Патент USA US2408753код для вставки
2,408,753 Patented on. e, Y1946 "UNITED STATES PATENT OFFICE Y TREATMENT 0F HYDEocARßoNs Robert E. Burk, Cleveland Heights, Ohio, assign or to The Standard Oil Company, Cleveland, Ohio, a corporation of Ohio Application June 22, 1943, Serial No. 491,755 s claims. (ol. 26o-_671) 1 This invention relates to the treatment of hy drocarbon stocks to form alkyl aromatics such sion of a process in which a single catalyst re covery system may be used for the isomerization and both the alkylation processes to separate the catalyst from the off-gas and make it available as ethyl benzene and iso-propyl benzene, and also branched chain aliphatics such as iso-hexanes, i or reuse. ' iso-heptanes, and iso-octanes, all of which are Cl Other objects of the invention will be apparent valuable for use as >an aviation gasoline base from „the following description of an illustrative stock, with lead tetraethyl, or blended vwith other example which is to be read in connection with stocks or in ratios other than those of normal the sheet of drawings forming a part of the speci recovery. . f , More particularly, the invention comprises a 10 fication. The cracking and separation of cracked products process in which hydrocarbons are unitary cracked so as to form an ethylene and propylene In accordance with the invention, a cracking containing fraction, an aromatic containing frac stock is subjected to “drastic” cracking, i. e., a tion, and a butane and pentane containing frac high temperature for a relatively short time. The tion; and the first fraction combined with the stock may vary from the lower gasoline range to latter two fractions through appropriate alkyla the kerosene range, although different stocks will tion and isomerization and alkylation procedures, yield somewhat different products, and in differ ent amounts when cracked, and the stock may respectively. ’ _ It is an object of the invention to provide a be selectedl with this in View, The temperature unitary process for alkylating aromatics and 20 may vary from about 1250° to 1750“ F., depending (isomerized) aliphatics formed 'inv the same on the stock, the-cracking time, and the relative y cracking process-by means of oleñns also formed amounts of the products wanted. The time may in said cracking process, so as to utilize a sub vary from about 0.1 to 0.25 seconds depending on stantial portionof the hydrocarbons formed in the stock, the temperature, and the relative cracking to provide products of the greatest value 25 amounts'of the products wanted. The pressure may vary from about atmospheric to about 300 pounds per square inch depending on the other aprocess in which essentially the same catalytic variables noted above. material may be used for the isomerization and 30 The stock is fed through an inlet I, to the both of the alkylations, >and which material com cracking furnace 2, following which it is imme for motor fuel purposes. ^ ’ ï A further object of the invention isfto provide prises essentially hydrogen fluoride and boron trifluoride. i ' Still a further object of the invention is the provision of a process in which the catalyst used in the- isomerizing and `alkylating is not delete riously affected by the products of the cracking operation, and which catalyst can be recovered l diately quenched with water or oil in the con duit 3, and fed to the tower 5. If the quench is oil it is removed at 6 with any other condensate. ' The vapor leaves the tower 5 through a conduit 1 and is subjected to a Water quench as it moves to the tower 8. The water is removed for the most part at 9. The hydrocarbons formed in the cracking op either or both of the alkylations. 40 eration are fractionated in the tower 8, the major A An additional object of the invention is the portion of the gaseous products leaving the top provision of a process in'which the catalyst used at I0, where they are compressed by the pump in one alkylation may be transferred to and used II and sent to the tower I2, where the C3 and in the other alkylation before separation of the lighter hydrocarbons are removed from the top at I3 asa gas and sent to the supply line I4. catalyst from the off-gas. ` Still a further object of the invention is to pro The C4 and heavier hydrocarbons are removed vide a> process oi great flexibility in which the ~ from the tower 8 through the conduit I5 and sent olei’ins may be used selectively for alkylating to the tower I8 by the conduit I1. Any C4 and either the aromatics or the iso-paraiiins, i. e., the heavier hydrocarbons separated in the tower I2 ethylene may be reacted with the aromatics and 50 may be added at I6 and sent to the tower I8. the prcpylene with the iso-parafûns, or the ethyl The tower I8 serves to separate the Ce and ene reacted with the iso-parañlns and the pro heavier hydrocarbons from the Cs and lighter pylene with the aromatics, or in which both ole hydrocarbons. The Ce and heavier hydrocarbons ñns may be reacted with both the aromatics and are removed at I9, and the C5 and lighter hydro iso-parafiins. f 55 carbons are sent to the tower 20 where any re . 'A further object of the invention is the provi continuously andreused in the isomerization and 3 2,408,758 4 maining C3 and lighter hydrocarbons are sepa further cracked, dealkylated or otherwise used or rated as a gas and added to the supply I4. The disposed of. C4 and C5 hydrocarbons may be separated in the The amg/lation of aromatz‘cs The benzene and/or toluene is then subjected to alkylation. Both may be alkylated together, particularly if they are separated as a single fraction, or each may be alkyl'ated separately. Alternatively, only one may be alkylated; for example, the toluene may be withdrawn and used for making explosives and only the benzene alkylated. The alkylation is carried out in the tower 2i, the C5 hydrocarbons being sent to the supply line 22, The C4 hydrocarbons are removed at 23 and if desired the butadiene may be sepa rated at 24, the butadiene removed at 25 and the remaining C4 hydrocarbons sent to the supply line 25. - If desired, the C5 and higher hydrocarbons may be returned by adjusting the valves 21 andl 28, and sent to a separate cracking furnace 0p erated at about 20° to 50° F. higher than the temperature of the furnace 2L forfur-ther crack ing. The products from this- second' cracking presence of hydrogen fiuoride as the essential catalyst promoted‘by a minor proportion of boron . 7 furnace may be fractionated in the manner de' triiluoride.v For illustrative purposes, it may be assumed that, the benzene is to be alkylated. Benzene is fed through conduit 42 to the aromatic alkylator 432. ri‘he valve 44 is opened and the valve 45 is scribed and the C5, C4 and lighter' hydrocarbons added to the respective supply lines 22, 26 and i4, The C5 and higher hydrocarbons are fed to the supply line Z 9. 20 closed. The mixture containing ethylene and lint accordance with anillustrative example, the propylenerisv admitted to the alkylator 43 through cracking stock: may be a heavy naphtha, i. e., a pipe- 46., The catalyst. is. admitted through the major portion boiling within. the range of 300 to conduit 471, valve 48 and conduit 49. Since the 450.“ F. The cracking temperature may be 1380° propylene. is more reactive they conditions may be to 1650" E, the time of cracking about 0.175 adjusted' sov that only thev propylene will react second and' the pressure about 5 pounds per square inch. Such a cracking operation will pro. and the.I product formed Will. be primarily iso propyl benzene (cumene). This is removed at âlßfandY returned at» 5| for fractionation so that the alkylate ends as one of the Wanted products Weight per cent on~ feed Ethylene __________________________ __ 17 to 23 30 in theY storage. 4l). The amount of benzene in the alkylator 43A generally is in excess of the Propylene __________________________ __ 27 to 33 stoichiometric amount of propylene to be reacted, Butadiene _________________________ __ 4 to 9 and` the unreacted benzene may be recycled Butylenes __________ __ ______________ __ 3 to 7 through the conduit 50, fractionated and re Butanes ___________________________ __ 7 to 9 , turned: to the alkylating zone through conduits Pentanes __________________________ __ 4 to 6 34` and`42’. The unreacted ethylene. and the Benzene ____________________________ __ 7 to 13 catalyst are» removed from the alkylator at 52. Toluene _________________________ __’__ 3 to 5 Xylenes 2 to 4 Valves 54, 51 and 58a are closed and- valves- 53, duce products of about` the following amounts: 58- andY 58, are open so- that ethylene and the The ethylene and prop-ylenel are fed into the 40 catalyst passte the conduit 59 to be used in the supply line t4, and to a suitableV gas holder Ma, alkylation of isopara-fñns to bel described later. from' which they may be withdrawn and used in The olefin containing gas and the benzene may the a'lkylation processes to- be described. The C4 befed tov the alkylator 43, concurrent, counter and'v C5 hydrocarbons are sent to their respective current or both;V Under the preferred conditions storage tanks 35 and Si. If desired the frac the. aromatic will be in the liquid phase and the t-icnator 2i may be omitted» and> the C4 and C5 catalyst and olefin in the gaseous phase. How hydrocarbons treated as a single> fraction and ever, all ofthe componentsñ may be in the vapor lsent to-a common storage tank. phase’or inY the liquid» phase, depending primarily The Cs and higher fraction contains a sub on the. temperature andpressure of the opera stantialV amount of benzene (C5), toluene (C1) 50 tion. In- a vapor phase operation, the tempera and xylenes (Ca). This fraction is fed from the ture` of the reaction, under the preferred condi supply line 29 tothe fractionator 52. Provision tions, is above the boiling point of hydrogen is also` made for augmenting the supply of ben fluoride atv the pressure used» (671° F. at atmos zene or other a-romatics which may be admitted pheric. pressure-l, for example, within the range through the valve 35; F., preferably 90° to- 150° F. In a The fractionator 52 preferably separates the liquid; phase operatiom the temperature would benzene and toluene; the former is sent through 13e-«25m 140° F. pipe 34 to a storage supply 35 and the latter The pressure mayA bef varied over a wide range, throughl pipe 36A to storage supply 37. If desired, but under the other conditionsv preferred a pres sure» of atmospheric to 25o" pounds per sq. in. pressure is; utilized. Under the preferred condi tions the pressure.> should below enough to per the benzene and toluene may be separated as a single fraction and sent to a common storage supply. The Xylenes and heavier aromatics are removedY from the bottom- of the fractionator 32 and sent to a fractionatorv 38. If desired, the toluene may be separated with the Xylenes and heavier aromatics. The fractionator 38 sepa mit the“ hydrogen fluoride catalyst to be gaseous except for such as may bev dissolved inv the ben f zene in the. liquidY phase'atßthe temperature used. The time; i‘n‘which'; the’reacti'on occurs will de pend;upon the sizeof. the reacting vessel, and the rate and nature ofv the. flowA of. materials through it. Under the preferred', conditions' the time of rates the> wanted aromatics- generally the Cs, C9 and Cio aromatics, such as Xylenes, ethyl benzene, iso-propyl benzene, ethyl methyl benzene, di ethyl' benzene, methyl iso-propyl benzene, etc., and they are removed through the conduit 39 and sent to storage 4d. The C7 hydrocarbons may be included in the wanted products depending on the operation of theV fractionators 32» and 38. The heavier alkylate is removed at llïlï and may be 75 reactiomiszvery shortfand is of' an order of from one-ñfth minute: to fifteen minutes, a time of from .20y to4300‘seconds being entirely satisfactory. ` The catalyst-used in the’ process, as` mentioned previously, is hydrogen fluoride promotedy by~ a minor proportionv of boron triiluoridel. . The 2,408,753 5 amount >of boron triñuoridemay vary from a trace u'p to 50 mol per cent.- Large amountsof upon the partial pressure ofthe boron fluoride and the temperature. This may be increased, if desired, by the pump 64a in the conduit 64 and boron trifluoride are not required. the boron trifluoride admitted. through the valve. , . >-.The amountofthe catalyst employed is Vnot critical except that a suflicient amount must be employed under toper mit the reaction pletion -desired. Larger amounts permit ,shorter times of reaction Aand corresponding alterations The isomerization is accomplished by .thor oughly mixing the liquid catalyst and the butane for thelrequired length of time, following which ~ the mixture is transferred to a separator 62 in in temperature and pressure and give »better yields. Under the conditions ofthe process it is preferred to employ the minimum amount that will achieve the desired Ycompleteness of the re action. In general the amount will vary from 15 about 2 to 50%, an amount of the order of about 4 to 15% is preferred. . which the hydrocarbons separate as an upperV layer and the catalyst separates as a lower layer.- Generally, the stratification may be accomplishedV by settling, but centrifuging or other separating techniques may be employed. , . The lower catalyst layer (which may be an emulsion of catalyst and hydrocarbon) is with drawn inthe conduit 63h and returned through ' The ymol ratio of olefin to benzene may be about 1 m01 of olefin to 1 to 8 mols of benzene, but the the conduit 64b to the isomerizer 6I where it malr be reused. In this way it will be apparent that higher ratios are'preferred and the excess ben-y 20 large quantities of fresh catalyst are notl re quired, but such as `may be necessary can be ad Vzene is then recycled. f VLAS a specific example, in which a propylene and mitted through the valves E5 and 65a. If the ethylene containing gas is fed to the alkylator, lower layer builds up with hydrocarbons, par and benzene is the aromatic to be alkylated, the ticularly unsaturates which may form a complex reaction may be carried out at a temperature of with thecatalyst, a portion of the lower layer 110° F. The contact time of the propylene and may -be withdrawn, the catalyst removed there the benzene may be 35 seconds, the pressure may from by heating, and the catalyst returned to the be 100 pounds per square inch. The amount of conduit 4l on any of the zones in which it’ is catalyst (hydrogen fluoride with a trace of boron triñuoride) may be about 14% based on the ben 30 The upper layer containing substantial portions zene >inthe reactor. The amounts of propylene of iso-butane iswithdrawn from the separator 62 and benzene may be 0.66 and 7.21 pounds per through the conduit 6B, and transferred .to the hour, respectively, the mol ratio of benzene to fractionator 61 in which the iso-butane is removed propylene being about 5.9> to 1.0. Under these at the top and transferred through the conduit conditions the iso-propyl benzene formed is about 35 68 to the iso-paraffin alkylator 69. The n-butane not isomerized is withdrawn from the fractionator "1.03 pounds per hour. ~ 4--While in the above examples benzene is de 61 by means of the conduit 10 and returned to scribed as the aromatic to be alkylated, toluene the isomerizer 6I through the conduit 64b. may be treated under the same conditions. If Provision is also made to admit an additional toluene is alkylated instead of benzene the prod 40 quantity of normal butane through the valve 12 uct will be primarily methyl iso-propyl benzene; if ‘the amount obtained in the cracking process if both benzene and toluene are alkylated to is not suñ‘lclent to utilize all of the olefin formed used. gether, both iso-propyl benzene and methyl iso propyl benzene will be formed as the primary products. Y » The isomerization of paramns The n-butane and n-pentane in the storages -3I and 30 are isomerized to form iso-butane and iso-pentanes. These may be isomerized together ¿or separately. However, they can be isomerized separately with facility because of the simplicity of recycling the unisomerized fraction. For i1 during cracking. . ' Y As has been mentioned previously, the isomer ization preferably is carried out under suñicient pressure to maintain the butane and the catalyst in .the liquid phase at the isomerizing tempera ture employed. This pressure is preferably ac complished by utilizing relatively high partial pressures of boron trifluoride and this partial pressure may be from 25 up .to 550 pounds per square inch. Since the catalytic activity ofthe catalyst depends in part upon the amount of lustrative purposes, it may be assumed that the ` boron triiluoride, the activity may be controlled butane is to be isomerized separately. It is re by regulating the partial pressure of the boron ‘moved from the storage 3l and fed through a trifluoride. The amount of catalyst 'used may vconduit 60 to an isomerizer B I. YCatalyst from the vary depending upon the speed of the reaction >conduit 41 may be admitted through the valve desired; in general, from 25 to 100 volume per Í62a and conduit 63. A pump 63a may be included cent of the catalyst based on the hydrocarbon »in the conduit 63 to place the catalyst under pres 60 is preferred. TheY temperature may vary from a The liquefied catalyst >sure and liquefy the same. relatively low figure, for example, --25o F. up to »is collected inthe receiver 1I. Above the liquid 215° F. Higher temperatures, however, not only trifluoride under pressure. fwill be gaseous boron require increased pressure to maintain the liquid The liquid catalyst is admitted to the isomerizer phase but also tend to undesirable cracking. The ‘5I through valve 65. The isomerization is car lengthl of time to which the hydrocarbon is sub ried out preferably w'th the catalyst in the liquid jected to the isomerizing catalyst may vary de phase, that is, with liquefied hydrogen fluoride pending upon the extent of isomerization desired .containing boron trifluoride dissolved therein. in a single pass. Inasmuch as provision is made :This is accomplished by employing a temperature for recycling, it may be more eiiicient to carry for the isomerization below the boiling point of out the reaction for shorter periods accompanied 70 the hydrogen fluoride at the pressure employed, by greater recycling; a period of from 15 minutes or in other words, a pressure at least as great as to 3 hours is preferred. l Áthe vapor pressure of the hydrogen fluoride at the It should also be understood that the tem temperature of the isomerization. Boron fluoride n perature, pressure, amount of catalyst, amount of l is dissolved in the liquefied hydrogen fluoride used ~-as the catalyst and the amount .dissolved depends lboron triñuoride and .the time of treatment are 2,4083753; more or less. interrelated' and that any one vari. ableshould be. selected and adjustedv with refer ence to the others for the most enîcient opera tion. This consideration, however, goes only to eiliciency and yields and not operability and, therefore, may be adjusted by those skilled in the: art in. view of .the descríption'herein. As an illustrative example', n-butane may be subjected tothe catalytic' action of 50 volume per cent' of liquid'v hydrogen iluoride in which is dissolved'> boron trifluoride in an amount as ,to 8 builds up‘too muchl in the form. off a catalyst hydrocarbon complex, a> portion. may be with drawn and the catalyst removedz therefrom. by heating and' the catalyst returned .to the con duit 't1Í or any of the zones utilizing the catalyst.. The upperV layer containing the alkylated products is withdrawn from the separator 'I6 through a conduit 'I3 and transferred to the fra'ctionator 19". The'alkylated products are-sep arated at the bottom of the fractionator through a. conduit 80 and sentito storage.v Since the amount of iso-butaneused preferably exceeds the amount stoichiometrically required; for reaction withA oleñns. provision.> is made for recyling the excess iso-butane through the conduit. 8l tothe 27 per cent iso-butane. alkylator 69. The above process- has. been described particu The butano fraction in the storage. 3 I' alsomay larly with reference to the isomerization of> bu contain butylenes, and if so, these may alkylate .tane but it may be carried- out in the same way with theÍ iso-butano in the isomerizer 6l.. Provi with pentane. In this event pentane is with drawn. from storage 30 and treated in the> same 20 sion is made for withdrawing such alkylates. at the bottom of the fractionator ‘61- through the manner as previously described. conduit 82 and transferring them through the If .the butano and pentane have not been sepa conduit lliV where they are separated with the rated. by a fractionator such as shown at 2'I so wanted alkylated- productsr in the conduit 80. the normal hydrocarbon for isomerization is a The alkylation reaction preferably should be mixture, or if it is desired to isomerize both the carried out with an excess of the. iso-parañìn to butane and pentane simultaneously by withdraw promote complete utilization of. the oleñn and ing from both the storages 30 and 3|, .this :can repress» polymerization thereof. In. general, the also be accomplished in Ithe same manner de mol. ratioy of oleñn to iso-paraíñn should be 1:2 scribed previously. Under such circumstances, however, it is desirable tov utilize an additional 30 to 12. The pressure should be sufûcient to main tain the isobutane and the catalyst inthe liquid fractionator .to separate the: iso-butane and iso phase. This may be accomplished preferably by pentane from the normal butane and, normal employing a relatively high partial pressure of pentane after isomerizationso that both of .the boron triiluoride. The temperature. may vary unisornerized, normal hydrocarbons may be re from _30° up to 160° F. In general, thetemper turnedthrough. the conduit 'lll> for further isom ature and partial. pressure of boron trifiuoride- in erization. provide a partial pressure ofA boron triñuoride of 300' pounds per square. inch'. Isomerization may be carried on for two hours at a temperature of 122° E'. The producty is found to contain about the alkylation zone- aret lower than in the isomer ization» zone. This suggestsy thatV the pump ‘I4 may be omitted and the pressure in the supply The- iso-parafñns isomerizedì in> the manner" de 110 li maintained at that desired in the alkylation. scribed previously are. then. alkylated with. an Any higher pressure for isomerization can be olefin. In the following illustrative. example it is supplied by the pump 64a.. The length of, the assumed that the n-butane has been i'somerized reaction may vary from 15 minutes. to. 3 hours separately and that the iso-butane4 will be. alkyl but the alkylation may be accomplished in some Allcylatz’on of iso-butano and/or iso-pedirme ated separately. The iso-butane coming. from what shorter time than the isomerization. The the fra'ctionator 6l is introduced into the. alkyl' amount of the catalyst may varyy from l0 to 100 ator 69 through the conduit. 63. Inasmuch as volume per cent depending upon theY speed of the alkylatíon preferably is carried' out 'm the the reaction. desired, temperature', and pressure. liquid. phase, >the catalyst may be introduced in is preferred to carryl out the' alkylation with the liquid phasefrom. the receiver ‘Il through. the 50 It a large amount of hydrogen fluoride and a- small valve T3. The olefin used> for the alkylation. in amount of boron `triiluoride or a large amount of this example is. the ethylene and catalyst con boron fluoride. and' a small amount of. hydrogen taining gas left over from. the alkylation of. the iiuoride.. aromatics, and which. existsy from. the. aromatic amount of boron tri-fluoride dissolved in alkylator 43 through conduit 52€ and valves: 53.-, Cn Ul theThe liquid hydrogen iiuoride depends on the pres 56, 58 and conduit 59. A. pump 'I5 maybe. pro sure' and temperature andV may be expressed in vided to liquefy .the hydrogen fluoride and place terms of its partial- pressure at a given temper the boron fluoride under the propel' pressure". ature. The amount of. the catalyst'„ the propor Since in the illustrative example the propylene tiony of the twovv ?luorides, the» temperature' and will have been used inr allrylatingY thearomatics’, 60 time. of the' reaction are morel or less'> interrelat the> product formed in the alkylation» of> iso-bu edi andY should be adjusted with referencey to each tane with the remaining ethylene. will? be the iso other. These adjustments arey concerned more meric hexanes. with efñciency and> yields> than> with operability The alkylation is accomplished by mixing the and may bey adjusted by' one skilled in the. art for iso-butano withV the catalyst> in'. the liquid phase the: most efñci'en-t operation in> view of the dis. in the presence of the oleñn; -after'the reaction closures herein. has proceeded to the desired extent, the mixture AS an illustrative example, iso-butano and is transferred to ythe separator 1S wherev the hy ethylene. in the' proportion of about 1:0.7 mols drocarbon and catalyst are separated preferably may be reacted atv 40° F. for 1% hours in the by gravity stratiñcati'on. The separa-tedA catalyst 70 presence of liquid> hydrogen fluoride. inl the layer (which may be a hydrocarbon-catalyst amount of 50 vol. percent of the iso-butano and emulsion) may be returned' through the conduit an amount of boron. triñuoride to provide apar "I7 to .the alkylat'or 69 and reused. In this way tial' pressure of läûîpounds’per. square inch; Con relatively small amounts of fresh» >catalyst are version> >t’olabout 60% in the.` gasoline. range is required from the supply 1|, If the 'catalyst layer 75 obtainedl The gasolinev contains: about 25% iso 2,408,753 Any pressure may- be used in the absorbing and desorbing operations. pentanes, 36 % iso-hexanes and 15% iso-heptanes. the remainder boiling below 350° F. ' ` ~ The above example has been described utiliz ing isoLbutane. The process- may be carriedl out under about the same conditions utilizing iso-- 'Alternative procedures In the examples described heretofore thevpro pylene isused to alkylate the aromatics,and the ethylene is utilized to alkylate the iso-lparafñns. If desired, this procedure may be reversed by closing valves> 44, »53, 55,~and 58 and opening pentane. For example, iso-pentane and ethylene ' may be introduced into the alkylator E9 in the ratio of about 1:0.4 mols at 40° F. for 11/2 hours in -the presence of 60 weight per centhydrogen ñuoride and an amount of boron trifluoride to provide a partial pressure of 50 pounds per square inch. TheA yield shows a conversion of about valves 45, 54, 56, 51 and 58a. I In this operation the propylene and ethylene containing supply in the line I4 is sent through the open valve 45 to the alkylator 69. The pro pylene being the more `reactive will be utilized 76%». About 30% is iso-butane which is recycled for alkylation, about 20% iso-hexanes, about 17% 1.5 to -alkylate the isofbutane and/or iso-pentane. The catalyst andunreacted ethylene will exit through the conduit 83, open valves 5l, 56; and 58a,.through the conduit 89, so that the aromatic gasoline range." ' ‘ ' alkylation is accomplished with the ethylene and mixture of .iso-butane" and iso» - Ii" desired a pentane may be `alkylated together under> about 20 catalyst contained therein which is admitted through the conduit 89. In this procedure it may the‘same conditions. or may not be necessary to admit additional cat ' Recovery of the catalyst alyst through the valve 48 depending on the amount desired with the aromatic alkylation. 'I‘he catalyst carried into the fractionator 19 with the hydrocarbon layer from the separator . The products leave the aromatic alkylator iso-heptanes, about 10% >iso-'octanes and 19% higher products, _most of which are nwithin lthe 16 isl removed at thetop of the fractionator 19 through conduit 52 whichvwill containthe sat through Vthe conduit 83 togetherwith unreacted uratedgases and the catalyst which will be sent gases, such as C1 toCs saturates and any small ` throughrvalve 54, conduit 85 and the catalyst will be absorbed and desorbed in the absorber 84 and desorber 88, respectively. In this operation the amount of unreacted oleiins.. In the illustrativo ¿example valves‘54 and 5_1 are’ closed,_valve `E55 is open so that the catalyst is sent to an absorber iso-paraii‘ins`V alkylated withy the propylene will 84»-through the conduit 8,5. The absorber may be have a slightly higher molecular weight.v For .a packed column or bubble -plate column» The example, if iso-butane is alkylated with propyl absorbent ifs-introduced as a liquid into the top ene the product will consist primarily of isomeric of the absorber 84 by meansof- a conduit 85a. heptanes,'such as'2,2l,3-trimethyl butane. _The 35 The catalyst is absorbed by or forms a loose product formed in the alkylation of the aro chemical combination with theV absorbent and is removed through the conduit 8B. Any> saturat matics will be primarily ethyl benzene. 'Additional alternative procedures' r ed C1 toACa hydrocarbons in theïsupplyl line I4 v .whichhavebeen carried throughthe alkylators ~ - 43 and 69, after the catalyst .has been extracted therefrom, exit as the oir-gas in conduit-»81 land If desired, both valves 44 and 45 may be opened and the mixture of ethylene and propylene >fed to both ofthe alkylation zones. 'I‘he alkylation may be used as fuel or for other purposes >`de in each zone may be suiiiciently vigorous to re-. e act both the propylene and ethylene in each zone . The `absorbent charged with the catalyst and removed through the conduit86 is ßsent to a de that the products exiting through the conduits :45 so 52 and 83 contain nothing but the saturated gases -sorber 88 where the catalyst is removed, and sent through conduit 44Í| Vfor use inthe isornerizing> or and catalyst. ~ In this event, valves 53 and 51 are either of the alkylating reactions. The denuded ça)'r_>sorbe'nt is returned through the conduit 85a catalyst from both alkylators is sent tothe ab-v ypending upon the composition therein. Ito the absorber 84.r , . Y Y . ¿ » ~ closed, valves 54 and 55„are opened so that the sorber 84. . , „ Si. „ IIt, willbe apparentin view -of theabove de scription that'the process is `extremely flexible in the mode of operation andthe productsto be obtained. In.- general, the -manneriny which the g _ The absorbent for- separating the catalyst from _the gas may beanyv'of a large -enumber of com «pounds which form a complexwithor otherwise >absorb hydrogen" fluoride and, boron triiluoride..` Hv`¿IElXa‘rnples are dihydroxyiluobcric acid; substi tuted `and unsubstituted- diarylketones, such as process is operated will depend upon„thecha’ráv racteristicsof theY wanted products,. the »mehrer beuzßphenone.. amines, isofparañins are to be blended either together or iniwhichthe alkylated aromatics and alkylated basic >nitrogen-.heterocy- . clic.- compounds, and other nitrogenous basic _com separately for products ofhigh anti-knock gaso-A pounds suchwas, diphenylamine, `coal tar bases, and chlorinated amines; certain aromatic ,hydro 1,60 line. . ‘ l ~ ~ , ~carbf‘ms,l ethers such as anisole `anddiphenyl ether; 'and certain metal fluorides. The temper The process has the additional advantage in that a singlecatalyst may be used for both isom erization and alkylation reactions» and maybe ¿ature-under; which they absorption operation is continuously reused and recycled through the 4carried out will depend upon the absorbent used various zones depending on the relative 'require .and -the g, pressure .conditions maintained Vand is ments of each. .such as to secure a desirable or maximum absorp-> l tion.` ` When benzophenone is the absorbent-_~ a `ten’iperature;from"near the melting pointoi’ `the . .benzophenone up »to 300511'. may be used,v pref erably 160 to 210° F; . The >desorbing may be ac‘ ,complished `at a higher temperature at-which the complex is destroyed _at least ïto some extent to i'reeîthe catalyst in theïvapor form. In the case `oi'fbenzophenone _a temperature within the range 2010300 to 530° F: may .bei used -for desorption. The process has the advantage of utilizing sub-. stantially all of the useful products of the vcrack ing to form highly desirable final products. In general, the cracking may be conducted'so` that the ,proportion of the aromatics and aliphatics to be isomerized and/or alkylated maywcorre-,~ spond. stoichiometrically with the oleflns formed by cracking and to be used in the alkylation proc .15 esses. . ~ ~ , » v _ l ' 2,408,753 11 12 It will be understood >that the description of hydrocarbon fraction boiling in the »butane the invention is illustrative of a process and that the drawing is to facilitate an understanding of the process. It is not intended to show appara tus either in form or scale that is necessarily suit pentane range and comprising a normal par añ‘inic hydrocarbon, and a C6 and heavier hy drocarbon fraction containing aromatics; intro able for practicing the invention. Similarly lno 5 ducing atleast part of the aromatic containing fraction and the lighter propylene and ethylene attempt is made to include all of the heaters, containing fraction into any alkylating zone and condensers, pumps and other apparatus that may reacting the propylene with at least a part of be necessary, as all of _these features will be ap parent to one skilled in the art in View of' lthe 10 the aromatic in the presence of a catalyst com# prising hydrogen fluoride and boron triiiuoride explanation of the process herein. c ‘ at a temperature of 80 to 210° F'., and at .a pres The invention is capable of many modinca sure of up to 250 pounds per square inch but tions in the details of operation, as will be ap not more than that necessary to maintain the parent to one skilled in the art, and all „such catalyst in the vapor phase,A withdrawing the modiñcations are to be included as arewithin 15 unreacted ethylene in admixture> with catalyst, the scope of the following claims. isomerizing the Vnormal parafûnic hydrocarbon Y in the aliphatic containing fraction-at a tem 1. The process which comprises heating hydro perature of «30° F'. to 215° F. in the presence of carbons to a relatively high temperature lfor a short time to form ethylene and propylene,~ C4 20 a catalyst comprising liquid hydrogen ñuoride in which is dissolved boron >triiluoride under a and C5 aliphatic Ahydrocarbons, and aromatics, Iclaim: partial pressure of 50 to 550 pounds per square separating Athe C3 and lighter hydrocarbons con inch, separating the isomer and transferring it taining propylene and ethylene, an aliphatic frac to a second alkylation zone, introducing the un tion selected from the group consisting of C4 hydrocarbons, >C5 hydrocarbons and a mixture 25 reacted ethylene and catalyst withdrawn from the first alkylation zone into the second alkyla thereof and comprising a normal parañ‘inic hy tion zone, alkylating the isomer at a temperature drocarbon, and a Cs and heavier hydrocarbon of ~30 to 160°A F. in the presence of liquid hy fraction containing aromatics; introducing the drogen fluoride containing dissolved boron' flu propylene and ethylene containing fraction and the aromatics into an alkylation zone and re acting the propylene with at least a part of the aromatics, isomerizing at least part of the normal parañinic hydrocarbon in the aliphatic 30 oride under a partial pressure of 50 to 200 pounds per square inch, transferring Vthe funre'acted prod ucts of the lighterfraction and catalyst contained in the same to a recovery zone, separating the fraction, transferring the ethylene from the iirst catalyst from the 'unreactedlighter products, and separating the C3 and lighter hydrocarbons con fraction boiling inV the butane-pentane range thereof and comprising a normal parafûnic hy drocarbon, and a Cs and heavier hydrocarbon the aromatic containing _fraction and the lighter alkylation zone and alkylating the isomerized 35 returning the catalyst for reuse. _ 6. The process which comprises heating a hydrocarbon with the ethylene. heavy naphtha hydrocarbon stock to `a temper 2. A process in accordance with claim 1 in ature within the range of about 1380 to 1650° F., which the »isomerization and both alkylations are for about 0.175 second to crack .said hydrocarbon carried out in the presence of a catalyst com stock and form ethylene and propylene, aliphatic prising hydrogen fluoride and boron triñuoride. hydrocarbons in the butane-pentane range, and 3. The process >which comprises heating hy aromatics, fractionating the products to yield drocarbons to a relatively high temperature for a C3 and lighter hydrocarbon fraction containing a short time to form ethylene and propylene, C4 propylene and ethylene,A an aliphatic hydrocarbon and C5 aliphatic hydrocarbons, and aromatics, taining propylene and ethyleneJ an aliphatic 4'5 and comprising a normal paraiiinic hydrocarbon, and a Cs and heavier hydrocarbon vfraction con fraction selected from vthe group consisting of taining aromatics¿introducing at least part of C4 hydrocarbons, C5 hydrocarbons and a mixture propylene and ethylene containing vfraction into fraction containing aromatics, isomerizing at »50 an alkylating zone and reacting the propylene with at least a part of the aromatic in the pres least part of the normal parañinic hydrocarbon ence of a catalyst comprising hydrogen fluoride in the aliphatic `fraction, introducing _the propyl and boron triñuoride'at a temperature of 90° ene and ethylene containing fraction and the to 150° ‘and at a ypressurenof about‘80 to 150 isomerized hydrocarbon into an alkylatinïg zone, and alkylating the isomerized hydrocarbon with V55 pounds ‘per square inch, withdrawing the un reac'ted _ethylene Iin admixture 'With catalyst, the propylene contained in the lighterwfraction, isomerizing the normal parafiìnic hydrocarbon in transferring the unreacted ethylene and intro the' aliphatic containing fraction at a temper ducing it and at least part of the aromatics into a second alkylation zone and alkylating said aromatics with the ethylene. 4. A process in accordance with claim 3 in which the isomerization and both alkylations are carried out in the presence of a catalyst com prising hydrogen ñuoride and boron triíiuoride. 5. The process which comprises heating a hy ature of 65° to 160° in the’presence of a 60 catalyst comprising 25’ to 100 volume per cent liquid hydrogen fluoride (based on rthe hydro carbon) in which is dissolved boron trifiuoride under a partial pressure of 150 to 350 pounds per square inch, separating the isomer andtran's 65 ferring it >to a second alkylation zone, introduc drocarbon stock boiling in the gasoline-kerosene ing the unreacted ethylene and catalyst With aliphatic hydrocarbons in the butane-pentane range, and aromatics, fractionating the products in' thepresence of liquid hydrogenñuoride con taining dissolved .boron fluoride under a partial drawn from the ñ'rst alkylation zone' into the range to a temperature Within the range of about second alkylation zone, the isomer being stoi 1250c to 1'750° for a time within the range of chiometrically in excess of the ethylene, alkylat about 0.1 to 0.25 second to crack said hydro carbon stock and form ethylene and propylene, 70 ing the’ isomer at a temperature of 10°v to 105° F. to yield a C3 and lighter hydrocarbon fraction containing propylene and ethylene, an aliphatic pressure of 50 to 200- 'pounds per square inch, recycling the unreacted' isomer, @withdrawing the 75 alkylated products," transferring the unreacted , 2,408,753 products of the lighter fraction and catalyst con tained in the same and contacting them with 14 8. The process which comprises heating a Y 13 heavy naphtha hydrocarbon stock to a tempera ture within the range of about 1380 to 1650° F., an absorbent, desorbing the catalyst from the for a time Within the range of about 0.1 to 0.25 absorbent, and returning the catalyst; for reuse. second to crack said hydrocarbon stock and form Ul '7. The process which comprises heating a hy ethylene and propylene, aliphatic hydrocarbons drocarbon stock boiling in the gasoline-kerosene range to a temperature within the range of about -1250° to 1750° F., for a time within the range of about 0.1 to 0.25 second to crack said hydrocar bon stock and form ethylene and propylene, ali phatic hydrocarbons in the butane-pentane in the butane-pentane range, and aromatics, fractionating the products to yield a C3 and lighter hydrocarbon fraction containing propyl ene and ethylene, an aliphatic hydrocarbon frac tion boiling in the butane-pentane range and comprising a normal parañinic hydrocarbon, and range, and aromatics, fractionating the products a Ce and heavier hydrocarbon fraction contain to yield a Cs and lighter hydrocarbon fraction ing aromatics; isomerizing the normal parañinic containing propylene and ethylene, an aliphatic 15 hydrocarbon in the aliphatic containing fraction hydrocarbon fraction boiling in the butane-pen tane range and comprising a normal parailìnic hydrocarbon, and a Ce and heavier hydrocarbon at a temperature of -5° F. to 160° F. in the pres ence of a catalyst comprising 25 to 100 volume per cent liquid hydrogen fluoride (based on the hydrocarbon) in which is dissolved boron trifluo ride under a partial pressure of 150 to 350 pounds 20 containing fraction at a temperature of _30° F. per square inch, separating the isomer and trans to 215° F. in ythe presence of a catalyst compris ferring it to an alkylation zone, transferring the ing liquid hydrogen iiuoride in which is dissolved lighter ethylene and propylene containing frac boron trifluoride and under a partial pressure of tion to the alkylation zone and reacting the pro 50 to 550 pounds per square inch, separating the pylene and at least part of the isomer at a tem 25 isomer and transferring it to an alkylation zone, perature of +10“ to 110° F., in the presence of fraction containing aromatics; isomerizing the normal parañinic hydrocarbon in the aliphatic transferring the lighter ethylene and propylene liquid hydrogen fluoride containing dissolved containing fraction to the alkylation zone and reacting the propylene and at least part of the boronfluoride under a partial pressure of boron trifluoride of 50 to 200 pounds per square inch, isomer at a temperature of -30 to 160° F. in the recycling the unreacted isomer, withdrawing the 30 presence of liquid hydrogen fluoride >containing alkylated products, withdrawing the unreacted dissolved boron ñuoride under a partial pressure ethylene in admixture with any catalyst, intro of boron trifluoride of 50 to 200 pounds per ducing at least part of the aromatic containing square inch, withdrawing the unreacted ethylene fraction and the withdrawn ethylene and catalyst in admixture with any catalyst, introducing at 35 into a second alkylating zone, and reacting the least part of the aromatic containing fraction ethylene with at least a part of the aromatic in and the withdrawn ethylene and catalyst into a the presence of a catalyst comprising hydrogen second alkylating zone, and reacting the ethylene with at least a part of the aromatic in the pres ence of a catalyst comprising hydrogen fluoride 40 and boron ‘.trifluoride at a temperature of 80 to 210° F., and at a pressure up to 250 pounds per square inch, but not more than that which will fluoride and boron triñuoride at a temperature of 90° to 150° F., and at a pressure of 80 to 150 pounds per square inch, withdrawing the unre acted products of the lighter fraction and cata lyst from the second alkylation zone and con tacting them with an absorbent, desorbing the maintain the catalyst in the vapor phase, With catalyst from the absorbent, and returning the drawing the unreacted products of the lighter 45 catalyst for reuse. ROBERT E. BURK. ~ fraction and catalyst from the secondì alkylating . zone, separating the catalyst from the unreacted lighter products, and'returning the catalyst for reuse.