Патент USA US2404444код для вставки
2,404,444 Patented July 23, 1946 UNITED STATE s2,404,444PATENT‘ OFFICE,1 rsoiunrnzArron PROCESS USING METAL HALIDE COMPLEXES '1 Charles A. Kraus, Providence, n. 1., and John 1). v(Jalfee, West?eld, N. J., assignors to Standard Oil Development 00mpany, va‘ corporation. ‘of’ Delaware ' No Drawing. Application November 1-6, 1943, " 12 Claims. Serial' No. (c1.510,490 zoo-683.5) _ _ ' 1 their activity for the promotion of hydrocarbon The present invention relates to the prepara tion of metal halide complexes which have been found to be suitable for aiding in the e?ecting of visomerizations and condensations. A principal object of ‘the invention is to isomer ize normal para?ins of at least four carbonlatoms per molecule to the correspondingbranched'chain paraf?ns under isomerization reaction conditions organic reactions such as, for example, the isom erization of normal para?ins to isoparai?ns, the alkylation of isoparaf?ns with monoole?ns, the polymerization of monoole?ns, the cracking of re in the presence of these novel catalyst complexes. Other objects of the invention will become appar duced petroleum crude oils, and the nuclear a1kyl~ ent upon a fuller understanding ofthe invention ation of aromatic hydrocarbons with alkyl halides, 10 to be hereinafter moreffully described. , alcohols and/or monoole?ns. The catalyst masses described herein remain Metal halides of the Friedel-Crafts type have active for catalyzing organic reactions for a been used in the past to induce a number of re greater length of time than‘has heretofore been actions among which are those mentioned above, found possibleusing the ordinary Friedel-C'rafts but particularly in the case of the aluminum hal- _ ides such as aluminum chloride no completely sat 16 type metalhalide catalyst. A simple and con venientmethod for the preparation of metal hal isfactory catalyst mass has as yet been devised. idegFriedel-Crafts type catalyst complexes suit-' Continued usage of aluminum chloride catalysts able for catalyzing the above mentioned organic for effecting the isomerization of normal par a?ins, the polymerization of ole?ns, the alkyla tion of isopara?ins with ole?ns, and the like, re reactions are also described. The catalyst mass 20 sults in a decomposition of the aluminum chloride to form liquid, highly carbonaceoussubstances comprises aluminum halide’ complexes which are economicalvto produce and have excellent cat alyst life when used to catalyze the abovejmen tioned reactions.v , 'The, aluminum halide-lower which are less ef?cacious for catalyzing these re actions than the solid fresh aluminum chloride. By the liquefying and degradation of aluminum chloride or aluminum bromide in carrying out such reactions, commercial'units oftentimes are required to be shut down ‘and the reactors andcat alkoxy metal halide reaction products. are of porous structure and-adapted for use in catalyz ing organic reactions. These complexes are rel atively stable and maintain catalytic activity over long periods of time. , I, _ The novel catalyst complexes of the presentin alyst beds cleaned and recharged with fresh cata- ' 30 vention are prepared in a number of ways. ' One lyst before proceeding with the reaction. This is often expensive and troublesome because of the character of the sludges formed with the alumi num chloride. In addition, of course, the catalyst life is materially reduced due to this sludge for mation and too frequently the catalyst must be replaced with fresh aluminum chloride or alumi num bromide catalyst compositions, thereby re sulting in an uneconomical operation. ' method of preparing these catalysts resides inithe ‘use of lower alkoxy metal halides or lower tri alkoxy metal halidesv being contacted and ‘ad mixed with a Friedel-Crafts' type catalyst of the metal halide type, followed by heat fusing of the resultant admixture to a temperature su?iciently ’ Attempts have been made in the past to im prove aluminum chloride catalysts for use in or ganic reactions, particularly hydrocarbon reac Z40 high to completely fuse the mass; Following fusion, the mass is kept at an elevated tempera ture of between about 80° C. and about 200° C. un til the liquid is converted into a dry solid material and evolution of alkyl halide is essentially com plete. , A catalyst so prepared has been found to tions,»by resorting to drastic‘ reaction conditions have the desired catalytic activities. A preferred and short contact times in order to minimize this method of preparing the-catalyst mass, however. sludge formation, but these expedients have not 45 involves not only the heat fusing of the resultant been particularly successful since appreciable admixture but a further heating, to a slightly cracking of the reactants occurred rather than a minimizing of the sludging tendency. Further more, under certain reaction conditions which are higher temperature for a length of time to allow for the removal by vaporization of any uncom bined or free metal halide contained in the cata particularly conducive to catalyzing some organic 50 lyst mass. The removal of the free halide may he accelerated by conducting'the sublimation un— reactions, such as the isomerization of the higher molecular weight straight chain para?ins, alumi .‘er. reduced ‘pressure. This method resulted in a num chloride has been found to be impractical catalyst complex which had even better catalytic activity than the ?rst method of. preparation. even under the best conditions known, because the cracking tendency of the aluminum chloride 55 Still a third method of preparing the catalyst appears to be superior to the isomerization tend mass resides in the preparation of the metal hal~ ide alcohol addition complex in the presence of ency and hence aluminum chloride is not particu larly suitable for this type of reaction. Further excess amounts of a Friedel-Crafts type metal more, aluminum chloride and aluminum bromide halide, followed by heat fusion, formation of the have been found to be relatively short lived in .00 alkoxy halide by splitting out hydrogen chloride, 2,404,444 3 4. . subsequent formation of active catalyst through vThey are non-volatile under the 1 elevated tem peratures customarily employed. If! desired, the elimination of the alkyl halide, and the removal catalyst complexes may be prepared on a carrier heatj Such a method, for example, would involve 'Y such as activated alumina, partially dehydrated the reaction of methyl alcohol in the amount of 11 bauxite, activated carbon, silica gel, alumina gel of excess. Friedel-Crafts typemetal halide mol With more than 1 mol of aluminum chloride. and the like. The preparation of» aluminum methoxy halides ~ may be carried out in an anhydrous carbon disule, ?de medium by adding alcohol to a re?uxing InlX~ ture of carbon disul?de and the metal halide. The 10 pregnation of the carrier mass with vapors of , Such a process involves the im aluminum chloride or aluminum bromide or other suitable ,Friedel-Crafts type catalyst, followed by contacting ill the impregnated mass with methyl resultant aluminum methoxy compound may then or ethyl alcohol vapors or some other suitable be separated from the solvent and heated at a temperature of 80° C.-200° C. in the presence'of lower alkyl monohydric alcohol into the carrier “ mass so impregnated. ' excess aluminum chloride to form a compound , This mass is then gradu ally heated to a temperature between about 40° C. 15 and 200° C., thereby forming the novel catalyst having an empirical formula of complexes within the carrier selected. A stream slcuoomimool of superheated inert vapor such as hydrogen, ni trosen, carbon dioxide and the like, may . be Methoxy aluminum chloridemay be mixed with passed through the carrier mass maintained at aluminum bromide and the active catalyst termed by fusing the mixture and then maintaining it 20 the desired temperature so that the mass is-thel'e ‘by freed of any free or uncombined metal'halide at a .su?'iciently elevated temperature to cause contained therein. 7 7 essentially .‘f?lll'e?iths of the methyl groups to be An excellent method for preparing the catalyst evolved as the methyl halide.- ‘* The empirical on a suitable support consists of mixing the alu composition of the catalyst following removal of» all free halide is AlX20CIrI3-Al0X 2.5 minum methoxide with the aluminum halide, fusing, and before evolution of the alkyl halide where may be chlorine or bromine, or both commences, soaking the inert carrier in the melt. chlorine and bromine in the same molecule- .A iur-ther vexample of a particular catalyst prea pared aoeordanoe with the process described herein involved the reaotionof AlGhOCI-Ia with 30 SbGls to give the thermal decomposition product. of vn1ethoxy chloride chemically commood in part, at least, with an antimony halide, the antimony/content vfalling between 01% by‘ weight .01.’ the aluminum compound and that re ' quired for the compound AlQlzOC‘I-IsASbQCl, de pending upon the experimental conditions, It is believed, based on- experimental determiner-l 3 tions, that the empirical iormula, AlClzOGHaAAlOCl ‘ represents a close approximation of the true The carrier may then be removed and the decom position to form the catalyst conducted at the proper temperature. ' The catalysts so formed vhave been 'foundto be particularly effective in catalyzing the isomer ization of normal para?ins to isopara?lns as will be more fully "hereinafter described. Although, as ‘has been stated heretofore, it is preferred to use the novel catalyst complexes substantially free of uncombined F'riedelaCrafts type metal halide, and, as has previously ‘been stated, some free and. uncombined FriedeleCrafts type metal halide catalyst may remain in admixture \with the v?I-ial catalyst complex, it is within :the con templation of the present invention to add fur-v composition of the type of compounds produced , ther amounts of FriedeleCrafts type‘ catalyst to the resultant catalyst mass and to employ such ‘3 but the invention should be understood as not i being-limited thereto but as being'dil'ected to 45 admixtures as catalysts where the activity'of the ?nal catalyst composition demands that-a "more the compounds ‘Produced by the reaction of . active catalyst be employed. In: general, the . v.F‘riedeleGrafts tyne metal halides with lower alkyl novel catalyst.oomplexes'herein described may monohydric alcohols or with the lower alkoxv be prepared by admixing a compoundha-vlng the l derivatives of metal halides accordance with ‘ the‘ methods herein outlined. .In general, the 60 formula > 1 tioned are heated at least to the fusion point and 1 preierably they are heated to a temperature be 1 tween about 80° C. and about 20.0” G. for .a period of time suf?oient to insure completion of the re . ~ (ROM/M992 admixtures of the reactants heretofore ‘men. with from one to six'mols of a metal halide "hav ing the formula . 55 action giving rise to theevolution of the alkyl halide. The unreaoted metal halide is removed ‘ by sublimation upon continued heating, prefer ‘ ably under reduced pressure. he will be seen ‘ .from the data hereinafter-set forth, active cata 1 lysts are produced by the .deoompositionof the metallic alkoxy halide in the presence of tree metallic halide and that it is preferable to .re move any free or unoombined li‘riedel-Craits type Friedelegrafts metal halide that type may metal be contained'therein, halide may be employed ' ' ‘ ~M'vXn ' V wherein R represents a lower alkyl group, pref erably methyl or ethyl, M and M’in at least one of the compounds represents a metal whose halide is a Friedel-Crafts type catalyst (M and M’ may be the same or a different metal), X represents a halogen such as, for example, chlorine or bro mine, y is an integer, 1, 2 or 3, while 2 represents '3-.-y, and 'n. represents an integer of 6 or less. Speci?c compounds contemplated as the ‘initial reactant in preparing the novel catalyst ‘com plexes are as follows: ' . in .asubstantial molar/excess of the amount of ' . lower alkyl monohydric-alcohol or lower alhoxy metal halide used, but in such a case it is pref AICIBI'OCHS AMDCzHsla ' erable to remove the excess or unoombined metal 170 AICI (OCHs) 2 SbClZQCI‘Ia halide from the ?nal catalyst complex prior to .using the samefor patalyzin‘g the heretpjoree ' mentioned organic reactions. 7 The resultant catalyst complexes appear as .a AlClzOCgHs and the like. Sb (OC_H_3)_3 , ' ‘Compounds representative of the class ‘ porous, brittle ‘mass, white to light yellow in color. 15 which. maybe employed in accordance with the‘ 2,404,444 tillate was collected in a graduated receiver; The process of the present invention are those custo marily identi?ed as the Friedel-Crafts type metal percentage of product boiling between 80° C. and halides. These are, for example, branched chain heptanes produced in the isomer ?gb Alcfgr I A1013” -' she; I 3 93° C. was a measure of the amount of the ' Tic,‘ Zrcl‘ 5 ization reaction. The catalyst mixture in Run No. 4,‘ although being heated at 150° 0., was heated for a su?icient length of time to decom UCI 4 4 pose the mass but not to remove from the mix ture the free metal halide contained therein. AS913 m The catalyst was prepared at 150° C. and then cooled, immediately to room temperature. and the like.‘ Table isomerization of N-heptane at room temper Gatalyst preparation v Reactants employedinpreparing ' atureinatmosphere ofdryHOl Decompo- Free sition tem- metal perature, ° 0. removed catalyst, molar ratios halide Catalyst N-heptane, grams 0. 0. AlBr2OGH3+AlBr3n _ .AlBr: ______________ __ 160 Yes__-__ ‘_._ AlOl2OGH3+AlBn _________________ ._ 160. Yes.--" CH|OH+ZAIBH ___________________ ..‘.'~ 180 Yes-._._ Distillate and reac- 80-930 0., tion contact vol. per cent time, hours 10 8 6 5 10 _____ _._-_ Agitation 5 7.1 5 v5 29.0 22.0 29.0 20 17 2.5 2.5 7.5 30 20' 20 20 15 ‘ 18 11.5 5.5 5.5 7.0 14.0 7 8 19 21.0 22.5 31.0 2.5 34.5 22 18 2 7 30 18 35.0 6.8 30 18 41.5 10.0 lFused. As previously pointed out, still a further modi 35 Having now fully described and illustrated the character of the invention, what is desired to be ?cation involves the reaction of a lower alkyl secured by Letters Patent is: monohydric alcohol such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, etc., 1. A process of isomerizing normal para?ins ‘containing at least four carbon atoms per mole mentioned Friedel-Crafts type metal halides. The 40 cule to form the corresponding branched chain paraf?ns which comprises contacting said normal resulting compounds are thought to have the fol para?ins under isomerization reaction conditions, lowing empirical formula, although there is no in the presence of a halogen-containing promoter, intention to limit the invention to this formula with two or more mols of one of the herein with a catalyst mass prepared by admixing a since at best it constitutes merely an empirical formula based upon analytical data. The for 45 metal halide of ‘the Friedel-Crafts type with an alkoxy derivative of an aluminum halide, and mula is believed to be as follows: heating the resultant mass to remove alkyl halide. 2. A process as in claim 1 wherein the catalyst mass is heated su?iciently to remove a major por wherein the characters have the same designa 50 tion of the uncombined metal halide of the tion as previously stated. Friedel-Crafts type therefrom. The following examples, the data of which are 3. A process as in claim 1 wherein the catalyst presented in the accompanying table, are illus mass is prepared from an aluminum halide and trative of the character of the invention. It is a methoxy derivative of an aluminum halide and not intended, however, that the invention be limited thereto. ’ 55 wherein the resultant catalyst mass is heated sufficiently to remove a major portion of the un Runs Nos. 1 and 10 are inserted in the table‘v combined metal halide and methyl halide there merely for comparative purposes. These cata from. lysts were CP grade of aluminum chloride and 4. A process of isomerizing normal para?lns aluminum bromide, respectively. The decom position temperature stated is that temperature 60 containing at least four carbon atoms per mole cule to form the corresponding branched chain to which the reaction mass was heated in order para?ins which comprises contacting said normal to eliminate the alkyl halide as formed in the para?ins under isomerization reaction conditions process of reaction. The resultant catalyst in in the presence of a halogen-containing promoter each instance, in the amount indicated in grams, was contacted at room temperature, under an 65 and a catalyst mass prepared by admixing an atmosphere of dry hydrogen chloride, with liquid normal heptane in the amount indicated and the admixture agitated for the speci?ed number of hours. The liquid was then separated from the solid catalyst complex and distilled in a distilla tion column packed with a glass spiral wrapped on‘a solid glass rod. The fractionating power of the column used was considered to be equivalent to about '7 theoretical plates. The distilland was measured by volume and on fractionation the dis 75 aluminum halide taken from the group consisting of aluminum chloride and aluminum bromide with an alkoxy derivative of an aluminum halide taken from the group consisting of aluminum chloride and aluminum bromide and heating the resultant mass to remove alkyl halide. 5. A process of isomerizing normal heptane to form the corresponding branched chain heptanes which comprises contacting said normal heptane under isomerization reaction conditions in the - amen/1 7 ‘erization reaction conditions in the presence of a ‘halogen-containing promoter and a catalyst mass prepared by admixing a metal halide, of the resultant mass to remove alkyl halide. 6. A process as in claim 5 wherein the catalyst mass is heated between about 80° C. and about 200° C. sufficiently to remove a major portion of mass to remove alkyl halide. the uncombined metal halide and alkyl halide therefrom. > ' ' '7. A process as in vclaim'5 wherein the catalyst mass is prepared from an aluminum halide and a methoxy derivative of an aluminum halide and wherein the catalyst mass is heated between about 80° C. and about 200° C, su?ciently to re move a‘ major portion of. the uncombined alumi num halide and methyl halide therefrom. _ 8 presence of a halogen-containing promoter‘ and a catalyst mass'prepared by admixing a metal halide of the Friedel-Crafts type with an alkoxy derivative of an aluminum halide and heating the 8. A process as in claim 5 wherein the »metal' Friedel-Crafts type with an alkoxy derivative of an aluminum halide and heating the resultant 10. A process as in claim 9 wherein the catalyst mass is heated between about 80? C. and’ about 200° C. su?lciently to remove a major portion of 10 the uncombined metal halide and alkyl halide therefrom. v 11. A process as in claim 9 wherein the catalyst mass is prepared from an aluminum halide and a methoxy derivative of an aluminum halide and 15' wherein the catalyst mass is heated between about 80° C. and about 200° C. su?iciently to remove a ‘ major portion of the uncombined aluminum hal - ide and methyl halide therefrom. t halide ‘is taken from the group consisting of alu 12. A process as in claim 9 wherein the metal minum chloride and‘ aluminum bromide and 20 halideis taken from the gro consisting of alu wherein the alkoxy derivative is of an aluminum minum chloride and alum,‘ m bromide and halide taken from the group consisting of alumi wherein the alkoxy derivative'is of an alumi num chloride and aluminum bromide, the re num halide taken from the group consisting of sultant catalyst mass being heated between about aluminum chloride and aluminum bromide, the 80° C. and about 200° C. sufficiently to remove a 25' resultant catalyst mass being heated between major portion of the uncombined aluminum about 80° C. and about 200° C. su?‘iciently to re halide and alkyl halide therefrom. ‘ ‘ move a major portion of the uncombined alumi 9. A process of isomerizing normal butane to num halide and alkyl halide therefrom. form the corresponding isobutane which com-A CHARLES A. KRAUS. prises contacting said normal butane underisom . JOHN D. CALFEE.