Ni/ZrO2-SiO2催化剂催化乙酰丙酸加氢合成γ-戊内酯  

γ-Valerolactone synthesis from levulinic acid hydrogenation over Ni/ZrO_2-SiO_2 catalyst

作　　者：王杰[1] 张因[1] 郭健健 赵丽丽[1] 赵永祥[1] WANG Jie;ZHANG Yin;GUO Jianjian;ZHAO Lili;ZHAO Yongxiang(Engineering Research Center of Ministry of Education for Fine Chemicals,School of Chemistry and Chemical Engineering,Shanxi University,Taiyuan 030006,Shanxi,China)

机构地区：[1]山西大学化学化工学院,精细化学品教育部工程研究中心,山西太原030006

出　　处：《化工学报》2018年第8期3452-3459,共8页CIESC Journal

基　　金：国家自然科学基金青年科学基金项目(21303097);国家国际科技合作专项(2013DFA40460)。

摘　　要：分别以ZrO_2、SiO_2及ZrO_2-SiO_2复合氧化物为载体,采用等体积浸渍法制备了Ni含量为10%(质量分数)的催化剂,考察了其催化乙酰丙酸液相加氢性能。采用N2-物理吸附、NH3-TPD、H2-TPR、XRD、TEM等表征手段对催化剂进行了表征。研究结果表明,在所制备的催化剂上,乙酰丙酸先经C=O加氢生成4-羟基戊酸,后者快速脱水酯化为γ-戊内酯。Ni/ZrO_2-SiO_2催化剂较Ni/ZrO_2与Ni/SiO_2催化剂具有高的金属分散度和丰富的表面酸性中心,表现出高的C=O加氢活性以及优异的乙酰丙酸加氢合成γ-戊内酯性能。在反应温度为200℃,氢气压力4 MPa的反应条件下,乙酰丙酸的转化率达到100%,γ-戊内酯的选择性大于99.9%。ZrO2、SiO2 and ZrO2-SiO2 oxide composite supported Ni catalysts with Ni content of 10%(mass)were prepared by incipient impregnation method and characterized by N2 physical adsorption,NH3-TPD,H2-TPR,XRD,TEM.The catalysts were evaluated for liquid phase hydrogenation of levulinic acid.The results showed that levulinic acid was first hydrogenated to 4-hydroxy valeric acid via C O hydrogenation andγ-valerolactone was then produced by immediate esterification of 4-hydroxy valeric acid.Compared to Ni/ZrO2 and Ni/SiO2 catalysts,Ni/ZrO2-SiO2 catalyst exhibited highest dispersion of metallic Ni and most surface acid sites.As a result,the Ni/ZrO2-SiO2 catalyst demonstrated highest activity for C O hydrogenation and superior performance for synthesis ofγ-valerolactone via levulinic acid hydrogenation.100%levulinic acid conversion and over 99.9%γ-valerolactone selectivity were achieved under reaction temperature of 200℃and hydrogen pressure of 4 MPa.

关 键 词：乙酰丙酸 γ-戊内酯 催化加氢 Ni/ZrO2-SiO2 

分 类 号：O643.36[理学—物理化学]