Selective hydrogenation of methyl oleate into unsaturated alcohols Relationships between catalytic properties and composition of cobalt-tin catalysts

The selective hydrogenation of methyl oleate into oleyl alcohol, intermedia te in the formulation of surfactant agents, is carried out over bimetallic catalysts containing, cobalt and tin. However the tin content modifies the rates of the hydrogenation of the esters (methyl oleate and oleyl oleate) a nd of the side reaction of the transesterification between the methyl oleat e and the alcohol formed. Indeed, the maximum of the unsaturated alcohol yi eld depends on the Sn/metal ratio. The analyses of the catalyst surface by XPS have shown that there are coexi stence of metallic particles (Co-0) and/or oxides (CoO) with two different tin oxides (SnOx, SnOy), the SnOx species being close to zerovalent metalli c particles. It is suggested that (I) [Co-0. . . (SnOx)(2)] should be the a ctive sites for the selective hydrogenation of ester, (2) the SnOy species favor the reaction of transesterification and (3) the free metallic particl es favor the hydrogenation of ethylenic bonds. On the other hand, the prepa ration method of the catalyst and the nature of the support modify the surf ace composition of the solid. The use of alumina or zinc oxide lead to the same yield of unsaturated alcohol whereas silica which has much more metall ic Co-0 species gives a low activity due to a large tin enrichment. Over Co Sn catalysts reduced with NaBH4 owing to the formation of cobalt aluminate, a small content of metallic cobalt is observed. The preparation of CoSn ca talyst via a sol-gel method improves the homogeneity and the dispersion of the active sites. But the strong interactions between cobalt and the suppor t do not allow the formation of both metallic cobalt and mixed active cente rs (Co-0 SnOx). Furthermore, some kinetic studies obtained with cobalt cata lysts show that (1) the transesterification reaction is faster than the hyd rogenation of esters, (2) the presence of methanol issued from the hydrogen ation and from the transesterification strongly modifies the oleyl oleate h ydrogenation. (C) 2000 Elsevier Science B.V. All rights reserved.