Synthesis of 3-buten-1-ol from 1,4-butanediol over ZrO 2 catalyst

Abstract

Dehydration of 1,4-butanediol was investigated over ZrO 2 at temperatures of 325–375 °C. Modification of ZrO 2 with a small amount of sodium hydroxide greatly enhanced the selectivity to 3-buten-1-ol. Temperature-programmed desorption of adsorbed NH 3 and CO 2 elucidated acidity and basicity of the catalysts, respectively. The number of acidic sites on the ZrO 2 decreased with increasing Na content, and disappeared at Na content of 1.0 mol%, whereas the number of basic sites increased with increasing Na content. In the relationship between Na content and the selectivity to products, selectivities to tetrahydrofuran and γ-butyrolactone simply increased with the number of acidic and basic sites, respectively. However, the selectivity to 3-buten-1-ol was maximized at an appropriate Na content. 3-Butan-1-ol is possibly formed by acid–base-concerted catalysis of monoclinic ZrO 2 in the dehydration of 1,4-butanediol.