from which an aqueous phase has been sep
arated, substantially none of the organic material in References Cited by the Examiner
said water-containing portion being condensed with the UNITED STATES PATENTS
steam. 2,413,674 12/1946 Weir ____________ __ 260-669
3. A process according to claim 2 wherein the aqueous 3,162,694 12/1964 Beavon ________ __ 260683.62
phase is separated by decanting. FOREIGN PATENTS
4. A process according to claim 2 wherein an aqueous
phase is separated from the water-containing portion of 10 541,797 12/ 1941 .Great Britain.
the gaseous reactor effluent after condensing steam in
DELBERT E. GANTZ, Primary Examiner.
said e?luent, and wherein said ef?uent from which said
aqueous phase has been separated forms the portion for C. R. DAVIS, Assistant Examiner.