EP 0 012 504 BI Europiisches Patentamt @ _)) exropoan Patent office @ Pubication number: © O12 504 Office européen des brevets Bl ®@ EUROPEAN PATENT SPECIFICATION @ Date of publication of patent specification: 06.01.82 @ int.ci2: CO7C 15/085, CO7C 2/66 79302362.3 ® Application numb @ Date of fling: 29.10.79 @ Production of isopropyibenzene. @ Priority: 14.12.78 US 969626 @ Proprietor: MOBIL OIL CORPORATION 150 East 42nd Stroet New York New York 10017 (US) @ Date of publication of application: 25.06.80 Bulletin 80/13 @® laventor: Kaeding, Warren William 700 Mountain Avenue @© Publication ofthe grant ofthe European patent: ‘Westfield, New Jersey 07090 Union County (US) (06.01.82 Bulletin 82/1 @ Representative: Cooper, John Anthony Designated Contracting States: ‘Mobil Court 3 Clements inn BE DEFR GB ITNL London WC2A 2€8 (GB) @ Retorances cos: US-A=3 758 483 Us-A-4016218 ‘Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shell be filed in a written reasoned statement. It shall not be deemed to have been fled until the opposition fee has been paid. (Art 99(1) European patent convention). Courier Press, Leamington Spa, England.6 6 35 55 0012504 Production of isopropylbenzene This invention relates to a process for the selective production of isopropylbenzene by catalytic propylation of benzene. ‘Alkylation of aromatic hydrocarbons using crystalline zeolite catalysts is well known. U.S. Patent 2,904,607 refers to alkylation of aromatic hydrocarbons with an olefin in the presence of a crystaline metalic aluminosilicate having uniform pore openings of about 6 to 15 Angstrom units, US. Patent 3,251,897 describes alkylation of aromatic hydrocarbons in the presence of X- or Y-type crystalline Zeolites, specifically their rare earth and/or hydrogen forms. US. Patents 3,751,504 and 3,751,508 described vapour phase alkylation of aromatic hydrocarbons with olefins inthe presence of @ specified type of zeolite catalyst. US. Patent 3,755,483 discloses vapour phase alkylation of aromatic hydrocarbons in the presence of a catalyst comprising zeolite ZSM-12. The reaction is carried out at temperatures between the critical temperature of the aromatic compound and 482°C (90°F). The critical temperature and pressure of benzene are 288.9°C (552°F) and 48.6 atm. (4.9 x 10? kPa) Harper at al have described the catalytic alkylation of benzene with propylene over a crystalline zeolite Petrochemical Preprints, American Chemical Society, Vol. 22, No 3, p. 1084, 1977). Extensive kinetic and catalyst aging studies were conducted with a rare earth-exchanged Y-type zeolite (REV) catalyst. ‘According to the invention @ process for the propylation of benzene with selective production of ‘sopropylbenzene comprises contacting a mixture of benzene and propylene at a temperature between 100°C and the critical temperature of benzene and a pressure between 10? kPa and 6 x 10° kPa witha catalyst comprising zeolite ZSM-12. The process is advantageously operated with the molar ratio of benzene to propylene within the range of 12:1 to 1:1, at a temperature between 180°C and 250°C: with the mixture contacting the catalyst as @ continuous stream st a weight hourly space velocity of 0.6 to 100, preferably between 5 and 40, The benzene/propylene mixture may be in the vapour or quid phase. Its unnecessary for practise of the invention to separate the propylene from the propane with which it is frequently industrially available in admixture. Furthermore, polyisopropyibenzene by- oducts, optionally together with n-propylbenzene and/or benzene, may be recycled and converted to isopropyibenzene. The zeolite Is usually employed in the form of a composite with a binder. Zeolite ZSM-12 is defined by the x-ray diffraction date furnished in U.S. Specification 3,832,449, namely: interplanar Spacing D (A) Relative Intensity 11.9402 M 10.102 M 4.76 £01 w 4.28 + 0.08 vs 3.98 + 0.08 M 3.87 £0.07 vs 3.49 +0.07 w 3.38 + 0.07 M 3.20 + 0.06 w 3.05 + 0.08 w 2.54 +£0.03 ‘The zeolite, when prepared in the presence of organic cations, is substantially catalytically inactive, possibly because the intracrystalline free space is occupied by organic cations from the forming solution. It may be activated by heating in an inert atmosphere at 540°C for one hour, for ‘example, followed by base exchange with ammonium salts followed by calcination at 640°C in air. The presence of organic cations in the forming solution may not be absolutely essential to its formation but does appear to favour it. ‘Natural zeolites may sometimes be converted to this zeolite by various activation procedures and. other treatments such as base exchange, steaming, alumina extraction and calcination, in10 15 2 20 a 65 0012 504 combinations. Natural minerals which may be so treated include ferieite, brewsterite, stibite, dachiarcite, epistlbite, heulandite, and clinoptilolite. When synthesized in the alkali metal form, the zeolite is conveniently converted to the hydrogen form, generally by intermediate formation of the ammonium form as a result of ammonium ion exchange and calcination of the ammonium form to yield the hydrogen form. in addition to the hydrogen form, other forms of the zeolite wherein the original alkali metal has been reduced to less than about 1.5 percent by weight may be used. Thus, the original alkali metal of the zeolite may be replaced by ion exchange with other suitable ions of Groups IB to Vl ofthe Periodic Table, including, by way of example, nickel, copper, zinc, palladium, calcium or rare earth metals. In practising the invention, it may be desirable to incorporate the zeolite in another material resistant to the temperature and other conditions employed in the process. Such matrix materials include synthetic or naturally occurring substances as well as inorganic materials such as clay, silica and/or metal oxides. The latter may be either naturally occurring or in the form of gelatinous precipitates or gels including mixtures of silica and metal oxides. Naturally occurring clays which can be Composited with the zeolite include those of the montmorillonite and Kaolin families, which families include the sub-bentonites and the kaolins commonly known as Dixie, McNamee-Georgia and Florida clays or others in which the main mineral constituent is halloysite, Kaolinite, dickite, nacrite or anauxit Such clays con be used in the raw state as originally mined or initially subjected to calcination, acid treatment or chemical modification. in addition to the foregoing materials, the zoolites employed herein may be composited with 2 porous matrix material, such as alumina, silica-alumina, silica-magnesi, siica-zirconla, silica-thoria, silica-berylia, silica-titanla as well as temary compositions, such as silica-alumina-thori, silica alumina-tirconia, sica-alumina-magnesia and silica-magnesia-zirconia. The matrix may be in the form Of a cogel. The relative proportions of zeolite component and inorganic oxide gel matrix on an anhydrous base may vary widely with the zeolite content ranging from between about 1 to about 99 percent by weight and more usually in the range of about 5 to about 80 percent by weight of the dry composite. “The process ofthis invention may be conducted with the organic reactants in either the gaseous cr the liquid phase or both. it may be carried out as a betch-type, semi-continuous or continuous ‘operation utilizing a fixed, fuidized or moving bed catalyst syster The following examples wil serve to illustrate the process ofthis invention without being limiting thereon: Example 1 65 parts by weight of ZSM-12 in the hydrogen form (designated HZSM12) were intimately mixed ‘with 35 parts of alumina binder, pressed into wafers, crushed and screened to a uniform particle size of 14—20 mesh. Benzene and propylene, in a mole ratio of 9.5/1, were passed over the catalyst at 200°C ‘and WHSV of 31.0 (benzene) and 1.8 (propylene). Holding the temperature and feed rate constant, the pressure was varied from 0 to 125 psig. (101.33 to 963.17 kPa). The products of the reaction were Collected, weighed and analyzed using standard laboratory techniques. The results are summarized in TABLE |.