双金属Ni-Cu催化剂对顺酐选择性加氢产物的调控  

Regulation of Ni-Cu bimetallic catalysts on selective hydrogenation products of maleic anhydride

作　　者：徐志任 斯吴强 胡文龙 黄卫国 邢闯 XU Zhiren;SI Wuqiang;HU Wenlong;HUANG Weiguo;XING Chuang(School of Biological and Chemical Engineering,Zhejiang University of Science and Technology,Hangzhou 310023,Zhejiang,China;Zhejiang Realsun Chemical Co.,Ltd,Taizhou 318000,Zhejiang,China)

机构地区：[1]浙江科技大学生物与化学工程学院,杭州310023 [2]浙江联盛化学股份有限公司,浙江台州318000

出　　处：《浙江科技大学学报》2024年第5期417-426,共10页Journal of Zhejiang University of Science and Technology

基　　金：浙江省自然科学基金项目(LY23B060002,LY23B060001);国家自然科学基金项目(22278376)。

摘　　要：【目的】为探索金属催化剂在α,β-不饱和羰基化合物上选择性加氢C-O、C-C双键的规律,设计了Ni-Cu双金属催化剂。【方法】通过蒸氨法制备一系列的Ni-Cu/SiO_(2)双金属催化剂,采用固定床装置进行常压顺酐(maleic anhydride,MA)加氢反应,研究了不同比例的Ni-Cu催化剂对顺酐选择性加氢产物的调控规律。【结果】Ni-Cu/SiO_(2)催化剂比表面积越大,氢气吸附能力越强,催化活性越高,其转化率均能达到99%以上。Ni、Cu含量和反应温度是影响顺酐选择性加氢产物分布的主要因素。Ni金属虽有利于γ-丁内酯(γ-butyrolactone,GBL)的生成,但其副产物丙酸较高。同时温度的升高也会造成酸类副产物上升,因此Ni金属适用于低温条件下的C-C加氢,主要生成丁二酸酐(succinic anhydride,SA);Cu金属参与反应得到的酸类副产物少,GBL+SA选择性高,因此Cu金属则更适用于高温条件下的C-O加氢,γ-丁内酯为主要产物。【结论】本研究结果能为顺酐加氢制γ-丁内酯联产丁二酸酐工艺大规模工业化生产提供参考。[Objective]In order to investigate the regularities on selective hydrogenation of C-O and C-C double bonds inα,β-unsaturated carbonyl compounds,Ni-Cu bimetallic catalysts were designed.[Method]A series of Ni-Cu/SiO_(2)bimetallic catalysts were prepared through ammonia evaporation method and the hydrogenation of maleic anhydride(MA)under atmospheric pressure was carried out in a fixed bed reactor.The regulation effect on selective hydrogenation products of maleic anhydride was studied when different proportions of Ni-Cu catalysts were applied.[Result]Ni-Cu/SiO_(2)catalysts exhibit a larger specific surface area,increasing hydrogen adsorption ability,and higher catalytic activity with conversion rates exceeding 99%.Metal(Ni,Cu)loading and reaction temperature are the primary factors influencing the distribution of selective hydrogenation products of maleic anhydride.Although Ni metal is conducive to the formation ofγ-butyrolactone(GBL),its byproduct is high in propionic acid.At the same time,the increase of temperature will also cause the increase of acid by-products.Ni metal proves suitable for C-C hydrogenation at low temperatures with succinic anhydride(SA)as the primary product;Cu metal participates in the reaction to obtain few acid byproducts,with high GBL+SA selectivity.Thus,Cu metal shows greater suitability for C-O hydrogenation at high temperatures with GBL as the primary product.[Conclusion]The findings of this study offer a valuable reference for the large-scale industrialization of maleic anhydride hydrogenation,aiming to co-produce GBL and SA.

关 键 词：Ni-Cu催化剂 选择性加氢 顺酐 Γ-丁内酯 丁二酸酐 

分 类 号：TQ050.43[化学工程]