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United States Patent (19) (11) 3,887,635 Parker Et Al

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United States Patent (19) (11) 3,887,635 Parker Et Al United States Patent (19) (11) 3,887,635 Parker et al. (45) June 3, 1975 54 ALKYLATION PROCESS UTILIZING 2,313,103 3/1943 Thomas......................... 260/683.47 HALOSULFURIC OR 2,353,596 7/1944 Shiffler et al.................. 260/683.58 TREHALOMETHYLSULFONCACID WITH 2,413,777 1/1947 Oakley et al................... 260/683.63 2,425,572 8/1947 Slotterbeck.................... 260/683.63 A CATALYST MODERATOR 2,460,719 2/1949 Stover............................ 260/683.43 75 Inventors: Paul T. Parker, Baton Rouge, La.; 2,468,529 4/1949 Voorhies, Jr. et al......... 260/683.59 Ivan Mayer, Summit, N.J. 3,655,807 4/1972 Rakow et al................... 260/683.63 3,766,293 10/1973 Parker et al................... 260/683.58 73) Assignee: Exxon Research and Engineering Company, Linden, N.J. Primary Examiner-Delbert E. Gantz 22 Filed: Aug. 27, 1973 Assistant Examiner-G. J. Crasanakis Attorney, Agent, or Firm-Leon Chasan 21 Appl. No.: 391,864 Related U.S. Application Data 57 ABSTRACT 63 Continuation-in-part of Ser. No. 201,389, Nov. 23, A hydrocarbon conversion process for producing high 1971, abandoned. octane alkylate by contacting a saturated hydrocar bon, preferably a C-C isoparaffin, and an olefin, 52) U.S. Cl........................ 260/683.47; 260/683.58 preferably a C-C monoolefin, with a catalyst (51) Int. Cl............................................... C07c3/54 formed from a strong halosulfuric acid and a catalyst (58 Field of Search....... 260/683.4, 683.43, 683.47, moderator. The catalyst moderator is selected from 260/683.58, 683.59 (1) water, (2) C-C monohydroxy alcohols, (3) di fluorophosphoric acid, (4) C-C monoether, (5) ar 56 References Cited omatic sulfonic acid, and (6) minor amounts of sulfu UNITED STATES PATENTS ric acid. 2,286, 183 6/1942 Bradley et al.................. 260/683.63 33 Claims, 1 Drawing Figure O O 2O 3O MOLE% WATER PATENTED JUN3 1975 3.887. 635 98 1CA 96 - 95 - 9 O GO MOLE% WATER 3,887,635 2 ALKYELATON PROCESS UTELIZENG duction period (up to 210 hours) during which a pre HALOSULFURIC OR dominant amount of C-alkylate is formed at the ex TRHALOMETHYELSULFONCACD WITH A pense of desired Cs alkylate. In the case of sulfuric acid CATALYST VODERATOR addition to the fluorosulfuric acid catalyst, it was ob served that the induction period diminished to 125 CROSS REFERENCE TO RELATED APPLICATION hours; however, this is still an economically undesirable This application is a continuation-in-part of applica time lag. In the latter instance the alkylation was con tion Ser. No. 201389, filed Nov. 23, 1971 now aban ducted at a temperature of 50°F. and a pressure of 100 doned. psig. Other additives such as mercaptans (U.S. Pat. No. O 2,880,255 - mercaptains must contain at least 8 car BACKGROUND OF THE INVENTION bon atoms per molecule) and amines (U.S. Pat. Nos. 1. Field of the invention 2,880,255 and 3,324, 196) have also been used ad The present invention concerns a hydrocarbon con mixed with fluorosulfuric acid. The above-mentioned version process. More particularly, the invention re additives have generally not provided the desired high lates to an improved alkylation process for the prepara 15 Cs hydrocarbon selectivity or have proven too expen tion of branched chain hydrocarbons by contacting sat sive for commercial utilization. urated hydrocarbons, preferably saturated isoparaffinic hydrocarbons, with olefins in the presence of an acid SUMMARY OF THE INVENTION catalyst system. Still more particularly thc invention re in accordance with this invention, it has been found lates to improving the alkylation selectivity of alkyla that hydrocarbon conversion reactions such as alkyla tion catalysts by utilizing a catalyst moderator. tion can be conducted in the presence of a catalyst mix 2. Description of the Prior Art ture formed from a strong acid such as halosulfuric acid Acid catalyzed hydrocarbon conversion processes (XSOH where X is halogen), trihalomethanesulfonic comprising contacting an alkane with an alkene are acid (CXSOH) or mixtures thereof and one or more well known. The reactants are generally contacted in 25 moderators, generally containing at least one oxygen the liquid phase and within a broad temperature range atom per molecule and including water, aliphatic and of about -100 to 100F. with an acid catalyst such as, cycloaliphatic alcohols and ethers, aliphatic, cycloali for example, sulfuric acid, fluorosulfuric acid or a halo phatic and aromatic sulfonic and carboxylic acids and gen acid, such as hydrofluoric acid. their derivatives and inorganic acids. The term 'mod Alkylation processes employing fluorosulfuric acid as 30 erator' as used herein, is defined as a compound a catalyst are described in U.S. Pat. Nos. 2,313,103, which, in combination with a strong acid, produces a 2,344,469 and U.K. Pat. No. 537,589. The use of other catalyst system of reduced activity vis-a-vis the strong acids such as trifluoromethanesuifonic acid as alkyla acid, and thereby decreases the probability of compet tion catalysts has also been described (T. Gramstad and ing side reactions, such as polymerization, which have R. N. Haszeldine, J. Chem. Soc., 1957, 4069-79). 35 a detrimental effect on product quality, while increas Alkylation reactions of the above-mentioned types ing catalyst selectivity, resulting in high quality alkylate have encountered difficulties directly resulting from product. the high activity of the strong acid catalysts used in the The alcohols preferably contain 1 to 10 carbon atoms reactions. For example, the intermediate alkyl carbo and 1 to 10 hydroxyl groups per molecule. The lower nium ion products generated in the strong acid medium 40 molecular weight saturated alcohols are most preferred undergo a number of side reactions which lead to the and contain desirably 1 to 7 carbon atoms, more pref formation of heavy products which then undergo erably 1 to 5 carbon atoms per molecule and 1 to 4 hy cracking reactions to form undesirable light hydrocar droxyl groups per molecule. The ethers are preferably bons. This results in a decrease in the production of de saturated and contain 2 to 10, preferably 2 to 5 carbon sired Cs to C products and in a lowering of the octane 45 atoms per molecule. In the latter instance while mono number of the products obtained. Additionally, strong ether compounds are preferred moderators, com acid catalyzed alkylation reactions have suffered from pounds containing up to 3 or more alkoxy groups are a general lack of selectivity with regard to the forma also contemplated. The sulfonic and carboxylic acids tion of Cs hydrocarbons. The octane number of alky preferably contain 1 to 10, most preferably 1 to 7 car late is enhanced by the presence of high concentrations 50 bon atoms per molecule. In addition, the acids can be of Cs hydrocarbons. Trimethylpentane is a particularly substituted with one or more carboxy or sulfo groups. valuable alkylate component. The acid derivatives include the esters and anhydrides In the use of strong acids such as fluorosulfuric acid, and preferably contain 2 to 20 carbon atoms, most attempts have been made to minimize competitive side preferably 2 to 10 carbon atoms per molecule. reactions and to maximize Ca hydrocarbon selectivity 55 The aliphatic, cycloaliphatic and aromatic portions by using low reaction temperatures, i.e. -112 to of the aforementioned moderators can be optionally -45°F.; however, difficulties encountered in maintain substituted with a variety of substituents such as halo ing these low temperatures has made this process eco gen atoms, and such groups as hydroxy, C to Cs alk nomically impractical. Additionally, in a further at oxy, C, to C5 perhaloalkyl, C. to C6 carboalkoxy, car tempt to maximize Ca hydrocarbon selectivity, the 60 boxy, C, to Co. hydrocarbyl, preferably C1 to Cs alkyl strong acids have been admixed with small amounts of or C to C cycloalkyl, or combinations thereof. additives such as BF (U.S. Pat. No. 2,366,731), hydro The inorganic acids will, in general, be less acidic gen halides (U.S. Pat. No. 2,259,723) and surfactants than the strong acid component of the catalyst System (U.S. Pat. No. 3,231,633) such as methyl isobutyl oxo and desirably will have Ho values, i.e. -log h (Ham nium chloride, dimethyl isopropyl sulfonium chloride 65 mett acidity function), greater than about - 1 (see or sulfuric acid. The function of the surfactant, in the Gould, E. Mechanism and Structure in Organic Chemis latter instance, is to reduce an appreciable reaction in try, New York, Holt, Rinehart and Winston, 1959, 3,887,635 3 106). Preferred inorganic acids contain 1 to 4 hydroxyl malonic acid groups per molecule. pthalic acid The catalyst moderators may be used effectively with diethylmalonate a wide variety of strong acids. Examples of strong acid 1,2,3-tricarboxypropane components of the strong acid moderator catalyst sys 5 dimethyl ether tem include halosulfuric acid such as fluorosulfuric diethyl ether acid, chlorosulfuric acid and bromosulfuric acid; diphenyl ether trihalomethanesulfonic acid such as trifluoromethane dioctyl ether sulfonic acid, trichloromethanesulfonic acid and ethyl methyl ether tribromomethanesulfonic acid; or mixtures thereof and 10 chloromethyl ethyl ether the like. Preferred strong acids include fluorosulfuric decyl nonyl ether acid, trifluoromethanesulfonic acid or mixtures 1-methoxycyclopentyl ethyl ether thereof. In addition, the phosphorus analog of ethylene oxide trihalomethanesulfonic acid, i.e. trihalomethanephos tetrahydrothiofuran phonic acid, may be an effective strong
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