Патент USA US2404537код для вставки
Patented July 23, l946 ' 2,404,537, , I ‘UNITED Pars 2,404,537 \ a, TREATMENT OF HrDI’tooARBoNs " Louis ‘Schmerling and Vladimir N. Ipatie?“, Chi- ‘ ,cago, IlL, assignors to Universal Oil Products Company, Chicago,,Ill., a corporation of Dela I ware - v . ‘ ‘No Drawing. lAp'Dlicatioh July 6; 1942, Y “Serial No. 449,946 “'16 claims. v (01. 260-15834) ' This invention relates to the treatment of iso; V the respective boiling points'which vare listed as" paraffinic- hydrocarbons to produce‘ therefrom: ' ‘follo'w's:~~* - 1 :3: :wi'I , ' branched chainpara?inic hydrocarbons-oi higher ‘ ' ' molecular weight; 1 ‘In a'more'speci?c sense,1th-is invention'is concerned withsaznovel- proc'esskfor ‘ @ mm? ,pressure» interacting alkylatable para?inic hydrocarbons,‘ herein termed isopai'af?ni'cuhydrocarbons, with alkyl esters of chloroformicacidto produce higher 760 760 160 boiling'para?ihic hydrocarbons of gasoline ‘boil ing range. , 760v - a ' , 760 28 15 20 10 In one speci?c embodiment, the present inven tion relates to a process’v for synthesizing hy drocarbons which comprises reacting an iso para?inic hydrocarbon with‘ an alkyl ‘chloro formate under alkylating conditions in the pres I5 ence of a Friedel-Crafts type metal halide cata lyst. ‘ ' Considerable'quantities of butanes, pentanes, and other parai?nic' hydrocarbons of relatively low molecular Weights are available in the rela 20 tively light hydrocarbon ‘material condensable ing head gasoline. These relatively‘light com ponents of casing head gasoline also includevcer tain amounts of the corresponding isopara?ins, namely, visobutane, isopentane, etc. The rela tively low boiling normal para?ins may also be isomerized into the corresponding isoparaf?ns by Friedel-Crafts type; metal halidesv which are; I utilizable as catalysts for promotingthe alkylaé'" tion of’ an isoparaf?n with an alkyl chlorofor=? matein accbrdance with thepresentinvention in-I s c1ude;suchjsaltfs as ‘aluminum chloride;aluminum bromide, zi chloride, zirconium chloride, ferric chloride, ant-i. mom’ chloride». bismuthflphloridé» and others;v ‘We prefer, however, to employ alu-j . from natural gas and usually referred to as cas minum chlorideas the Friedelecraifts type; cata" lyst in such- alkylation' reactions because ;it 25 usually, higher (in. catalytic “activity than‘; e" other Friedel-Craits type metal halides in'a given ‘f. reaction under speci?ed‘ conditions. Aluminum." chloride may be used as such, maybe ‘supported’, ' by a refractory carrier suchas alumina,‘silica, 1 porcelain, etc., or it may be used in solution in‘ a; tanes and pentanes are formed ‘as by-products'in 80 »_ solvent such as a nitropara?in, particularly nitro the cracking of petroleum fractions and of ‘other methane. , Other Friedel-Crafts-type metal hal hydrocarbon oils to produce‘gasoline. ides andparticularly chlorides maymbev added ,to Alkyl esters of chloroformic acidhwhic'h are the aluminum chloride or to its'solution'ior the utilizable as alkylating agents in the‘ process of ' suitable treatment.‘ Further quantitiesofjbu purpose, of modifying the, activity of . the , the present invention have the general formula: num _ chloride.- , ’ ClCOOR, in which R represents'an alkyljgroup. Alkyl chloroiormates are readily obtainable by byi‘While alkyl amyiaudn‘pr chloroformates isoparalilil'nici:I vmayib‘e‘ .e?e'cted ‘in. ‘the. ,1 the treatment of an alcohol with phosgene, Thus, ' presence,oflaluminumchloridegandother Fried s, as indicated in the following equation, reaction of Crafts type catalysts._ at temperature 011mm 1 molecule of phos‘gefne with 1 ~vmolecul'esofiisoh about , gzor to. about-1 pro'pyl alcohol results ‘in .the' formation,v oi 11 ,mole- , peraturepf from about-10 1 ,c, ‘neau'selrof Meme. , _ to'about ‘7Q?! C, is ,pre- , , cule each of isop-ropyl chloroformate andehyd'ro- ' ferred; IPressures‘utilizableyinlthe'process may @_ gen chloride: - H - i 03H10H +0001, Isopropyl . gene ‘ ' ‘ ' varyfrom'substantially atmospheric? to about 50..‘ 0100065111, ill am Phos- alcohol v Isopropyl_‘_ , ; Hydro- chloroformate , ‘ gen}, . : @ > v ' i-'~ ride ‘Some of the alkyl’chloroformates which are ‘ often referred to as alkyl 'chlorocarbonate’s' have atmospheres or more.‘ Inorder ‘to obtainwhighw, yields of hydrocarbon products of gasoline boil- _ ' ing range with relatively'srnall amounts of jun-l - 'GhIQ'..~-w ‘ ‘ , desira'ble‘side reactions, such as polymerization, formation of organic compounds I containing ~ Q chlorine, etc, it is desirable to maintain a molar », ~_ excess of isoparailin hydrocarbon-to alkyl chloro , V 2,404,537 3 formate throughout the entire reaction period. organic compounds and catalyst are passed un“ Generally from about 2 to 25 molecular propor der alkylating conditions and in which sumcient ‘ tions of ,isopara?inic hydrocarbons should be present per molecular proportion of alkyl chloro time is given for the completion of the desired isopara?in alkylation. ~The products from such; formate introduced to an alkylation reaction mix ture in order to form a substantially saturated a reaction zone are then directed to a separating zone in- which the alkylation‘products are sep-L hydrocarbon material and to avoid undesirable polymerization and decomposition reactions. - aratedfrom. the unconverted iso'parai?nic hydro ’ v The reactions which occur during the treat; ment of _an isoparaflinic hydrocarbon with an alkyl chloroformate in the presence of a Friedel-f carbon, catalyst, and a‘mixture of hydrogen chlo 10 ride and carbon dioxide. . The recovered uncon ' verted isopara?inic hydrocarbon‘and catalyst are then recycled to contact vwith'the mixture of 150'- I ' ,para?'lnic hydrocarbon and alkyl chloroformate Crafts type metal halide, or mi ture of said metal halides, apparently involve the combination of being charged to the process. Hydrogen chloride the isobutane with the ester of chloroformic acid may also be recycled if desired. accompanied by splitting out of'carbon; dioxide and hydrogen chloride as illustrated’ by the fol ’ lowing equation: - i—C4Hm + C1C0OQ3H7 Isobu- Isopropyl tane chloroformate ‘ . e , ‘ The activity of the Friedel-Crafts type catalyst employed in the‘ process is dependent upon the _ —'—-> A101: C1Hm‘ + 002I» + ' 1101 ‘ ' Hep, tane ‘ ' Oar- -Hyd.ro- V .bon dioxv ' ide vlien; , ch10: ; ride ' 4 . 'viding a mixing zone through which the reacting w ' particular metal-"halide ormetal halide mixture so utilized. The different Friedel-Crafts type 20 metal halide mixtures which may be employed , to catalyze the alkylation are not necessarily ' g 1' ' ' ‘ equivalent in their action particularly when react; . ing differentisoparaf?ns with various alkylchlo roformates' having alkyl,1groups of increasing V ‘ The us'eof chloroformates (or chlorocarbonatese 7' > _ carbon chain length and'degree of branching. ' ' as they are often called) :has the advantage over v‘The following‘ examples ‘are given to illustrate i the similar use of other esters in that no :ireeV the character of'theresults obtained ‘by, theluse l‘ l organic acid'is produced during such reaction.“ ‘ of the. present process, although, the "data. pre- . ' Acco'rdingly,-the aluminum chloride used as 'cata-- , senté'd', are ‘not ' introducediwith the‘ intention‘ of i lyst in the process does not 'form an aluminum ‘chloride-organic acid complex, and hence only .30 unduly limiting catalytic and not stoichiometric amounts of alu-‘ invention.“ ‘ " the generally " broad scope "of the E ' ' V r . . EXAMPLEI minum chlorideare'necessary for the reaction; _ Although'the mechanismsof the reactionslina ' 'Alkylation of isobutane by ethyl chloroformate' volved are not understood completely and should], was carried ‘out by charging to a rotatable auto; not be construed to limit the scope of the 'inyenf - clave (lined with glass or nickel) a mixture; oi the tion, the interaction, for example, of'isobutanez, 'is‘obutan'e; ethyl chloroformate, “and catalyst in with isopropyl chloroformate yields heptanes.‘ the amounts indicated‘i'n Table, I.’ _, Table I._jAm1/zationlof isobutane with-ethyl ' which, ‘include 2,2,3-trimethylbutane, generally. . known as triptane. 3Heptanes so formed may re act rurther with an additional quantity ofthe < 40 e - . chloroformate 1 alkyl chloroformate such as isopropylg chloro~~ Run number forrnate to form ‘a para?in hydrocarbon of still higher molecular weight such as -a decane.v > Dec-I ' anes'and other hydrocarbons ‘:of relatively high . 1. - 2 e 3 ' ._~ 4 molecular weight may undergo decomposition and further conversion reactions in the presence of the catalyst to produce'lowenand higher boiling hydrocarbons which are generally paraf?nic in naturelg/ ' ' V’ ' ' ’ Reactants, g.: . ‘ of 'mixing su?icient‘ to“ effect substantially com 110 81 V 172 Aluminum chloride__ _ 40_ V. 40 Autoclave lining ___________________ ..' . ‘Nickel :20 _Glass agitation islstojpped ‘and the reaction mixture ‘is separated into}, used catalyst, unconverted iso paraiiin; alkylation product, and a mixture of hydrogen chloride an'dacarbon dioxide,’ the latter : ' Maximum ______ __ »2‘ 1 4 30 7 4 1B ,50 25 10 18 43 17 40 1 50 _ 7 Duration of run, hours _____________ __ ~ Products, g.: V 5 . , 6_ . '70 . 4 ' 7. ‘ : Gondensible'gas _______ _. 173 Liquid hydrocarbon layer ' Catalyst layer _________ __ _ 70. 152 . 0 27 15 66 43 54 28 45 75 64 Hydrogen chloride, carbon diox-I ide, and lcss.__._'____; _______ __ Distn.‘ of hydrocarbon layer,. volume‘ ‘ percent: - . ' " a . Liquid-fractions: - ' ‘ ' 38 59' ' ' i Condensible gas__;______; ‘ plete reactionof the‘alkyl chloroformat'e with so the ,isopara?imthe isopali‘sl?in being present ;in. excess :of‘tli'ea1kyl chloroformateat all times‘, the - \ .401 Nickel ' - Temperature, °C_ _ _ hydrocarbon and catalyst at the chosen operat ing temperature and pressure- and'to introduce gradually thereto an alkyl chloroformate or a. mixturev comprising essentially an alkyl chloro-Iv , 50 168 ' Final at 20° O_ ___ procedureis .to, agitate a mixture, of para?inic ~ r 110 172 Initial, nitrogen added- operation. In batch type operation, the preferred 7 110 _ ' carried 'out either in batch or continuous types of‘ formatsv and . anisopara?inic hydrocarbon or. an ~ _____ Pressure, atm.: The process of the present invention may be 7 visoparaf?nicjhydrocarbon fraction; After a time , Y‘ Ethyl chloroiormate. ' Isobutane __________ _. . ___;__ ___-V“ '3 3f; ______ __ . '4 (52 ' .Below 40° C____'__-__ ' V ____ __ 12 Between 40 and 75° 0-. ____ __ 30 37 22 Between 75 and 95° 0.. ___._ .7 ______ __ 7 4 Residue__- ________________ ._~______ _. 9 ' 9 Analysis ‘of .condensable gas, mole percent: > > - ' ' _ r Ethane _________________________________ .. Propane_ . Butane--Ethyl chloride ____ __-___'__.___ -77.5 721.6 ' bons_'_'_;_____~_;:_;__i_;_~ _____ _- ' ' 0.9 1._6 i I ' ~2. 79.6 . 80;2 16.6 ___.___-_ ' r .5._8 -_‘__-__.'_ __________ __ Pentane ' and‘ higher ' hydr 8 - . 79. _10. ‘ i 3. 8 ' 1 12.74 ' 8 two ' materials k resulting from the decomposition of the alkylfchloroformate. The recovered cata rutilligedgin?a subseguentalkylation treatment. lyst andexce'ss of f-unconvertedisopara?in may be _ Sometimes hydrogen chloride is added to the ‘ref’. 7» actionnniggture, said hydrogen chloride either being introduced from’ an outside source or re covered ‘from a previous alkylation run.,. 'T-heprocess may be made‘ continuous by pro 1 Vapor pres. of isobutane; no nitrogen added. . 1 Preceded by 2 hours at room temperature. " , , . ' ’ ‘ I . . a Consists of butane, 22.1; ethyl chloride, 18.0; pen ane and higher hydrocarbons, 59.9%. . - 4 Consists of butane, ' ‘ 44.8; ethyl chloride, 25.4;rpentane and higher ' hydrocarbons, 29.8%. "The results given in Table i show that alkyla tion' occurred in good yields atltemperaturevof , 40° C. or higher. It isi’interesting to‘note that 2.4043537‘ the, liquid‘pro'duct boiled‘ at; a relatively low rem-'7 'we-aaimiajs our?inventionz; perature and most'of' it boiled between§40°~ and‘ 75° C. with very little boilingabove'v 100° C. a ‘ 1 ' EXAMPLE VII . . ‘ " ‘ 1. A "process for;"s'ynthesi'zirigf hydrocarbons r v ’ which“ comprises 'reacting‘an iso'paia?'lnic'*lji'ydr‘63-‘v carbo'n‘jwitha-n alkyl cl’iloroforniateiuhder alkyl ' afti‘ngjconditions in the presence‘ of a lf‘riedelq A total of' 120 grams'of isopropylchlorofo‘r'mate ‘ CIfaftstype iinetal halide catalyst. was added slowly toi'a glassareactor"containing a ' “'-‘ I , 2,: AQ process: fonsynthesizing 7' hydrocarbons -‘ well stirred mixture of 205 grams of‘ isobuta‘n'e- ‘ which comprises: reacting: an isopara’f?nic hydro_-' andv v20' grams of aluminum. chloride. ":The reac . carbon withlan alkyl chloroformate ‘ati'a temper-* tion temperature was maintained‘até‘aboutfthei ature of from about —20° to about 100° C. in the‘ presence'fof a _ FriedellCrafts [type metal "halide boiling point of isobutane"under=lrffatmospheref pressure by permitting the isobutane Ito-reflux: under a well cooled ‘condenser while. the isopro~ Catalyst-Y , . - . ‘ _3. A process for synthesizing hydrocarbons 1 which comprises reacting an iso'paraf?nic' hydro-I pyl chloroformate was" introduced ."graduall'y't'o. the reaction mixture 'over a periodof‘3 hours. Hydrogen chloride was evolved at ‘aimoderate? 15 carbonwithan alkyl‘ ‘chloroiorrnalte' at a tempera; ture‘ ‘of 'from about ‘>—'20° to-about- 100" C‘. under rate duringthe time that vthe isopropyl chloro formate was added but‘ this'e'volution‘ became ' a pressure of, from substantially atmospheric to more rapid during an additional 3 hour periodlof stirring which followed vthe intrOduction‘oFall of ‘the isopropyl chloroformate. The ‘ increased ~20 rate ofreac'tion might have been due to aniin‘»v crease in reaction temperature 'to‘about--3° C. which occurred after part of the isobutane had distilledifrom the reaction mixture during the last partiof the stifring'treatment. From the reaction product, Was. obtained 52 grams of col orless liquid hydrocarbon material and 42 grams - about 150 atmospheres in‘ the presence of ‘a FriedeleCraits type metal halide catalyst. 4. A process for synthesizing"hydrocarbons which comprises reacting an iso'para?lnic‘ hydroé" ca'rbon' with an alkyl ‘chloroformate under-jalk'yl: ating'conditions in the 'presencefot'a iFr'iedele > Crafts ' metal halide catalyst, ’ whilev main-' ' tainingfa molar‘excess of said isopara?lnic hydr I. the entire reaction period. . carbon'lto said ‘alkyl ‘chloroformate throughout’ . 1 5. A process for synthesizing. hydrocarbons which comprises reacting an isopara?'inic hydro dish brown oil. In addition to the liquid hydro carbons and catalyst, the recovered materials 30 caribon with an alkyl chloroformate at a tempera ture of from about ~720° C. to about 100° C. un comprised 148 grams of condensible gases of used catalyst having the appearance of a red (chie?y isobutane) and 41 grams of a mixture of hydrogen chloride and carbon dioxide. The rel atively large loss of 62 grams was probably due to a mechanical loss of hydrogen chloride and carbon dioxide. The condensible gas consisted of 28.5 mole per cent of propane, 67.2% of bu tane, and 4.3% of pentanes. The 52 grams of der a pressure of from substantially atmospheric to about 50 atmospheres in the presence of a Friedel-Crafts type ‘metal halide catalyst while maintaining a molar excess of said isopara?inic hydrocarbon to said‘ alkyl chloroformate throughout the entire reaction period. 6. A process‘ for synthesizing hydrocarbons colorless liquid hydrocarbon material recovered 40 which comprises reacting an isopara?inic hydro carbon with an alkyl chloroformate under alkyl in this run represent 125% by weight of the pro pylene which may be considered available from ' ating conditions in' the presence of an aluminum’ halide catalyst. the isopropyl chloroformate. Distillation sepa 7. A process for synthesizing hydrocarbons rated the liquid product into fractions having the boiling ranges and refractive indexes indicated in 45 which comprises reacting an isopara?inic hydro carbon with an alkyl chloroformate under alkyl Table 2. Table 2.-—-Distillation of normally liquid hydro- ' carbon product formed by reactionnf isobutane ' ating conditions in the presence of an aluminum chloride catalyst whilemaintaining a molar ex cess of said isoparaf?nic hydrocarbon to said al with isopropyl chloroformate in the presence of kyl chloroformate throughout the entire reaction 50 period. aluminum chloride [Charge: 69 cc. (48.7 g.)] Fraction No. Boiling rgndge, Vol. of traction, cc. 8. A process for synthesizing hydrocarbons which comprises reacting an isopara?inic hy drocarbon with an alkyl chloroformate at a tem Refractive index @ 20° C. 65 perature of from about —20° to about 100° C. in the presence of an aluminum chloride catalyst while maintaining a molar excess of said isopar af?nic hydrocarbon to said alkyl chloroformate throughout the entire reaction period. 9. A process for synthesizing hydrocarbons which comprises reacting an isoparaf?nic hydro carbon with an alkyl chloroformate at a tem perature of from about --20° to about 100° C. under a pressure of from substantially atmos From the above table it is to be noted that the pheric to about 50 atmospheres in the presence product obtained by reacting isobutane with iso 65 "of an aluminum chloride catalyst while mainpropyl chloroformate contained relatively large taining a molar excess of said isopara?inic hy amounts of hydrocarbons boiling in the range of drocarbon to said alkyl chloroformate through the pentanes, hexanes, heptanes, octanes, and out the entire reaction period. a, higher molecular weight paraf?nic hydrocarbons 10. The process of claim 9 further character of gasoline boiling range. 70 ized in that said isopara?inic hydrocarbon com The foregoing speci?cation and examples in prises isobutane. ' ' ' dicate the character and practical value of the 11. The process of claim 9 further character-, present invention, although it is not intended ized in that said isoparaf?nic hydrocarbon com-' that either section should impose undue limita prises isopentane. 76 12. A process for synthesizing hydrocarbons tions thereon. } ‘2,404,582 , 7?: from substantially atmospheric-to'about50 at: I which comprises reacting ; an - isopara?inic hydro carbon vwith an alkyl ohloroformatew at a tem mospheres in the presence-of an aluminum "chlo ride catalyst. while maintaining, a molar excess; ' perature‘ of from about —20‘j.toabout‘10p“-,C. under'a pressure of from substantially atmos-v pheric to about 50 atmospheres in the presence) of said isobutane to said ethyl 'chloroforrnate throughout the entire reaction period. of aluminum chloride and'another Frieydel-tCrafts ' portion of ethyl‘ chloroformate and from about 2', ' chloroformate throughout .thee'entire reaction ' , .7 1 13, A process for synthesizing hydrocarbons which comprises reacting an isoparaf?nic hydro: carbonrwith an» alkyl chloroformate ata ,tem ' gasoline boiling range and-high ‘antiknockrvalue which‘comprises contacting one moleculanpro type catalyst while maintaining a, molar excess of-said isopara?inic hydrocarbon to said alkyl peri'od.~v ] 15.-A process forsynthesizing hydrocarbons of to ‘about 25 molecular proportions of isobutane‘. with an aluminum chloride catalyst at a ‘semi-1 . perature of» fromryabout 40° toabout 100°‘ C. _ under --a pressure of *from ‘substantially atmos- ' pheric . to' about :50: atmospheres.= 1 perature‘ of from’ about 720° to about ‘100910. . '16." A process for synthesizing hydrocarbons ‘of under- a»; pressure , of: _from substantially atmlo'se.‘ 115' vgasoline boiling range and highrantiknock value pheric to about 50 atmospheres in the presence which comprises contacting one molecular pro-' ofa composite comprisingvessentially, aluminum, of a propyl chloroformate ~and from'about: chloride Vanda refractory carrier ‘while maintain-. ' ' 2portion to about 26 molecular proportions of isobutane ing a molar excess of- said isopara?inichydroe, with'an aluminum chloride catalyst at a tem carbon torsaid alkyl ' chloroformate I throughout 20~ "perature of from about —20"»-to ‘about 100°C. the entire ‘reaction ‘period, » under a pressure of from substantiallyatmosw ‘_‘;14;;A<_ process for'synthesizing hydrocarbons ‘ of gasoline boiling range and high antiknock value which comprises reacting isobutane V with , I _ ethyltchloroformate at a temperature of, from 25; "about'lio‘ito about (51009» C. under a pressureof pheric‘ to about 50'atmospheres. > LOUIS SCHMERLING; : ; -,_>VLADIMIR N. IPA'I‘IEER,"