Vapor-Phase Dehydration of 1,3-butanediol over CeO2–ZrO2 Catalysts

The dehydration of 1,3-butanediol was investigated over CeO2–ZrO2 catalysts prepared by impregnation at temperatures of 325–375 °C. Pure CeO2 selectively catalyzed the dehydration of 1,3-butanediol to form 3-buten-2-ol and 2-buten-1-ol, while pure ZrO2, which was less active than pure CeO2, catalyzed the dehydration to 3-buten-1-ol. In the CeO2/ZrO2 catalyst in which CeO2 was supported on zirconia, the presence of a small amount of CeO2 suppressed the formation of 3-buten-1-ol and induced the dehydration of 1,3-butanediol to form 3-buten-2-ol and 2-buten-1-ol and the subsequent dehydrogenation of 3-buten-2-ol to form 3-buten-2-one and butanone. The activity would be related to the redox features of CeO2. The monoclinic phase of zirconia support decreased while the cubic CeO2 phase increased as CeO2 content was increased. In contrast, in the ZrO2/CeO2 catalyst in which ZrO2 was supported on cubic CeO2, only the cubic CeO2 phase was observed and ZrO2 species appeared in the form of a solid solution of CeO2–ZrO2 with fluorite structure. Regardless of zirconia loading, ZrO2 species did not affect the catalytic activity of ZrO2/CeO2, which was controlled by CeO2 species.