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particularly important issue in the fine chemical and pharmaceutical industry where the E factor-the amount of waste generated per kilogram of product-is particularly high. Stoichiometric reductions, oxidations, heterosubstitution reactions, and other reactions produce high amounts of inorganic salts. Catalytic methods are environmentally attractive by reducing waste and energy consumption, and offering simpler technologies. Although about 90% of the chemical processes applied in industry are catalytic transformations, there is an ever-increasing demand to develop more active and more selective catalysts. Environmental catalysis was the topic of a special symposium; 152 a journal is devoted to the subject,153 and reviews are also available.154-159 Examples of catalytic reactions and processes relevant to hydrocarbon chemistry are numerous. The technologies of the oil refinery with extremely low 0.1) E factors are excellent examples demonstrating the possibilities that can be achieved by the development of selective catalytic methods, particularly by the use of various solid acids (see detailed discussions in 2). Further examples of commercially highly successful processes are the oxidation catalyst TS-1 developed by Enichem researchers l60 ,161 (see Sections 9.1.1, 9.2.1, and 9.4.1), the homogeneous aqueous-phase Rh-catalyzed hydroformylation (see Sections 7.1.3 and 7.4.1), and single-site metallocene polymerization catalysts, which allow the preparation of tailored polymers with new properties (see Sections 13.3.2).162-164 In addition to large-scale industrial applications, solid acids, such as amorphous silica-alumina, zeolites, heteropoly acids, and sulfated zirconia, are also versatile catalysts in various hydrocarbon transformations. Zeolites are useful catalysts in fine-chemical production (Friedel-Crafts reactions, heterosubstitution).165-168 Heteropoly compounds have already found industrial application in Japan, for example, in the manufacture of butanols through the hydration of butenes. 169 These are water tolerant, versatile solid-phase catalysts and may be used in both acidic and oxidation processes, and operate as bifunctional catalysts in combination with noble metals. 158 ,170-174 Sulfated zirconia and its modified versions are promising candidates for industrial processes if the problem of deactivation/reactivation is solved. 175-178 A monograph by Sheldon and van Bekkum gives a detailed treatment of heterogeneous catalytic processes applied in the fine-chemical industry. 179 Clay materials proved to be extremely useful catalysts in organic chemistry.180,181 A particular example is clayzic,161,182 a highly active catalyst in various Friedel-Crafts reactions. It is appropriate and very instructive to briefly discuss a relatively new and very successful approach, namely, the development of catalysts with designed and atomically engineered active centers. Thomas and coworkers used micro- and mesoporous solids and carried out delicate structural and compositional variations to prepare specific catalysts capable of promoting regioselective, shape-selective, and enantioselective conversions.183-185 This strategy resulted in the development of framework-substituted CoALPO-18 and MnALPO-18 molecular sieves for the selective aerobic oxidation of linear alkanes to the corresponding monocarboxylic acids,186 and that of hexane to adipic acid. 187 Framework-substituted MALPO-36
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