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Patented \Aprr5, v1938 2,112,847 ‘ UNITED ‘STATES PATENT- ‘OFFICE 1,113,847 ,. . TBEATllIENTOI‘ HYDROOABBONS Vladimir Ipatie? and Herman‘l’lnca. Chicago, Universal Oil Products Com pany, Chicago, 111., a corporation of Delaware No Drawing. Application May 1, 1937, Serial No. 149,164 - . 6 Claims. (CL 260-169) polymerization of the ole?n involved. In other . This invention relates particularly to the treat ment of para?in hydrocarbons which are gaseous ' words,vat the selected low temperatures employed ' at ordinary temperatures and pressures, and par .the rate of the polymerization reactions is re ticularly isobutane. ' duced while apparently the rate of the alkylation 5 In, a more speci?c sense, the invention is con . reactions is not reduced to the same extent so 5 cerned with a novel process 'for-ealkylating iso-. , that alkylation takw place in preference to poly-I butane with ole?ns which are normally gaseous to merization. . a produce saturated hydrocarbons of higher molec The total reactions occurring when isobutane is ular weight which can be utilized ‘as constituents alkylated with an ole?n such as propylene within 10 of motor fuel for automobile and aeroplane en the preferred range of conditions will necessarily 10 gines. involve to some extent not only‘ simple alkylation _ The cracking process which is operated princi pally with the object of producing gasoline from heavier and less valuable petroleum fractions 15 incidentally produces considerable yields of ?xed gases comprising hydrogen, methane, ethane, propane, and butanes as well asethylene, pro pylene, and butylenes in varying quantities and' proportions. corresponding to the addition of one or more molecules of the ole?n to the isopara?ln but also . some reaction of polymerization and some reac- ' tions of decomposition, so that the net result is 15_ the production of a mixture of hydrocarbons hav-' major ing a considerable proportion bolling‘range of mono- and but containing di-alkylated a In most instances, these gases are ' products as will be shown in a later example. 20 considered to have merely a fuel value though at tempts are made from time to time to utilize the The actual operation of the process admits of 20 some modi?cation depending upon the normal ole?nic constituents for the manufacture of hy phase of the reacting constituents and whether drocarbon derivatives on a commercial basis. batch or continuous operations arev employed. In a simple type of batch operation involving sub stantially only the pure compounds isobutane and 25 propylene the isobutane is cooled to a tempera In one application of the present process the 25 isobutane and propylene present in cracked gas mixtures are utilized as a source of additional yields of motor fuel fractions to augment those. ture of 0° C. or below in the presence of a minor primarily produced by the‘cracking operation. ; percentage of anhydrous aluminum chloride and While the process is particularly applicable to 'alkylation is eifected by the gradual introduction 30 the utilization of the hydrocarbons in cracked gas . of. propylene under the surfacev of the liquid 30 mixtures, and particularly selected fractions pro which may be mechanically stirred to prevent duced therefrom in the stabilizers of cracking. subsidence‘ of the solid aluminum chloride par- , plants, it is also applicable to the treatment of. ticles. A small percentage of hydrogen chloride is ._ ‘ isobutane and propylene produced from anyother preferably admitted along with the stream of ole 35 source. ?n vapor, and for eifecting more rapid and com- 35 In one speci?c embodiment the present inven plete alkylation it is best practice to add also a‘ tion comprises the alkylation of isobutane with small percentage of a more reactive ole?n’ such propylene at temperatures of 0° C. or below with as, for example, isobutylene or normal butylenes._ catalysts comprising aluminum chloride and hy After a treatment is completed the aluminum 40 drogen chloride. _' 'I chloride layer is allowed to settle, and the upper 40 In a preferred embodiment of the invention the hydrocarbon layer is removed by 'decantation and desired allwlation reactions are activated or so subjected to'fractionation for the removal of un- , -' celerated by the presence of small quantities of combined hydrocarbons as a light overhead and ole?ns more reactive than propylene which may the recovery of an intermediate motor fuel frac--. 45 be added continuously during a run or used to treat the catalyst prior to its use in the alkylation reactions with propylene. This point will be de veloped in greater detail in a later portion of the speci?catiom > 50 An essential feature of the present invention is , the utilization of sui?ciently' low temperatures of treatment so that the ordinarily vigorous action tion. . ' - , v ‘ v 45 ' In continuous operation'liquid isobutane con taining suspended therelnthe requisite amount of aluminum chlorldeand cooled to a suitably low temperature mayv be. pumped through a tubular treater at the entrance to which it receives the 50 necessary addition of propylene and hydrogen chloride, the desired allrylation taking place dur-i ,_ ‘ of aluminum chloride in catalyzing condensation, ing pasage through the treater and the frac- ‘ reactions among hydrocarbons is moderated and tionaticn of the products being accomplished in .55 reactions of alkylation occur rather than simple ., va submlent ‘fractions-for. The details of con-1“ a 2 2,112,841 _ tinuous process ofthis general character are more pm chloride. or less familiarlto those skilled in oil refinery operations and any necessary addition to or modi- ' Y _ 7 However, by maintaining the proper excess of the paraffin hydrocarbon the course of the reactions may be kept principally ,?cations of the above general procedures will be 'in the direction of production of‘ alkylated prod-_ more 'or less obvious, and ‘can be made without j pots of a saturatedrather thanfan ole?nicfcharéf departing from the general scope, of the invention. acter; In‘order to balance up ‘any disproportion" The preliminary activation of the" alkylation on the side of either the ole?n or the para?ln, to‘ I‘ reaction may be effected by treating the granular produce products of the desired degree‘of alkyla tion either may be added from outside sources to aluminum chloride intended for use in the reac produce a mixture of proper proportions. It will 10 tions with either normal or isobutylenes by pass beshown in subsequent examples that there is ing a limited amount of these compounds in liq uid-phase in contact with the granular material some production of isodecanes as well as isohep during vigorous agitation. The pronounced'ef tanes, the former compounds corresponding to alkylation of isobutane by two isopropyl groups. fect of this activation upon the speed of subse 15 20 quent alkylation ‘reactions with propylene is The process may be utilized for the direct im somewhat diilicult to explain on a theoretical provement of low antiknock value gasolines by basis though it may be suggested that intermedi suspending aluminum chloride therein at the re ate addition compounds are formed which are the real catalysts of the reaction in the presence quired low temperatures and passing a. propor tioned mixture of isobutane and propylene into of the'hydrogen chloride which is continuously the suspension along with a trace of hydrogen added. It is further possible that a certain amountof morereactive olefinv which is com vent and a reaction medium and the alkylation 15 chloride. . The gasoline functions both as a sol products are formedand blended with the gaso line at the same time to increase its antiknock of reaction which has the e?ect of energizing the value to an extent depending upon’ the amount of bined with the aluminum chloride tends to alkyl ate the isobutane and evolve considerable energy less reactive - propylene. It has been observed alkylated'products formed. that the activating effect is gradually lost so-that in a strict sense it is notrentirely catalytic. ‘This feature of the present process is important from 30 a practical standpoint since, when using pure , y . The following examples are given as illustrative of the type of results normally obtainable by the use of the present process, although it is not given with the intention of limiting the scopev of the 30 propylene or at least propylene free from other .invention in exact conformity with the data pre ole?ns, the. speed of the alkylation reactions is sometimes below a practical level at the tempera ‘tures necessary to prevent polymerization. The sented. ' I ‘ Example I Granular anhydrous aluminum chloride was 35 35 preliminary treatment of granular aluminum "placed in a reaction vessel which was cooled to a'temperature of —'30° C. To activate this ma chloride with relatively highly reactive ole?ns, such as isolmtylene or normal‘ butylenes, has been terial a total of two parts by weight of an equal mixture of isobutane and isobutyiene was con-‘ tacted with the material. Leaving the activating 40 observed to have a still further effect of‘practical signi?cance, in‘ that there is a greatly decreased 40 tendency for the chloride particles to become very hydrocarbon mixture in place the liquid mixture ?nely divided under vigorous agitation but rather to maintain their original size, which prevents of isobutane and propylene was contacted in such a way that the charge entered below the surface the carrying o? of the catalyst in colloidal sus- - of the hydrocarbon liquid containing the sus pension in continuous processes. aluminum chloride while reaction prod 45 The reacting hydrocarbons required for 'the pended 45 ucts were siphoned from the reaction vessel at present process may be obtained from any con a su?iciently high level to avoid removal‘ of the venient source. As a rule the best sources are the cracked gas mixtures produced in the pyrolysis of heavy oils ‘with the primary object of producing . catalyst particles; - The charge consisted of ap proximately 7'7 per cent of isobutane and 23 per- _ cent of ‘propylene, calculated on a gas basis; and 50 The technique of hydrocarbon frac a steady feed of a small amount of hydrogen tionation is su?icientiy developed at the present chloride was maintained during the run. ' -_ _ time so that it is commercially feasible‘ to pro 3250 volumes of isobutane-propylene mixture duce relatively pure propylene and isobutane.- A produced 650 volumes of liquids boiling within the method which may be employed to obtain propyl . ordinary range of commercial gasoline or up to 5'5 1 55 ene which is not contaminated with paraiiin hy approximately 225° C. 90% of the'total liquid drocarbons consists in the use of solvents which products boiled below.220° C. and the'octane selectively abstract ole?ns from the gas mixtures, number of this gasoline fraction was ‘81 when which oieilns are then ' separately fractionated. tested by the motor method. Careful fraction In such a process the residual unabsorbed paraf ?n mixture may be employed as the source of the ation indicated that 42% of the total liquid prod 50 gasoline. required isobutane. .Propylene may also ‘be pre- 7 " ucts- consisted of isoheptanes boiling between 88 pared by the selective catalytic dehydrogenation of propane or propane fractions. ' . Over the preferred low temperature conditio and 90° C. and another 20 percent of the liquid _ products correspondedyto isodecanes boiling -be-' ‘tween 150 and‘154° C. of operation and in the presence of an excessoi' _ ' isobutane, one molecule of propylene ‘tends to re act with its molecular ‘equivalent of isobutane while the excess-of isobutane remains unaffected. when more propylene is used than corresponds to . v Example II .k - ' ; t5 A run was made at the upperlimit of tem-j perature corresponding to the economical and practical operation of the The general 70 about one mole'of propylene to three moles of . procedure was the same as iriExampie I in‘ ' isobutane there is an increased tendency for poly--v to the relative proportions: the hydrocarbons merirationgreactions‘to occur in preference to alkylation reactions; " m is to be expected to - some .extent on account of the readiness with .78 which propylene aloneis polymerized by alumi reacted in the‘ presence of chloride. , In‘this case, however, 30001volurne‘s oi’ isobutane-y propylene mixture produced .600 volumes of liq-v uiids boiling up to 220° 0., 92% .0! which boiled 3 2,112,847 below 200° C. The octane numberof the 200° 0.. end point fraction was 83 by the motor method 3. A process for the production of alkyl deriva tives of isobutane which comprises subjecting said isobutane to the action of propylene and a minor and it was noted that there was a somewhatv proportion of a more reactive ole?n in the pres higher percentage of material boiling below the 50% point in the distillation test. In comparison with the ?rst case, a careful fractionation showed that 39% of the total liquid products consisted of isoheptanes instead of 42% as in the first ex ample. I . ence of aluminum chloride and hydrogen chloride at a temperature of 0° C. or below. . - 4. A process for the production of alkyl deriva tives of isobutane which comprises subjecting said isobutane to the action of propylene and a minor proportion of 'a butylene in the presence of alumi The foregoing speci?cation has disclosed the num chloride and hydrogen chloride at a tem character and scope of the present invention and perature of 0° C. or below. _ the examples have shown its practical aspects 5. A process for the production of alkyl deriva~ but neither section is to be considered as unduly , tlves of isobutane which comprises subjecting said limiting. isobutane to the action of propylene and a minor This application is a continuation-in-part of I proportion of a normal butylene in the presence 15 I our co-pending application Serial No. 103,389, of aluminum chloride and hydrogen chloride at a 10 ?led September 30, 1936. ‘ We claim as our invention: 1. A processior the production of alkyl deriv atives of isobutane which comprises subjecting said isobutane to the action of propylene in the presence of aluminum. chloride and hydrogen temperature of 0° C. or below. _ chloride at a-temperature of 0° C. or below. perature of 0° C, or below. . 2. A process for the production of alkyl derivaé . ‘- VLADIMIR IPA'I'IEFF. 25 tives of isobutane which comprises subjecting said isobutane to the action of propylene in the pres ence of aluminum chloride and hydrogen chloride at temperatures within the range of 0° C. —50° C. . ’ ' 6. A process for the production of alkyl deriva tives of isobutane which comprises subjecting said isobutane to the action of propylene and a minor proportion of isobutylene in the presence of alu minum chloride and hydrogen chloride at-a tem HERMAN PINES.