l|ll|lllllllllllllllllIlllll||||lllllllllllllllllllllllllllllllllllllllllll US005493067A ‘ Unlted States Patent [19] [11] Patent Number: 5,493,067 Angstadt et al. [45] Date of Patent: * Feb. 20, 1996 [54] SOLID SUPERACID ALKYLATION 5,321,197 6/1994 Angstadtetal. ..................... .. 585/721 ALKYLATIONCATALYST COMPOSITIONS METHOD USING AND THE SAME 5,324,8815,391,532 2/19956/1994 KresgeS0191 9‘ et a1- a1. - .. Inventors: HowardElmer J. PIHollstein, Angsmdt’ Wilmington, Media’ Del.; 5,420,092FOREIGN 5/1995 PATENTSoled et al.DOCUMENTS ........................... .. Chao-Yang Hsu, Media, Pa. 61-183230 8/1986 Japan . [73] Asslgnee'- . aggmhggngglnc' (R&M)’ 61-2426411-245853 10/198910/1986 iJapan.Japan. p ’ ' 1‘245854 10/1989 Japan. [*1 Notice: The portion of the term of this patent OTHER PUBLICATIONS (8121;352:132? to Feb' 13’ 2013’ has been Ito et al., “Solid acid catalysts for isobutane alkylation” CA Selects Abstract No. 106: 216817b, Issue 13, 20, (1987). “Superacids Catalyze Alkylation of Xylene”, Chemical [21] Appl. No.: 151,446 Week, Nov. 25, 1987, p. 28. [22] Filed: Nov- 12! 1993 Primary Examiner—As0k Pal [51] Int. C16 ..................................................... .. c070 2162 Mame)” Agent’ 0’ Fi""—Q- T°dd Dickinsm; Stephen T [52] U.S. c1. .......... .. 585/731; 585/730 Fan‘ [58] Field of Search .................................... .. 585/731, 730 [57] ABSTRACT [56] References Cited Isoparaf?ns and ole?ns are alkylated by contact with a solid superacid such as sulfated zirconia optionally containing U.S. PATENT DOCUMENTS added metals, and containing added heteropolyacids . (HPA’s) or polyoxoanions (POA’s). The presence of I-IPA’s 3:322:31‘eftalal' ' or POA’s in the solid superacid catalyst results in higher 5:036:035 7/1991 Baba et 3L . " yields of desired high-octane components in the product 5,212,136 5/1993 Angstadt et a1_ . mixture than are obtained in the absence of HPA’s or POA’s. 5,214,017 5/1993 Angstadt et al. 5,321,196 6/1994 Ohgoshi et a1. ...................... .. 585/709 24 Claims, N0 Drawings 5,493,067 1 2 SOLID SUPERACID ALKYLATION of Group IV-A or IV-B metal hydroxides or oxides, followed CATALYST COMPOSITIONS AND by calcination and stabilization, and the use of such catalysts ALKYLATION METHOD USING THE SAME in alkylation of isobutane with isobutene at 60° C. (3) In the Ito et al Japanese Kokai Patent, SHO BACKGROUND OF THE INVENTION 61-242641, Oct. 28, 1986, application SHO 60-84515 ?led Apr. 22, 1985, which corresponds to (2) above, a solid acidic The reaction of isobutane with low (C2-C5) molecular catalyst for alkylation of isoparaf?n with ole?n is disclosed. weight ole?ns to produce C6—C9 paraf?ns is commonly The catalyst is obtained by adding a rare earth element or its referred to as alkylation. In commercial practice this reaction compounds, and a sulfate radical or its precursor to a is carried out in the presence of acid type catalysts such as 10 supporting member made of hydroxide or oxide of Group IV concentrated sulfuric acid or HF. The reaction is an impor metals, followed by sintering at 400°~800° C., for stabili tant process to the petroleum industry as it upgrades chemi zation. Hydroxide or oxide, of at least one type of metal cal compounds in crude oil for which there may be little chosen from titanium, zirconium, hafnium, silicon, germa value to high octane fuel components. The two acids men‘ nium and tin is used; particularly hydroxide or oxide of tioned above are the catalysts of choice as the process is now zirconium or titanium is preferred. Tantalum and cerium or practiced commercially, but each of them while producing a their compounds are disclosed as the most desirable rare satisfactory alkylate for fuel blending has serious draw earths; praseodymium, neodymium, sarnarium and gado backs. The use of HF presents a signi?cant ecological hazard linium are also disclosed. The alkylation reaction is prefer should it escape into the atmosphere, and the sulfuric acid ably run in liquid phase. process is very corrosive and energy consuming as it needs (4) In Hosoi et al Japanese Kokai Patent HEI 1-245853 to be operated at below ambient temperatures in order to 20 disclosure date Oct. 2, 1989, Application No. SHO provide a satisfactory alkylate. Certain solid compositions 63-73409, Mar. 29, 1988, solid acid catalyst for alkylation is with acidic properties have been found to catalyze this disclosed, containing a Group 11b, Group Va, Group Va or reaction as subsequently disclosed. Group VIIa metal or compound thereof, and sulfate or precursor of sulfate, on a carrier made from hydroxide or THE PRIOR ART 25 oxide of Group III and/or Group IV metals, followed by baking and stabilizing. Sulfated zinc/zirconium hydroxides, Solid superacid catalysts have been proposed for use as chromium/zirconium hydroxides, vanadium/zirconium alkylation catalysts. See for example Hollstein et al US. Pat. hydroxides, manganese/zirconium hydroxides, zinc/tita Nos. 4,918,041 and 4,956,519 issued Apr. 17, 1990 and Sep. nium hydroxides, zirconium/titanium hydroxides, zirco 11, 1990 respectively, disclosing solid superacid catalysts 30 nium/aluminum hydroxides are disclosed. It is desirable to useful in alkylation and other reactions comprising a sul run the reaction in liquid phase. fated calcined metal oxide or hydroxide of Group 111 or Group IV, e. g. zirconium; metal oxide or hydroxide of (5) In Shimizu et a1 Japanese Kokai Patent HEI l-245854, Group V, Group VI or Group V11, e.g. manganese; 3 O and disclosure date Oct. 2, 1989, Application No. SHO a metal oxide or hydroxide of Group VH1, e.g. iron. See also 63-73410, Mar. 29, 1988, a solid acid catalyst for alkylation Angstadt et al US. Pat. No. 5,212,136 issued May 18, 1993, 35 of isobutane by ole?ns is obtained by adding a sulfate or disclosing solid superacid catalysts useful as alkylation precursor thereof to a carrier comprising compound metal catalysts comprising sulfated and calcined mixtures of a hydroxides or compound metal oxides of two or more kinds support comprising an oxide or hydroxide of a Group IV-A of metals selected from titanium, zirconium, silicon and tin. element, an oxide or hydroxide of molybdenum and an oxide Sulfated zirconia/titania, zirconia/tin oxide, zirconium/sili con catalysts are disclosed. Running the reaction in liquid or hydroxide of a Group I-B, lI-B, IlI-A, III-D, IV-B, V-A or 40 VI-A metal other than molybdenum, or a metal of the phase is disclosed as desirable. Lanthanide Series of the Periodic Table. See also Angstadt (6) Chemical Week, Nov. 25, 1987, on page 28, discloses et al US. Pat. No. 5,214,017 issued May 25, 1993, disclos superacids obtained by sulfating zirconium, titanium and ing solid superacid catalysts useful as alkylation catalysts, iron oxides, as catalysts for alkylation of orthoxylene by comprising sulfated and calcined mixtures of a support 45 styrene. comprising an oxide or hydroxide of a Group IV-A element, DESCRIPTION OF THE INVENTION an oxide or hydroxide of a Group VI, VII or V111 metal, an oxide or hydroxide of a Group I-B, II-B, III-A, Ill-B, IV-B, The present invention provides an alkylation process V-A or VI-A metal and an oxide or hydroxide of a metal of which minimizes the processing problems of the existing the Lanthanide Series of the Periodic Table. other disclo 50 processes using sulfuric acid or HP, and obtains bene?ts sures of solid superacids useful in alkylation processes are from the use of heteropolyacids (HPA’s) or polyoxoanions contained in: (POA’ s) in combination with solid superacids. (l) Hatakeyarna et al Japanese Kokai Patent, SHO The HPA’s or POA’S, when incorporated with the 61-183230, Aug. 15, 1986, disclosing sulfated zirconia strongly acidic solid acids, which are generated for example alkylation catalysts and their use in alkylation of butenes and by treating zirconia with ammonium sulfate and then cal isobutane at a temperature in the range from —20° C. to +10° 55 cining at high temperatures, produce superior alkylation C. under pressure of from 0 to 50 kglcmz, the alkylation catalysts. That is, the alkylate produced by the HPA modi?ed being carried out in either gaseous phase or liquid phase, the sulfated zirconia has a higher proportion of 8-carbon com latter preventing inactivation that is caused by deposition of pounds than that obtained when using only the sulfated coke on the catalyst and extending the life of the catalyst, zirconia, and the proportion of the 8-carbon fraction con and the reaction being carried out either by a suspension or 60 taining the high octane trimethylpentanes is also greater than ?xed bed process. that obtained either with the more traditional acids or the (2) Abstract No. 106:2168l7b, CA Selects: Catalysis unmodi?ed solid superacids. Additionally the amount of (Applied & Physical Aspects), Issue 13, Jun. 29, 1987, Ito et heavier ends, C9-C1” produced during the alkylation is a1, Jpn. Kokai Tokyo Koho JP 61,242,641 (86,242,641), Oct. greatly reduced. Additionally the alkylation reaction can be 28, 1986, disclosing alkylation catalysts prepared from 65 carried out at room temperature to provide good yields of sulfate ion or its precursors and rare earth metals or their alkylate product, thus eliminating the need for sub-ambient compounds, e.g. lanthanum nitrate, on supports consisting cooling and resulting in a more energy efficient operation. 5,493,067 3 4 PREPARATION OF SUPERACID HPA OR POA Feb. 7, 19892 the formula of which is disclosed as CATALYST K6PW11VO40N3, (2) a site-speci?c framework-substituted The solid superaeid catalyst according to the invention is HPA or POA as disclosed in Ellis et al U.S.