Патент USA US2404499код для вставки
july 23» 1945- J. c». lvERsoN 2,404,499 ISOMERIZATION OF HYDROCARBONS Filed May 30, 1942 9 c» mo2zm3 @__ w.: «NNW mEm KMZQOU mw Í? g n@ lNvr-:NTOR JOHN o. lv RsoN ATTORNEY 2,404,499 Patented July 23, 1946 UNITED STATES PATENT- OFFICE y 2,404,499 ISOMERIZATION OF HYDROCARBONS _John O. Iverson, Chicago, Ill., assignor to Univer sal Oil Products Company, Chicago, Ill., a cor poration of Delaware Application May 30, 1942, Serial> No. 445,145 13 Claims. (Cl. 260-683.5) y l » This invention relates to a process for the s 2. A Y strictly thermal or high temperature thermal isomerization of paraii'in hydrocarbons and par catalytic methods. ticularly those of normal or mildly b-ranched structure to produce more highly branched isomers therefrom. more or less readily brought about by lContact with such metal halides as aluminum chloride While the process is particularly applicable to the isomerization of individual hydrocarbons such as normal butane representing normally gaseous isomerizable parafilns and normally liquid paraf v . The isomerization of parañin hydrocarbons is and aluminum bromide. Alternative metal hal ides not necessarily of equal efficiency include zirconium chloride, zinc chloride, ferric chloride or their bromides, or mixtures of these With each fin hydrocarbons such as pentanes and hexanes, 10 other or With aluminum halides. These halides may be used in a variety of Ways for the isomer the process of the invention may be applied to the treatment of hydrocarbon mixtures comprising both parailins and naphthenes such as, forex ample, straight-run petroleum fractions of gaso line boiling range, valthough other types of hydro 15 carbon conversion reactions in addition to isomer- « ization will take place in such treatments. As a result of these treatments the antiknock prop ization of hydrocarbons. One of the oldest ‘and simplest methods consists in rellluxing the liquid in the presence of granular and finely `divided metal halides preferably With the addition of small amounts of Water or hydrogen halide, the lower boiling isomerv being taken overhead and con densed. Other methods employ aluminum` chlo erties of the gasolines charged are improved by ride, for example, supported on `relatively inert The isomerization of paraflin and naphthene hydrocarbons to produce’more highly branched the hydrocarbon containing dissolved or entrained 20 granular materials over which the hydrocarbon the sum total of the reactions taking place. or hydrocarbon mixture to be isomerized is passed More speciñcally the present invention is con in liquid or vapor phase along with the hydrogen cernes with a mode of operation which involves halide. More recent developments in continuous closely cooperating steps, the process being par processes have involved the passage of hydrocar ticularly suitable for use in connection .Withgran-k ular metal halide catalysts of the Friedel-Crafts 25 bons to be isomerized through beds oi granular aluminum chloride and the further passage of type such as aluminum chloride. aluminum chloride into a reactor after the addi tion of a hydrogen halide. In a packed reactor, structure is becoming increasingly important in 30 this operation serves to maintain a definite amount of active metal halide on the surface of connection with petroleum refining. The isomer the packing. The present process is concerned ization of normal butane is important in view of with improvements in this type of operation so the fact that isobutane is considerably more re compounds or compounds with more condensed active than normal butane and can, for example, that some of the operating diii'ìculties commonly be more readily alkylated with oleiins such as 35 encountered are obviated. In one speciñc embodiment as applied to nor butenes to produce octanes of high antiknock mal butane representing saturated isomerizable value.v Butenes formed by the dehydrogenation hydrocarbons the present invention comprises of isobutane yield octenes which When hydrogen passing said normal butane and hydrogen chloride ated yield octanes of higher antiknock rating than those produced by subjecting normal butane to a 40 through a stationary bed of granular aluminum chloride under a temperature and pressure ade similar series of steps. Normal butane generally quate to effect isomerization while simultaneously occurs in larger amounts than isobutane so that introducing a portion of the cooler normal butane its isomerization is frequently necessary if the charge at spaced points in the aluminum chloride greatest possible utilization must be made of the gaseous products from petroleum distilling and 45 bed to control undue temperature rise therein, cracking operations. v - In the case of normally liquid hydrocarbon mix' ilures such as straight run gasoline fractions either passing the products from the aluminum-chloride contact into contact with granular absorbent ma terial for the removal of aluminum chloride con tained in products While introducing further of close cut or rather WideV boiling range proc esses involving isomerization of paraffins are of 50 amounts of cooler butane charge at spaced points in the absorbent material to control temperature deñnite Value in that the treated fractions have therein, fractionating the products from contact increased antiknock rating so that the process with the absorbent to produce hydrogen chloride,v ovlTers a means of greatly improving the quality isobutane and normal butane, recycling said hy of gasolines Without the excessive losses frequently encountered when fractions are reformed by 65 drogen chloride to commingle with normal bu 2,404,499 ' 3 tane charge, recovering said isobutane and re cycling said normal butane to further isomer Vizing treatment. In its broader aspect the feature of employing portions of hydrocarbon charge at a temperature lowerthan that obtaining in isomerizing reaction zones to counteract the tendency for undue tem peratures `rises `in .isomerizing- _reactors is 1appli- passes through line 9 containing valve I0 and line 9’ containing Valve Ill' to -contact with gran ' ular aluminum chloride contained in catalyst chamber I3 while a substantially equal portion passes through line I I containing valve I2 into and through the granular catalyst contained in catalyst chamber I4. In this strictly parallel op eration of the two catalyst chambers the'eii‘luent cable to any type .of continuous flow isomerizing materials `from chamberfIS pass through line I5 process such as, for example, a process in which 10 containing valve I5 while those from chamber I4 isomerization is effected by merely passing the pass through line I1 containing valve I 8, the hydrocarbon charge mixed with a hydrogen hal streams combining in line I9 containing valve ide through a stationary bed ofVv granular ymetal 2D «and passing to Vthe succeeding chambers con halide either alone or on a support,~or.in_processes where isomerization is effected '.by the uselof _rela tively finely divided catalyst which is carried up ` l Wardly through a reaction zone by lan ascending ` taining granular material. In case it is desired to 1.5 .operate the twocatalyst chambers in series, the -eiliuent materials from chamber I3 may be 'di Verted through line 33 containing valve 34 with >valve I6 lclosed and pass through line 31 contain stream of vapors of hydrocarbons followed by sep aration of hydrocarbons and powdered catalyst ing .valve .38 through line 25 containing valve 25 with return of the latter yto further catalytic use 20 and leading to line I I and thence through cham . either with or without intermediate regeneration. The features of the present invention and par ticularly the use of relatively cool charge to con trol temperature in theisomerizing zones will be more fully described in connection with the a+ tached drawing which shows diagrammatically by the Áuse of conventional ñgures in general side elevation an arrangement of apparatus in which the'process may be conducted. The description of the operation'is given in connection with the . treatment of normal lbutane in the interest of ber I4 with valves 36 and 24 closed so that the total eñ‘iuent materials passthrough line I] con taining valve I8 to line I9. When chamber I4 is to be used as the ñrst ofthe series the chargev is introduced through line I I containing Valve ,I2 with valve 25 closed and the e?liuent materials from chamber I4 _pass through line 35 contain ing valve 3S with valves I8 and 34 closed and thence through line 31 containing valve 38 to line 23 containing valve 24 and into catalyst chamber I3 by way of >line 9’ with valve I 0" ` simplifying the description and making it more closed.- The eñluent materials in this case pass I readily understandable though it is to be under through line I5 containing valve I6 with valve 34 stood that a similar characteristic flow may be closed into line I 9. , used on other individual hydrocarbons or on hy 35 To eiiect cooling of the reaction zones an un 1 drocarbon4 mixtures particularly those represent 3 ed by 'hydrocarbon fractions of gasoline boilingv heated portion of the charge passes through line 2i containing Valve 22 and may be then passed through line 2l containing valve 28 to interme Referring to the drawing normal butane is in diate points ,in the `catalyst chambers by way of troduced to the plant b-y Way of line I contain 40 line 29 containing valve 39 and leadingv to cata ` ing Valve 2 -leading t0 a charging pump'3 which lyst chamber I3 or line 3| containing valve 32 . discharges through -line 4 containing valve 5. Re and leading to catalyst chamberk III. The cool cycled normal butane‘enters line I from line |23 ing _or “quenching” fluid is .shown as being intro ` containing valvev I'24 as will be subsequentlyde duced at _one `single point in each chamber al scribed. In accordance lwith the present inven 45 though >it is comprised within the scope of the ` tion `the `main portion ofthe char-ge to the isom- ‘ invention to introduce the .cooling material at er'izing plant is'heated and passed to contact any point or plurality kof points which are found ` with granular aluminum chloride while a minor necessary to produce the best results. To provide i portion is reserved .for effecting cooling in _the for intermediate cooling between chambers when isomerizing zone wherein there is a tendency for 50 they .are used in series, a regulated portion of temperatures to Vrise unduly due to the eXo -cooling fluid may .be _introduced either through thermic vnature of the isomerization reaction. valve 2I’ .into line 23 :or line 25 with valve 28 Thus, the major portion of the charge is passed closed. « from Aline 4 through line 6 containing valve 'I and In the second stage of the isomerizing process l through a suitable heater 8 in which the charg 55 the _partially isomerized Ämaterials lfrom the ñrst ing material is brought to an optimum tempera zone in which they were contacted with alumi ture for its isomerizing treatment. Unheated num chloride are passed to a secondary treating portions of 'the charge are passed through line zone containing granular and preferably absorb 2| containing valve 22, and line 53 containing ent material such as, for example, porous refrac valve 54 for cooling purposes as will be described 60 tories, granular aluminas, such as bauxite clays 1in proper sequence. Provision is «made for pass ' either raw or acid treated, kieselguhr, etc, In ing a portion of the original charge through a Ithis stage further isomerizing action may occur ¿secondary heater 5I” in line 5I so that this por as the partially converted hydrocarbons contact tion of the charge may carry additional heat to the absorbent which has taken up any aluminum the stream of hydrocarbon material from the 65 chloride .carried over from the ñrst zone and at `catalyst supply chambers I3 and I4 and permit the same time metal halide-hydrocarbon com _substantially ‘vapor phase operation in the reac plexes are absorbed and removed from the reac tion chambers 45 and ‘46 >while a substantial tion products. Thus, in the ordinary operation` amount -'ofxliquid‘phase ismaintained in the cat of the process products of the primary isomeriz „ alyst -supply chambers. 70 ing zone pass through _line I9 and valve 20 into -The embodiment ofthe invention contemplates chambers containing granular absorbent mate 1the use of lisomerizing reactors either in parallel, _> rial, these chambers being used in parallel, se ‘series or series-parallel connection. ThuS, in ries or series-parallel connection as in the case `parallel operation of reactors containing alumi of the primary chambers, and .being provided num chloride the >portion ofV the heated.> Charge 7.5 with means for temperature control by the in range. ' 2,464,4ee troduction our unheatedïcharge. produc-tsv from _line |,9Vmay be introduced by-'way of line 4| containing valve 42 to a packed chamber 45, and another portion >of _the primary reaction products may be passed'through line 43 contain ing valve 44 to packed' chamber 46. ,A line' 39> 6 phase in the primary zone andvapor phase in secondary zone.' In the caseof normal butane‘ satisfactory isomerization may be effected in theI `setup of the present character by passing the" normal butane through the aluminum chloride catalyst chambers in substantial liquid phase and > eiïecting isomerization in the succeeding second containing valve 40 is also provided for the di version or bypassing of a portion of the original heated charge to the secondary reaction cham ary zone in vapor phase. In the case of normally liquid isomerizable hydrocarbons substantially liquid «phase conditions may be maintained bers as a means of temperature control therein. When chambers 45 and 46 are operating in par-_ allel, the efliuent materials from chamber 45V will follow line 41 containing valve 48 while those throughout the primary and secondary zone. In the case of normal butane temperatures of from approximately 150 to 200° F. may be maintained in the primary zone under pressures ofthe order of 250 to 350 pounds per square inch while slight from -chamber 46 follow line 49 containing valve 50, the two streams uniting in line 10 containing valve 1| and passing to the succeeding fraction ly higher temperatures of the order vof 200 to 220.D F. and the same or slightlyA lower pressure ls ating zone. When the packed chambers are uti used in the second zone.. The amount of hydro lized in series with chamber 45 as the nrst cham gen chloride present at any stage of the isomeri ber the effluent materials from this chamber will pass from line 41 through line 64 containing valve 20 zation may be varied to control the rate and character of the reactions. As a rule, amounts> 65 with valves 48 and 61 closed and follow line of from about 1 to about 20 mole per cent of 68 containing valve 69 and line 56 containing lvalve 51 to enter line 43, withvalves 44 and 55 hydrogen chloride in respect to the hydrocarbon . with valves 50 and 65 closed and through line 68v are fractionated to recover those of desired char-. or hydrocarbon mixture undergoing isomerization closed. When chamber 46 is to be used as the first in a series the eilluent materials will pass 25 may be used. Following the isomerization stages the products from line 49 through line 66 containing valve 61 acteristics, hydrocarbon recycle stocks and hy containing valve 69 to now through line 54' and valve 55 into line 4| with valves 42 and 51 closed. In this case the total effluent materials will pass through line 41 containing valve 48 into line 16. drogen chloride. Thus, the total products from the secondary isomerizing zone may be caused to pass through condenser 'l2 wherein substan tially complete liquefaction of all products isy ob For cooling purposes in the secondary zone tained and the liqueñed material passes through containing granular material line 5I containing valve 52 leading through heater 5|" and line 5|' line 13 containing valve 14 to a receiver 15 pro containing valve 52’ serve to admit heated 0r cooler charge to line 4| or line 43. Line 53 con taining valves 53’ and 54 permits the passage of cooling fluid to line 58 containing valve 59 vided with a gas release line`16 containing a valve To permit intermediate cooling between charn dividing‘the lower section from the small upper- 11 for the’removal of uncondensed‘gases. In the next step the hydrogen chloride is re covered for reuse by a convenient means such as distillation under relatively high pressures above which has branch lines 6|] containing valve 6| leading to an intermediate point in chamber 45 40 300 and usually of the order of 450 pounds »per square inch. Thus'a pump 80 takes suction on and branch line 62 containing valve 63 leading the liquid material in receiver 15 by way of line to an intermediate point in chamber 46. Again 18 containing valve 19 and discharges through these single points of introduction are merely line 8| containing valve 82 into a high pressure to illustrate any single or any multiple points fractionating column 83 containinga plate 84 which may be used as circumstances may require. section. The vapors of hydrogen chloride andv some light hydrocarbons pass through line 85 containing valve 86 and reflux is condensed dur containing valve 51. , In the preceding description the ilow through 50 ing passage through overhead condenser 81 after which hydrogen chloride passes through line 88 the catalyst chambers and packed chambers has containing upstream pressure control valve 89, been indicated as being upward but dovvnflows line 88 leading to an intermediate accumulator may also be used without departing from the 90 for the intermediate storage of hydrogen chlo scope of the invention. . The preferred arrangement of the isomerizing 55 ride and whatever hydrocarbons have passed overhead as vapor. From receiver 90 hydrogen zones permits considerable ñexibility in opera chloride is passed through line k9| ycontaining tion. Thus the major amount of isomerization ' valve 92 to line 93 leading to line 6 and thence may be brought about in the primary zones des to the primary isomerizing step. Hydrogen chlo ignated as “catalyst chambers” in contact with ride suñicient to make up any incidental losses granular aluminum chloride catalyst in the pres in the processing is admitted from line 93 con ence of hydrogen chloride; or the aluminum chlo bers when they are used in series line 53 leads to both line 54’ containing valve 55 and line 56 taining valve 94 as required. ride in the primary zone may serve in the absence of added hydrogenI chloride merely as a source . chloride is admitted only to the packed reaction of supply of catalytic material to be deposited on granular materials in the second zones desig . ' To provide for operation in which hydrogen n 65 chambers line 9 | ' containing valve 92' is provided to permit the recirculated hydrogen chloride and any hydrogen chloride introduced from iline 93 chloride is introduced to assist in the isomerizing to be introduced into line 5| ahead of Secondary action. The choice of operating procedure will heater 5|” and thence to the packed chambers. depend upon the character of the hydrocarbon The bottoms from fractionator 83 pass through or hydrocarbon mixture which it is desired to 70 nated as “packed chambers,”` towhich hydrogen isomerize. Similarly both temperature, pressure and flow rate may be varied in the primary and secondary zones so that substantially vapor phase conditions may be made to obtain in both zones, liquid phase conditions in both zones or liquid 75 line 95 and a cooler 95' and are then split into a stream passing through line 96 and valve 91 and leading to line 10 to increase the'amount of liquid and promotev more effective condensa tion in condenser 12. `The main stream of bot 2&4045499, toms.. isfpassed. through. >line 90 .containing valve. mannerA with Y an overall. _yield of; riso-,butane ~ from.z normal butane of 90 perk cent,"V the plant pro-._v ' duces4 a yield of f5`20barrels of iso-butane per . 90 to'l a' treating >stage’designated as |00 where it is treated to remove any traces of hydrogen chloride, aluminum chloride or aluminum chlo stream ride complexes preferably by contact withY alka line material such as aqueous caustic soda, be Thus the treated materials from Zone |00 Ypass through line |0| containing valve |02 10 and enter the isobutane fractionator |03 designed to effect a substantially accurate separation of this hydrocarbon. The vapors from fractionator _|03 pass through line |04 containingr valve |05 and are liquefied during passage through con , . . l. A process for the isomerization of normal» butane which comprises passing a portion of a fore` the ñnal fractionation to produce isobu tane and normal butane and separate heavy ma terials. day. I claim as my invention: normal butane charge mixed with hydrogen chloride through a stationary bed of granular aluminum chloride ata temperature and pres sureV adequate to effect isomerization while simul taneously introducing vfurther portions of the normal butane chargent spaced points in the aluminum chloride bed to control the tempera 15 ture therein, passing the products from the denser |06 after which `they pass through line aluminum chloride bed'into contact with granular I06’_ to a. receiver |01. To assist in controlling absorbent material while introducing further the fractionation in fractionator |03 a controlled portions of the butane charge at spaced points'` portion of the condensed liquid. is returned to a in the absorbent material. to control the tem point `’near the top of the fractionator by a pump 20 perature therein, fractionating the products re ||Il which takes suction in on line |08 by way of sulting from contact with the absorbent to re lineIIlS’ and discharges through line ||| con. cover hydrogen chloride, isobutane and normal> Vtaininglvalve ||2, the main portion of the iso. butane, recycling said hydrogen chloride to com butane as a product of the process following line mingle with the normal butane charge, recover |08 and valve |09 to storage or use in other 25 ing said isobutane and recycling said norma processes. butane to further isomerizing treatment. f The bottoms from fractionator |03 consist 2. A process for the isomerization of normal ing largely of normal butane together with some butane which ,comprisesr passing. a portion of heavier hydrocarbons pass through line | I3 con a normal butane charge mixed with> hydrogen taining valve | I4 to a fractionator ||5 operated 30 chloride through a stationary bed of granular to effect the separation of normal butane. Thus aluminum chloride at a temperature of from the vapors of this compound pass through line about 150 to about 200° F. and a pressure of from I I6 containing valve I |`| andare liqueiied by pas about 250 to about 350 pounds per squarev inch sage through condenser IIB after which they to effect isomerization while simultaneously in flow through line ||8’ to a receiver ||9. Again troducing further portions of the normalV butane to assist in controlling the fractionation in frac charge at spaced points in the aluminum chlo tionator ||5 pump |25 takes a portion of the ride bed to control temperature therein, passing liquid from receiver ||9 by way of line |20 and the products from the aluminum chloride bed line |20' and discharges it through line |26 con into contact with granular absorbent material taining valve |21 into a point near the top of the 40 at a temperature of from about 200 .to .about fractionator. The production of normal butane 220° F. -and under a' pressure corresponding to follows line |20 containing valve |2| to recycle substantially vapor phase 'conditions while in pump |22 which discharges through line |23 con troducing further portions of the butane chargeV taining valve |24 into line I to commingle with at spaced points in the material to control tem. the fresh charge. Hydrocarbons heavier than 45 perature therein, fractionating the products _from normal butane are withdrawn as bottoms from contact with the absorbent under a pressure substantially in excess of 300 pounds per square inch to recover hydrogen chloride, isobutane and fractionator | I5 through line |28 and through a. condenser |29 and are then removed through line |30 containing valve |3| to a suitable storage. f , The following example is given to show typical charge rates, yields and operating conditions used in a process of the present character though without the intent of correspondingly limiting the scope of the invention. The process is used to isomerize normal butane and the-total combined feed to the process in cluding fresh and recycled butane is 1,078 barrels per day. 0f this materialr 269 barrels are pre heated to a temperature of 190° 1*". and passed in 50 normal butane, recycling said hydrogen chloride to commingle with the normal butane charge, recovering said isobutane and recycling said normal butane to further- isomerizing treatment. 3. A process for the isomerization of normal butane which comprises passing a portionof a normal butane charge mixed with hydrogen chloride through a stationary bed of granular aluminum chloride at a temperature of from about 150 to about 200° F. and a pressure of from about 250 to about 350 pounds per square inch to effect isomerization while simultaneously series through catalyst Supply chambers con introducing further portions of the normal taining granular aluminum chloride. 695 bar butane charge at spaced points in the aluminum rels of the combined feed and 14,600 pounds of chloride bed to control temperature therein, pass hydrogen chloride are passed through the main ing the products from the aluminum chloride (25 heater preceding the packed reaction chambers bed into contact with granular absorbent ma and heated to a temperature of 275° F. 114 barrels per day of the combined feed at a tem perature of 157° F. is injected into the reactors which are used in parallel to oii'set the tendency toward temperature rise due to the exothermic character of the i'somerizing reaction. A pres-> sure of 250 pounds per square inch is maintained . upon both the saturators and the reactors and the hourly liquid space velocity per volume of reactor packing is 0.25. ` In operating in this terial at a temperature ofv from about 200 to about 220° F. while introducing further portions of the butane charge at spaced points in the absorbent material to control temperature there in, fractionating the products from contact with the absorbent under a pressure substantially in excess of 300 pounds per square inch to recover hydrogen chloride, isobutane and normal butane, recycling said hydrogen chloride to commingle with the normal butane charge, lrecovering said 2,404,499 10 ular absorbent material While introducing fur ther portions of said fraction at a lower tempera ture at spaced points along the line of flow isobutane and recycling said normal butane to further isomerizing treatment. 4. A process for the isomerization of normal butane which comprises passng a portion of through the absorbent material tocontrol tem perature therein, fractionating they products from , a normal butane charge mixed With hydrogencontact with the absorbent to separate -hydrogen chloride through a stationary bed of granular chloride, a treated fraction of improved anti aluminum chloride at a temperature of from knock value and a higher boiling fraction, re about 150 to about 200° F. and a pressure of from cycling said hydrogen chloride to commingle with about 250 to about 350 pounds per square inch to effect isomerization with a substantial amount 10 the charge, recovering said treated fraction andV recycling said higher boiling fraction to further of said butane in liquid phase While simultane ously introducing furtherV portions of the normal treatment. Y . '7. A process for isomerizing saturated hydro carbons which comprises heating a portion of the butane charge at spaced points in the aluminum chloride bed to control temperature therein, passing the products from the alumium chloride bed into contact with granular absorbent ma terial at a temperature of from about 200 to saturated hydrocarbon charging stock to isom- ì erizingtemperature, passing the thus heated hy drocarbons' together with a hydrogen halide v about 220° F. and under a, pressure correspond ì ing to substantially vapor phase conditions while through a stationary bed of granular metal halide a pressure substantially in excess of 300 pounds per square inch to recover hydrogen chloride. bed hrough a body of solid absorbent material while introducing an additional portion of said charging stock to at least one intermediate point isonierizing catalyst under isomerizing conditions, introducing further portions of the butane charge 20 simultaneously introducing another portion of said charging stock to at least one intermediate at spaced points in the absorbent material to point of said bed to control the temperature in control temperature therein, fractionating the the bed, passing the products from the catalyst products from contact with the absorbent under isobutane and normal butane, recycling said hy drogen chloride to commingle With the normal butane charge, recovering said isobutane and recycling said normal butane to further isomeriz of said body to control the temperature therein, , and fractionating the products discharging from said body to separate isomerized hydrocarbons 30 therefrom, ing treatment. 3. A process for isomerizing paraiiinic hydro 5. A process for the isomerization of a normal carbons which comprises heating a portion of the paraiiin hydrocarbon which comprises passing a paraiiinic hydrocarbon charging stock to isom portion of the charge of said hydrocarbon mixed erizing temperature, passing the thus heated hy with hydrogen chloride through a stationary bed of granular aluminum chloride under a temper ature and a pressure adequate to eiïect isomeriza 35 drocarbons together with a hydrogen halide tion while simultaneously introducing further por tions of the hydrocarbon charge at spaced points through a stationary bed of'granular metal halide isomerizing catalyst under isomerizing conditions, simultaneously introducing another portion of in the aluminum chloride bed to control temper- " said charging stock to at least one intermediate ature therein, passing the products from the alu-_ 40 point of said bed to control the temperature in the bed, passing the products from the catalyst minum chloride bed into contact with granular bed through a body of solid absorbent material absorbent material while introducing further while introducing an additional portion of said portions of the hydrocarbon charge at spaced charging stock 'to at least one intermediate point points in the absorbent material to control tem perature therein, fractionating the products from contact with the absorbent to separate hydrogen chloride, a lower boiling isomeric hydrocarbon fraction and unconverted normal parail‘ìn hydro 45 therefrom_ characterized in that said charging‘stock com aluminum halide. 6. A process for treating a gasoline fraction under a temperature and a pressure adequate to eiîect a substantial increase in the antiknock value thereof While simultaneously introducing further portions of said fraction at a lower tem perature at spaced points in said bed to control , 10. The process as deñned in claim 7 further characterized in that said catalyst comprises an isomerizing treatment. ` stationary bed of granular aluminum chloride ' prises a naphthene hydrocarbon. unconverted paraffin hydrocarbon to further bons to increase the antiknock Value of said frac tion which comprises passing a portion of said fraction mixed with hydrogen chloride through a ` 9. The process as defined in claim 7 further carbon, recycling said hydrogen chloride to com mingle with the paraffin hydrocarbon charge, re covering said isomeric fraction and recycling said composed predominantly of saturated hydrocar of said body to control the temperature therein, and fractionating the products discharging from said body to separate isomerized hydrocarbons 55 - 11. The process as defined in claim 8 further characterized in that said catalyst comprises an aluminum halide. 12. The process as deiined in claim 7 further characterized in that said catalyst comprises aluminum chloride and in that said hydrogen halide in hydrogen chloride. 13. The process as defined in claim 8 further characterized in that said catalyst comprises alu minum chloride and in that said hydrogen halide temperature therein, passing the products from 65 is hydrogen chloride. the aluminum chloride bed to contact with gran JOHN O. IVERSON.