Sept 17, 1946- B. l.. EvERlNG Erm.. l ` 2,407,873 POLYMERIZATION OF CIAJEFINvS v All@ úlefzk F415 47 /449 59 3. v @7l ,Cßlzody' ¿i zzz@ Sept. 17, 1946*.- 2,407,873 B. L. EVERING ETAL POLYMERIZATION OF OLEFINS Filed Noi. 13, _1945 2 sheets-sheet 2 œ NNN _ NNN. e ,rma „rd „MJU„ :_ È JMW„@2%M „i 2,401,873 Patented Sept. 17, 1946 UNITED STATES; PATENT’ OFFICE A 2,407,873 PÜLYMERIZATIÜN OF OLEFINS Bernard L. Evering, Chicago, Ill., Edmond L. d’Ouville, Pittsburgh, Pa., and Don R. Carmody, Newton, Iowa, assignors to Standard Oil Com pany, Chicago, Ill., a corporation of Indiana Application November 13, 1943, Serial No. 510,112 `11 Claims. (Cl. 26o-683.15) l 2 This invention relates to the polymerization of oleñns and particularly normally gaseous oleñns hydrocarbon for making the complex We effec such as butenes by means of a liquid aluminum ln other Words, when a complex is prepared by halide-hydrocarbon complex catalyst and it per tains more particularly to a particular catalyst employed and the method of preparing, fortify ing a continuation-impart and using said catalyst. of our This copending application applica tion Serial No. 287,089, now Patent No. 2,354,652, issued August 1, 1944. When hydrocarbons are isomerized by means of aluminum halides such as aluminum chloride and aluminum bromide in the presence of hydro gen chloride a liquid aluminum halide-hydro carbon complex is formed Which itself is an actï'e catalyst for promoting isomerizatiou. After this catalyst is relatively spent for eifecting isomeriza tion it is still active for the alkylation or poly merization of oleñns and even if the catalyst is tively limit the hydrocarbon ' content thereof. continuously adding an olefin, this olefin is con tinuously absorbed or combined inthe complex until the aluminum chloride content thereof reaches extremely small proportions.. We have found that the aluminum chloride content of the complex should-be upwards of `50% and should preferably be within the approximate range of to 80%. A complex prepared from an aro matic-free distillate from a Mid-Continent crude and anhydrous aluminum chloride may for ex emple have approximately the following analysis: Weight per cent Aluminum _____________________________ „12.5 Chlorine ________________________________ __ 44 Hydrocarbon __________________________ __ 43.5 In an effort to ascertain the chemical struc relatively spent for alkylation of oleñns with isoparaiîins it is still relatively active for effecting cleñn polymerization. ture of the complex a portion of it was carefully An object of this invention is to provide a process in which an aluminum chloride-hydro in a water reflux condenser, a solid carbon carbon complex which is relatively spent in one` ~\ reaction may be used as a catalyst in another reac tion. A further object is to provide a method and means for effectively utilizing such complex until it is substantially completely spent. A further object is to provide an improved method and, f' >means of contacting olefins with an aluminum chloride-hydrocarbon complex for producing vis cous hydrocarbons of high molecular Weight. Other objects Will become apparent as the detailed description of the invention proceeds. It has long been known that oleñns could be polymerized With aluminum chloride (U. S. 1,385,620) and it has been proposed that such polymerization be effected by means oi a suspen sion of anhydrous aluminum chloride in petro- ‘i leum ether (U. S. 1,745,028). When anhydrous aluminum chloride is thus employed for effecting polymerization a complex is formed with the oleñn and it has been suggested that this complex itself acts as a polymerization catalyst by absorbing the olefin. In such cases it was deemed necessary to hydrolyze the resulting liquid in order to obtain the desired polymer. Our invention is an im provement over these known processes. decomposed by addingV Water drop by drop With constant stirring. The products were collected dioxide-acetone tower, a gas absorption tube to remove hydrogen chloride, and a permanent gas collector. The hydrocarbon layer was extracted with ether and the ether distilled from the hy drocarbon layer. The 45 volume percent over head from the distillation of the hydrocarbons had the following characteristics: Boiling range _____________ _`_ ____ __ 1421°-553° F. Refractive index_ __ ________ -_ N2"D 13820-15377 The distillation revealed plateaus at 300° F. and again at 440° F., which fractions Were character ized by pronounced terpene odors. The fraction showed varying degrees of unsaturation. The activity of the aluminum chloride-hydro carbon complex is dependent upon the nature of the bound hydrocarbon as well as the amount thereof. Complexes of little or no catalytic activity yield on hydrolysis a coke-like hydrogen deficient organic material which is often insoluble in organic solvents. Active complexes on the other hand yield on hydrolysis a hydrocarbon or“ the lubricating oil viscosity range, e. g. with a molecular Weight oi about 300 to 500 and with an average of more than 1 double bond, gener The aluminum chloride-hydrocarbon complex 50 ally 2 to âdouble bonds per molecule. For a catalytically active complex it is important that of our invention is preferably initially prepared the hydrocarbon constituent Which'is liberated on by reaction of aluminum chloride with a satu rated hydrocarbon instead oi an olefin and the saturated hydrocarbon is preferably substantially hydrolysis have a certain minimum hydrogen to-carbon ratio in relation to the total aluminum free from aromatics. By employing a saturated 55 chloride content of the complex. There should 2,407,873 3 4 be no less than 1.0 mol of aluminum chloride for each double bond in the hydrocarbon obtained on Y produced in the isomerization step with an ex traneous olefin or for Íeffecting polymerization hydrolysis. Catalysts which contain about 2 mols of extraneous oleñns. By initially preparing the of `aluminum chloride per double bond are very complex in the substantial absence of olefins we avoid the danger of employing a complex hav .suitable for polymerization. Catalysts have been used for isomerization in which the aluminum chloride ratio was as high as 10 mols of aluminum chloride per double Ábond in the oil produced on hydrolysis. Our preferred catalyst is one which ing an excessive hydrocarbon content and assure the production of the most suitable type of com plex for effecting polymerization. Once the com _plex is formed its activity may be maintained by contains from 1.0 to 5 mols of aluminum chloride 10 merely supplying make-up aluminum chloride, preferably .to a portion of the complex which is hydrolysis of the complex. The number of double `withdrawn from the system and before that com bonds can be determined by hydrogenation or plex isreturned to the system or charged to a per double bond in the oil which results from the » . subsequent conversion zone. The complex from Our active complex catalyst is a rather viscous 15 the isomerization system maybe employed for liquid khaving a specific gravity in the'general alkylation and then for polymerization or if de vicinity of 1.5 and it is not appreciably soluble in sired the complex may be sent directly from the hydrocarbons. When a hydrocarbon charging isomerization to the polymerization system. stock is introduced at the rbase of a column of such Our invention- will lbe more clearly understood complex under sufficient pressure to maintain 20 from the following detailed description read in substantially liquid phase conditions the hydro conjunction with the accompanying drawings carbon becomes intimately dispersed in the col which form a part of this specification and in umn of complex so that the presence of a second which phase is not readily discernible. On continued Figure 1 is a schematic ñow diagram illustrat introduction, however, we have found that a clear 25 ing the integration of the polymerization process hydrocarbon liquid separates from the top of a with isomerization and/or alkylation, and complex column as a _separate and distinct phase. Figure 2 is a iiow diagram illustrating a com, This product liquid may' mechanically entrain mercial application of‘our polymerization process some of the complex but entrained material may per se. be separated out in a settler and returned'to the 30 Referring to Figure 1, isomerization is effected column or adsorbed on a coke filter. For effec in system I0, alkylation in system II and poly other methods. v tive conversion the column -shoruld be at least 5 merization in system I2. The charging stock for feet in height and should preferably be l0 to 30 the isomerization may be normal butane, normal feet in height. „By using a column of complex of proper activity and height the losses of alu minum chloride by solution in the effluent p-rod uct stream is substantially eliminated. We prefer pentane, hexanes, heptanes, octanes or alight 35 paramnic naphtha, preferably a straight-run naphtha having an end point not substantially higher than about 150 to 160° F. Such charge is to avoid the introduction of solid aluminum chlo introduced to the isomerization system through riderper se into the column but any small amount line I3, hydrogen chloride is introduced through of aluminum chloride which may reach the col 40 line I4 and aluminum chloride through line I5. umn as make-up catalyst is quickly taken up by The aluminum chloride and hydrogen chloride the complex and thus utilized in maintaining the react with a portion of the charge to form the aluminum chloride content of the complex at the complex as hereinabove described and 'this com desired level. ‘ . plexthen elîects conversion of the remainder of Glenn-containing gases _ from any suitable 45 the charge at temperatures of about 100° F. to source may be employed in our process. These 250° F. or higher and at pressures from about 100» may be gaseous oleñns containing 2, 3 or 4 carbon pounds per square inch to 1000 pounds per square atoms per molecule or a mixture of any two or inch, for example,` about 450 pounds per square more of such oleñns. Also, we may use the inch, the pressure preferably being sufficient to dimers, trimers and higher polymers as charg 50 maintain the reactants in liquid phase conver ing stock for the polymerization. Dilution with sion conditions. The contact time~ may Vrange paraflinic hydrocarbons is not objectionable and from about 1 to 120 minutes depending upon in fact is highly beneficial in that such saturated the other conditions of the reaction. As the re hydrocarbons serve to dilute the polymerization action progresses a liquid complex is continu products and thus make possible the continuous ously formed.- This complex is withdrawn with removal of polymerization product from catalyst the hydrocarbons through line I 6 to separator complex. A feature of our invention is the facil I1. In separator I1 the liquid complex settles ity with which oleñns may be polymerized from out and is withdrawn through line I8. The conventional refinery streams of Ca or C4 hydro isomerization reactor may be of the type illus carbons such, for example, as streams contain 60 trated in our copending application but it is ' ing normal and isobutane, butene-l, butene--Z preferably a tower-type reactor wherein the hy and isobutylene or streams containing propane drocarbons pass as a dispersed phase upwardly and propylene or mixtures of said streams. By >through a column of complex and where make-up regulating the polymerization conditions We may aluminum chloride is continuously introduced obtain polymers of _the gasoline boiling range, 65 into this column either as a solution in a part of the incoming charge or in admixture with re heavier polymers. cycled complex.l polymers of the lubricating oil range or even Another feature of our invention is the multiple use of our improved catalyst complex. It may ñrst be employed for the cracking, dispropor tionation orisomerization of saturated hydrocar The products from separator I'I pass through line I9 to a stripping andfractionation system 70 20 from Wh'ich hydrogen chloride may be re turned by line 2 I to the isomerization system. A bons, this step being an ideal method of prepar ing the complex in the first place from aluminum chloride. The complex may then be employed either for promoting alkylation of the isoparañins 7 5 light'isomerizaticn product‘such as isobutane may be withdrawn through line 22 and a, further light product may be withdrawn through line 23 and a heavy product through line 24. This frac 12,407,873 6 tionation system forms no part of our `present invention and therefore requires no detailed de scription but it should be understood that such system includes separation and recovery of hy drogen chloride and the various hydrocarbon tion reactions they are :still highly effective for effecting olefin polymerization. The catalyst complex introduced into polymer izer I2 through line 45 may be fortified by alumi num chloride introduced through line 4B, such amount of aluminum chloride being employed components which are discharged from separa that the resulting complex will have an alumi tor I 1. num chloride content of about 40 to 80%, gener A part of the complex leaving the bottom of ally about 50%. Usually the complex will con separator Il through line I8 may be recycled through line 25 to the isomerization system, a l0 tain sufficient hydrogen chloride for polymeriza tion reaction. Any additional small amounts of part or all of it may be introduced through line hydrogen chloride may be introduced through 26 into alkylation system I I and a part or all of line lil. An olefin charging stock is introduced it may be introduced through line 21 to polymer through line 43. This olefin charging stock is ization system I 2. Into the alkylation system preferably a refinery gas stream rich in isobutyl We may also introduce make-up aluminum chlo ene and normal butenes but also containing con ride through line 28, hydrogen chloride through siderable amounts of corresponding paraffin hy line 29, an olefin or aromatic hydrocarbon drocarbons, i. e. butane and isobutane. Alter through line 3.0 and an isoparafün hydrocarbon natively, th'e charge may consist essentially of a through line Si. The isoparafñn may come from an external source 32 or from the isomerization system through line 33. rI‘he alkylation reaction may be effected at temperatures from about 0 to 212° F. depending on the olefins used, and un der pressures from about 0 to about 1000 pounds per square inch gauge. The isoparafñnic hydro carbons should be present in amounts equal to ‘and preferably in excess of the oleñnic hydrocar bons. The ratio of isoparafñn to olefin charged (external ratio) may vary from about 1:1 to 6:1 or more. Intimate Contact between the alumi num chloride-hydrocarbon complex and the hy drocarbon feed stocks may be obtained by rapid mixture of propane and propylene or it may con sist of a mixture of hydrocarbons of from 2 to 5 carbon atoms at least a substantial portion of which is oleñns. In the speciñc example here inafter set forth the olefin charge consists of a butane-butylene stream containing about 15% isobutylene, 25% normal butenes, 55% butanes and the remainder Cs and C5 hydrocarbons. The conditions in polymerizer I2 may be varied depending upon the type of olefin charged and the products desired. In the polymerization of these gaseous olefins to gasoline type or lubricat ing oil type fractions we may use temperatures of about 0° to elif)n F. and pressures sufficient to keep the reactants in liquid phase. Predomi stirring or by mixers or circulating systems or by tower-type reactors. Examples for 'more specific operating conditions are set forth in United 35 nantly gasoline type fractions may be produced at the higher temperatures and heavier lubricat States Patents 2,303,560-1-2. ing oil fractions will predominate in the product The reaction mixture is withdrawn from alkyl when the lower temperatures are used. For ation system II through line 35i to separator 55 heavy products the polymerization may range wherein the complex is separated from hydro from 40° to 0° F. or even lower, but for our pur carbons. If the catalyst is not spent with regard poses the best temperatures are in the general to alkylation it may be Withdrawn through line vicinity of about 20° to 30° F. Intimate contact 35 and at least a part of it may be recycled between the oleñnic feed gas and lthe catalyst through line 3l to the alkylation system. It is may be obtained by the use of mechanical stir possible to res-tore a part of the activity of the rers or circulating systems but remarkably supe complex by addition of aluminum chloride and rior results are obtainable by the use of a simple it is thus possible to use complex from separator tower type reactor as will be hereinafter de 3b in isomerization chamber I@ by returning it scribed in more detail. The temperature may be through line 33 and line 25. maintained by the use of suitable cooling coils. The hydrocarbon product of the alkylation re The aluminum chloride complex andthe poly action :is Withdrawn from separator 35 through merized hydrocarbons may be withdrawn through line 39 to fractionation system ¿i0 from which line d!! to separato-r 50 from which complex may material lighter than isobutane 4may be removed be withdrawn through line 5I and either re through line di, isobutane ‘for recycling may be cycled through line 52 or be Withdrawn from withdrawn through line 112, a .light `alkylate may the system through line 53, a part usually being be withdrawn through line ¿i3 and a heavy prod recycled for further fortification for use with uct through line Mi. It should be understood aluminum chloride and another part being With that any type of stripping, fractionation and re drawn. covery system may be employed. The polymerized hydrocarbons are Withdrawn The catalyst from the alkylation reaction may no longer be effective for promoting the reaction 60 from the separator through line 54 and a part of them may be recycled through line 55 to the between olefin and isoparaffin and yet may not polymerization reactor or system I2. The re be spent as regards further catalyst activity. For this reason a part or all of it may be withdrawn from separator 35, line 33 and line A15 to poly merization system I2 wherein olef'lns are poly- ‘ merized to form hydrocarbons suitable for use as gasoline ‘or as lubricating oil depending upon the conditions maintained in the polymerizer. The complex withdrawn from separator 35 may con tain slightly more or slightly less bound hydro carbon than the catalyst withdrawn from sepa rator Il but generally speaking complexes from these Sources are quite similar in composition mainder may be introduced into a fractionation system ë-â from which unreacted light gases are withdrawn through line lil, low boiling liquids through line 53, light polymer through line 59 and heavy polymer through line §93. Here again it will be understood that any type of fractiona tion stripping and product recovery means may be used. If the fraction withdrawn through line 558 consists essentially of isobutane this fraction may be introduced to alkylation zone I i through line 3l and if it is predominantly normal butane it may be charged to isomerization system I0 Vand activity. Although these vcomplexes Vmay be relatively spent for the isomerization and 'alkyla 75 through Eline I3. Other methods of utilizing vari V2,407,873 7 8 `ous products will be apparent to thoseskilled in the art from the above description. An outstanding feature of our integrated proc mixerßl or through line ‘l0 to the top of tower 62. Spent caustic is removed from the system through line 'i I. The neutralized butane-butylene stream then ess as herein described is the multiple use of our speciñc type of improved aluminum chloride hydrocarbon complex. This complex is prefer 5 passes by lines 72 and 12a or 12b into one or both of the calcium chloride dryers 13 and 13a. The dried stream leaves the top of the dryers ably initially prepared by a reaction such as isomerization which involves a saturated hydro carbon so that the resulting complex will contain «not more than 50% and preferably yonly about 20 to 45% of bound hydrocarbon. This bound through line 'id at a pressure a little over 200 . pounds per square inch and passes through heat exchanger 'l5 wherein it is cooled from about 100D F. to about 70° F. The stream is then joined by recycled product stream from line 16 hydrocarbon, While derived from saturated hy drocarbons, is unsaturated in character. The which brings the resulting temperature down to character of the bound hydrocarbons from the about 40° F. The mixture next passes through -isomerization or alkylation complex should be 15 cooler Tl which lowers the temperature of the such that on hydrolysis of the complex it will stream to about 0° F. About 0.86 pound per hour yield a viscous oil of about 300 to 500 molecular of anhydrous hydrogen chloride is then intro weight which is characterized by limited unsat duced to the stream through line i8 and the uration, our preferred catalyst for polymeriza stream is introduced through branch line 19a, tion containing about 2 mols of aluminum chlo 20 10b and/o1' line 19e into polymerization towers ride per double bond in the oil which results 80d, 80h, and/or 00e, respectively. Each of these from complex hydrolysis. towers is about 41/2 feet in diameter by about The activity of our complex may be measured 121/2 feet in height and each is provided with by its heat of hydrolysis. In the case of alumi cooling coils tía, Sib and 0|c for removing num chloride complexes the activity for isomer 25 103,000 B. t. u. per hour. The cooling is effected ization or alkylation should be within the ap proximate limits of 60 to 75 large calories per b-y vaporization oi propane or other suitable re irigerant Within the cooling coils, the refriger ant vapors being returned by lines 32, 82a, 82h and 02e and line 83 to knock-out drum 84, then . gram atom of active aluminum; for polymeriza tion the activity should be Within the approxi -mate limits of 50 to 67 large calories per gram 30 to compressor 85, condenser 86 rand refrigerant atom of active aluminum. In the case of alumi holding drum 87. A part of the refrigerant from the holding drum passes by lines 88 and 89 num bromide complexes the activity should be within the approximate limits of 67 to 82 large calories per gram atom of active aluminum for through cooler 1l and thence by lines 90 and 83 isomerization or alkylation and within the ap- . proximate limits of 57 to 75 large calories per gram atom of active aluminum in the case of polymerization. The expression “active alumi to knock-out drum 04. The remainder of the re frigerant passes by line 0i and lines 02a, 92h and 92e to inlet ends of coils Bla, Bib and ßlc. Before initiating the polymerization each of the reactors is charged with an aluminum chlo num” means the aluminum content of the hy ride-hydrocarbon complex which has preferably drolizable aluminum compound in the liquid 40 been prepared by reaction of aluminum chloride complex material; inactive aluminium compounds with a saturated light hydrocarbon in the pres such `as oxides or hydroxides are thus not in ence of hydrogen chloride as hereinabove de cluded by the expression “active aluminum.” scribed so that said complex will have a hydro Since our invention is primarily concerned carbon content of about 20 to 60%.. A heat of with` oleñn polymerization we will now describe 45 hydrolysis within the approximate range of 50 an example of a commercial application of the to 67 large calories per gram atom of active yalu invention in a plant for producing 800,000 gallons minum will on hydrolysis yield an oil of about 300 per year of a butene polymer having a viscosity to 500 molecular weight there being about 1 to 5 of the order of ’700 to 1800 seconds Saybolt uni mols of aluminum in the complex per double versal viscosity at 210° F. The charge in this bond of the oil thus produced on hydrolysis. The case is a reñnery butane-butylene stream of ap complex can be prepared from the butane-butyl proximately the following composition: ene charge itself provided that proportions and complex-forming conditions are employed to in Mol per cent Volume per cent sure a complex of the above characteristics but 55 we prefer to prepare the initial complex by treat ing pentane, light naphtha or similar hydrocar Propylenc ___________________________________ __ 0. l 0. 1 Propane__ ._ 0.7 0.7 Isobutane_ _ Butylcnes__ Normal butane.. ' _ _ 46. 7 47. 2 _. _. 4l. 2 8. 9 40. 3 8. 8 Pentanes ____________________________________ __ l. 7 2. 0 Amyleucs ___________________________________ _ _ 0. 7 0. 9 bons with aluminum chloride in the presence of hydrogen chloride. Each reactor is about one-half iilled with such 60 complex and the charging stock is dispersed into the base of the complex by suitable distributors so that the charging stock passes upwardly as a Of the butylenes about 36% is isobutylene, 26% dispersed phase in the column of complex. The temperature in the reactors is maintained within butene-l and 38% butene-2. About 685 barrels per day (about 1200 gallons per hour) of this 65 the relatively narrow limits of about 20 to 30° F. charging stock is introduced by pump 6| at about although this temperature may be as high as 40° 260 pounds pressure into caustic tower 62 which F. if larger amounts or lower viscosity products may be about 2?/2 feet in diameter by about 12 may be tolerated and may be lower than 20° F. feet high. 41 barrels per day of 10% aqueous if heavier products are desired. 'I‘he feed inlet sodium hydroxide is introduced by pump B3 to 70 temperature may be approximately the same as line 64. The overhead streamqleaves tank 62 the average reactor temperature, theV pressure through line 65, is admixed with caustic from should be sufficient to maintain liquid phase con line 66, passed through mixer Sl and introduced version conditions and may be of the order of `100 into caustic settler S8. The settled caustic is re- ~ `turned >by pump 69 either through line 66 toV to' 500, for example 185 pounds per square inch. The space, velocity maybe ofthe order of 'about amers, Si cosity of about 50 seconds Saybolt at 100° F., an 0.1 to 10, for example 2`volumes of inlet stream (including recycled material) per volume of com A. P. I. gravity of about 43 and a flash of 130° F. The heavy polymer which is withdrawn from the base of the tower at the rate of about 60 to plex in the reactor per hour. Relatively low space velocities (.1 to 2) may be necessary with 65 barrels per stream day is forced by pump |22to cooler |23 and thence to storage. .This heavy polymer has the following characteristics: relatively inactive catalyst, and relatively high space velocities (2-10) with catalyst of high ac tivity, assuming a column height of about 5 to 20 feet. An amazing feature of this system is the Viscosity __________ __ 900 sec. Saybolt at 210° F. remarkably effective conversion which is effected Gravity A. P. I __________________________ _.. 29 without any mechanical mixers, stîrrers or circu- 10 Pour _______________________________ __ +35° F. lators the charging stock and diluted products Flash ___________________________ __ S50-400° F. being lighter than the complex passes upwardly To maintain the catalyst at the desired activ therethrough and leave the top of the reactors ity in this process complex from storage tank 96 through line 03 to settling tank 00. This tank or complex withdrawn from the reactors through may be maintained at a pressure of about 175 15 lines |25a., i255, l25c, lines |26 and |21 is intro pounds per square inch and a temperature of duced through line |28 to fortification tank |29 about 30° F. The complex which settles out in into which powdered aluminum chloride is added this tank is Withdrawn through line 95 to catalyst from source |30. The added aluminum chloride storage drum 90. About 2500 barrels per day of is intimately mixed withthe complex so that the the product leaving the top of tank 94 is recycled 20 aluminum chloride content thereof will be in creased to such an extent that when this fortified complex is returned to the polymerization re scribed. `The remainder of the product stream actors it will maintain the aluminum chloride passes through line 08 to settling drum 99 from content of the complex in said reactors within which additional catalyst is‘separated and re 25 the desired range of about 40 to 80% or prefer turned through line |00 to storage drum 90. The ably about 45 to 55%. About 2 to 10, for »example through line 76 by means of pump 97 for admix ture with the incoming stream as hereinabove de product stream next passes through lines |0| and about 6 pounds of aluminum chloride is usually |0|a or |0|b to clay towers |02a andl |021) which required per barrel of total polymer produced. operate at pressures of about 165 pounds per In this particular case about 25 pounds per hour square inch. The products leaving the clay 30 of aluminum chloride is introduced into the forti towers through line |03 pass through heat ex fying chamber along with an equal or greater changer '15 wherein they are heated to about 70° F. and then passed through heater |04 wherein amount of complex and the resulting mixture in the form of a viscous complex or paste is intro they are heated to about 270° F. at which tem duced by pump |31, line |32 and branch lines perature they are introduced into flash drum |05 35 133e, |335 and _|33c to reactors 80a, 30h and 80e which operates at aboutV 135 pounds per square respectively. Instead of adding the make-up inch. This tower is provided with a heater |05 aluminum chloride in fortified complex it may be for maintaining a tower bottom temperature of added by making new complex with substantially about 335° F. The overhead which leaves the equal amounts of aluminum chloride and poly tower at about 300° F'. is cooled in cooler |01 and 40 mer (such as heavy polymer produced in our introduced into butane surge drum |08 at about process) the latter being introduced through line 100° F. About 543 barrels per d_ay of butanes with |30. By simply fortifying the complex, however, residual butenesare introduced from the base of we not only minimize the necessary amount of this surge drum through line |00 to an alkylation added aluminum chloride but we obtain better system. Any gases purged from the top of the 45 control. , surge drum through line ||0 may be combined It should be noted that aluminum chloride per with gases discharged from the top of catalyst se is not the effective catalyst in our polymeri storage drum 90 through line |||,` scrubbed with spent caustic and then introduced into a fuel gas line. ` " ` ’ zation reactorand we prefer to avoid any intro 50 ductionv of solid aluminum chloride into the re actors, the make-up being added in the form of fortified complex which in turn equalizes with the The bottoms from flash drum |05 are heated preferably in a Dowtherm system a diphenyl or diphenyl oxide being heated in furnace ||2 to a temperature , `of about 500° and >then passed complex in the columns of catalyst in the re actors. Should any small amounts of entrained uncombined aluminum chloride actually enter through exchanger‘l I3 and returned to the fur 55 or the reactor it quickly becomes associated with nace at approximately theV same temperature. the complex' therein. The remarkable advan The stream which passes through exchanger | |3 tages oifered by our system are due in large meas is then heated to about 500° F. which steam is ure to the use of our particular catalyst complex introduced through line H4 t0 stripping tower H5 which may be about 2 feet in diameter to 60 as distinguished from the use of solid aluminum chloride. In other words, we obtain la control of about 24 feet in height, which may operate at \ reaction and product produced which would be about 5 pounds per square inch gauge with a bot impossible in the case of solid aluminum chloride tom temperature of about 450° F. and a top tem catalysts, wherein such difficulties as hot spots, perature of about 500° F. 152 pounds per hour dead spots, channeling, plugging, etc. are always of 110 pounds steam is introduced at the base of this stripper through line H0. To‘the overhead from the stripper 'about .4 pound'per hourof encountered, Another feature of our invention < is the use of a relatively stationarycolumn of liquid complex in the reactor, the passage of dis ammonia is added through -line Il] and theover persed charging stock continuously therethrough, head stream then passes through cooler ||8 «to separating drum H9 from thebottom of `which zo and the maintenance of substantially constant complex activity by carefully controlling rates of water is withdrawn through- line |20 and from adding make-up and withdrawing relatively the side of which a light polymer stream is with spent complex. ` ` drawn through line |2|. This light polymer The nature of the conversion and of the pro stream may amount to about 35 to 40 barrels per stream day and is characterized 'by a‘Saybolt vis 75 duced products can be `controlled by regulating .f Y -v y - - 11 , . the space velocity, the height of the columnof complex and the activity oi the complex to obtain understood that this example is-by way of illus' tration and not by way of limitation. Various any desired extent of olefin clean-up. By using modifications of apparatus and alternative oper a relatively high column and/or a suiiiciently low ating conditions will be apparent from the above spacevelocity the oleñn clean-up may be almost Ul detailed description to those skilled in the'art. quantitative with a relatively active complex. We claim: Y l Byusing higher space velocities and relatively 1. The method of utilizing aluminumY chloride short column oi complex, particularly with rela in catalytic hydrocarbon reactions which com'-v tively "inactive complex, the-oleñn clean-up may v prises first contacting it with a substantially aro be relatively small and the polymerization will be 10 matic-free normally liquid saturated hydrocar relatively selective, i.` e., will be largely limited bon fraction under conditions for effecting isom tothe ‘polymerization of isobutylene. The fol erization of said hydrocarbon fraction and the lowing table will illustrate how the polymeriza formation of an aluminumY chloride complex tion and the nature of polymerized products vary which on hydrolysis would yield a hydrocarbon with different percentages of olefin clean-up in oil of lubricating oil viscosity and which complex the case of speciñc oleflnic gas hereinabove den contains from about 1 to 5 mols of aluminumchlo scribed whereinothere are about 2 parts of normal ride per double bond in the oil which would re butenes to about 1 part of isobutenes and where sult from said hydrolysis, Yseparating said alumi the complex contains in the general vicinity of num chlorideV complex from isomerized hydro 50% by weight of bound hydrocarbon. carbons, and subsequently treating normally gas eous oleiins in the presence of said aluminum Selective polymerization of isolanti/Iene Vchloride complex under conditions for effecting polymerization of said gaseous olefins. Y' . W cight ÑVeight 2. The method of converting normally gaseous Per cent Per cent Per cent 1 clean-up of i-Ql: of n-QF reacting polymer polymer 20 40 60 80 44 69 88 97 7 24 44 71 78 62 52 44 22 38 48 56 of ole?ins reactmg Pi‘ìëîîlt Pâfáeït 25 oleflnic hydrocarbons to hydrocarbons of higher molecular weight which comprises contacting said oleñnic hydrocarbons under conditions for effect ing polymerization with an aluminum chloride 30 complex originally formed during the isomeriza tion of normally liquid saturated hydrocarbons by contact with an aluminum chloride catalyst under . The heavy polymer which may have a viscosity range from 700 to 1800 seconds Saybolt at 210° F. is extremely valuable for a large number of spe~ cial applications. It is a particularly valuable component of specialty or premium lubricants and coating compositions. It is likewise valu able for the preparation of lubricant addition isomerization conditions, said complex being- one which on hydrolysis would yield a hydrocarbon oil of lubricatingy oil »viscosity and which contains from about _1 to 5 mols of aluminum chloride per double bond `in the oil which would result from said hydrolysis. _ , Y. ' _ _ . , . 1 Í 3. `The method of utilizing aluminum chloride in hydrocarbon conversion processes which meth agents which may be prepared by treating said polymer with oxygen, sulfur, chlorine, phos 40 od comprises treating parañinic hydrocarbons phorous, etc. or compounds thereof. with an aluminum chloride catalyst., in the pres ence of hydrogen chloride 'to effect an> isomeriza The light polymer likewise has Valuable proper tion reaction and to produce a complex of lowered ties which cannot be duplicated by natural pe troleum oils and for example a fraction having activity forthe isomerization reaction, said com the following specifications is outstandingly su 45 plex beingronde which on hydrolysis would yield a hydrocarbon oilofV lubricatingoil.viscosity and perior as an ice machine oil, air compressor lu bricant and a variety of other uses. ' which contains from about l to 5 mols? of alumi num chloride. per double bond. in the oil which <Viscosity at 100° F_____ __'_____ '7.5-9 centistokes would result from said hydrolysis, and subse PourfF ______________ __Y__V___V„ -85 max. quently contacting said. catalyst of lowered isome Carbon residue ______________ _,001 max. verizatiron activity with a hydrocarbon _stream conf Color, NPA _________________ __ 2 max. Neutralization No., mg. KOH/gm _______________ __`__ 0.05 max.' Flash, °F ___________________ __ 180 min. Dielectric strength __________ __ 25,000 max. sis’ting substantially entirely of normally-gaseous hydrocarbons containing oleñns under >conditions forl effecting the production therefrom of normal 5% Iilìy liquidO hydrocarbons of branched-chain, struc, ure. A-remarkable and unpredictable advantage of fered by our polymerization process is the large yield of polymer obtainable from a'given amount of catalyst. Based on fresh feed the aluminum chloride requirements are only about 1% by weight and the hydrogen chloride requirements are only about .01% by weight or less. We may obtain upwards of 20 gallons of polymer per pound of aluminum chloride with our process while processes employing solid aluminum chlo ride as a catalyst produces only about 2 to 3 gallons of polymer per pound of aluminum chlo ride. Furthermore, our process is remarkably simple in Yoperation and is free from most of the troublesome-operating difliculties which inevita bly arise from the use of solid aluminum chloride catalyst. While we have described in considerable detail , . v ., . ` ` 4. The method of utilizing aluminum 'chloride in catalyticîhydrocarbon reactions which. com prises iîrstV contacting it‘with a substantiallyaro matic free normally liquid saturatedhydrocarbon fraction under conditions for effecting isomeriza tion of said hydrocarbon fraction and the forma tion> of ,an> aluminum chloride complex, separat-. ing said aluminum chloride complex from isomer ized hydrocarbons, subsequently treating a mix ture of isoparañìns with olefìns in the presence of said aluminum chloride complexunder condi tions for effecting alkylation, and contacting ole ñnic hydrocarbons with a substantiallyspent cat ‘alyst from the alkylation system under conditions for effecting polymerization of said voleflnic hy drocarbons.V Y Y i - . I ». Y ~ v K 5. The method of polymerizing normally gas eous oleiins which comprises continuously pass a speciíic example of our invention it should be 75 ing said oleiins upwardly in the liquid phase 131 14 through a column at least ilve feet in height or therein, `returning an aliquot portion of the with catalytically active liquid aluminum chloride ali phatic hydrocarbon complex in a polymerization zone, said complex .being immiscible with hydro finery gas stream, treating another portion. of the drawn stream in substantial amounts as the re cycle stream ior admixture with the incoming re carbons and polymer products and having an alu UK withdrawn stream to remove catalyst containi nants therefrom and fractionating said last minum chloride content in the range of about named portion or the product stream after the 40% to about 80% by weight and at least one treating step. mol AlCls per double bond in the oil which results 7. The method of polymerizing normally gas from hydrolysis of said complex, continuously in eous oleñns from a hydrocarbon stream contain troducing with said oleñn's a substantial amount 10 ing said olelins in admixture with normally gas of liduelied normally gaseous parai‘lin hydrocar bons for lowering the viscosity and density ci polymerization products by dilution and thus ía cilitating their separation from the heavier com plex in which hydrocarbons are substantially in soluble, maintaining the column at substantially constant polymerization temperature by precool ing the introduced hydrocarbons to a temperature below the polymerization temperature and by ab stracting heat from the column by indirect heat " exchange with a coolant circulated through the polymerization zone, continuously separating di luted products from complex in the upper part of the polymerization zone, continuously remo-ving \ cous paramn hydrocarbons which method com prises continuously distributing said stream in liquid phase at a lowpoint in a column of active liquid aluminum chloride-aliphatic hydrocarbon complex, said complex being immiscible xwith hy drocarbons and polymer products, containing in its composition amounts of hydrocarbon constitu ents in the range of about 20% to about 50% by weight, being one which on hydrolysis would yield a hydrocarbon oil of lubricating oil viscosity and further characterized by having from about l to 5 mols of aluminum chloride per double bond in the oil which would result from said hydrolysis, passing said distributed stream upwardly through separated diluted products from the upper part ' at least about 5 feet of said column of said coni of »the polymerization zone at a point spaced from the column of complex whereby the bulk of the complex is retained in the polymerization zone and employing a space velocity, column height plex under conditions for effecting polymeriza and complex activity in the polymerization zone ‘ continuously separating polymerization products for effecting an olefin clean-up within the range of about 40% to at least about 80%. diluted with unreacted paraflin hydrocarbons from the bulk of the complex in the upper part of the polymerization zone, continuously with 6. The method of producing polymers of lubri cating oil viscosity from oleñns higher boiling .Y tion as the main reaction, continuously removing heat from said column by passing a coolant in indirect heat exchange relationship therethrough, drawing a stream of diluted products from the stream consisting essentially of paralîñns and o e upper part of the polymerization zone ata point spaced from the top of the column of complex whereby the `bulk of the complex is retained in ñns higher boiling than ethane and lower` boiling than pentane to remove other components there the polymerization zone, treating a minor por tion of the withdrawn product stream to remove from, combining said treated stream with a re cycled stream hereinafter defined, cooling said any entrained catalyst material therefrom, frac tionating the treated products to obtain at least combined. stream to a temperature below the tem one fraction of lubricating oil Viscosity, and re than ethylene and lower boiling than amylene ' which method comprises treating a refinery gas cycling a major portion of the withdrawn product introducing the cooled stream at the base of a 45 stream prior to the treating step to said low point in said column of active complex in said poly polymerization zone containing a column at least merization zone. about iive feet in height of active liquid aluminum 8. The method of polymerizing olefms contain chloride-aliphatic hydrocarbon complex, said ing more than two and less than five carbon complex being substantially immiscible with hy drocarbons and polymer products and containing 50 atoms per molecule from a liquefied gas stream consisting essentially of a mixture of said 01e in its composition an amount of hydrocarbon iins with normally gaseous paraffin hydrocar constituents within the approximate range oi' bons containing more than two carbon atoms about 20% to about 60% by weight, said complex per molecule which method comprisesV cooling being further characterized by containing at least one mol AlCla per double bond in the oil which 55 said liquefied _stream to a temperature below the temperature employed for effecting polymer results from hydrolysis of said complex, dispers ization, introducing the cooled stream at the .base ing .the cooled stream at the base of said column of a column at least five feet in height of an and passing said stream upwardly as a dispersed active liquid aluminum chloride-aliphatic hy liquid phase through said column, removing heat from said column by indirect heat exchange of 60 drocarbon complex which has a hydrocarbon content in the range of about 20% to 60% by complex in the column with a coolant circulated weight, which is immiscible with hydrocarbons therethrough and effecting said heat removal at and polymer products and which on hydrolysis a rate to maintain the column at a substantially would yield a hydrocarbon oil of lubricating oil constant polymerization temperature, maintain ing a pressure in the polymerization zone sufli 65 viscosity and which contains about 1 to 5 mols of aluminum chloride per double bond in the oil cient to maintain the hydrocarbons in liquid which would result from hydrolysis, passing the phase, employing a space velocity in the range of introduced stream as a dispersed phase upwardly about .l to l0 and sufficient to obtain an olefin through said column of active liquid complex in clean-up of at least about 40%, separating prod ucts diluted with unreacted normally gaseous 70 a conversion zone under a pressure suücient to maintain liquid phase conversion conditions and parañins from the bulk of the complex in the at a temperature and rate for effecting polymer polymerization zone and continuously withdraw ization as the main reaction, removing heat from ing a diluted polymer product stream from the the column of complex by indirect heat exchange upper part of the polymerization zone at a point spaced from the top of the column of complex 75 of complex in the column with a circulating cool perature employed for effecting polymerization, 15 azione@ ant, separating liquid polymerization products di luted with said normally gaseous parafûnic hy drocarbons from the bulk of the complex material in the conversion zone, withdrawing a diluted liquid product stream from the upper part of the conversion zone to a settling zone, removing fur ther amounts of complexfrom the diluted liquid product stream in said settling zone,‘_treating at 16 product and Which contains at least 20% >but not more than 50%` of hydrocarbon constituents in its composition, and at least one'mol AlCl3 per double bond in the oil which results from hy drolysis ‘of said complex, passing said dispersed stream upwardly through said column under polymerization conditions which include a pres sure sufficient to maintain the hydrocarbons in least a portion of the diluted liquid product liquid phase, a polymerization temperature and stream from the settling zone to remove residual 10 a space velocity and column height sufficient to amounts of catalyst material and fractionating eiîect an olefin clean-up within the range of about said treated portion of the product stream. 40% to at least about 80%, abstracting heat from 9. The method of claim 8 which includes the said column by passing a coolant in indirect heat steps of separately withdrawing a major portion of the diluted product stream from the settling zone,' cooling said major portion and recycling said major portion to the base of the column of active liquid aluminum chloride-hydrocarbon complex. exchange relationship therethrough, continu ously separating diluted polymer product from complex in the upper part of the polymerization zone, continuously withdrawing a stream of di luted polymer product from an upper point in the polymerization zone which is spaced from the 10. The method of obtaining viscous hydro column of complex, treating atleast a portion carbons from butylenes which method comprises of the withdrawn product stream to remove cat# cooling a liquefied dry :butane-butylene stream alyst contaminants therefrom and fractionating containing substantial amounts of butanes, nor said treated portion to obtain at least one viscous mal butylenes and isobutylene to a temperature liquid fraction. ’ ' ' below the temperature employed for eiïecting 25 l1. The methodrof claim 10 which includes the polymerization, contacting the cooled stream in steps of recycling a major portion of the with a polymerization zone with a mass of active liquid drawn Yproduct stream and returning it to the aluminum chloride-aliphatic hydrocarbon com polymerization zone in admixture with the lique pleX, eiïecting said contacting by -continuously ñed .loutane-butylene stream. ' ‘ ' dispersing said cooled stream at a low level in 30 a column at least ñve feet in height of such ac tive liquid complex which is immiscifble with said stream and with the polymerized hydrocarbon BERNARD L. EVERING. EDMOND L. D’oUvlLLE. DON R.` CARMODY.