Mg-Al双金属氧化物高效催化偶联反应制备碳酸甘油酯  

Preparation of Glyceryl Carbonate Through High Efficiency Coupling Reaction Using Mg-Al Bimetallic Metal Oxides

作　　者：申琦 孙立鹏 闫昊[1] 霍祎晨 刘熠斌[1] 陈小博[1] 杨朝合[1] SHEN Qi;SUN Lipeng;YAN Hao;HUO Yichen;LIU Yibin;CHEN Xiaobo;YANG Chaohe(State Key Laboratory of Heavy Oil Processing,China University of Petroleum,Qingdao 266580,China;SINOPEC Shenli Oilfield Petroleum Development Center Co.,Ltd.,Dongying 257077,China)

机构地区：[1]中国石油大学(华东)重质油全国重点实验室,山东青岛266580 [2]中国石化胜利油田石油开发中心有限公司,山东东营257077

出　　处：《石油学报(石油加工)》2025年第2期453-465,共13页Acta Petrolei Sinica(Petroleum Processing Section)

基　　金：国家自然科学基金项目(22108305);山东省自然科学基金项目(ZR2022MB015)资助。

摘　　要：为开发高效的无卤非均相催化剂用于吸附和活化CO_(2)以制备碳酸甘油酯,在前期研究的基础上,采用立方体氧化镁相同的制备方法,以Al为第二金属、pluronic P123为模板剂,通过水热合成法制备了不同Mg/Al摩尔比(1/5、1/3、1/1、3/1、5/1)的5种双金属氧化物催化剂用于CO_(2)和甘油偶联反应制备碳酸甘油酯,并通过XRD、SEM、N 2吸附-脱附、O_(2)-TPD、NH 3-TPD、CO_(2)-TPD、XPS等表征手段分析上述催化剂的物理化学性质。结果表明:Mg/Al摩尔比为1/3的Mg 1Al 3具有最多的强碱性位点以及较多的氧空位,具有最强的CO_(2)吸附活化能力;同时,较高的中等酸性位点占比和总酸量有利于促进环氧丙烷的吸附活化及抑制甘油向副产物甘油醚的转化,提高碳酸甘油酯选择性。以Mg 1Al 3为催化剂,在温度140℃、压力2 MPa的条件下反应2 h,甘油转化率为79%,碳酸甘油酯选择性为64%。It remains a major challenge to develop efficient halogen-free heterogeneous catalysts for adsorbing and activating CO_(2)to synthesize glycerol carbonate.Based on previous studies,Five bimetallic oxide catalysts with different Mg/Al molar ratios(1/5,1/3,1/1,3/1,5/1)were prepared by hydrothermal synthesis for the preparation of glycerol carbonate in the coupling reaction of CO_(2)and glycerol using the same method of preparation as that used for cubic magnesium oxide with Al as the second metal and pluronic P123 as the templating agent,and the physicochemical properties of the above catalysts were measured by methods of characterization such as XRD,SEM,N 2 adsorption-desorption,O_(2)-TPD,NH 3-TPD,CO_(2)-TPD,XPS.The results showed that Mg 1Al 3(Mg/Al molar ratio of 1/3)exhibited the highest concentration of strong basic sites and higher oxygen vacancy ratio,thereby demonstrating superior CO_(2)adsorption and activation capabilities.Additionally,a higher proportion of medium acid sites and the total acid amount facilitated the adsorption and activation of propylene oxide while suppressing diglycerol formation as a byproduct during glycerol conversion,ultimately enhancing the selectivity of glycerol carbonate.By employing Mg 1Al 3 as the catalyst under reaction conditions of temperature of 140℃and pressure of 2 MPa for 2 hours,a glycerol conversion rate of 79%with a selectivity of 64%towards glycerol carbonate was achieved.

关 键 词：碳酸甘油酯 二氧化碳 环氧丙烷 Mg-Al双金属氧化物 偶联反应 

分 类 号：TQ233.2[化学工程—有机化工]