不同助剂对Ni/Al_(2)O_(3)催化顺酐液相加氢选择性的影响  

Effect of different additives on liquid phase selective hydrogenation performance of maleic anhydride over Ni/Al_(2)O_(3)

作　　者：朱金剑 杨霞霞 穆展鹏 宋国良 李子涵 刘伟 许岩 张景成 ZHU Jinjian;YANG Xiaxia;MU Zhanpeng;SONG Guoliang;LI Zihan;LIU Wei;XU Yan;ZHANG Jingcheng(CNOOC Tianjin Chemical Research and Design Institute Co.,Ltd.,Tianjin 300131,China;China University of Petroleum,Beijing 102249,China)

机构地区：[1]中海油天津化工研究设计院有限公司,天津300131 [2]中国石油大学(北京),北京102249

出　　处：《无机盐工业》2024年第4期143-150,共8页Inorganic Chemicals Industry

摘　　要：采用超声辅助沉淀法分别使用P、Mg、Mo、Cu助剂制备了系列镍基顺酐加氢催化剂。采用N_2物理吸附-脱附、X射线衍射(XRD)、氢程序升温还原(H_(2)-TPR)、氨程序升温脱附(NH_(3)-TPD)等方法对催化剂进行了表征分析,考察不同助剂对催化剂晶型结构、还原性能、酸强度、BET比表面积和孔结构等的影响。结果表明,助剂高度分散在催化剂体系中,同时助剂的引入使催化剂比表面积和孔容呈现不同程度的减小,此外添加助剂提高了催化剂还原温度,增强了活性金属与载体之间相互作用力,导致催化剂还原程度不同,使Ni^(0)及具有L酸特性的Ni^(δ+)数目不同,进而影响氢气活化及C=C/C=O键吸附能力。使用固定床顺丁烯二酸酐液相连续加氢反应对催化剂进行性能评价,结果发现,Ni-Mo/Al_(2)O_(3)催化剂具有最优的γ-丁内酯选择性,在反应压力为5 MPa、反应温度为150℃、氢酐物质的量比为5∶1、空速为1 h^(-1)的工艺条件下,顺酐转化率为99.48%、γ-丁内酯选择性为54.34%。A series of nickel⁃based maleic anhydride hydrogenation catalysts were prepared by ultrasound⁃assisted precipi⁃tation method using P,Mg,Mo,and Cu additives,respectively.The catalysts were characterized and analyzed by N_(2)physical adsorption⁃desorption,X-ray diffraction(XRD),programmed temperature⁃raising reduction(H_(2)-TPR),and ammonia⁃pro⁃grammed temperature⁃raising desorption(NH_(3)-TPD),to investigate the effects of different additives on the crystalline struc⁃ture of the catalysts,the reduction performance,acid strength,BET specific surface area and pore structure.The results showed that the additives were highly dispersed in the catalyst system,while the introduction of the additives caused the specific surface area and pore volume of the catalysts to show different degrees of reduction.In addition,the additives in⁃creased the reduction temperature of the catalysts and enhanced the interaction force between the active metals and the car⁃riers,which led to the different degrees of reduction of the catalysts,and resulted in different numbers of Ni0 and Ni^(δ+)with the characteristics of L-acid,which in turn affected the hydrogen activation and the adsorption capacity of the C=C/C=O bonds.The performance of the catalyst was evaluated using a fixed⁃bed maleic anhydride liquid⁃phase continuous hydroge⁃nation reaction,and it was found that the Ni-Mo/Al_(2)O_(3)catalyst had the optimalγ-butyrolactone selectivity.Under the pro⁃cess conditions of reaction pressure of 5 MPa,reaction temperature of 150℃,molar ratio of 5∶1 for hydrogen anhydride,and space velocity of 1 h-1,the conversion rate of maleic anhydride was≥99.5%,the selectivity ofγ-butyrolactone was≥54.34%.

关 键 词：助剂 Ni/Al_(2)O_(3) 顺酐 液相加氢 Γ-丁内酯 

分 类 号：O643.36[理学—物理化学]