非平衡负离子与ZnO-ZrO_(2)固溶体协同催化CO_(2)与H_(2)O反应制甲醇  

Preparation of methanol from CO_(2) and H_(2)O catalyzed by non-equilibrium anion and ZnO-ZrO_(2) solid solution

作　　者：徐瑞 杨凡 贾显枝 刘璐[1] 赵彬然[1] 马晓迅[1] XU Rui;YANG Fan;JIA Xianzhi;LIU Lu;ZHAO Binran;MA Xiaoxun(School of Chemical Engineering,Northwest University,Xi’an 710069,Shaanxi,China)

机构地区：[1]西北大学化工学院,陕西西安710069

出　　处：《化工进展》2021年第12期6714-6720,共7页Chemical Industry and Engineering Progress

基　　金：国家自然科学基金(21536009);陕西省重点研发计划(2020ZDLGY11-06);陕西省科技计划(2017ZDCXL-GY-10-03)。

摘　　要：近年,CO_(2)加氢制甲醇技术初步克服了催化剂选择性低和稳定性差的难题,实现了工业化生产。然而作为氢源,氢气的廉价替代品却极少被报道。本文利用二元金属氧化物ZnO-ZrO_(2)固溶体作为催化剂,在负电晕等离子体的辅助下将CO_(2)和水蒸气转化为甲醇。结果表明,甲醇产量达到33.56μmol/h,是单独等离子体和单独催化剂条件下甲醇产量之和的1.4倍,催化剂与等离子体联用产生协同性。甲醇产量随反应电流和水蒸气流量的增大而增大,随CO_(2)流量的增加而降低。X射线衍射(XRD)、X射线光电子能谱分析(XPS)和CO_(2)-程序升温脱附(CO_(2)-TPD)表征发现,催化剂在负电晕等离子体反应条件下晶面间距增大,氧空位增多,这增强了催化剂的CO_(2)吸附性能。CO_(2)-漫反射傅里叶红外光谱(CO_(2)-DRIFTs)分析结果表明,负电晕等离子体处理后的催化剂反应过程中会产生羧酸盐(COO-),是形成甲醇的主要中间物种。CO_(2) and water vapor was converted into methanol with the catalyst of ZnO-ZrO_(2) solid solution and the aid of negative corona plasma,which provided synergistic effect when employed together.The yield of methanol was 33.56μmol/h,which was 1.4 times of the sum of those under plasma alone and catalyst alone.The methanol yield increased with the increase of reaction current and steam flow rate,but decreased with the increase of CO_(2) flow rate.The results of XRD,XPS and CO2-TPD showed that the crystal plane spacing and oxygen vacancies of the catalyst increased under negative corona plasma condition,which enhanced the CO_(2) adsorption on the catalyst.The CO_(2)-DRIFTs results showed that carboxylate(COO-)was the main intermediate species during the methanol formation.

关 键 词：二氧化碳 等离子体 催化剂 甲醇 协同作用 醇 

分 类 号：TQ531.7[化学工程—煤化学工程]