2166 Preparation of Hybrid Organo-Inorganic Catalysts Based on MSM-41 Mesoporous Molecular Sieves and Their Properties in Synthesis of Ethyl tert-Butyl Ether N. V. Vlasenko, Yu. N. Kochkin, and A. S. Kovalenko Pisarzhevskii Institute of Physical Chemistry, National Academy of Sciences of Ukraine, Kiev, Ukraine Received January 14, 2009 Abstract—A series of sulfoorganosilica (vinyl-containing) catalysts based on MSM-41 mesoporous molecular sieves were prepared by template synthesis. The structure and properties of these catalysts and their catalytic characteristics in synthesis of ethyl tert-butyl ether were examined. ORGANIC SYNTHESIS AND INDUSTRIAL ORGANIC CHEMISTRY ISSN 1070-4272, Russian Journal of Applied Chemistry, 2009, Vol. 82, No. 12, pp. 2166–2173. © Pleiades Publishing, Ltd., 2009. Original Russian Text © N.V. Vlasenko, Yu.N. Kochkin, A.S. Kovalenko, 2009, published in Zhurnal Prikladnoi Khimii, 2009, Vol. 82, No. 12, pp. 2023– 2030. Methyl tert-butyl ether (MTBE) is widely used today in production of reformulated gasolines. The world output of MTBE in 2002 was 22 million tons. However, because of solubility in water and poor biodegradability, the use of MTBE is planned to be restricted in the coming years [1–3]. Its candidate substitute is ethyl tert-butyl ether (ETBE) whose production in Europe increased from 2 in 2005 to 4 million tons in 2007. An attractive feature of ETBE is the possibility of using it in production of bioethanol and of gasolines with decreased volatility. In industry, alkyl tert-butyl ethers are produced using various sulfonic cation-exchange resins as catalysts [4, 5]. They are characterized by high activity and selectivity but have certain drawbacks: low mass- exchange characteristics, poor heat resistance, and tendency to swell under the action of polar reagents, which gives rise to technological problems in practical use. Mineral acid catalysts, in particular, zeolites, are free of these drawbacks. However, they are signi- ficantly inferior to sulfonic cation-exchange resins in activity and performance, and synthesis of ETBE in their presence occurs at a higher temperature than in the presence of sulfonic cation-exchange resins [6–10]. It appeared possible to decrease the optimal temperature of ETBE synthesis with simultaneous increase in the performance by making acid centers of zeolite catalysts accessible to reactant molecules [11– 14]. This was proved in studies of ETBE synthesis from ethanol and isobutylene in the presence of hydrogen forms of zeolites: mordenite–clinoptilolite rock, ZSM-5, and BEA, in which the sizes of the entrance windows are different: 0.4, 0.6, and 0.7 nm, respectively [15–17]. For example, at 80°ɋ and 1 MPa, the performance of H-BEA wide-pore zeolite with respect to the target product is comparable with that of Amberlyst 15 commercial sulfonic cation-exchange resin [16]. Studies of zeolite catalysts whose acidity spectrum includes centers of different nature and strength also showed that specifically weak acid centers [Q(NH 3 ) ≤ 100 kJ mol –1 ] are active in ETBE synthesis. Strong acid centers are responsible for side reactions of diethyl ether formation and isobutylene dimerization [10]. The development of mineral–organic acid catalysts in which acidic sulfo groups grafted to the surface of a wide-pore inorganic support are distributed in the porous structure makes it possible to combine the advantages of sulfonic cation-exchange resins and zeolites as catalysts and to avoid their inherent drawbacks. Such mineral–organic catalysts, in contrast to ion-exchange resins, do not swell in the reaction medium and are characterized by high rate of attainment of the adsorption equilibrium, because it is not limited by internal diffusion. DOI: 10.1134/S1070427209120155