有序介孔炭负载铜基催化剂Cu/CMK-3用于气相甲醇氧化羰基化反应  

Copper Supported Mesoporous Carbon Cu/CMK-3 for Catalytic Oxy-carbonylation of Methanol in Vapor Phase

作　　者：王瑞玉[1] 刘亚丽[2] 樊星[2] 魏贤勇[2] WANG Rui-Yu;LIU Ya-Li;FAN Xing;WEI Xian-Yong(Low Carbon Energy Institute,China University of Mining&Technology,Xuzhou,Jiangsu 221006,China;Key Laboratory of Coal Processing and Efficient Utilization,Ministry of Education,China University of Mining&Technology,Xuzhou,Jiangsu 221116,China)

机构地区：[1]中国矿业大学,低碳能源研究院,徐州221006 [2]中国矿业大学,煤炭洁净加工与高效洁净利用教育部重点实验室,徐州221116

出　　处：《无机化学学报》2020年第4期769-776,共8页Chinese Journal of Inorganic Chemistry

基　　金：中央高校基本科研业务费(No.2017XKZD10)资助项目。

摘　　要：通过纳米浇铸法合成了有序介孔炭CMK-3,再通过浸渍法制备了Cu/CMK-3催化剂,并将其用于气相甲醇氧化羰基化反应。N2吸附-脱附测试、X射线衍射(XRD)以及透射电镜(TEM)的表征结果表明,Cu/CMK-3具有序介孔结构,活性Cu物种均匀分散于CMK-3的表面及孔道中,粒径为10~20 nm,远小于相同条件下制备的铜/活性炭(Cu/AC)催化剂。固定床反应器的活性评价结果显示450℃下制备的Cu/CMK-3催化活性最高,反应10 h内碳酸二甲酯(DMC)的时空收率(STY)达到286 mg·g^-1·h^-1,选择性为76%。长周期活性评价结果表明Cu/CMK-3稳定性较相同条件下制备的Cu/AC有大幅提高,50 h内DMC的STY降低了20%,75 h内降低了28%。Ordered mesoporous carbon CMK-3 was synthesized via the nanocasting route,and used to prepare Cu/CMK-3 catalyst for dimethyl carbonate(DMC)synthesis by oxidative carbonylation of methanol in a gas-phase reaction.The effect of activation temperature on the catalyst structure and catalytic performance were investigated.N2 adsorption-desorption,X-ray diffraction(XRD)and transmission electron microscopy(TEM)results revealed that the Cu/CMK-3 catalysts were mesoporous,the active copper species dispersed well in the surface and pore channels of CMK-3,their diameter were between 10~20 nm,far less than that of Cu/activated carbon(Cu/AC).The corresponding catalytic activity in a fixed-bed reactor increased with the activation temperature and the Cu/CMK-3 catalyst prepared at 450℃exhibited the best catalytic activity.The space time yield(STY)was 286 mg·g^-1·h^-1 and the selectivity for DMC was 76%in 10 h running.A long periodic test also confirmed a better catalytic stability of Cu/CMK-3 compared to Cu/AC,the STY of DMC declined by 20%after 50 h reaction and 28%after 75 h reaction.

关 键 词：非均相催化 负载型催化剂 纳米浇注法 介孔Cu/CMK-3 碳酸二甲酯 甲醇 氧化羰基化 

分 类 号：O643.3[理学—物理化学]