Ni/γ-Al_(2)O_(3)催化剂的2-MF气相加氢合成2-MTHF性能研究  

Preparation of Ni/γ-Al_(2)O_(3) and Their Catalytic Performance for 2-MFGas Phase Hydrogenation

作　　者：方姿予 张炜 谈立美 种思颖 张雅静 王康军 FANG Zi-yu;ZHANG Wei;TAN Li-mei;CHONG Si-ying;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》2023年第5期461-472,I0002,共13页Journal of Molecular Catalysis(China)

基　　金：辽宁省高等学校创新人才支持计划(辽教函[2020]389号);辽宁省兴辽英才计划(XLYC1907029);沈阳市中青年科技创新人才支持计划(RC210365);沈阳化工大学项目(LDB2022001)。

摘　　要：2-甲基四氢呋喃(2-MTHF)是极具市场潜力的生物燃料、绿色溶剂和化学中间体.采用浸渍法制备Ni/γ-Al_(2)O_(3)催化剂,在固定床反应器评价其2-甲基呋喃(2-MF)气相加氢合成2-甲基四氢呋喃(2-MTHF)反应性能.通过XRD、N2等温吸附-脱附、H2-TPR、NH3-TPD、TEM、H2吸附和XPS对催化剂结构和表面性质进行表征,研究Ni负载量、焙烧温度和反应条件对催化剂性能的影响规律.结果表明:Ni/γ-Al_(2)O_(3)催化剂的Ni金属面积、晶粒尺寸、反应温度和压力都会影响2-MF的转化率;孔结构、酸量和反应温度是影响2-MTHF选择性的主要原因,平均孔径大、酸量大和适宜的反应温度有利于提高2-MTHF选择性. 400℃焙烧的负载量为15%的Ni/γ-Al_(2)O_(3)催化剂, Ni金属面积大、晶粒尺寸小、总酸量多,催化剂表面的金属活性中心与酸性中心协同作用促进了2-MF呋喃环上C=C加氢生成2-MTHF,性能较优.在2 MPa、100℃、WHSV=2.7 h^(-1)、H2/2-MF=6.4的条件下,该催化剂上2-MF转化率为99.8%, 2-MTHF选择性为98.0%,催化剂可以稳定运行40 h.2-methyltetrahydrofuran(2-MTHF)is a biofuel,green solvent and chemical intermediate with great market potential.Ni/γ-Al_(2)O_(3) catalyst was prepared by impregnation method,which was used for the gas phase hydrogenation of 2-methylfuran(2-MF)to 2-methyltetrahydrofuran(2-MTHF).The structure of the catalyst was characterized by XRD,N2 isothermal adsorption-desorption,H2-TPR,NH3-TPD,TEM,H2 adsorption and XPS,and the Ni loading,calcination temperature and reaction conditions were investigated.The results show that Ni metal area,grain size,reaction temperature and pressure of Ni/γ-Al_(2)O_(3) catalyst will affect the conversion of 2-MF.Pore structure,acid content and reaction temperature are the main factors affecting the selectivity of 2-MTHF.Large average pore size,large acid content and suitable reaction temperature are beneficial to improve the selectivity of 2-MTHF.The Ni/γ-Al_(2)O_(3) catalyst with a loading of 15%calcined at 400℃has large Ni metal area,small grain size and large total acid content.The synergistic effect of metal active center and acid center on the surface of the catalyst promotes the hydrogenation of C=C on the 2-MF furan ring to 2-MTHF,which has better performance.Under the conditions of 2 MPa,100℃,WHSV=2.7 h−1 and H2/2-MF=6.4,the conversion of 2-MF is 99.8%and the selectivity of 2-MTHF is 98.0%.The catalyst can run stably for 40 hours.

关 键 词：2-甲基四氢呋喃 2-甲基呋喃 气相加氢 Ni/Al_(2)O_(3) 

分 类 号：O643.32[理学—物理化学]