Cu对Ni-Cu/SiO_2催化1,4-丁炔二醇加氢性能的影响

Effect of Cu Additive on the Hydrogenation of 1,4-Butynediol over Ni-Cu/SiO_2 Bimetallic Catalyst

采用超临界干燥法和等体积浸渍法制备了不同Ni/Cu比例的Ni-Cu/SiO_2双金属催化剂,利用ICP、 BET、 XRD、 H_2-TPR、 H_2-TPD、 NH_3-TPD等手段对催化剂进行了结构表征,考察了不同Ni/Cu比例对催化剂结构以及1,4-丁炔二醇加氢性能的影响.结果表明,少量Cu的引入不仅能够提高Ni活性物种的分散性,而且Ni-Cu双金属间的相互作用改善了NiO物种的还原性能及氢活化能力,有利于氢和1,4-丁炔二醇在活性位点的快速转化.在反应温度50℃,氢压1 MPa,反应时间3 h的加氢评价条件下, Ni/Cu比为3∶1时, 15Ni5Cu/SiO_2催化材料不仅可以实现BYD的完全转化,而且能够有效降低难分离副产物2-羟基四氢呋喃的含量,具有最优的加氢活性和对1,4-丁烯二醇及1,4-丁二醇的选择性.

The second metal modified Ni-Cu/SiO2 catalysts with different mass ratios of 3∶1,1∶1 and 1∶3 were prepared by supercritical drying and incipient impregnation method.And the promotion effect of Cu additive was thoroughly characterized by ICP,BET,XRD,H2-TPR,H2-TPD,NH3-TPD etc.and tested on the hydrogenation of 1,4-butynediol.It was found that the addition of appropriate amount of Cu into the Ni-based catalyst could not only improve the dispersibility of active Ni species,but also promote the metal reduction ability and the hydrogenation adsorption/activation capacity,which are benefit for the hydrogenation of 1,4-butynediol.The catalyst activity was tested under a condition of 50℃,1 MPa H2 pressure and reaction duration of 3 h,the results showed that 15 Ni5 Cu/SiO2 with a little amount of Cu addition could achieve the complete 1,4-butynediol conversion and possess the superior 1,4-butenediol and 1,4-butanediol selectivity with the lowest byproduct which is difficult to separate.