United States Patent [72] Inventors Delbert L. Button Allison Park, Pa; Lawrence J. Kirby, Tokyo, Japan [21] Appl.No. 47,586 [22] Filed "June 18,1970 (45) Patented Sept. 21, 1971 [73] Assignee Gulf Research & Development Company Pittsburgh, Pa. Continuation-in-part of application Ser. No. ‘723,998, Apr. 25, 1968, now abandoned. [54] THERMAL HYDRODEALKYLATION PROCESS 8 Claims, 1 Drawing Fig [521 US.Chovn snes 60/6T2NC, 203/88, 208/48 R, 208/78, 208/99, 208/102, 260/668 F, 260/672 R, 260/674 R [51] Inte, . ‘Bo1d 3/06, CO7e 3/58, C10g 9/16 [50] Fleld of Search 260/672 NC 156) References Cited UNITED STATES PATENTS 3,152,980 10/1964 Coonradtet al 208/78 voRoceN (1 3,607,960 3,213,150 10/1965 Cabbage. 260667 3,288,875 11/1966 Payne et ai. 260/672 3,291,849 12/1966 King eta 2601672 3,296,120 1/1967 Doelp eta 208/143 3,296,323 1/1967 Myerset al. 260/672 3,390,200 6/1968 Sze. 260672 OTHER REFERENCES Fowle & Pitts“ Thermal Hydrodealkylation” Chem. Eng. Progress 58 (4) 37- 40 (April 1962) Primary Examiner—Delbert E. Gantz ‘Assistant Examiner—G. E. Schmitkons Atiorneys—Meyer Neishloss, Deane E. Keith and Thomas G. Ryder ABSTRACT: In a process for the thermal hydrodealkylation ‘of an alkyl aromatic, such as toluene, to produce benzene, ‘mixture of diphenyls and high-boiling polymers is separated as bottoms from the effluent of a primary hydrodealkylation zone. This mixture is mixed with recycle hydrogen and flash vaporized, the vapor comprising polyphenyls and hydrogen ng pasied to an auxiliary reactor wherein the polypheny are converted to benzene. The flash vaporization selectively rejects substantially all of the high-boiling polymer com Pounds which would otherwise tend to form coke in the aux iliary reactor, 4. varon 1 —= Hvorocen3,607,960 PATENTED SeP2 1 1971 a9und, wvauis YOdvA uBWATOd” 6 196 rT | Als Vl ie > v 68 N390HGAH dn-ayv INVENTORS DELBERT L. BUTTON LAWRENCE J. KIRBY3,607,' 1 ‘THERMAL HYDRODEALKYLATION PROCESS RELATED APPLICATIONS ‘This application is a continuation-in-part of Ser. No. 723,998, filed on Apr. 25, 1968 and now abandoned and is re- 5 Iated to Ser. No. $96,125, filed Nov. 22, 1966 and now aban- doned and to Ser. No, 816,145, filed Mat. 14, 1968. This invention relates to’ a process for the thermal hhydrodealkylation of alkyl aromatic compounds, More-par- ticularly, this invention relates to such process wherein higher benzene selectivity end increased benzene yields are obtained, 10 ‘he yield of benzene inthe thermal hydrodealkylation of an alkyl aromatic may be increased somewhat by conducting the thermal hydrodealkylation of the alkyl aromatic in. the presence of diphenyl. However, the presence of diphenyl dur- ing the hydrodealkylation of an alkyl aromatic auch as toluene depresses the éealkylation reaction rat of toluene to benzene. Moreover, in order to obtain a high selectivity to benzene, eg about 98 percent, when thermal hydrodealkylatng a mixture ‘of toluene and diphenyl (selectivity to benzene being defined as the ratio of the amount of benzene which is actually ob- tained {0 that which theoretically could be obtained if all of the alkyl aromatic which has reacted were converted to benzene), the process must be operated at not more than about 75'percent conversion per pass. This requires that a relatively high amount of the unconverted reactant materi be recycled to the reactor for conversion to benzene. The necessity for recycling alarge amount of reactant material ata given temperature requires thermal hydrodeatkylation unit and recovery apparatis of increased size fora given benzene product capacity, and also requires the recycle of extra hydrogen commensurate with the total amount of fresh and recycle aromatics used. Itis an object of this invention wo prov mal hydrodealkylation process. Itis another object ofthis invention to provide a thermal hhydrodealkylation process for alkyl aromatics which results in teased yields of benzene without a decrease in the reaction ‘ate ofthe alkyl aromatic to benzene. Ttis a further object of this invention to provide a thermal hydrodcalkylation process for alkyl aromatics in which the main dealkylation reactors can be operated at conversions per pass of 80 percent or higher and sill attain a high benzene Selectivity forthe overall proces ts sill another object to provide a means for separating polyphenys from high boiling compounds which have been Separated from the effluent fom a primary hydrodealkylation reaction zone easier in the operating sequence and then in- 69 toducing the polyphenys to an ausary easton zone for ‘These and other objects are attained by the practice of this invention which, briefly, comprises subjecting a gaseous {ure comprising atleast one alkyl aromatic and hydrogen In a 65 primary reaction 2one to reaction temperaturesin the range of from abou ‘An effluent. comprising un- reacted hyaogen and alkyl aromatic, benzene. product, polyphenyis (primarily diphenyl) and higher boil 5 removed from the primary reaction zone. 7 then passed to a separation zone in which a mixture compris: ing unreacted sky! aromatic, polyphenyls an higher boiling polymers are removed. The mixture is mixed with hydrogen ‘Containing gas and then flash vaporized to separate a a vapor constituents having a boiling point below about 750° to 800" 75 ‘an improved ther- 960 2 F. at atmospheric pressure (e.g. hydrogen, alkyl aromatics and polyphenyls) from the liquid higher boiling polymers boiling at atmospheric pressure at about 750° to 600° F, and above. ‘The vaporous constituents are then subjected to temperatures in the range of from about 900° to 1500" F. in an auniliary reaction zone to convert atleast a portion of the polyphenyis. to benzene. The flash vaporization of the feed to the auxiliary reactor permits the selective rejection of high-boiling polymer ‘compounds which cause coke formation in the preheater for the auxiliary reaction zone. The benzene product from the ef- fluents from the primary reaction zone and from the auxiliary reaction zone is recovered. Ina preferred embodiment, the ef- fluent from the auxliary reaction zone is combined with the ‘effluent from the prima n zone before the effluent from the primary reaction zone is passed to the separation zone and the benzene product is recovered from the separa- tion zone. Thus, the product separation equipment normally used for the separation of the products and unconverted reac tants from the primary reaction zone is also used to separate the products and unconverted reactants obtained from the auatliary reaction zone. This use of the auxiliary reaction zone provides an in- tegrated process for converting to benzene a portion of the diphenyl content contained in the polymer or polyphenyl bot- ‘toms formed during the thermal hydrodealkylation reaction, ‘thus increasing the total yield of benzene and overall process selectivity to benzene. This increase in the total yield of benzene is achieved without depressing the reaction rate of alkyl aromatic to benzene in the main reaction zone. Thus, the process of this invention will provide favorably high benzene Selectivity when the primary reaction zone is operated at a ‘minimum conversion level of about 50 itustratd wit reference tothe accompanying raving Inthe interest of simplification of the drawing presented herein, nu- merous valves, pumps, and other related pieces of process equipment have been omitted from the figure. However, it is to be understood thatthe addition of these omitted items may be accomplished without changing the nature and scope of this invention, Referring to the. drawing, the alkyl aromatic feed stock is fed into the system by way of line 11, The alkyl aromatic can be, for example, toluene, m-xylene, o-xylene, p-xylene, mixed xylenes, ethylbenzene, propylbenzene, butylbenzene and other Cy and Cy alkylbenzenes and mixtures of any of these ‘The feed stock can also contain up to 10 percent by weight of heavy paraffins containing from six to 12 carbon atoms, a8 described in U.S. Pat. No. 3,363,019. Line 11 is provided with pump 12, for compressing the feed to an elevated pressure. The compressed feed is then passed by line 13 to a heat exchanger 14 in which it is indirectly heated with hot product effluent obtained as hereinafter described, Makeup hydrogen-contais at an elevated pressure is ‘Heater 22 but preferably is added before process temperatures of 600° F. are obtained. A portion of this hydrogen-containing ‘gas can be passed through line 16 and combined withthe feed to the auxiliary reactor 94 hereinafter described. The rem: portion of the hydrogen-containing makeup gas is com- bined withthe allyl aromatic fed in line 21 Hyérogen-containing recycle gas is introduced into line 18 from Tine 17 through line 18. The makeup hydrogen gas stream, as well asthe hydrogen-containing recycle gas stream, nneed not be pure hydrogen. These streams can contain between about 40 and 100 percent hydrogen by volume. Preferably, the makeup hydrogen gas stream passed through Tine 16 contains 90 percent or more hydrogen; and the com-3,607,960 3 bined makeup hydrogen and hydrogen-containing reeycle gas which is combined withthe alkyl aromatic feed inline 21 con- tains from 45 1095 percent by volume of hydrogen. The reactant feed stream comprising the alkyl aromatic and hydrogen can contain a hydrogen to aromatic hydrocarbon mol ratio within the range of from about 1.5 10 20.0 and, preferably, from about 3 to 10. the reactant feed stream is heated in the heat exchanger 1d. The reactant stream is then passed through line 19 toa second indirect heat exchanger 20 Iwherein the reactant stream is further indiectly heated with reaction effluent, The preheated reactant stream is pasted from the exchanger 20 by line 21 wherein itis combined with makeup hydrogen from line 18 as hereinabove described, and then is passed to a heater or fumace 22 wherein inal heating of the reactant feed stream up to the reaction temperature is accomplished. The reactor feed stream heated to reaction temperature in the heater or furnace 22 is then passed by line 23 tothe first reactor 24, An effluent is recovered through the top ofthe reactor 24by line 25. This effluent optionally can be ‘quenched toa lower temperature by dcest mixing with cool hydrogen-containing recycle stream obtained from a. high- pressure flash drum more fully described hereinafter and in- troduced by line 26. The effuent inline 25 is thereafter in- twoduced into the botiom ofa second reactor 27 and a pressure of from about 100 to 1000 p.s.ig. with a contact time or residence time of the reactants in the reactor of from about In a preferred embodiment of this invention, the reaction is 10 20 as 30 ‘An effluent is recovered from the top of the reactor 27 by line 28. The effluent in line 28 then optionally can be {quenched to a temperature below the reaction temperature by direct mixing with a portion of the cool recycle stream ob- tained from the high pressure flash drum hereinabove men- tioned and introduced by a line 29, as described in U.S. Pat. No. 3,188,359. Alternatively, the effluent in line 28 can be quenched by direct mixing with a portion of the liquid phase ‘obtained from the high pressure flash drum. Cooling also can be accomplished by insertion of a steam generated in line 28 fr in heat exchangers 20, 30 and 31, as more fully described elsewhere, or by a combination of this procedure together with direct quenching as described above. ‘As previously mentioned, the quenching of the effluent from reactors 24 and 27 is optional. Therefore, lines 26 and 29 cean be omitted if a quench is not employed at these points, Moreover, quenching at these points also can be accom- plished by means of liquids or gases other than the hydrogen- containing recycle stream illustrated. ‘A portion of the effluent in line 28 is passed by line 29 to a reboiler 30 associated with the bottom of a product stripper tower more fully discussed hereinafter, to provide the heat ‘duty ofthe stripper tower. In reboiler 30, the effluent gives up 1 portion of its heat by indirect heat exchange with a liqui stream withdrawn from the lower portion of the stripper ‘The remaining effluent in line 28 is passed to a reboiler 31 associated witha flash drum, more fully described hereinafter, to provide the heat duty for the flash drum. The effluent is removed from reboiler 31 by line 32 and is combined with the effluent removed from reboiler 30 by line 33. ‘The effluent inline 32 is combined with the effluent in line 96 from the auxiliary reactor (more fully described hereinafter) and the combined effluents are passed by line 34 to indirect heat exchanger 20, wherein they give up a portion of their heat to preheat the feed in line 19. From indirect heat exchanger 20, the stream is passed to a hydrogenation ‘chamber 35 wherein itis subjected to mild hydrogenation con- ditions as deseribed in U.S. Pat. Nos. 3,310,593 and 35 45 50 60 65 10 15 4 3,310,594, Any additional hydrogen required to satisfy the hhydrogenation requirements can be supplied in the form of ‘makeup gas or recycle gas. In chamber 38, any materials containing aliphatic unsatura- tion in the liquid product stream are hydrogenated to satu- rated products, thereby facilitating subsequent fractionation. The thus-treated liquid product stream is then passed by line 36 to heat exchanger 14 wherein the effluent gives up addi- tional heat to the reactant feed stream in line 13, thereby being cooled. Accordingly, the hot effluent recovered from reactor 27 supplies the heat duty of the flash tower and the product stripper in addition to supplying the major portion of the heat to bring the reactant feed stream up to reaction tem- perature. ‘The hot effluent can then be passed from the exchanger 14 by line 37 to a suitable cooler 38. Cooler 38 can be any suita- ble arrangement of coolers comprising @ water cooler, air cooler, or a combination thereof which will sufficiently cool the effluent for passage by line 39 to a high-pressure flash drum 40 maintained at a pressure of about 400 psig. and a temperature of about 100° F Ii high-pressure flash drum = vaporous stream compris- ing hydrogen, methane and “small amounts of entrained benzene product is separated from a major benzene liquid product stream. The vaporous stream is removed from drum 40 by line 41 and separated into two streams with the major portion thereof being passed by line 42 to a recycle compres- sor 43 and the minor portion of the stream being passed for further treatment byline 44 as discussed hereinafter. ‘The recycle gas stream is compressed in compressor 43 t0 an elevated pressure suitable for recycle to the reactors thereby raising the temperature ofthis stream. The thus-com- pressed recycle stream is passed by line 17 optionally to line 29 and/or line 26 for use as quench material in the reactor ef- fluent streams as discussed above; and to line 45 for use as ‘quench material in the efluent stream forthe auxiliary reactor as hereinafter described. Another portion of this recycle stream can be passed by line 18 to line 15 wherein it can be ‘combined with hydrogen-rich makeup gas. The combined gas stream is thereafter combined with the hydrocarbon feed to be dealkylated prior to the heat exchange steps hereinabove discussed, Optionally, another portion ofthis recycle stream is passed by line 17 to line 97 and subsequently into lines 16, 85, 88 and 89 and introduced into the auxiliary reactor 94 as an additional or alternative source of hydrogen for this reactor. Optionally, a vaporous stream of minor portion in line 44 recovered from the high pressure flash drum can be further treated to obtain maximum recovery of entrained benzene product material. To accomplish this end, the vaporous stream in line 44 is passed to an indirect heat exchanger 46 ‘wherein it is cooled to a temperature of about 65°F. by in direct heat exchange with refrigeration flash vapors obtained as hereinafter described, The vaporous stream cooled in the indirect heat exchanger 46 is then passed by line 47 through a refrigeration cooler 48 to further cool the vaporous stream to a temperature of about 40° F. The thus-cooled vaporous stream is then passed by line 49 to a separator $0 maintained at a temperature of about 40° F. and a pressure of about 380 In Separator drum 50, a vapor stream, referred to herein as refrigeration flash vapors, is separated and recovered from a liquid benzene stream. The refrigeration flash vapors of reduced temperature are passed by line SI to the heat exchanger 46 to precool the vaporous stream in tine 44 as described above, The reftigeration flash vapors are recovered from heat exchanger 46 by line 52 and passed to a hydrogen plant, not shown, for manufacturing fresh hydrogen. The liquid benzene stream separated in drum 50 is ‘withdrawn and passed by line $3 to line 54 wherein itis com- bined withthe liquid stream recovered from the high-pressure separator drum 40. The thus-combined stream is then passed to the upper portion of a product stripper tower 55.3,607,960 5 Stripper tower $5 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.si.g. to about 400 ps... with heat being supplied to the lower portion ofthe stripper tower by passing a liquid stream withdrawn from the lower portion 5 thereot by line $6 to heat exchanger 30 and thereafter return- ing the heated withdrawn stream to the tower by line 87 to supply the heat duty ofthe stripper tower. In stripper tower 85 a vaporous stream containing a small amount of benzene is recovered from the liquid product in- troduced thereto by line 84 and removed from the upper por- tion of the tower by line 58. The vaporous stream in line $8 can be passed through refrigeration drum 48 to cool this, stream to about 40° F. from whence it is withdrawn and passed by line $9 to separator drum 60 msintained at a temperature of about 40° F. and a pressure of about 290 ps... 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. 20 therefrom by line 62. ‘A sttipped liquid product stream comprising benzene is recovered from the bottom of the stripper tower 85 by line 63 and is passed through Tine 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 10 1s 2s ator tower 65 is designed to withdraw a benzene product stream from the upper portion thereof by Tine 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 ine 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 retuned to the top portion of the fractionator above the point ‘of withdrawal of benzene product material by line 7. Line 72, ‘which is connected to line 79, 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, Cy diphenyls and tiphenyls In order to supply the heat duty ofthe fractionator, which is ‘maintained at a temperature in the range of from about 210° F.to about 425° Fa portion ofthe stream 74 is passed by ine 78 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 ofthe liquid stream from line 74 i passed by line 79 to flash drum 80 which is operated at @ pressure of about 15 psig, and a temperature of about 360° F. The heat duty for the flash drum 80 is supplied by passing a liquid ‘stream withdrawa from the lower portion thereof by lin 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 70, 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 ig removed from the flash drum 80 by line 86 and is passed to line 85, 30 3s 40 45 50 35 60 6s 5 6 22 wherein itis further heated. The stream is then passed from OO=-{ ‘The reaction in 94 can b3,607,960 7 hydrogen. However, a mixture of recycle gas and makeup hydrogen introduced through lines 15, 17, 97 and 16 can be used, and if necessary, recycle gas alone introduced through lines 17, 97 and 16 can be employed. The use of high purity hydrogen at this stage of the process tends to increase the selectivity which is obtained in the auxiliary reactor 94, “Moreover, the use of high-purity hydrogen has the further ad- vantage that it reduces the total volume of reactant gas in the auxiliary reactor which, in turn, reduces the required size of such auxiliary reactor. Furthermore, when high-purity gas is used in the auxiliary reactor 94, a relatively greater amount of hhydrogen gas is recovered from this reactor in the product recovery system and it subsequently enriches the recycle hydrogen stream which is recycled to primary reactors 24 and 27 and thereby reduces the normal requirement of makeup hydrogen supplied to these reactors, ‘Asa safety factor in the refrigeration section of the process herein described, provision is made for introducing a portion of the alkyl aromatic feed, when necessary, to the vaporous streams in lines 44 and 88 by way of lines 98 and 99 to avoid freezing of any benzene material, cooled in refrigeration exchanger 48. ‘The use of the ausiliary reactor as described herein results| in 3 to 4 percent higher overall yields of benzene being ob- tained than in a conventional ‘thermal hydrodealkylation process wherein only fresh and unconverted alkyl benzenes are charged to a main reaction zone. Moreover, there is ob- tained a high benzene selectivity even at high conversions per ass through the main reactors. Therefore, the main reaction zones are normally operated at conversions of from 85 to 95 percent per pass and the additional reaction zone is normally ‘operated at conversions of from 60 to 90 percent per pass. These advantages are obtainable without the additional cost or complexity of adding any extraneous material, without in- ‘creased hydrogen consumption that is unproductive of addi- tional benzene product, and without formation of products requiring different separation facilities. Furthermore, the aux- iary reactor does not influence the performance of the pri- ‘mary reactors and, if it must be shut down for maintenance, this can be done without affecting the operation of the prima- ry reactors. ‘The practice of this invention, ie, the lash vaporization of the charge to the auxiliary reactor, selectively rojectssubstan- tially all of the high-boiling coke forming polymer compounds ‘and provides an all vapor feed to the furnace which heats the feed to the auxiliary reactor. This, coke formation in the fur- ‘ace is minimized resulting in fewer shutdowns of the auxiliary reactor. ‘When the flash vaporization unit 99 is omitted and the feed ‘containing high-boiling materials is fed directly to the furnace for the auxiliary reactor, coking of the preheater coils may result. This coking is believed to be caused by the buildup of the higher boiling point polymer compounds in the charge to the auxiliary reactor. The buildup of these compounds raises the dew point of the charge to the auxiliary reactor above the ‘temperature at which liquid hydrocarbons form coke, ic., about 650° to about 700° F. While this elevation of dew-point ‘may be partially avoided by rejecting an aliquot portion of the polymer bottoms continuously bled from the fractionator 65, even a 15 percent mot rejection of polymer yields a charge to the auxiliary reactor of about 694°. dew point. For example, when 10 mol percent of polymer bottoms it rejected from the fractionator 65 and the flash vaporization unit 90 is omitted, the charge to the auxiliary reactor has a ‘dew point of about 715° F. However, when no polymer is re- jected from the fractionator 68 and the flash vaporization unit, 90 is operated to reject 10 mol percent of the polymer, the charge to the auxiliary reactor has a dew point of only about 595° F, At a 5 mol percent polymer rejection rate from the fash vaporization unit 90, the dew point is only raised to about 610° F. Thus, lees polymer need be rejected to minimize the risk of coking in the preheater for the auxiliary reactor. The dew points discussed above were measured at 460 p.s.ig. 10 20 25 30 35 40 4s 50 35 60 6s 0 15 8 Furthermore, the use of the fash vaporization unit 90 results in a better selectivity-conversion relationship ata given polymer rejection rate. Thus, when the flash vaporization unit is omitted and 10 porcent of the polymer bottoms are rejected from the bottom of the fractionator 68, and the system is ‘operated at 85 percent toluene conversion, there is obtained an overall selectivity to benzene of about 97.9 percent. By con- trast, when the flash vaporization technique of this Invention is employed and the system is operated at 5 percent polymer re- ate and at 85 percent toluene conversion, the overall ty is about 98.3 percent; and at 95 percent toluene conversion, the selectivity is about 98 percent. It will be seen, therefore, that the use of the flash vaporization technique of this invention and the selective rejection of heavy ends not only insures a noncoking, all vapor feed to the auxiliary rexc- tor but also reduces the loss of benzene precurtors by per- ‘mitting the unit to operate at alow rejection rate ‘The present invention, therefore, rejects preferentially only the heavy ends of the polymer, insures an all vapor feed to the preheater coils of the auxiliary reactor, avoids formation of coke in the preheater for the auxiliary reactor to allow for longer operating periods without shutdown, reduces the amount of polymer that must be rejected and provides higher selectively The following example illustrates the practice of the inven- tion, EXAMPLE ‘This example illustrates a continuous process in which all amounts are expressed in mols per hour of material. A feed ‘comprising 2161.9 mols of hydrogen, 1083.8 mols of methane, 72.0 mols of CH, 8.1 mols of C34, 36.9 mols of benzene and 501.6 mols of toluene (of which 441.5 mols of toluene are fresh feed and the remainder are recycle) is pre- hheated in a furnace to a temperature of about 1215° F. at about 460 p.s.ig. and is charged to a first primary reactor where the temperature increases to about 1285° F. The fist primary reactor effluent is fed to the second primary reactor where the temperature rises to: about 1340" F. The nominal re- sidence time ofthe feed in the primary and secondary reactors is about 56 seconds, The effluent from the secondary reactor comprises 1663.0 mols of hydrogen, 1600.0 mols of methane, 59.4 mols of C,H, 439.8 mols of benzene 75,2 mols of toluene, and 9.4 mols of polymer, giving a net selectivity 94.5 percent for this primary reactor system. After quenching with reoycle gas, the effluent is passed through a series of heat ‘exchangers wherein the temperature is lowered to about 500° F. before entering the hydrogen treater for product purifica- tion, The treated effluent is further cooled to about 100° F. ‘and then flashed in a high-pressure separator. The liquid is ‘charged to a stripper and the gas returns in part to a recycle 288 compressor, and in partis rejected as fuel. The liquid is Stabilized in the stripper and charged to a fractionator operated at a temperature of 308° F. and a pressure of 15 ig. wherein itis separated into two fractions. One fraction ‘comprises substantially pure benzene in an amount of 402.9. ‘mols. The second fraction is withdrawn from the bottom of the fractionator and comprises 1.9 mols of benzene, 75.2 mols of toluene and 9.4 mols of polymer. This fractionator bottom stream is mixed with hydrogen and charged to an auxiliary reaction system, which operates at conditions resulting in a 75, percent conversion of diphenyl compounds, a 15 percent con- version of fluorene-type compounds, and a negligible conver- mn of condensed aromatic compounds such as antracene, ‘The unconverted polymer is recycled by mixing it with the stream containing polymer recovered as fractionator bottoms from the primary reaction system and charging the mixture to the auxiliary reaction system, Upon the attainment of a steady state composition, the gross charge comprises 1.9 mols of benzene, 75.6 mols of toluene, and 27.1 mols of polymer. The gross charge is passed to. flash drum which is operated at a temperature of 360° F.3,607,960 9 and a pressure of 15 p.siig. A vaporous stream is removed from the flash separator comprising 1.5 mols of benzene and. ‘57.5 mols of toluene. This stream is cooled and recycled tothe feed to the primary reactor. A liquid stream is removed from the bottom of the flash separator comprising 0.4 mols of benzene, 18.1 mols of toluene and 27.1 mols of polymer, the polymer containing naphthalene, C,, diphenyl, Cys fluorene, Cys diphenyl, Cy, luorene, C,, antracene-phenanthrene, and yey aromatics including pyrene, chrysene, and other ‘con- ddensed-ring aromatics. This bottoms stream is mixed with recycle hydrogen comprising 270.7 mols of hydrogen and 30.1 mols of methane and the mixture is charged to a flash drum heated to a temperature of 610" F. and maintained at a pres- sure of 460 p.s.ig. A liquid polymer is purged from the bottom of this separator comprising 0.1 mols of toluene and 1.36 mols, of high-boiting polymer. A vapor feed is removed from the top ‘of the flash drum comprising 270.7 mols of hydrogen, 30.1 ‘mols of methane, 0.4 mol of benzene, 18.0 mols of toluene ‘and 25.7 mols of condensed aromatics and polyphenyls. This ‘vapor feed is then preheated to about 1230? F, and is charged to an auniliary reactor wherein the nominal residence time or holding time is about 110 seconds to an average reactor tem- perature of 1250° F. and is charged to an auxiliary reactor ‘wherein the nominal residence time or holding time is about N10 seconds to an average reactor temperature of 1250" F, and a pressure of about 460 p.si.g. The effluent from this reactor comprises 238.4 mols of hydrogen, 47.4 mols of ‘methane, 31.8 mols of benzene, 2.7 mols of toluene and 17.7 ‘mols of aromatic polymer. This effluent is quenched, cooled to 500" F., passed through a hydrogen treater for product pu- fication, further cooled to 100° F., and then charged to a high-pressure separator. The liquid is charged to a stripper nd the gas returns in part to a recycle compressor and in part is rejected fuel. The liquid is stabilized in the stripper and charged to a fractionator wherein it is separated into two frac- tions. One fraction comprises substantially pure benzene in the amount of 31.1 mols. The second fraction, which is withdrawn from the botiom of she fractionator, comprises a trace of benzene, 0.4 mol of toluene and 17.7 ‘mols of ato- ‘matic polymer. This bottoms product is recycled by combin- ing it with the bottoms product from the primary reaction system to produce a misture comprising 1.9 mols of benzene, 75.6 mols of toluene, and 27.1 mole of polymer, which is charged to the auxiliary reaction system, ‘The selectivity to ‘benzene without the auxiliary reactor is about 94.5 mol per- cent. The overall selectivity to benzene for the combined rexc- tion (ie. for the reactions which take place in the primary reactors and the reactions which take place in the auxiliary reactors) based on the fresh feed to the entire unit is about 98.3 mol percent. Obviously, many modifications and variations of the inven- tion as hereinabove set forth can be made without departing from the sprit and scope thereof. ‘What we claim is: 1, Ina process forthe thermal hydrodealkylation of an alkyl aromatic to produce benzene which comprises: ‘a. subjecting a gaseons mixture comprising atleast one alkyl ‘aromatic and hydrogen sy reaction zone to tem- pperaturee in the range of from about 1000” to 1800° F. to effect a minimum conversion level of at least about 50 percent; b. recovering an effluent comprising + Ind bydrogen 10 and alkyl aromatic, benzene product and polyphenyls from said primary reaction zone; «. passing said effluent from said primary reaction zone to a Separation zone wherein a bottoms mixture comprising 5 unreacted alkyl aromatic, diphenyls, and substantially all higher boiling polymer compounds is separated; 4, subjecting atleast a portion of said bottoms mixture to a high temperature treatment in an auxiliary reaction zone toeffect at least a partial conversion to benzene; and «recovering benzene product from the effluents from said primary reaction zone and from said auxiliary reaction ‘one; the improvement which comprises: ‘mixing the bottoms mixture from the separation zone with hydrogen-containing gas and continuously flash vaporizing said mixture to seperate as a vapor con- stituents having a normal boiling point below about 750° F. and rejecting liquid higher boiling polymers; and I. subjecting said vapor in an auxiliary reaction zone to temperatures in the range of from about 900" to 1500" F. whereby at least a portion of said diphenyl is con- verted to benzene. 2. The process of claim 1 wherein the effluent from said auxiliary reaction zone is combined with the effluent from said primary reaction zone before said effluent from said primary Teaction zone is passed to said separation zone, and the benzene product is thereafter recovered from the combined effluents 3. The process of claim 2 wherein the reaction in said pri- ‘mary reaction zone is conducted at a pressure of from about 100 to 1090 ps... for from about 10 to 600 seconds and the hydrogen to aromatic hydrocarbon mol ratio is within the ange of from about 1.5 to 20.0; said flash vaporization is con- ducted ata pressure of from about 300 to 800 p.s.i.g. and tem. peratures in the range of from about 450° to 750° F.; and wherein the reaction in said auxiliary reaction ducted ata pressure of from about 300 to 800 psig, for from about 10 to 200 seconds and the hydrogen to hydrocarbon ‘mol ratio is within he range of from about 1.5 to 20.0 4. The process of claim 2 wherein the reaction in said pri- ‘mary reaction zone is conducted at temperatures in the range ‘of from about 1050" to 1400° F. and a pressure of from about 4400 to 600 p.si.g. for from about 10 to 100 seconds and the hydrogen t0 aromatic hydrocarbon mol ratio is within the range of from about 3 to 10; said flash vaporization i con- ‘ducted at a pressure of from about 400 to 600 I psig. and a temperature of from about 500” to 650° F.; and wherein the reaction in said auxiliary reaction zone is conducted at tem- peratures in the range of from about 1000° to 1300" F. and a pressure of from about 400 to 600 p.s..g. for from about 20 to 120 seconds and the hydrogen to aromatic hydrocarbon mol ratio is within the range of from about 4 to 10. 5. The process of claim 2 wherein at least a portion of said ‘unreacted alkyl aromatic is separated from the mixture ob- tained from the separation zone and recycled to said primary reaction zone, 6. The process of claim 2 wherein said alkyl aromatic is toluene. 7. The process of claim 1 wherein a catalyst is employed in the auxiliary reaction zone 8. The process of claim 1 wherein a noncatalytc auxiliary reaction zone is employed, 10 20 25 30 35 40 4s 50 35 « 0 1