镍基催化剂上2-甲基呋喃气相加氢:载体的影响  

2-Methylfuran Vapor-phase Hydrogenation on Nickel-based Catalysts:The Effect of Support

作　　者：张炜 王金鼎 张金玉 王金山 张雅静 王康军 ZHANG Wei;WANG Jin-ding;ZHANG Jin-yu;WANG Jin-shan;ZHANG Ya-jing;WANG Kang-jun(College of Chemical Engineering,Shenyang University of Chemical Technology,Shenyang 110142,China)

机构地区：[1]沈阳化工大学化学工程学院,辽宁沈阳110142

出　　处：《分子催化（中英文）》2024年第4期331-341,共11页Journal of Molecular Catalysis(China)

基　　金：沈阳市中青年科技创新人才支持计划(RC210365);辽宁省教育厅项目(LJKQZ20222266);辽宁省科技厅联合基金(2023-BSBA-276);沈阳化工大学达标立项项目(LDB2022001)。

摘　　要：2-甲基四氢呋喃(2-MTHF)是一种重要的新型绿色溶剂,可以由生物质衍生物2-甲基呋喃(2-MF)催化加氢制备.采用浸渍法制备了负载型镍基催化剂(Ni/SiO_(2)、Ni/ZSM-5和Ni/MgO),并对其与2-MF气相加氢制备2-MTHF的性能进行研究,以考察载体性质对催化剂性能的影响.通过N_(2)等温吸附-脱附、XRD、H2-TPR、NH3-TPD、Py-IR和TEM等手段对催化剂进行了表征.研究结果表明,催化剂活性顺序为Ni/SiO_(2)>Ni/ZSM-5>Ni/MgO,SiO_(2)载体具有较大的比表面积和孔径,能够提高Ni物种的分散度,降低Ni的晶粒尺寸,从而提高催化剂的活性;MgO载体比表面积小且与Ni形成MgNiO_(2)物种,较难还原,只能提供少量的活性位Ni,催化剂的活性比较低.催化剂酸量对2-MTHF选择性影响较大,酸量顺序为Ni/MgO<Ni/SiO_(2)<Ni/ZSM-5,Ni/MgO催化剂表面酸量少,对2-MTHF选择性较高;Ni/ZSM-5催化剂具备最多的酸量,副产物增多,降低了2-MTHF的选择性.SiO_(2)负载的催化剂比表面积、孔容、孔径较大,酸量适中,表现出最优的催化性能,2-MF转化率为97.4%,2-MTHF选择性为98.4%.2-Methyltetrahydrofuran(2-MTHF)is an important new green solvent,which can be prepared by catalytic hydrogenation of the biomass derivative 2-methylfuran(2-MF).Supported nickel-based catalysts(Ni/SiO_(2),Ni/ZSM-5 and Ni/MgO)were prepared by impregnation method.The performance of the catalysts,for the synthesis of 2-MTHF from 2-MF hydrogenation in vapor-phase was studied,and the influence of support properties on catalyst performance was investigated.The catalysts were characterized by N_(2) isothermal adsorption-desorption,XRD,H2-TPR,NH3-TPD,Py-IR and TEM.The results showed that the activity of the catalysts followed the order of Ni/SiO_(2)>Ni/ZSM-5>Ni/MgO.The SiO_(2) support with large specific surface area and pore size can improve the dispersion of Ni species,reduce the grain size of Ni,and thus improve the activity of the catalyst.The specific surface area of the MgO support is small,and it forms the MgNiO_(2) species with Ni,which is difficult to be reduced,so it can only provide a small amount of active Ni,and the activity of the catalyst is relatively low.The acidity of the catalyst has a significant impact on the selectivity of 2-MTHF,with the order of acidity being Ni/MgO<Ni/SiO_(2)<Ni/ZSM-5.The surface acidity of Ni/MgO catalyst is low,resulting in higher selectivity for 2-MTHF.The Ni/ZSM-5 catalyst has the highest acidity,leading to an increase in by-products and a decrease in 2-MTHF selectivity.The catalyst of Ni/SiO_(2) exhibited optimal catalytic performance with a large specific surface area,pore volume,pore size and moderate acidity,with a 2-MF conversion rate of 97.4%and a 2-MTHF selectivity of 98.4%.

关 键 词：2-甲基呋喃 2-甲基四氢呋喃 气相加氢 载体 

分 类 号：O643.32[理学—物理化学]