Патент USA US2385300код для вставки
Patented Sept. 18, 1945 , ‘ UNITED ' STATES2,385,300 PATENT 2,385,300 OFFICE CONVERSION OF EYDROGARBONS Herman Pines‘and Vladimir N. Ipatie?, River side, 111., assignors to ‘Universal Oil Products Company, Chicago, 111., a corporation or Dela. ware No Drawing. Application January 29, 1043, ~ Serial No. 478,972 7 Claims. (01. 260-666) carbons and para?lnic hydrocarbons of lower mo This invention relates to a process for eiiect lecular weight than those charged to the proc ing hydrocarbon conversions and more particu larly to a process for converting alkyl cyclopen tane hydrocarbons into alkyl cyclohexanes by re acting said alkyl cyclopentane hydrocarbons with paraiilnic hydrocarbons in the presence of a cat alyst. The present process is a contribution to‘the art - of producing reactions between different types or hydrocarbons to synthesize other hydrocarbon compounds or increasing molecular weight. Var ious alkylated eyclopentane hydrocarbons can be illustrated by adding alkyl radicals to the base member oi this series, namely cyclopentane. However, the actual syntheses of diiierent alkyl ‘ess. The ease with l~which. the above reaction oc curs is probably due to' the presence of a tertiary ' carbon atom in the alkyl cyclopentane molecule. Because of the di?iculty in following thevcharac ter 01 such reactions and the possible formation of certain proportions of intermediate addition compounds with the catalyst in reactions of the present type. the above explanation is not of iered as being entirely adequate. It also omits mention of the formation of small amounts oi .gaseous hydrocarbons of low molecular weight such as‘methane and ethane which sometimes occurs to a minor extent. However, under prop cyclopentane and alkyl cyclohexane hydrocarbons erly controlled "conditions, decomposition reac tions to undesired gaseous hydrocarbons may be do not follow such a simple mechanism. One speci?c embodiment of the present in-' kept low and the alkylation may be regulated by cyclopentane hydrocarbon .with a para?inic hy 20 controlling the temperature, the nature and amount or the catalyst. the proportion of par drocarbon in the presence of an alkylating cat; a?lnic hydrocarbons to alkyl cyclo'pentane hydro alyst to form a substantial yield of alkylated and vention comprises a process for reacting an alkyl polyalkylated cyclohexane hydrocarbons. carbons, etc., so that'high yields of the desired . compounds will be produced. The present process is particularly concerned with a simultaneous cleavage or breaking of a 26 paramnic hydrocarbon and the alkylation of an alkyl cyclopentane with fragments resulting ' We have discovered that isomerization and - alkylation of’ alkyl cyclopentane hydrocarbons can be accomplished simultaneously and more advantageously by the process of the present in vention than- by isomerization alone. In this ization can accompany alkylation when an alkyl 30 process, the alkyl cyclopentanes are reacted with straight and/or branched chain para?ins in the cyclopentane hydrocarbon is destructively al presence or an alkylating catalyst including sul iwlated with a paramnic hydrocarbon. The fol i'uric acid, hydrogen ?uoride, mixtures of hydro lowing equahlon illustrates the destructive alkyla gen ?uoride and boron ?uoride, and Friedel tion of methyl cyclopentane with iso-octane: Crafts type metal halides together with a hydro 35 gen. halide.» Under the preferred conditions of irom said cleavage or breaking of a para?inic hy drocarbon. Furthermore, it appears that isomer operation, which are discussed hereinafter in re lation to the di?erent aikylating catalysts, an al mlation productis formed consisting not of more highly alkylated‘ cyclopentane hydrocarbons but of alkylated cyclohexane hydrocarbons. In other words, isomerization occurred either before, after, or during the alkylation reaction. By this proc ess, the alkylation of alkyl cyclopentane hydro 45 carbons with para?inic hydrocarbons, including isoparaf?ns and normal para?ins, to form alkyl cyclohexane hydrocarbons is accomplished rap idly under operating conditions which are rela The ‘above equation indicates that methyl cy tively easy to control. cyclopentane may be reacted with 2,2,4-trimethyl pentane to form 1,2-dimethyl-4-ethyl‘cyclohex 50 Another advantage of the process is the fact that nearly complete conversion of the alkyl cy are together with isobutane. Other branched clopentane hydrocarbons into alkyl cyclohexanes chain para?inic hydrocarbons and less-branched can be obtained. Furthermore, the cyclohexane chain para?inic hydrocarbons can also undergo hydrocarbons formed by this process may be a similar reaction under suitable conditions of operation to form alkylated cyclohexane hydro- 5s separated from unconverted cyclopentane by 2 assasoo drocarbons and dehydrogeuated catalytically or thermally into alkyl benzene hydrocarbons while the unconverted or incompletely converted alkyl cyclopentane hydrocarbons are returned to fur ther treatment with para?inic hydrocarbons in the presence of an alkylating catalyst as herein set forth. The di?erent allwl cyclopentane hydrocarbons and paraiilnic hydrocarbons employed in the the rate of undesirable reactions which fre quently result in deposition and/or degradation 7 of the desired alkylation product. While the process of the present invention may be eii'ected in either batch or continuous types of operation, it is usually carried out on a continuous basis by withdrawing from the reaction zone a complex mixture of excess unreacted alkyl cyclo pentanes, desired alkylated cycloh'exanes, higher process need not be entirely pure as any hydro 10 boiling hydrocarbons, and catalyst; said complex carbon fraction or fractions containing alm cy mixture being withdrawn at substantially the clopentane hydrocarbons and paramnic hydro same rate as that at which the hydcarbons ~ carbons may be utilized in the process. Thus, a charged are supplied to the alkylation reactor. hydrocarbon fraction containing substantial At least a portion or the recovered_used catalyst amounts of methyl-, ethyl-, and higher alkyl 15 and unreacted alkyl cyclopentanes may be re cyclopentanes in admixture with straight ‘and cycled to further treatment with para?lnic hy branched chain paraiiins may be converted as drocarbons in the presence of some freshly added alkylating catalyst. > _ herein set forth to obtain substantial yields of alkyl cyclohexane hydrocarbons. Batch type operation of the present process The catalysts employed in the process of the 20 may be carried out by gradually introducing a present invention are not necessarily equiva para?inic hydrocarbon fraction or a para?in con lent in their action and accordingly. the condi taining fraction to a reaction vessel containing tions of operation and particularly the reaction a mixture of the alkyl cyclopentane hydrocarbon temperature are dependent upon the catalyst and the catalyst. The reaction vessel is prefer employed in a particular reaction. Thus, with 25 ably equipped with an eflicient mixing or stirring 7 hydrogen ?uoride or mixtures of hydrogen ?uo device so as to insure intimate contact of the re ride and boron ?uoride, a reactor temperature of acting hydrocarbons and catalyst. Upon com . from about -20° to about 200° C. is employed at pletion of the alkylation reaction, a hydrocarbon a pressure of generally not more than about 35 product is separated from the catalyst and said atmospheres; while sulfuric acid is utilizable gen 80 hydrocarbon product is further fractionally dis eralhr at a temperature of from about —5‘‘ to tilled to separate alkylated cyclohexane hydro about 120° C. when employing catalysts con carbons from unconverted or incompletely con taining an acid of phosphorus, such as solid phos verted paraiilnic and cyclopara?lnic hydrocarbons phoric acid, the temperature utilized is from which are returned to further treatment in the about 100° to about 450° C. and the pressure is 35 presence of an alkylating catalyst as hereinabove generally between about 1 and 70 atmospheres. set forth. Catalysts of the Friedel-Crafts type are utilizable The following example indicates results ob under dii’ferent conditions of operation depend tainable by the present process, although it is in ing upon the particular Frledel-Crafts type cata troduced with no intention of limiting the scope lyst employed. 'I'hus, aluminum chloride may be 40 of the invention in exact correspondence thereto. utilized at a temperature of from about —'l0° to 4 molecular proportions of methyl cyclopen about 150° C. while ferric chloride requires a tane are reacted with 0.5 molecular proportions somewhat higher average temperature and zinc of 2,2,4-trimethyl pentane in the presence. of hy chloride is utilizable only at still higher temper drogen ?uoride at a temperature 010100“ C. The atures and particularly at a temperature of from 45 resultant reaction mixture, after separation about 150° to about 450° C. therefrom of unconverted methyl cylclopentane The details of operation of the present process and 2,2,4-trimethyl pentane, contains substantial are relatively simple since alkyl cyclopentane amounts of allgvlated cyclohexane hydrocarbons. hydrocarbons are liquid under ordinary condi The character of the present invention and its tions of temperature and pressure. Accordingly, 50 novelty and utility in producing alkyl cyclohex the process of the present invention is carried out by contacting an alkyl cyclopentane hydro carbon with ,a para?lnic hydrocarbon generally ane hydrocarbons can be seen from the preced ing speci?cation and example, although neither section is intended to limit unduly its generally containing 4 or more carbon atoms per molecule broad scope. in the presence of an alkylating catalyst under 55 We claim as our invention: the preferred operating conditions until alkyla 1. A process for producing substantial yields tion has occurred and a substantial yield of an of alkyl cyciohexane hydrocarbons which com essentially saturated hydrocarbon product is prises reacting an alkyl cyclopentane hydrocar formed containing a relativelyhigh proportion of bon and an isopara?inic hydrocarbon in the pres alkyl cyclohexane hydrocarbons. The molar 60 ence of an alkylating ‘catalyst while maintaining ratio of alkyl cyclopentane hydrocarbons to par a molar excess of alkyl cyclopentane hydrocar a?lnic hydrocarbons should be greater than 1 and bon to isopara?inic hydrocarbon throughout the preferably greater than 3, the exact ratio being reaction. somewhat dependent upon the particular 2. A process for producing substantial yields of alkyl cyclopentane and para?inic hydrocarbons 65 alkyl cyclohexane hydrocarbons which comprises charged to the process. The ratio of alkyl cyclo reacting an alkyl cyclopentane hydrocarbon and pentane hydrocarbon to parailinic hydrocarbons an isopara?inic hydrocarbon in the presence of charged is subject to some variation and is af an alkylating catalyst comprising sulfuric acid fected considerably by the method of introducing as its essential active ingredient. the c hydrocarbon, the e?iciency of mix 70 3. A process for producing substantial yields lngve I - of alkyl cyclohexane hydrocarbons which com prises reacting an alkyl cyclopentane hydrocar bon and an isopara?lnic hydrocarbon in the pres ence of an aykylating catalyst comprising hydro peratures there is generally a marked increase in 75 gen ?uoride as its essential active ingredient. It is advisable to carry out the process of the present invention at as low a temperature as possible and as is practical, since at higher tem- - 3 a,sas,soo reacting an alkyl cyclcpentane hydrocarbon and 7 4. A process for producing substantial yields or alkyl cyciohexane hydrocarbons which com prises reacting an alkyl cyclopentane hydrocar an isoparaiiinic hydrocarbon in the presence of an alkylating ‘catalyst while maintaining a molar ratio of alkyl cyclopentane hydrocarbon to iso paramnic hydrocarbon or more than three bon and an isoparaiiinic hydrocarbon in the pres ence of an alkyintlng catalyst comprising a Friedel-Craits type metal halide as its essential active ingredient. ~ throughout the reaction. ' 7. A process for producing substantial yields oi’ ‘ alkyi cyclohexane hydrocarbons which comprises 5. A process for producing substantial yields reacting an alkyl cyciopentane hydrocarbon and oi alkyi cyclohexane hydrocarbons which com prises reacting an alkyl cyclopentane hydrocar 10 a. paramnic hydrocarbon in the presence of an alkylating catalyst while maintaining a molar bon and a para?inic hydrocarbon in the presence ratio of alkyl cyclopentane hydrocarbon to par- " of an ‘alkylating catalyst while maintaining a mo lar excess oi alkyl cyclopentane hydrocarbon to para?lnlchydrocarbon throughout the entire re ' action. 6. A process for producing substantial yields of alkyl cyciohexane hydrocarbons which comprises aiiinic hydrocarbon of more than three through- _ out the reaction. » 15 HERMAN PINES. VLADIMIR N. IPA'IfIEI'I'.