Catalytic Hydrogenation of γ-Butyrolactone to Butanediol over a High-Performance Cu-SiO2 Catalyst

Abstract

High-performance Cu catalysts were developed for the selective hydrogenation of γ-butyrolactone (GBL) to 1,4-butanediol (BDO). Among the various catalysts prepared by ammonia evaporation (AE) and impregnation (IM) methods with silica or MFI zeolite supports, the 5% Cu-SiO2-AE catalyst was the best one. It exhibited 95% selectivity for BDO and 71% conversion of GBL after 2–8 h reaction at 200 °C and 4 MPa H2, with high stability in five-cycle runs. Comprehensive characterizations showed that the AE method favored generating nano Cu particles with an average size of 2.9 nm on the 5% Cu-SiO2-AE catalyst. The silica support derived from a sol demonstrated an advantage over the MFI zeolite in the preparation of a highly dispersed and stable Cu catalyst, in view of its anti-sintering and robust composition of Cu0, Cu+, and Cu2+ in the cycling operation. The reaction pathways for GBL to BDO over the Cu catalysts were found to commonly involve reversible reactions of hydrogenation and dehydrogenation, along with subsequent dehydration to form THF. The high performance of the Cu catalysts in the conversion of GBL to BDO was attributed to the high dispersion of Cu, the presence of stable active sites, and fewer strong acid sites in the catalyst.