ABO_(3)载氧体A/B位金属对乙烷化学链氧化制乙烯性能影响实验研究  

Experimental Study on the Effect of Metal at A/B Site of ABO_(3) Oxygen Carrier on the Performance of Chemical Chain Oxidation of Ethane to Ethylene

作　　者：杨仲卿[1] 牛浩男 唐波[2] 李秀权 冉景煜[1] YANG Zhongqing;NIU Haonan;TANG Bo;LI Xiuquan;RAN Jingyu(Key Laboratory of Low-grade Energy Utilization Technologies and Systems,Ministry of Education(Chongqing University),Shapingba District,Chongqing 400044,China;School of Energy and Power Engineering,Chongqing University,Shapingba District,Chongqing 400044,China)

机构地区：[1]低品位能源利用技术及系统教育部重点实验室(重庆大学),重庆市沙坪坝区400044 [2]重庆大学能源与动力工程学院,重庆市沙坪坝区400044

出　　处：《中国电机工程学报》2024年第15期6086-6094,I0021,共10页Proceedings of the CSEE

基　　金：国家自然科学基金项目(面上项目)(52276099);重庆市研究生科研创新项目(CYB23034)。

摘　　要：钙钛矿载氧体因其低廉的成本、A/B位掺杂金属的灵活多变、优良的氧储存释放性能而受到关注,被广泛应用于化学链式氧化反应中制备乙烯。该文采用柠檬酸络合法制备不同A/B位金属的ABO_(3)钙钛矿型载氧体,通过研究A/B位金属变化对乙烷催化反应性能的影响,得到具有最佳反应活性的载氧体。运用XPS、O_(2)-TPD等方法对催化剂的结构进行表征,为探究其本征反应特性规律,通过动力学研究发现,在形成钙钛矿载氧体的不同A/B位金属中,BaCoO_(3)具有最佳的反应性能,其中乙烷转化率最高达到60%,乙烯选择性达到75%,乙烯收率最高为46%。BaCoO_(3)经过12次循环反应后,乙烯选择性基本保持不变,乙烷转化率降低约4%。通过表征分析发现,比表面积和孔径略微减小,表明载氧体具有优良的稳定性。Perovskite oxygen carriers have attracted much attention due to their low cost,variability of A/B-site metals,and excellent oxygen storage and release performance.They are widely used in the preparation of ethylene in chemical chain oxidation reactions.In this paper,different ABO_(3) perovskite oxygen carriers are prepared by using the citric acid complexation method.The effect of A/B metal on the reaction performance of oxygen carrier ethane is studied,and the oxygen carrier with the best reaction performance is obtained.The structure of the catalyst is characterized by XPS,O_(2)-TPD and other methods.According to kinetic studies,BaCoO_(3) has the best reaction performance among the different A/B position metals forming perovskite oxygen carriers,with the highest ethane conversion of 60%,ethylene selectivity of 75%and ethylene yield of 46%,showing its intrinsic reaction characteristics.After 12 cycles of BaCoO_(3),the specific surface area and pore size decreases slightly,the ethane conversion decreases by about 4%,and the ethylene selectivity remains basically unchanged,indicating that the cycle stability of oxygen carrier is excellent.

关 键 词：乙烯 化学链式氧化 钙钛矿载氧体 半径及价态 氧化脱氢 

分 类 号：TK01[动力工程及工程热物理]