United States Patent (11) 3,607,960

72 Inventors Delbert L. Button 3,213, 150 10/1965 Cabbage....................... 260/667

Allison Park, Pa.; 3,288,875 1 1/1966 Payne et al................... 260/672
Lawrence J. Kirby, Tokyo, Japan 3,291,849 12/1966 King et al...................... 260/672
21 Appl. No. 47,586 3,296,120 1/1967 Doelp et al... 208/143
22 Filed June 18, 1970
45) Patented Sept. 21, 1971 3,296,323 1/1967 Myers et al... 260/672
73) Assignee Gulf Research & Development Company 3,390,200 6/1968 Sze............................... 260/672
Pittsburgh, Pa. OTHER REFERENCES
Continuation-in-part of application Ser. No. Fowle & Pitts “Thermal Hydrodealkylation' Chem. Eng.
723,998, Apr. 25, 1968, now abandoned. Progress 58 (4) 37-40 (April 1962)
Primary Examiner-Delbert E. Gantz
Assistant Examiner-G. E. Schmitkons
Attorneys-Meyer
Ryder Neishloss, Deane E. Keith and Thomas G.
(54) THERMAL HYDRODEALKYLATION PROCESS
8 Claims, 1 Drawing Fig.
52 U.S. Cli.......................................................260/672 NC, ABSTRACT: In a process for the thermal hydrodealkylation
203188,208148 R, 208/78, 208/99, 208/102,
260/668 F, 260/672 R, 260/674 R of an alkyl aromatic, such as toluene, to produce benzene, a
51 int. Cl......................................................... B01d3/06, mixture of diphenyls and high-boiling polymers is separated as
C07c3/58, C10q9/16 bottoms from the effluent of a primary hydrodealkylation
(50 Field of Search............................................ 260/672 zone. This mixture is mixed with recycle hydrogen and flash
NC vaporized, the vapor comprising polyphenyls and hydrogen
being passed to an auxiliary reactor wherein the polyphenyls
56) References Cited are converted to benzene. The flash vaporization selectively
UNITED STATES PATENTS rejects substantially all of the high-boiling polymer com
3,152,980 10/1964 Coonradt et al.............. 208778 pounds which would otherwise tend to form coke in the aux
iliary reactor.

67 WAPOR
StreAM
Ak-Us is
HYDROGEN

TO
HYDROGEN
PANT

POLYMER
PRGE
 3,607,960
2
THERMAL, HYDRODEALKYLATION PROCESS F. at atmospheric pressure (e.g. hydrogen, alkylaromatics and
RELATED APPLICATIONS polyphenyls) from the liquid higher boiling polymers boiling
at atmospheric pressure at about 750 to 800 F. and above.
This application is a continuation-in-part of Ser. No. The vaporous constituents are then subjected to temperatures
5 in the range of from about 900' to 1500 F. in an auxiliary
723,998, filed on Apr. 25, 1968 and now abandoned and is re
lated to Ser. No. 596,125, filed Nov. 22, 1966 and now aban reaction zone to convert at least a portion of the polyphenyls
doned and to Ser. No. 816,145, filed Mar. 14, 1969. to benzene. The flash vaporization of the feed to the auxiliary
This invention relates to a process for the thermal reactor permits the selective rejection of high-boiling polymer
hydrodealkylation of alkyl aromatic compounds, More par 10 compounds which cause coke formation in the preheater for
ticularly, this invention relates to such a process wherein the auxiliary reaction zone. The benzene product from the ef.
higher benzene selectivity and increased benzene yields are fluents from the primary reaction zone and from the auxiliary
obtained. reaction zone is recovered. In a preferred embodiment, the ef.
Toluene can be dealkylated to benzene by subjecting it in fluent from the auxiliary reaction zone is combined with the
the presence of hydrogen to an elevated temperature and 15 effluent from the primary reaction zone before the effluent
elevated pressure for a controlled length of time. As a result of from the primary reaction zone is passed to the separation
such reaction conditions, the methyl group is cleaved from the Zone and the benzene product is recovered from the separa
toluene and replaced by hydrogen. The mechanism probably tion Zone. Thus, the product separation equipment normally
involves the generation of methyl and phenyl radicals and the used for the separation of the products and unconverted reac
combination of these radicals with hydrogen to form methane tants from the primary reaction zone is also used to separate
and benzene. The overall hydrodealkylation reaction is highly the products and unconverted reactants obtained from the
exothermic. auxiliary reaction zone.
The yield of benzene in the thermal hydrodealkylation of an This use of the auxiliary reaction zone provides an in
alkyl aromatic may be increased somewhat by conducting the tegrated process for converting to benzene a portion of the
thermal hydrodealkylation of the alkyl aromatic in the 25 diphenyl content contained in the polymer or polyphenylbot
presence of diphenyl. However, the presence of diphenyl dur toms formed during the thermal hydrodealkylation reaction,
ing the hydrodealkylation of an alkylaromatic such as toluene thus increasing the total yield of benzene and overall process
depresses the dealkylation reaction rate of toluene to benzene. selectivity to benzene. This increase in the total yield of
Moreover, in order to obtain a high selectivity to benzene, e.g. benzene is achieved without depressing the reaction rate of
about 98 percent, when thermal hydrodealkylating a mixture 30 alkyl aromatic to benzene in the main reaction zone. Thus, the
of toluene and diphenyl (selectivity to benzene being defined process of this invention will provide favorably high benzene
as the ratio of the amount of benzene which is actually ob selectivity when the primary reaction zone is operated at a
tained to that which theoretically could be obtained if all of minimum conversion level of about 50 percent. Moreover, in
the alkyl aromatic which has reacted were converted to the process of this invention, a benzene selectivity of about 98
benzene), the process must be operated at not more than. 35 percent may be obtained when operating the primary reaction
about 75 percent conversion per pass. This requires that a Zone at a conversion in excess of 80 percent, normally
relatively high amount of the unconverted reactant material between 85 and 95 percent conversion per pass.
be recycled to the reactor for conversion to benzene. The The preferred embodiment of this invention will be further
necessity for recycling a large amount of reactant material at a 40 illustrated with reference to the accompanying drawing. In the
given temperature requires athermal hydrodealkylation unit interest of simplification of the drawing presented herein, nu
and recovery apparatus of increased size for a given benzene merous valves, pumps, and other related pieces of process
product capacity, and also requires the recycle of extra equipment have been omitted from the figure. However, it is
hydrogen commensurate with the total amount of fresh and to be understood that the addition of these omitted items may
recycle aromatics used. be accomplished without changing the nature and scope of
45 this
It is an object of this invention to provide an improved ther invention.
mal hydrodealkylation process. Referring to the drawing, the alkyl aromatic feed stock is
It is another object of this invention to provide a thermal fed into the system by way of line 11. The alkyl aromatic can
hydrodealkylation process for alkyl aromatics which results in be, for example, toluene, m-xylene, o-xylene, p-xylene, mixed
increased yields of benzene without a decrease in the reaction 50 Xylenes, ethylbenzene, propylbenzene, butylbenzene and
rate of the alkyl aromatic to benzene. other C9 and Co alkylbenzenes and mixtures of any of these.
It is a further object of this invention to provide a thermal The feed stock can also contain up to 10 percent by weight of
hydrodealkylation process for alkyl aromatics in which the heavy paraffins containing from six to 12 carbon atoms, as
main dealkylation reactors can be operated at conversions per described in U.S. Pat. No. 3,363,019.
pass of 80 percent or higher and still attain a high benzene 55 Line 11 is provided with pump 12, for compressing the feed
selectivity for the overall process. to an elevated pressure. The compressed feed is then passed
It is still another object to provide a means for separating by line 13 to a heat exchanger 14 in which it is indirectly
polyphenyls from high boiling compounds which have been heated with hot product effluent obtained as hereinafter
separated from the effluent from a primary hydrodealkylation described.
reaction Zone earlier in the operating sequence and then in 60 Makeup hydrogen-containing gas at an elevated pressure is
troducing the polyphenyls to an auxiliary reaction zone for introduced through line 15. Hydrogen can be added to the
conversion to benzene. feed at any point before the feed stream reaches process
These and other objects are attained by the practice of this heater 22 but preferably is added before process temperatures
invention which, briefly, comprises subjecting a gaseous mix of 600 F. are obtained. A portion of this hydrogen-containing
ture comprising at least one alkyl aromatic and hydrogen in a 65 gas can be passed through line 16 and combined with the feed
primary reaction zone to reaction temperatures in the range of to the auxiliary reactor 94 hereinafter described. The remain
from about 1000 to 1800 F. An effluent comprising un ing portion of the hydrogen-containing makeup gas is com
reacted hydrogen and alkyl aromatic, benzene product, bined with the alkyl aromatic feed in line 21.
polyphenyls (primarily diphenyl) and higher boiling polymers Hydrogen-containing recycle gas is introduced into line 15
is removed from the primary reaction zone. This effluent is 70 from line 17 through line 18. The makeup hydrogen gas
then passed to a separation zone in which a mixture compris stream, as well as the hydrogen-containing recycle gas stream,
ing unreacted alkyl aromatic, polyphenyls and higher boiling need not be pure hydrogen. These streams can contain
polymers are removed. The mixture is mixed with hydrogen between about 40 and 100 percent hydrogen by volume.
containing gas and then flash, vaporized to separate as a vaporPreferably, the makeup hydrogen gas stream passed through
constituents having a boiling point below about 750 to 800' 75 line 16 contains 90 percent or more hydrogen; and the com
 3,607,960
3 4.
bined makeup hydrogen and hydrogen-containing recycle gas 3,310,594. Any additional hydrogen required to satisfy the
which is combined with the alkyl aromatic feed in line 21 con hydrogenation requirements can be supplied in the form of
tains from 45 to 95 percent by volume of hydrogen. makeup gas or recycle gas.
The reactant feed stream comprising the alkyl aromatic and In chamber 35, any materials containing aliphatic unsatura
hydrogen can contain a hydrogen to aromatic hydrocarbon tion in the liquid product stream are hydrogenated to satu
mol ratio within the range of from about 1.5 to 20.0 and, rated products, thereby facilitating subsequent fractionation.
preferably, from about 3 to 10. the reactant feed stream is The thus-treated liquid product stream is then passed by line
heated in the heat exchanger 14. The reactant stream is then 36 to heat exchanger 14 wherein the effluent gives up addi
passed through line 19 to a second indirect heat exchanger 20 10 tional heat to the reactant feed stream in line 13, thereby
wherein the reactant stream is further indirectly heated with being cooled. Accordingly, the hot effluent recovered from
reaction effluent. The preheated reactant stream is passed reactor 27 supplies the heat duty of the flash tower and the
from the exchanger 20 by line 21 wherein it is combined with product stripper in addition to supplying the major portion of
makeup hydrogen from line 5 as hereinabove described, and the heat to bring the reactant feed stream up to reaction tem
then is passed to a heater or furnace 22 wherein final heating 15 perature.
of the reactant feed stream up to the reaction temperature is The hot effluent can then be passed from the exchanger 14
accomplished. The reactor feed stream heated to reaction by line 37 to a suitable cooler 38. Cooler 38 can be any suita
temperature in the heater or furnace 22 is then passed by line ble arrangement of coolers comprising a water cooler, air
23 to the first reactor 24. An effluent is recovered through the cooler, or a combination thereof which will sufficiently cool
top of the reactor 24 by line 25. This effluent optionally can be 20 the effluent for passage by line 39 to a high-pressure flash
quenched to a lower temperature by direct mixing with a cool drum 40 maintained at a pressure of about 400 p.s.i.g. and a
hydrogen-containing recycle stream obtained from a high temperature of about 100 F.
pressure flash drum more fully described hereinafter and in In high-pressure flash drum 40, a vaporous stream compris
troduced by line 26. The effluent in line 25 is thereafter in ing hydrogen, methane and small amounts of entrained
troduced into the bottom of a second reactor 27. 25 benzene product is separated from a major benzene liquid
The thermal hydrodealkylation reaction which occurs in product stream. The vaporous stream is removed from drum
reactors 24 and 27 is conducted at temperatures in the range 40 by line 41 and separated into two streams with the major
of from about 1000 to 1800°F. and a pressure of from about portion thereof being passed by line 42 to a recycle compres
100 to 1000 p.s.i.g. with a contact time or residence time of sor 43 and the minor portion of the stream being passed for
the reactants in the reactor of from about 0 to 600 seconds. 30 further treatment by line 44 as discussed hereinafter.
In a preferred embodiment of this invention, the reaction is The recycle gas stream is compressed in compressor 43 to
conducted at temperatures in the range of from about 1050 an elevated pressure suitable for recycle to the reactors
to 1400°F. and a pressure of from about 400 to 600 p.s.i.g. for thereby raising the temperature of this stream. The thus-com
from about 10 to 100 seconds. pressed recycle stream is passed by line 17 optionally to line
An effluent is recovered from the top of the reactor 27 by 35
line 28. The effluent in line 28 then optionally can be 29 and/or line 26 for use as quench material in the reactor ef
quenched to a temperature below the reaction temperature by fluent streams as discussed above; and to line 45 for use as
direct mixing with a portion of the cool recycle stream ob quench material in the effluent stream for the auxiliary reactor
tained from the high pressure flash drum hereinabove men as hereinafter described. Another portion of this recycle
tioned and introduced by a line 29, as described in U.S. Pat. 40 stream can be passed by line 18 to line 15 wherein it can be
No. 3,188,359. Alternatively, the effluent in line 28 can be combined with hydrogen-rich makeup gas. The combined gas
quenched by direct mixing with a portion of the liquid phase stream is thereafter combined with the hydrocarbon feed to be
dealkylated prior to the heat exchange steps hereinabove
obtained from the high pressure flash drum. Cooling also can discussed. Optionally, another portion of this recycle stream is
be accomplished by insertion of a steam generated in line 28
or in heat exchangers 20, 30 and 31, as more fully described 45 passed
88 and
by line 17 to line 97 and subsequently into lines 16, 85,
89 and introduced into the auxiliary reactor 94 as an
elsewhere, or by a combination of this procedure together additional or alternative source of hydrogen for this reactor.
with direct quenching as described above. Optionally, a vaporous stream of minor portion in line 44
As previously mentioned, the quenching of the effluent recovered
from reactors 24 and 27 is optional. Therefore, lines 26 and 29 0 treated to from the high pressure flash drum can be further
obtain maximum recovery of entrained benzene
can be omitted if a quench is not employed at these points. product material. To accomplish this end, the vaporous
Moreover, quenching at these points also can be accom
plished by means of liquids or gases other than the hydrogen whereininit line
stream 44 is passed to an indirect heat exchanger 46
is cooled to a temperature of about 65° F. by in
containing recycle stream illustrated.
A portion of the effluent in line 28 is passed by line 29 to a 55 direct heat exchange with refrigeration flash vapors obtained
reboiler 30 associated with the bottom of a product stripper as hereinafter described. The vaporous stream cooled in the
tower more fully discussed hereinafter, to provide the heat indirect heat exchanger 46 is then passed by line 47 through a
duty of the stripper tower. In reboiler 30, the effluent gives up refrigeration cooler 48 to further cool the vaporous stream to
a portion of its heat by indirect heat exchange with a liquid a temperature of about 40° F. The thus-cooled vaporous
stream withdrawn from the lower portion of the stripper 60 stream is then passed by line 49 to a separator 50 maintained
tower, at a temperature of about 40 F. and a pressure of about 380
p.s.l.g.
The remaining effluent in line 28 is passed to a reboiler 31 In separator drum 50, a vapor stream, referred to herein as
associated with a flash drum, more fully described hereinafter, refrigeration flash vapors, is separated and recovered from a
to provide the heat duty for the flash drum. The effluent is 65 liquid benzene stream. The refrigeration flash vapors of
removed from reboiler 31 by line 32 and is combined with the reduced temperature are passed by line 51 to the heat
effluent removed from reboiler 30 by line 33. exchanger 46 to precool the vaporous stream in line 44 as
The effluent in line 32 is combined with the effluent in line described above. The refrigeration flash vapors are recovered
96 from the auxiliary reactor (more fully described from heat exchanger 46 by line. 52 and passed to a hydrogen
hereinafter) and the combined effluents are passed by line 34 70 plant, not shown, for manufacturing fresh hydrogen.
to indirect heat exchanger 20, wherein they give up a portion The liquid benzene stream separated in drum 50 is
of their heat to preheat the feed in line 19. From indirect heat withdrawn and passed by line 53 to line 54 wherein it is com
exchanger 20, the stream is passed to a hydrogenation bined with the liquid stream recovered from the high-pressure
chamber 35 wherein it is subjected to mild hydrogenation con separator drum 40. The thus-combined stream is then passed
ditions as described in U.S. Pat. Nos. 3,310,593 and 75 to the upper portion of a product stripper tower 55.
 3,607,960
S 6
Stripper tower 55 is maintained at a temperature in the
range of from about 110°F. to about 450°F, and a pressure in
the range of from about 290 p.s.i.g. to about 400 p.s. i.g. with
heat being supplied to the lower portion of the stripper tower
by passing a liquid stream withdrawn from the lower portion
thereof by line 56 to heat exchanger 30 and thereafter return
ing the heated withdrawn stream to the tower by line 57 to
supply the heat duty of the stripper tower.
In stripper tower 55 a vaporous stream containing a small
amount of benzene is recovered from the liquid product in
troduced thereto by line 54 and removed from the upper por
tion of the tower by line 58. The vaporous stream in line 58
can be passed through refrigeration drum 48 to cool this
stream to about 40°F. from whence it is withdrawn and passed
by line 59 to separator drum 60 maintained at a temperature
of about 40 F. and a pressure of about 290 p.s.i.g. In separa
tor drum 60, a vapor stream is separated from a liquid stream
comprising benzene, the vaporous stream is removed
therefrom by line 61 and the liquid stream is removed
therefrom by line 62.
A stripped liquid product stream comprising benzene is
recovered from the bottom of the stripper tower 55 by line 63
and is passed through line 63 to line 64 and then into frac
tionator 65. The liquid stream in line 62 recovered from
separator drum 60 is also connected to line 64 in order that
this recovered liquid material may be passed to fractionator
65.
Fractionator tower 65 is designed to withdraw a benzene
product stream from the upper portion thereof by line 66
which is provided with cooler 67 for cooling the benzene
product stream to a temperature of about 100°F. To assure
recovery of a high purity benzene product stream from the
fractionator, the benzene stream is withdrawn from the frac
tionator at about the fifth tray and any lower boiling materials
are withdrawn from the top of the tower by line 68, cooled in
cooler 69 to a temperature of about 180°F. and then passed to
separator 70, All or a portion of this material is employed as a
cool reflux stream and is withdrawn from separator 70 and
returned to the top portion of the fractionator above the point
of withdrawal of benzene product material by line 71. Line 72,
which is connected to line 70, is provided for withdrawing any
excess reflux material from the fractionation system. Any
lighter than benzene material is withdrawn from separator 70
by line 73.
A liquid stream comprising unconverted alkyl aromatics,
polyphenyl-type aromatics, and higher-boiling, condensed
aromatics which are chiefly polymer bottoms is removed from
the bottom of fractionator 65 by line 74. The polyphenyls in
clude diphenyl, methyl diphenyl, C. diphenyls and triphenyls.
In order to supply the heat duty of the fractionator, which is
maintained at a temperature in the range of from about 210
F. to about 425 F., a portion of the stream 74 is passed by line
75 through heat exchanger 76 and then returned to the frac
tionator 65 by line 77. Heat for the heat exchanger 76 is sup
plied by introducing steam through line 78. Alternatively, heat
can be supplied to heat exchanger 77 by indirect heat
exchange with the effluent from hydrogenation reactor 27.
The remainder of the liquid stream from line 74 is passed by
line 79 to flash drum 80 which is operated at a pressure of
about 15 p.s. i.g. and a temperature of about 360° F. The heat
duty for the flash drum 80 is supplied by passing a liquid
stream withdrawn from the lower portion thereof by line 81 to
heat exchanger 31 and thereafter returning the heated
withdrawn stream by line 82 to the flash drum 80.
In the flash drum 80, unconverted alkyl aromatics are
removed overhead by line 83, cooled to about 100° F. and
recycled to the feed in line 11. A portion of the entire part of
the cooled liquid stream from line 83 can be employed as ad
ditional feed to the auxiliary reactor 94 by passing it through
line 84 into line 85. A stream comprising polyphenyls and
high-boiling materials is removed from the flash drum 80 by
line 86 and is passed to line 85.
if the conversion level in the system is sufficiently high, i.e.,
above about 94 percent, recovery of unconverted alkyl aro
matics for recycle to the thermal hydrodealkylation reactors
may not be justified. In that instance, the flash drum 80,
reboiler 3 and lines 81, 82, 83 and 86 can be eliminated and
the liquid stream withdrawn from the bottom of fractionator
65 by line 79 can be passed directly to line 85.
Makeup hydrogen is introduced into line 85 through line 16
O as hereinbefore described. The gaseous stream can be passed
to heat exchanger 87 wherein it is indirectly heated with hot
effluent from the auxiliary reactor as hereinafter described.
Thereafter, the stream is passed by line 88 to furnace 22
wherein it is further heated. The stream is then passed from
5 furnace 22 by line 89 to flash vaporization unit 90.
The flash vaporization unit 90 is operated at a temperature
of from about 450° to 750 F. and a pressure of about 300 to
800 p.s.i.g. In a preferred embodiment of the invention, this
unit is operated at a temperature within the range of 500 to
650 F. and a pressure of 400 to 600 p.s.i.g. The hydrogen to
aromatic hydrocarbon mol ratio of the feed to the flash
vaporization unit may be within the range of 1.5 to 20 and,
preferably, from about 4 to 10.
High-boiling hydrocarbons, preferably those boiling about
25 750 F. at atmospheric pressure are withdrawn as a liquid from
the flash vaporization unit 90 by line 91 and are purged from
the system. An all vapor feed is withdrawn from the top of
flash vaporization unit 90 and is passed by line 92 to furnace
22 wherein it is further heated. The stream is then passed from
30 furnace 22 by line 93 to auxiliary reactor 94 wherein at least a
portion of the polyphenyls is converted to benzene. The
overal reaction which takes place in the auxiliary reactor as
exemplified by C. diphenyl is represented by the following
equation;
35
C-C -
The reaction in the auxiliary reactor 94 can be conducted
thermally attemperatures in the range of from about 900 to
40 1500 F. and preferably, between 1000 to 1350 F., at pres
sure of from about 300 to 800 p.s. i.g. and, preferably, between
400 and 600 p.s.i.g. with a contact time or residence time of
from about 10 to 200 seconds and, preferably, from 20 to 120
seconds. The hydrogen to aromatic hydrocarbon mol ratio in
45 the auxiliary reactor may be from 1.5 to 20 and, preferably,
from about 4 to 10. While it is not necessary to use a catalyst
in the auxiliary reactor, nonhydrogenation-dehydrogenation
catalysts, such as natural clays, aluminas, silica-aluminas and
sulfided metal (e.g., Ni) supported catalysts can be used.
50
When a catalyst is employed in this auxiliary reactor, relative
ly less severe reaction conditions than those indicated above
for thermal conversion can be used. The auxiliary reactor 94 is
preferably sized to provide a sufficient reactant holding time
55 to obtain a maximum temperature of about 1300 F. at about
400 p.s. i.g. The auxiliary reactor is advantageously operated
at a lower temperature and so as to permit a longer contact
time than is the case with the main reactors, since the selec
tivity to benzene for a feed stock containing chiefly diphenyls
60 is improved at lower temperatures than those favoring the
selectivity to benzene of a feed stock containing chiefly
toluene or similar alkylbenzenes.
An effluent is recovered from auxiliary reactor 94 by line
95. The effluent in line 95 is quenched with recycle gas from
65 line 45. The quenched effluent is then passed to indirect heat
exchanger 87, wherein it gives up a portion of its heat to pre
heat the stream in line 85. The effluent is passed from heat
exchanger 87 through line 96 and is combined with the
product effluent stream from primary reactors 24 and 27.
TO It is preferred that the hydrogen-containing gas introduced
through line 16 which is combined with the polyphenyls in line
85 be of relatively high purity, e.g., 80 percent or more by
volume of hydrogen. Therefore, makeup. hydrogen gas is
preferred instead of recycle hydrogen-containing gas which
75 can contain only from 50 to 80 percent by volume of
 7
3,607,960
8
hydrogen. However, a mixture of recycle gas and makeup Furthermore, the use of the flash vaporization unit 90
hydrogen introduced through lines 15, 17, 97 and 16 can be results in a better selectivity-conversion relationship at a given
used, and if necessary, recycle gas alone introduced through polymer rejection rate. Thus, when the flash vaporization unit
lines 17, 97 and 16 can be employed. The use of high purity is omitted and 10 percent of the polymer bottoms are rejected
hydrogen at this stage of the process tends to increase the from the bottom of the fractionator 65, and the system is
selectivity which is obtained in the auxiliary reactor 94. operated at 85 percent toluene conversion, there is obtained
Moreover, the use of high-purity hydrogen has the further ad an overall selectivity to benzene of about 97.9 percent. By con
vantage that it reduces the total volume of reactant gas in the trast, when the flash vaporization technique of this invention is
auxiliary reactor which, in turn, reduces the required size of 10 employed and the system is operated at 5 percent polymer re
such auxiliary reactor. Furthermore, when high-purity gas is jection rate and at 85 percent toluene conversion, the overall
used in the auxiliary reactor 94, a relatively greater amount of selectivity is about 98.3 percent; and at 95 percent toluene
hydrogen gas is recovered from this reactor in the product conversion, the selectivity is about 98 percent. It will be seen,
recovery system and it subsequently enriches the recycle therefore, that the use of the flash vaporization technique of
hydrogen stream which is recycled to primary reactors 24 and 15 this invention and the selective rejection of heavy ends not
27 and thereby reduces the normal requirement of makeup only insures a noncoking, all vapor feed to the auxiliary reac
hydrogen supplied to these reactors. tor but also reduces the loss of benzene precursors by per
As a safety factor in the refrigeration section of the process mitting the unit to operate at a low rejection rate.
herein described, provision is made for introducing a portion The present invention, therefore, rejects preferentially only
of the alkyl aromatic feed, when necessary, to the vaporous 20 the heavy ends of the polymer, insures an all vapor feed to the
streams in lines 44 and 58 by way of lines 98 and 99 to avoid
freezing of any benzene material, cooled in refrigeration preheatercoke in
coils of the auxiliary reactor, avoids formation of
the preheater for the auxiliary reactor to allow for
exchanger 48.
The use of the auxiliary reactor as described herein results amount of polymerperiods
longer operating
that
without shutdown, reduces the
must be rejected and provides higher
in 3 to 4 percent higher overall yields of benzene being ob 25 selectively.
tained than in a conventional thermal hydrodealkylation The following example illustrates the practice of the inven
process wherein only fresh and unconverted alkyl benzenes tion.
are charged to a main reaction zone. Moreover, there is ob
tained a high benzene selectivity even at high conversions per EXAMPLE I
pass through the main reactors. Therefore, the main reaction 30
zones are normally operated at conversions of from 85 to 95 This example illustrates a continuous process in which all
percent per pass and the additional reaction zone is normally amounts are expressed in mols per hour of material. A feed
operated at conversions of from 60 to 90 percent per pass. comprising 2161.9 mols of hydrogen, 1083.8 mols of
These advantages are obtainable without the additional cost methane, 72.0 mols of CH, 8.1 mols of C+, 36.9 mols of
or complexity of adding any extraneous material, without in 35 benzene and 501.6 mols of toluene (of which 441.5 mols of
creased hydrogen consumption that is unproductive of addi toluene are fresh feed and the remainder are recycle) is pre
tional benzene product, and without formation of products heated in a furnace to a temperature of about 1215 F. at
requiring different separation facilities. Furthermore, the aux about 460 p.s. i.g. and is charged to a first primary reactor
iliary reactor does not influence the performance of the pri where the temperature increases to about 1285 F. The first
mary reactors and, if it must be shut down for maintenance, 40 primary reactor effluent is fed to the second primary reactor
this can be done without affecting the operation of the prima where the temperature rises to about 1340°F. The nominal re
ry reactors. sidence time of the feed in the primary and secondary reactors
The practice of this invention, i.e., the flash vaporization of is about 56 seconds. The effluent from the secondary reactor
the charge to the auxiliary reactor, selectively rejects substan comprises 1663.0 mols of hydrogen, 1600.0 mois of methane,
tially all of the high-boiling coke-forming polymer compounds 45 59.4 mols of CH, 439.8 mols of benzene 75.2 mols of
and provides an all vapor feed to the furnace which heats the toluene, and 9.4 mols of polymer, giving a net selectivity 94.5
feed to the auxiliary reactor. This, coke formation in the fur percent for this primary reactor system. After quenching with
nace is minimized resulting in fewer shutdowns of the auxiliary recycle gas, the effluent is passed through a series of heat
reactor. exchangers wherein the temperature is lowered to about 500
When the flash vaporization unit 90 is omitted and the feed 50 F. before entering the hydrogen treater for product purifica
containing high-boiling materials is fed directly to the furnace tion. The treated effluent is further cooled to about 100 F.
for the auxiliary reactor, coking of the preheater coils may and then flashed in a high-pressure separator. The liquid is
result. This coking is believed to be caused by the buildup of charged to a stripper and the gas returns in part to a recycle
the higher boiling point polymer compounds in the charge to 55 gas compressor, and in part is rejected as fuel. The liquid is
the auxiliary reactor. The buildup of these compounds raises stabilized in the stripper and charged to a fractionator
the dew point of the charge to the auxiliary reactor above the operated at a temperature of 308 F. and a pressure of 15
temperature at which liquid hydrocarbons form coke, i.e., p.s.i.g. wherein it is separated into two fractions. One fraction
about 650° to about 700°F. While this elevation of dew-point comprises substantially pure benzene in an amount of 402.9
may be partially avoided by rejecting an aliquot portion of the 60 mols. The second fraction is withdrawn from the bottom of the
polymer bottoms continuously bled from the fractionator 65, fractionator and comprises 1.9 mols of benzene, 75.2 mols of
even a 15 percent mol rejection of polymer yields a charge to toluene and 9.4 mols of polymer. This fractionator bottom
the auxiliary reactor of about 694 F. dew point. stream is mixed with hydrogen and charged to an auxiliary
For example, when 10 mol percent of polymer bottoms is reaction system, which operates at conditions resulting in a 75
rejected from the fractionator 65 and the flash vaporization 65 percent conversion of diphenyl compounds, a 15 percent con
unit 90 is omitted, the charge to the auxiliary reactor has a version of fluorene-type compounds, and a negligible conver
dew point of about 715 F. However, when no polymer is re sion of condensed aromatic compounds such as antracene.
jected from the fractionator 65 and the flash vaporization unit The unconverted polymer is recycled by mixing it with the
90 is operated to reject 10 mol percent of the polymer, the stream containing polymer recovered as fractionator bottoms
charge to the auxiliary reactor has a dew point of only about 70 from the primary reaction system and charging the mixture to
595° F. At a 5 mol percent polymer rejection rate from the the auxiliary reaction system.
flash vaporization unit 90, the dew point is only raised to Upon the attainment of a steady state composition, the
about 610°F. Thus, lees polymer need be rejected to minimize gross charge comprises 1.9 mois of benzene, 75.6 mols of
the risk of coking in the preheater for the auxiliary reactor. toluene, and 27.1 mols of polymer. The gross charge is passed
The dew points discussed above were measured at 460 p.s.i.g. 75 to a flash drum which is operated at a temperature of 360° F.
 9
3,607,960
10
and a pressure of 5 p.s.i.g. A vaporous stream is removed and alkyl aromatic, benzene product and polyphenyls
from the flash separator comprising 1.5 mols of benzene and from said primary reaction zone;
57.5 mols of toluene. This stream is cooled and recycled to the c. passing said effluent from said primary reaction zone to a
feed to the primary reactor. A liquid stream is removed from separation zone wherein a bottoms mixture comprising
the bottom of the flash separator comprising 0.4 mols of 5 unreacted alkyl aromatic, diphenyls, and substantially all
benzene, 18.1 mols of toluene and 27.1 mols of polymer, the higher boiling polymer compounds is separated;
polymer containing naphthalene, C. diphenyl, Ca fluorene, d. subjecting at least a portion of said bottoms mixture to a
C. diphenyl, C. fluorene, Cantracene-phenanthrene, and high temperature treatment in an auxiliary reaction zone
Cs aromatics including pyrene, chrysene, and other con to effect at least a partial conversion to benzene; and
densed-ring aromatics. This bottoms stream, is mixed with 10 e. recovering benzene product from the effluents from said
recycle hydrogen comprising 270.7 mols of hydrogen and 30.1 primary reaction zone and from said auxiliary reaction
mols of methane and the mixture is charged to a flash drum zone; the improvement which comprises:
heated to a temperature of 610 F. and maintained at a pres I. mixing the bottoms mixture from the separation zone
sure of 460 p.s.i.g. A liquid polymer is purged from the bottom with hydrogen-containing gas and continuously flash
of this separator comprising 0.1 mols of toluene and 1.36 mols 15 vaporizing said mixture to separate as a vapor con
of high-boiling polymer. A vapor feed is removed from the top stituents having a normal boiling point below about
of the flash drum comprising 270.7 mols of hydrogen, 30.1 750 F. and rejecting liquid higher boiling polymers;
mols of methane, 0.4 mol of benzene, 18.0 mols of toluene and
and 25.7 mols of condensed aromatics and polyphenyls. This II. subjecting said vapor in an auxiliary reaction zone to
vapor feed is then preheated to about 1230 F. and is charged 20 temperatures in the range of from about 900 to 1500
to an auxiliary reactor wherein the nominal residence time or F. whereby at least a portion of said diphenyls is con
verted to benzene.
holding time is about 110 seconds to an average reactor tem 2. The process of claim 1 wherein the effluent from said
perature of 1250 F. and is charged to an auxiliary reactor auxiliary reaction zone is combined with the effluent from said
wherein the nominal residence time or holding time is about 25 primary reaction zone before said effluent from said primary
1 10 seconds to an average reactor temperature of 1250' F. reaction zone is passed to said separation zone, and the
and a pressure of about 460 p.s. i.g. The effluent from this benzene product is thereafter recovered from the combined
reactor comprises 238.4 mois of hydrogen, 47.4 mols of effluents.
methane, 31.8 mols of benzene, 2.7 mols of toluene and 17.7 3. The process of claim 2 wherein the reaction in said pri
mols of aromatic polymer. This effluent is quenched, cooled 30 mary reaction zone is conducted at a pressure of from about
to 500 F., passed through a hydrogen treater for product pu 100 to 1000 p.s. i.g. for from about 10 to 600 seconds and the
rification, further cooled to 100' F., and then charged to a hydrogen to aromatic hydrocarbon mol ratio is within the
high-pressure separator. The liquid is charged to a stripper range of from about 1.5 to 20.0; said flash vaporization is con
and the gas returns in part to a recycle compressor and in part ducted at a pressure of from about 300 to 800 p.s.i.g. and tem
is rejected fuel. The liquid is stabilized in the stripper and 35 peratures in the range of from about 450° to 750 F.; and
charged to a fractionator wherein it is separated into two frac wherein the reaction in said auxiliary reaction zone is con
tions. One fraction comprises substantially pure benzene in ducted at a pressure of from about 300 to 800 p.s. i.g. for from
the amount of 31.1 mols. The second fraction, which is about 10 to 200 seconds and the hydrogen to hydrocarbon
withdrawn from the bottom of the racticiator, comprises a mol ratio is within the range of from about 1.5 to 20.0.
trace of benzene, 0.4 minol of ioluene and 7.7 mols of aro 40 4. The process of claim 2 wherein the reaction in said pri
matic polymer. This bottoms product is recycled by combin mary reaction zone is conducted at temperatures in the range
ing it with the bottoms product from the primary reaction of from about 1050 to 1400°F. and a pressure of from about
system to produce a mixture comprising 1.9 mols of benzene, 400 to 600 p.s.i.g. for from about 10 to 100 seconds and the
75.6 mols of toluene, and 27.1 mois of polymer, which is hydrogen to aromatic hydrocarbon mol ratio is within the
charged to the auxiliary reaction system. The selectivity to 45 range of from about 3 to 10; said flash vaporization is con
benzene without the auxiliary reactor is about 94.5 mol per ducted at a pressure of from about 400 to 600 p.s.i.g. and a
cent. The overall selectivity to benzene for the combined reac temperature of from about 500 to 650 F.; and wherein the
tion (i.e. for the reactions which take place in the primary reaction in said auxiliary reaction zone is conducted at tem
reactors and the reactions which take place in the auxiliary peratures in the range of from about 1000 to 1300 F. and a
reactors) based on the fresh feed to the entire unit is about 50 pressure of from about 400 to 600 p.s.i.g. for from about 20 to
98.3 mol percent. 120 seconds and the hydrogen to aromatic hydrocarbon mol
Obviously, many modifications and variations of the inven ratio is within the range of from about 4 to 10.
tion as hereinabove set forth can be made without departing 5. The process of claim 2 wherein at least a portion of said
from the spirit and scope thereof. unreacted alkyl aromatic is separated from the mixture ob
What we claim is: 55 tained from the separation zone and recycled to said primary
1, In a process for the thermal hydrodealkylation of an alkyl reaction Zone.
aromatic to produce benzene which comprises: 6. The process of claim 2 wherein said alkyl aromatic is
a subjecting a gaseous mixture comprising at least one alkyl toluene.
aromatic and hydrogen is a primary reaction zone to tem the7,auxiliary
The process of claim 1 wherein a catalyst is employed in
reaction zone.
peratures in the range of from about 1000 to 1800°F. to 60
effect a minimum conversion level of at least about 50 8. The process of claim 1 wherein a noncatalytic auxiliary
percent; reaction zone is employed.
b. recovering an effluent corprising :::i5:30ted hydrogen
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