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 acid. 15 phosphoric acid Illustrative, non-limiting examples of useful modera phosphorus acid tor compositions include: sulfuric acid sulfurous acid Water monofluorophosphoric acid methanol 20 difluorophosphoric acid ethanol orthophosphoric acid n-propanol pyrophosphoric acid isobutanol polyphosphoric acid 3-chloro-2-methyl-1-butanol 6-mercapto-4-methoxy-2-hexanol 25 Preferred catalyst moderators contain either a hy 2,2-dimethyl-4-methylthio-3-perfluoromethyl-1- droxy group, such as alcohols or a hydroxy group pre hexanol cursor, such as ethers which cleave, it is speculated, to 44-dimethyl-3-phenolthio-1-heptanol form alcohols under the acidic conditions of the subject 5-carbethoxy-4,4-dimethyl-1-pentanol invention. Of these, the most preferred compounds are 2-decanol 30 the alcohols and water. It is noted that the catalyst cyclopropanol moderator and strong acid can be premixed prior to in cyclopentanol troduction into the reactor, thereby forming the cata 2-chlorocyclohexanol lyst system. The catalyst may also be formed in situ. 2-methyl-3-methylthio cyclohexanol The exact mechanism by which the moderator com cyclodecanol 35 pounds effectuate increased catalyst selectivity while 1,2-dihydroxyethane reducing competitive side reactions such as polymer 1,2,3-trihydroxypropane ization, is not known. However, the active catalyst spe 2,4,5-trihydroxypentane cies of the subject invention is postulated to be an equi 1,3,5-trihydroxycyclohexane librium mixture comprising several components. For 1,2-dihydroxycyclooctane 40 example, it is speculated that the addition of water to pentaerythritol fluorosulfuric acid, results in initial ionization of the methylsulfonic acid strong acid followed by hydrolysis: 2-chloroethylsulfonic acid propylsulfonic acid ethyl propanesulfonate 45 H2O + HSO3F - Hot + SO3F methyl-2-phenoxyethanesulfonate (l) benzenesulfonic acid formic acid H2SO + HF acetic acid propionic acid 50 The equilibrium is believed to lie towards the right and, butyric acid therefore, little, if any, free water should exist in the heptanoic acid strong acid system. Similar mechanisms can be postu decanoic acid lated for other moderators such as alcohols and ethers. benzoic acid 55 By the very nature of the postulated mechanism, it is ethyl acetate clear that the manner in which the active catalytic sys methylbutanoate tem is formed is immaterial. Thus, in the above exam propyl decanoate ple, mixing HF and H2SO4 in appropriate amounts ethylbenzoate should result in the same catalyst system as would be 2-chlorobutanoic acid obtained by mixing water with FSOH. 2-hydroxy-5-methylhexanoic acid 60 In view of the above, when the catalyst system is de phenyl acetate scribed as "being formed from' a strong acid and a trifluoroacetic acid moderator, it is not meant to be limited to any one cata 3,3,3-trifluoropropionic acid lyst formation mode; rather, this description is used ethanoic anhydride 65 merely for convenience in providing a simple definition propionic anhydride of the active catalyst system. butanoic anhydride Aromatic compounds are generally not preferred as oxalic acid catalyst moderators since competitive sulfonation of 3,887,635 S 6 the aromatic ring occurs under the alkylation reaction col with two hydroxyl groups. Hence, as the number of conditions. However, if the aromatic nuclei are suffi hydroxyl groups or latent hydroxyl groups per molecule ciently deactivated, with regard to electrophilic substi of moderator increases, the required amount of moder tution, they may then be effective moderators. Thus, ator compound will decrease. for example, electron withdrawing groups such as Although the broad concentration ranges are gener -COOH, -SOH, -COOR and the like are believed ally independent of the type of moderator used, the to sufficiently deactivate aromatic rings to permit their preferred or optimal range will vary depending on the use in the subject process. In general, aromatic ring structure of the moderator, the reaction temperature, substituents with Hammett O'meta and opera values equal the concentration and nature of the olefin in the feed to or greater than 0.01 are acceptable. For a more de 10 and the olefin space velocity. tailed discussion of the Hammett equation and electro As indicated above, trifluoromethanesulfonic acid philic aromatic substitution in general, see Mechanism has been found to be a particularly effective alkylation and Structure in Organic Chemistry, by Edwin S. Gould, catalyst when used with a moderator. As disclosed in 1959, Holt, Rinehart and Winston, Inc., pp. 220-227 Chemical and Engineering News, Jan. 18, 1971 and J. and 412-463. Additionally, it is noted that highly basic 15 Org. Chem. 39 (1), Jan. 15, 1971, the acid is a stable, materials such as amines, for example triethylamine, colorless liquid with a strong, pungent odor and fumes cannot generally be used in the concentration range of copiously in moist air. Moreover, simple alkyl esters of the subject process due to reaction with the strong acid. the acid can be used as alkylation agents. The acid is While inorganic acids such as HCl, HBr and HI may non-oxidizing and has been shown to be one of the be used as moderators, their effectiveness is diminished strongest proton acids known. However, while alkyla by their tendency to form stable halides with the olefin tion rates are high, competing polymerization reactions reactants. Halide formation, however, is not an impor are also high, thus diminishing, somewhat, the effi tant problem with HF. Additionally, oxidative acids ciency of this acid as an alkylating agent. Moreover, Cs such as HNO3 and HClO4 cannot be used as moderators alkylate selectivity is low. These difficulties can be due to oxidative side reactions with the olefins. 25 overcome by utilizing a moderator with the acid, result It has been found that the amount of moderator used ing in a substantial decrease in polymerization side re in forming the catalyst system is an important variable actions with a corresponding increase in Ca hydrocar in the production of high quality alkylate. It has been bon selectivity in the alkylate vis-a-vis the pure acid. determined that the desired amounts of moderator will In addition to their use in classical alkylation pro vary dependent, in part, on the alkylation temperature. 30 cesses as hereinabove described, the catalyst systems of Thus, for example, attemperatures between about, say, the subject invention may also be used in self-alkylation 0 and 40°F, useful amounts of moderator can range processes. The C6-C1s branched chain olefins and between about 5 and 45 mole % based on acid, prefera C-C isoparaffins are preferred reactants. The pro bly between 10 and 30 mole % and still more preferably cess is generally conducted in the liquid phase whereby between 15 and 25 mole %, e.g. 20 mole %. In some in 35 the isoparaffin is dimerized and the olefin is saturated stances, however, it may be desirable to use somewhat producing an alkylate-type product of high quality. lower or higher amounts of moderator, e.g. 50 mole % Self-alkylation processes are generally described in . based on acid, where, for example, increased catalyst U.S. Pat. No. 3, 150,204. Undesired side reactions are activity or selectivity is desired. minimized using these catalyst systems, thereby provid In this connection, reference is made to the figure 40 ing high yields of the desired products. which shows the effect of water addition to fluorosulfu In general the amount of olefin contacted with the ric acid on Chalkylate MON (Motor Octane Number) catalyst can range from about 0.05 to 1000 volumes of at 0°F. Specifically, the graph refers to the alkylation of olefin per hour per volume of catalyst inventory in the isobutane with butene-1 in the presence of a catalyst reactor (v/v/hr.), i.e. olefin space velocity. Preferably, system formed by adding varying amounts of water to 45 the olefin space velocity ranges from about 0.05 to 10.0 fluorosulfuric acid. It is noted that optimum results are v/v/hr., and still more preferably from about 0.05 to 1.0 obtained between about 15 and 20 mole % of water v/v/hr., e.g. 0.1 v/v/hr. The volume % of total catalyst based on acid. in the reaction mixture or emulsion (when liquid phase At higher alkylation temperatures, say, between operations are used) in the reactor can range from about 40 and 100F, increased amounts of moderator 50 about 30 to 80 volume 96 based on total reaction mix may be desirable due to the increased strong acid activ ture and preferably from about 50 to 70 volume %. The ity. Thus, it is within the purview of this invention to isoparaffin concentration, including alkylate, in the hy use an amount of moderator ranging between about 50 drocarbon phase (in a liquid phase process) can range and 100 mol % based on acid at these higher tempera from 40 to 100 volume 76 based on the total volume of tures. In fact, under appropriate conditions, these 55 the hydrocarbon phase and preferably from 50 to 90 higher amounts of moderator may also be utilized at volume %. Such isoparaffin concentrations can be the lower temperatures disclosed hereinabove, if de maintained by recycling unreacted isoparaffin to the sired. reactor. In the case of hydroxyl-containing moderators, (or Suitable olefinic reactants include C2-C12 terminal moderators containing hydroxyl precursors, i.e. latent 60 and internal monoolefins such as ethylene, propylene, hydroxyl groups,) amounts of added moderator to the isobutylene, butene-1, butene-2, trimethylethylene, the strong acid may fall below the above-specified ranges. isomeric pentenes and similar higher monoolefinic hy It appears that the efficiency of hydroxy compounds is drocarbons of either a straight chain or a branched directly related to the overall number of hydroxyl chain structure. Preferably, the C-C6 monoolefins groups or latent hydroxyl groups present per molecule. 65 are used, although the highly-branched C-C mono Thus, ethanol with one hydroxyl group should have olefins may also be used. Cycloolefins may also be moderator activity similar to 0.5 mole of ethylene gly used. The reaction mixtures may also contain small 3,887,635 7 8 amounts of diolefins. Although it is desirable from an sired, a portion of the catalyst can be continuously re economic standpoint to use the normally gaseous ole generated or reactivated by any suitable treatment and fins as reactants, normally liquid olefins may be used. returned to the alkylation reactor. Thus the invention contemplates the use of reactable As in other alkylation processes, more accurate con polymers, copolymers, interpolymers, crosspolymers, trol of the quality of the final product may be obtained and the like, of the above-mentioned olefins, such as, if the reaction system is provided with a recycling fea for example, the diisobutylene and triisobutylene poly ture wherein the partially converted hydrocarbons are mers, the codimer of normal butylene and isobutylene, mixed with fresh feed and returned to the feed disper of butadiene and isobutylene, and the like. Mixtures of sion device in the reactor. However, due to the high two or more of the olefins above described can be used 10 conversion efficiency of the present catalyst systems, it as the process feedstock. is preferred to effect alkylation in a once-through oper The instant catalyst systems are particularly suited ation with short reaction times. for use in refinery alkylation processes. The process of In general, reaction and/or recovery schemes and ap the invention contemplates the use of various refinery paratus employed in conjunction with prior art liquid cuts as feedstocks. Thus, C, C, C4 and/or Cs olefin 15 acid catalyst systems can be used with the catalyst sys cuts from thermal and/or catalytic cracking units; field tems of the present invention. Examples of potentially butanes which have been subjected to prior isomeriza applicable process techniques and apparatus are de tion and partial dehydrogenation treatment; refinery scribed in U.S. Pat. Nos. 2,433,944, 2,479,366, stabilizer bottoms; spent gases; normally liquid prod 2,701,184, 2,717,913, 2,775,636, U.K. Pat. Nos. ucts from sulfuric acid or phosphoric acid catalyzed po 20 543,046, 577,869, 731,806, 738,348, 803,458, lymerization and copolymerization processes; and 804,966 and 881,892, the disclosures of which are products, normally liquid in character, from thermal herein incorporated by reference. and/or catalytic cracking units, are all excellent feed In carrying out alkylations using the catalyst systems stocks for the present process. Such feeds are prefera of this invention, a wide temperature range may be uti bly dried to control excess water buildup, i.e. about 5 25 lized, i.e. about-80 to 100°F.; however, fairly low re to 15 ppm (weight) of water before entering the reac action temperatures are preferred. Therefore, tempera tOr. tures ranging from about-80 to 70°F., most prefera The hydrocarbon feedstocks that are reacted with bly from about -20° to +40°F. are usually employed. the olefins desirably comprise straight and/or branched When sulfuric acid is the promoter, a preferred temper chain C-C paraffins such as hexane, butane and the 30 ature range of about -20° to +30°F., i.e. 0° to 20F., is like, and preferably, C-C isoparaffins such as isobu used, thereby substantially eliminating the induction tane, isopentane, isohexane and the like. While open period noted in U.S. Pat. No. 3,231,633. Where the re chain hydrocarbons are preferred, cycloparaffins may action is carried out at temperatures above about also be used, such as cyclopropane. 10F., it is necessary that the reaction be conducted Preferably, the olefin is first diluted with the paraffin 35 under superatmospheric pressure, if both the reactants before being introduced into the reactor. The olefin and catalyst are to be maintained substantially in the concentration in the paraffin feed ranges from 0.5 to 25 liquid state. Typically, the alkylation reaction is con volume 96 based on total feed and preferably below 10 ducted at pressures varying from about 1 to 20 atmo volume 96. Translated into volume ratios, high volume spheres. ratios of paraffin to olefin ranging from 10:1 to 200: 1 40 In general, it is preferable to use pressures sufficient or higher are preferred, although somewhat lower ra to maintain the reactants in the liquid phase although tios may be used, i.e. 3:1. Correspondingly high volume a vapor phase operation is also contemplated. Autore ratios of paraffin to olefin are also desired within the frigerative reactors and the like may be employed to reaction zone. Preferably, the paraffin?olefin ratio maintain liquid phase operation. Although it is pre therein ranges from about 20:1 to 2000:1 or higher. 45 ferred to run the reaction neat, solvents or diluents may The process may be carried out either as a batch or be employed, if desired. continuous type of operation, although it is preferred In another embodiment of the invention the catalyst for economic reasons to carry out the process continu may be employed incorporated with a suitable solid ously. It has been generally established that in alkyla carrier or support. Any solid carrier may be used that tion processes, the more intimate the contact between 50 is substantially inert to the catalyst under the reaction the feedstock and the catalyst the better the yield of conditions. Active supports may be rendered inert by saturated product obtained. With this in mind, the pres coating them with an inert material such as antimony ent process, when operated as a batch operation, is trifluoride or aluminum trifluoride. Examples of such characterized by the use of vigorous mechanical stir carriers include silica gel, anhydrous AlF3, aluminum ring or shaking of the reactants and catalyst. 55 phosphate, carbon, coke, firebrick and the like. When In continuous operations, in one embodiment, reac supported catalysts are used, the reactants, in vapor tants may be maintained at sufficient pressures and and/or liquid form, are contacted with the catalyst par temperatures to maintain them substantially in the liq ticles at conversion conditions. The catalyst materials uid phase and then continuously forced through disper 60 may be maintained in a fixed bed, moving bed or fluid sion devices into the reaction zone. The dispersion de bed reaction zone. vices may be jets, porous thimbles and the like. The re The aforedescribed olefins and saturated hydrocar actants are subsequently mixed with the catalyst by bons are contacted with the catalyst for a time suffi conventional mixing means such as mechanical agita cient to effect the degree of alkylation desired. In gen tors and the like. After a sufficient time, the product eral, the time of contact is subject to wide variation, the can then be continuously separated from the catalyst 65 length of residence time being dependent in part upon and withdrawn from the reaction system while the par the reaction temperature, the olefin used and the cata tially spent catalyst is recycled to the reactor. If de lyst concentration employed. By way of illustration, 3,887,635 typical contact times can range from about five minutes The hydrocarbons were allowed to melt, decanted from to one hour or more. Much shorter contact times, i.e. the acid, washed with 10% NaOH solution and then an as low as 0.1 seconds, can also be used, if desired. alyzed. m Tables I and II summarize results obtained using BRIEF DESCRIPTION OF THE DRAWING fluorosulfuric acid admixed with water or sulfuric acid The FIGURE shows the relationship between the moderators vis-a-vis pur fluorosulfuric acid to catalyze amount of catalyst moderator (water) added to fluoro alkylations conducted in continuous glass reactors and sulfuric acid and C6-alkylate MON. capillary reactors. It is first noted that there was a substantial increase DESCRIPTION OF THE PREFERRED O EMBODIMENTS in the alkylate research and motor octane numbers wher: the strong acid was admixed with a moderator, The invention will be further understood by refer vis-a-vis the strong acid catalyst alone. Additionally, it ence to the following examples: is noted that water and sulfuric acid are effective cata EXAMPLE lyst moderators, particularly at concentrations of about 15 20 mole % (based on acid). Moreover, high isoparaffin isoparaffin-olefin alkylation reactions were per ?olefin volume ratios and low olefin space velocities, formed in a continuous manner. The apparatus en ployed for the purposes of these studies comprised the e.g. about 0.1, appear to favor high Cs alkylate selectiv following types: ity. 20 Additionally, results obtained from alkylations per A. Continuous Glass Reactors formed in capillary reactors, at short contact times and 1. A cylindrically-shaped glass reactor with a volume high olefin space velocities, were consistent with the of 300 cubic centimeters was used in the reactions continuous glass reactor data. wherein low hydrocarbon space velocities, i.e. 13 to 18 EXAMPLE 2 v/v/hr., on acid were employed. The reactor was 25 equipped with a flat-blade mechanical stirrer to pro Table III summarizes data obtained using vide thorough contacting of the reactants and catalyst, trifluoromethanesulfonic acid, i.e. CFSOH/modera a dry ice cooled condenser through which condensed tor catalyst systems. The mode of operation and reac hydrocarbon feed comprising isoparaffin diluted with tion conditions are similar to those used in Example 1. olefin was introduced, a sidearm leading to a cooled re 30 It is noted that the use of a catalyst moderator with ceiver wherein alkylate product was collected, and a CFSOH or FSOH/CFSOH leads to enhanced re nitrogen inlet tube through which nitrogen was intro search and and motor alkylate octane numbers. duced in order to prevent backmixing of the catalyst EXAMPLE 3 and incoming feed. 2. An elongated glass reactor with a volume of 35 Table IV summarizes alkylation experiments using cubic centimeters was used in the experiments wherein olefins other than butene-1, including refinery olefin high hydrocarbon space velocities, i.e. 91 V/v/hr., on streams, as the process feedstock. Reaction conditions acid were employed. This reactor was provided with were similar to those described above. The refinery C4 means for recycling catalyst carried cver with product. olefin stream composition is shown below: Otherwise, it was similar to the reactor described in 40 (1). Wit. 9% The above-described continuous glass reactors were - -o-o-c-e-r-r " Popane 0.96 immersed in a cooling medium, i.e. a dry ice-alcohol Propylene 0.14 mixture, in order to maintain the reactants and catalyst 45 Isobutane 35.13 in the liquid phase. The reactors were first charged with n-butane 2.89 Butene- 1.46 the catalyst and cooled to the desired temperature. The Isobutylene 7.55 catalyst was then diluted with isoparaffin. Olefin di Trans-butene-2 6.15 Cis-butene-2 11,67 luted with further amounts of isoparaffin was then Isopertaine 3.21 added to the reactor through the condenser. Alkylate 50 n-pentane 0.02 product was continually withdrawn and collected in a 3-methylbutene- 0.52 Butadiene 0.02 receiver and cooled with dry ice-alcohol mixture. The Pentene- 0.1 product was washed with 10% NaOH solution and then 2-methylbutene-1 0.16 analyzed. The strong acid component of the catalyst Total Olefin Content, Wt. 76 47.78 was routinely distilled prior to use. 55 B. Capillary Reactor The data confirm the broad applicability of the cata For very short contact time operation, a capillary re lyst systems to a range of olefins. Even ethylene, which actor was used. The hydrocarbon feed and catalyst cannot be alkylated efficiently with sulfuric acid, is eas were separately injected through capillary tubing under ily converted to high quality alkylate product with the a pressure of 150 to 250 psig into a 0.05 x 0.05 inch 60 catalysts of this invention. Furthermore, refinery mixed mixing chamber which was connected to a 8-10 foot olefin streams containing predominantly C4 olefins length of 18 gauge stainless steel hypodermic tubing. yield high quality alkylate. The feed lines, mixing chamber and reactor capillary Finally, it is noted that isobutylene (see Run 4) can were all immersed in a dry ice-alcohol cooling bath be converted to high octane alkylate using the catalyst held at the desired temperature. The mixture of cata 65 system of the invention. This is an important result lyst and hydrocarbons from the capillary reactor was since isobutylene is extremely difficult to alkylate with collected in a receiver and cooled with liquid nitrogen. conventional HF or HSO alkylation catalysts. 3,887,635 1. 12 EXAMPLE 4 acetic acid and chlorosulfuric acid are not selective in Several batch runs were conducted with the catalyst producing alkylate with high trimethylpentane content. system supported on a solid carrier. In the test runs, the However, difluorophosphoric acid, diethylether, etha catalyst and solid support were placed in a 3-neck, one nol and benzene-sulfonic acid appear to be quite effec liter flask fitted with a stirrer, dry-ice reflux condenser 5 tive in producing high quality alkylate. dditi protected by a calcium chloride-containing dryer and Table VII shows the effect of water addition to a gas inlet. Isobutane was fed to the flask for 7.5 min- fluorosulfuric acid on alkylate quality. Note the in utes at a rate of 5.5 liters (gas) per minute. After five creased amount of trimethylpentanes in the alkylate minutes, from the start of the isobutane flow, butene-l 1O product as the water E. ne tO was admitted at a flow rate of 0.055 liter per minute 20 mole % based on acid, followed by a rather rapid de (gas). The flow of butene-1 was continued for nine crease in these compounds for water concentrations intes. The reaction was allowed to continue under greater than about 20 mole %. The data is graphically reflux for six minutes after the flow of hydrocarbons represented in the figure.

TABLE I

Run No. l 2 3 4 5 Reaction Conditions' Olefin butene-l isoparaffin isobutane Isoparaffin?olefin (volume) ratio in feed to reactor) 111 111 11 176.911 176.9/1 Temperature, F. O () O O O Feed rate, vivifhr. on cata lyst (total hydrocarbon) 04 104 9 13.7 3. Olefin space velocity, vivihr. on catalyst 8.63 8.63 7.55 0.08 0.08 Catalyst - acid 100% FSOH FSOH FSOH 100% FSOH FSOH - moderator o 4 mole % 2O mole % 2O mole 9 HO HSO, HO Volume Catalyst, cc 5 5.7 15 100 00 Volume C alkylate yield? volume olefin' 1.77 1.73 1.76 74 1.72 Product Distribution, Wt.% C 5.08 1.98 4.18 1.37 0.16 C-C, 6.84 420 5.40 1.90 0.32 Total C 78.9 86.11 82.48 93.33 98.33 Trimethylpentanes 64.09 77.0 70.54 73.95 94.33 C * 9.89 7.65 1.94 3.40 1.9 C-C alkylate research clear octane number' 94.30 97.50 96.0 93.70 O0.50 C-C alkylate motor clear octane number 92.80 95.70 94.50 92.10 98.10 C* alkylate motor clear octane number 92.20 95.00 94.00 91.90 98.00 'Runs performed in continuous glass reactors. Determined by gas phase-liquid chromatography using a 300 foot capillary column with 0.01 inch i.d. and coated with DC-550 silicon oil, in conjunction with a hydrogen flame ionization detector. 8Calculated by computer from gas phase-liquid chromatography analysis. Based on fluorosulfuric acid.

had ceased. At the end of the reaction period, the reac TABLE II tion mixture was quickly cooled in a dry-ice-alcohol bath and a sample of the hydrocarbon layer was de Run No. 1 2 canted, washed with 10% NaOH solution and analyzed. 55 Reaction Conditions The experimental results are shown in Table V. Olefin Butene- Butene While the data are not as good as that obtained in the Isoparaffin Isobutane Isobutane continuous reactor studies, nevertheless they are in the Isoparaffin?olefin (volume ratio in feed to reactor) 88.4 88.4 desired direction and suggest the applicability of the Temperature, F. 40 40 catalyst systems impregnated on solid carriers in alkyla 60 Volume 26 acid in reactor 50.5 40.7 tion reactions. Olefin space velocity, viv?hr. on catalyst 34.81 53.3 EXAMPLE 5 Catalyst - acid 100% FSOH FSOH - moderator 20 mole A series of experiments were performed with various 9,4} HO catalyst moderators. The experimental conditions were 65 Volume Cs' alkylate yield/ volume olefin' 77 1.74 similar to those described in Examples 1-3. The experi Acid loading, volume olefin? mental results are set forth in Table VI. volume acid 0.01 0.016 The data indicate that moderators such as trifluoro Contact time, seconds 1.13 1.10 3,887,635 13 14 TABLE II-Continued TABLE II-Continued

Run No. 2 . Run No. 2 Product Distribution, Wt.%.' Cs' alkylate motor Cs 3.84 1.69 5 clear octane number' 92.70 96.60 Cs-C, 4,03 2.68 Total C 86.63 92.29 Trimethylpentanes 69.94 86.9 "Runs performed in capillary reactors. C 5.50 3.34. 'Determined by gas phase-liquid chromatography using a 300 foot capillary C-C alkylate research column with 0.01 inch i.d. and coated with DC-550 silicon oil, in conjunction with clear octane number' 94.20 99.40 a hydrogen flame ionization detector. C-C alkylate motor 10 ("calculated by computer from gas phase-liquid chromatography analysis. clear octane number' 93.00 96.90 Based on fluorosulfuric acid. TABLE III

Run No. 2 3 4 Reaction Conditions' Olefin butene-l Isoparaffin isobutane isoparaffin?olefin (volume ratio in feed to reactor) 88.4/1 176.9/1 176.911 176.9/1 Temperature, F. () O O O Feed rate, V/v/hr, on cata lyst (total hydrocarbon) 9 9 91 91 Olefin space velocity, v/v/hr. on catalyst 1.02 0.51 0.51 0.5 Catalyst - acid 100% CFSOH CFSOH FSOH/CFSOH FSOH/CFSOH - moderator - 20 mole % -- 20 mole % HO(3) HO(3) Volume catalyst, cc 5 15 15 15 Volume C alkylate yield/ volume ocfin 1.79 17 1.98 1.71 Product Distribution, Wt.% 4.33 0.42 17.46 0.07 C-C, 6.00 0.85 1.56 0.56 Total C 86.47 96.55 79.38 97.08 Trimethylpentanes 79.78 91.7 72.95 93.50 C." 3.20 2.18 1.60 2.29 C-C alkylate research clear octane number' 96.80 00.60 98.70 O.00 C-C alkylate motor clear octane number' 95.20 97.50 97.00 97.70 C." alkylate motor clear octane number 94.90 97.30 96.80 97.50 "Runs performed in continuous glass reactors. '; mole ratio. 'Based on total acid, 'Determined by gas phase-liquid chromatography using a 300 foot capillary column with 0.01 inch i.d. and coated with DC-550 silicon oil, in conjunction with a hydrogen flame ionization detector. 'Calculated by computer from gas phase-liquid chromatography analysis. TABLE IV

Run No. 2 3 4 Reaction Conditions' Olefin Propylene Propylene Ethylene Isobutyl ele Isoparaffin Isobutane Isobutane Isobutane Isobutane Isoparrafin?olefin (volume) ratio in feed to reactor) 1841 1841 1801 176.6/ Temperature, F. O O O O Feed rate, vlv/hr. on cata lyst (total hydrocarbon) 91.0 13. 13.7 18.0 Olefin space velocity v/v/hr. on catalyst 0.505 0.07(5) O.08(5) O. 105) Catalyst - acid FSOH FSOH FSOH FSOH - moderator 20 mole 20 mole 20 mole 20 mole % (4) 9. (4) c(4) %(4) HO HO HO HO Volume catalyst, cc 15 100 100 100 Volume C," alkylate yield/ volume olefin' 1.62 1.56 1.725) 73 Product Distribution, Wt.% Cs 2.13 0.42 0.00 1.33 C-7 34.97 1745 28.06 1.44 Total C 58.50 79.41 66.75 92.93 Trimethylpentanes 56.92 78.57 66.6 90.40 C 4.40 2.53 5.19 4.30 C-C alkylate research clear octane number' 96.00 98.70 01.00 100.00 C-C alkylate motor clear octane number' 94.20 97.10 97.20 98.50 Cs' alkylate motor clear octane number' 93.90 96.90 96.70 98.00 Run No. 5 6 7 8 3,887,635 1S 16 TABLE IV-Continued

Run No. l 2 3 4 Reaction Conditions' Olefin 2-methyl- Refinery Refinery Refinery butene-2 Colefin Colefin Colefin Isoparaffin Isobutane lsobutane isobutane Isobutane lsoparaffin?olefin (volume ratio in feed to reactor) 170/1 13.4/l 18.5/1 181.51 Temperature, F. () O O O Feed rate, v/v/hr. on cata lyst (total hydrocarbon) 9.0 6.3 90 3.1 Olefin space velocity, v/v/hr. on catalyst 0.50(5) 0.145) ().505) 0.07(5) Catalyst - acid FSOH 100% FSOH FSOH FSOH - moderator 20 mole - 20 mole 20 mole %(4) % (4) Çc4) HO HO HO Volume catalyst, cc 15 00 5 100 Volume Cs' alkylate yield/ volume olefin 2.505 84 1.85 1.83 Product Distribution, Wt, % Cs 34.37 S46 7.48 5.72 C-C, 1.69 3.9 2.02 l,04 Total C 61.22 86.13 86.59 91.56 Trimethylpentanes 59.8 66.53 - 8.60 88.23 C* 2.72 4.50 3.91 34 C-C alkylate research clear octane number' 99.70 92.20 99.80 100.20 C-C alkylate motor clear octane number' 98.40 90.70 97.40 98.20 Cs' alkylate motor clear octane number' 98.00 90.60 97.00 98.00 'Runs performed in continuous glass reactors. Determined by gas phase-liquid chromatography using a 300 foot capillary column with 0.01 inch i.d. and coated with DC55() silicon oii, in conjunction with a hydrogen flame ionization detector. Calculated by computer from gas phase-liquid chromatography analysis. 'Based on fluorosulfuric acid. 'Approximate value.

TABLE V

Run No. 1(1) 2(2) 3(1) Reaction Conditions Olefin Butene-1 Isoparaffin lsobutane Carrier Anhydrous AlFa Anhydrous AlF Calcined silica gel Weight of carrier in catalyst, grams' 20 20 25. Isoparaffin?olefin (volume ratio in feed to reactor) 1 10.6/ 0.671 ll. 111 Temperature, F. Olefin space velocity, vivihr. on catalyst --- 0.13 -- Reaction time, minutes 15 20 60 Catalyst - acid 100% FSOH FSOH 100% FSOH - moderator --- 20 mole % HO'6 - Volume C alkylate yield/ volume olefin m 1.78 - Product Distribution, Wt.%.' Cs 3.13 5.82 6.02 C-C, 4.99 5.80 4.51 Total C 85.73 79.38 84.60 Trimethylpentanes 71.40 70.68 73.52 C 6.15 9.00 4.87 C-C alkylate research clear octane number' 95.60 97.40 96.70 Cs' alkylate motor clear octane number 93.80 94.60 94.70 'Runs performed in batch-type glass reactors. 'Runs performed in continuous-type glass reactors. "Weight of FSOH on carrier - 15 grams. 'Determined by gas phase-liquid chromatography using a 300 foot capiliary column with 0.01 inch i.d. and coated with DC-550 silicon oil, in conjunction with a hydrogen flame ionization detector. "Calculated by computer from gas phase-liquid chromatography analysis. "Based on acid. 3,887,635 17 18 TABLE VI

Run No. 2 3 Reaction Conditions' Olefin Butene Isoparaffin Isobutane lsoparaffin?olefin (volume ratio in feed to reactor) 110.6/ Temperature, F. O Olefin space velocity, viv?hr. on catalyst 0.2 Catalyst - acid FSOH - moderator 20 mole 20 mole 20 mole %(5) %5) %5) CFCOOH HFPO, CSOH Volume Cs" alkylate yield/ volume olefin 1.73 1.74 .76 Product Distribution, Wt.% Cs 0.75 0.49 1.97 C-C, 0.84 0.53 2.52 Total C 95.55 98.26 94.13 Trimethylpentanes 84.64 94.14 72.00 C 2.86 72 1.38 C-C alkylate research clear octane number' 97.60 100.10 92.30 C-C alkylate motor clear octane number' 95.80 98.30 90.90 Cs' alkylate motor clear octane number 95.60 98.20 90.80 Run No. 4 5 6 Reaction Conditions' Olefin. Butene-1 isoparaffin Isobutane Isoparaffin?olefin (volume ratio in feed to reactor) 110.6/1 Temperature, F. () Olefin space velocity, viv?hr. on catalyst 0.12 0.2 0.13 Catalyst - acid FSOH -- moderator 10 mole 2 mole 20 mole %(4) %(5) % (5) Volume Cs alkylate yield/ CHSOH CHOCHs Ethanol volume olefin 1.73 1.72 173 Product Distribution, Wt.%2) C 0.1 0.00 0.43 C-C, 0.12 0.14 0.38 Total C 98.89 99.33 98.44 Trimethylpentanes 95.27 95.92 95.44 C." 0.88 0.53 0.75 C6-Ca alkylate research clear octane number 100.50 O0.70 100.80 Cs-Ca alkylate motor clear octane number: 98.50 98.40 98.40 Cs' alkylate motor clear octane number 98.40 98.30 98.30 "Runs performed in continuous glass reactors. "Determined by gas phase-liquid chromatography using a 300 foot capillary column with 0.01 inch i.d. and coated with DC550 silicon oil, in conjunction with a hydrogen flame ionization detector. "Calculated by computer from gas phase-liquid chromatography analysis. 'Used as the monohydrate - effective hydroxyl content is 20 mole % based on fluorosulfuric acid. "Based on fluorosulfuric acid.

TABLE VII T - - - - - Run No. 2 3 4 T-m------Reaction Conditions) Olefin isoparaffin Butene isoparaffin?olefin (volume isobutane ratio in feed to reactor) 176.9/1 1 10.6/1 10.6/t 176.9/1 Temperature, F. O O 0. O Feed rate, v/v/hr. on cata lyst (total hydrocarbon) 13.7 14.8 14.2 3.7 Olefin space velocity, Vlvihr, on catalyst 0.08 0.13 0.3 0.08 Catalyst - acid FSOH FSOH FSOH FSOH - moderator 5 mole 10 mole 20 mole %(4) %(4) 94) HO HO HO 3,887,635 19 20 TABLE VII - Continued

Run No. l 2 3 4. Volume catalyst, cc 100 96 100 00 Volume C alkylate yield/ volume olcfin' 1.74 1.74 173 72 Product Distribution, Wt.% Cs 1.37 .91 .40 ... 6 C-C, 1.90 1.63 73 .32 Total C 93.33 95.40 97.60 98.33 Trimethylpentanes 73.95 85.50 9.72 94.33 C 3.40 2.06 1.27 19 C-C alkylate research clear octane number' 93.70 97.80 99.50 100.50 C-C alkylate motor clear octane number' 92,10 96.00 97.60 98.0 C alkylate motor clear octane number' 9,90 95.80 97.50 98.00 Run No. 5 6 7 Reaction Conditions' Olefin Butene-1 Isoparaffin Isobutane isoparaffin?olefin (volume ratio in feed to reactor) 88.4/1 88.4/1 .111 Temperature, F. () O O Feed rate, vivifhr. on cata lyst (total hydrocarbon) 91.O 9.0 9.0 Olefin space velocity v/v/hr. on catalyst 1.02 1.02 7.55 Catalyst - acid FSOH FSOH FSOH - moderator 25 mole 30 mole 50 mole (7(4) % (4) % (4) HO HO HO Volume catalyst, cc 5 5 15 Volume Cs' alkylate yield, volume olefin' 1.72 1.67 50 Product Distribution, Wt.% Cs 49 00 1.98 C-C, .90 2.33 3.05 Total C 94.54 84.66 50.82 Trimethylpentanes 88.02 79.34 46.63 C* 3.07 12.03 43.85 C-C alkylate research clear octane number' 99.20 98.40 98.10 C-C alkylate motor clear octane number' 96.80 96.20 95.20 C. alkylate motor clear octane number' 96.50 95.0 9.60 'Runs performed in continuous glass reactors. 'Determined by gas phase-liquid chromatography using a 300 foot capillary column with 0.01 inch i.d. and coated with DC-550 silicon oil. in conjunction with a hydrogen flame ionization detector. *Calculated by computer from gas phase-liquid chromatography analysis. Based on tcid. What is claimed is: ing said olefin feed into said alkylation zone, so as to 1. An alkylation process comprising introducing a provide a saturated hydrocarbon?olefin volume ratio in paraffin feed and an olefin feed into an alkylation zone said olefin feed of between about 3:1 and 200:1. and contacting said feeds therein, at alkylation condi 7. The process of claim 1, wherein the catalyst is tions, with a catalyst formed from a strong acid selected formed within the alkylation zone. from the group consisting of halosulfuric acid, 8. The process of claim 1, wherein said catalyst is trihalomethanesulfonic acid and mixtures thereof, and supported on a solid carrier. the addition of about 5 to 100 mole %, based on acid, 50 . 9. The process of claim 1 wherein said contacting is of (1) water, (2) a C1-C saturated aliphatic monohy conducted substantially in the liquid phase. droxy alcohol or (3) a mixture of water and said alco 10. An alkylation process comprising contacting a hol. Saturated paraffin and an olefin, in an alkylation zone, 2. The process of claim 1, wherein said catalyst is at alkylation conditions, with a catalyst formed from a formed from said strong acid and about 5 to 45 mole 55 strong acid selected from the group consisting of halo % water, based on said strong acid. Sulfuric acid, trihalomethanesulfonic acid and mixtures 3. The process of claim 1, wherein said catalyst is thereof, and the addition of about 5 to 100 mole % wa formed from said strong acid and about 10 to 30 mole ter, based on acid, said contacting conducted substan % water based on acid. tially in the liquid phase. 4. The process of claim 1, wherein said catalyst is 60 11. The process of claim 10, wherein the catalyst is formed from said strong acid and ethanol. formed within the alkylation zone. 5. The process of claim 1, wherein said contacting is 12. The process of claim 10, wherein said catalyst is conducted at a temperature of about -80 to 100°F., at formed from fluorosulfuric acid and about 5 to 45 mole a pressure of about 1 to 20 atmospheres, and at an ole % water, based on acid. fin space velocity of about 0.05 to 1000 volumes of ole 65 13. The process of claim 12, wherein said catalyst is fin per hour per volume of catalyst. formed from fluorosulfuric acid and about 10 to 30 6. The process of claim 1, wherein said olefin feed is mole % water, based on acid. diluted with saturated hydrocarbon prior to introduc 14. An alkylation process comprising contacting a 3,887,635 21 22 saturated paraffin and an olefin, in an alkylation zone, therein, with a catalyst formed from fluorosulfuric acid, at alkylation conditions, with a catalyst formed from a and the addition of from 5 to 45 mole %, based on acid, strong acid selected from the group consisting of halo of ethanol, said contacting conducted at a temperature sulfuric acid, trihalomethanesulfonic acid and mixtures ranging from -80' to +100°F., and at an olefin space thereof, and the addition of about 5 to 100 mole % wa velocity ranging from about 0.05 to 1000 volumes of ter, based on acid, said catalyst supported on a solid olefin per hour per volume of catalyst and wherein said carrier. monoolefin feed is diluted with isoparaffin prior to in 15. An alkylation process comprising contacting a troducing said monoolefin feed into said zone, so as to saturated hydrocarbon and an olefin at alkylation con provide an isoparaffin?olefin volume ratio in said ditions with a catalyst formed from a strong acid se 10 monoolefin feed of about 3:1 to 200:1, thereby forming lected from the group consisting of halosulfuric acid, a reaction mixture comprising a hydrocarbon phase trihalomethanesulfonic acid and mixtures thereof, and and a catalyst phase and recovering alkylate product of the addition of about 5 to 100 mole %, based on said high octane number from said reaction mixture. strong acid, of difluorophosphoric acid. 25. The process of claim 24, wherein the isoparaffin 16. The process of claim 15, wherein the catalyst is 15 concentration in the hydrocarbon phase of said reac supported on a solid carrier. tion mixture ranges from about 50 to 90 volume % 17. An alkylation process comprising contacting a based on total hydrocarbon. C-C12 olefin and a C-Cio paraffin at alkylation con 26. The process of claim 24, wherein the olefin con ditions with a catalyst formed from a strong acid se centration in said monoolefin feed diluted with isopar lected from the group consisting of halosulfuric acid, 20 affin is about 0.5 to 25 volume % based on total hydro trihalomethanesulfonic acid and mixtures thereof, and carbon feed to the reactor. the addition of about 5 to 100 mole %, based on acid, 27. The process of claim 24, wherein the olefin con of a C-C5 saturated aliphatic monoether. centration in said monoolefin feed diluted with isopar 18. The process of claim 17, wherein said catalyst is affin is below about 10 volume % based on total hydro formed from said strong acid and about 5 to 45 mole 25 carbon feed to the reactor. %, based on acid, of said ether. 28. The process of claim 24, wherein the isoparaffin 19. The process of claim 17, wherein said catalyst is ?olefin volume ratio within the reactor ranges from formed from said strong acid and diethyl ether. about 20:1 to 2000:1. 20. The process of claim 17 wherein said catalyst is 29. The process of claim 24, wherein the volume per supported on a solid carrier. 30 cent of catalyst in the reaction mixture ranges between 21. An alkylation process comprising contacting a about 30 and 80 volume % based on total mixture. C-C monoolefin and a C-C isoparaffin with a cat 30. The process of claim 24, wherein said catalyst is alyst formed from a strong acid selected from the group supported on a solid carrier. consisting of halosulfuric acid, trihalomethanesulfonic 31. An alkylation process comprising contacting a acid and mixtures thereof, and the addition of about 5 35 C-C6 monoolefin and a C-Cs isoparaffin with a cat to 100 mole %, based on said strong acid, of an aro alyst formed by mixing a major amount of fluorosulfu matic sulfonic acid. ric acid with a minor amount of sulfuric acid, where 22. The process of claim 21, wherein said catalyst is said contacting is conducted at a temperature ranging formed from said strong acid and about 5 to 45 mole from about -20 to 30F. %, based on said strong acid, of said aromatic sulfonic 40 32. The process of claim 1, wherein the temperature acid. at which the process is conducted ranges between 23. The process of claim 21, wherein said catalyst is about 40 and 100°F. supported on a solid carrier. 33. The process of claim 2, wherein the temperature 24. An alkylation process comprising introducing a 45 at which the process is conducted ranges between CA-C6 isoparaffin feed and a C-C6 monoolefin feed about -20 and -40°F. into an alkylation zone and contacting said feeds, ck sk k :k :