CO2对CuO-ZnO-Al2O3催化剂前体老化及催化性能的影响

CHEMICAL INDUSTRY AND ENGINEERING PROGRESS 2013年第32卷第11期 ·2644·化 工 进 展

CO 2对CuO/ZnO/Al 2O 3催化剂前体老化及催化性能的影响

陈 雄，郑华艳，杨 浩，李 忠

（太原理工大学煤科学与技术教育部和山西省重点实验室，山西 太原 030024）

摘 要：采用并流共沉淀法制备CuO/ZnO/Al 2O 3甲醇合成催化剂前体，在通入CO 2条件下老化，采用XRD 、FT-IR 、DTG 、H 2-TPR 、XPS 等表征手段对制备的前体及焙烧后的催化剂进行表征，研究不同CO 2通入量对前体晶相转变、微观结构及其焙烧后催化性能的影响。研究结果表明，老化阶段通入CO 2后，沉淀母液的pH 值趋于7，产生CO 32?离子，进而影响Zn 2+的沉淀，促进Cu 2+进入Zn 5(CO 3)2(OH)6晶格中取代Zn 2+形成绿铜锌矿(Zn,Cu)5(CO 3)2(OH)6物相，有助于增强焙烧后催化剂的Cu-Zn 之间协同作用，增加活性组分Cu 分散度。CO 2通入量为40 mL/min 时，制备的催化剂在浆态床合成甲醇过程中表现出良好的催化活性和稳定性，甲醇时空收率（STY ）达到301.78 g/(kg ?h)，失活率仅为0.15%/d ，与未通入CO 2辅助老化制备的催化剂相比，时空收率提高了9.72%，平均失活率降低了33.33%。

关键词：CO 2辅助老化；浆态床；CuO/ZnO/Al 2O 3催化剂；甲醇合成

中图分类号：O 643；TQ 53 文献标志码：A 文章编号：1000–6613（2013）11–2644–07 DOI ：10.3969/j.issn.1000-6613.2013.11.019

Influence of CO 2 in ageing process on the catalytic property of

CuO/ZnO/Al 2O 3 catalyst

CHEN Xiong ，ZHENG Huayan ，YANG Hao ，LI Zhong

（Key Laboratory of Coal Science and Technology of Ministry of Education and Shanxi Province ，Taiyuan University of

Technology ，Taiyuan 030024，Shanxi ，China ）

Abstract ：The CuO/ZnO/Al 2O 3 catalysts were prepared by co -precipitation ，and the effects of CO 2 addition during the aging process on the phase composition of precursors ，the microstructure of the calcined catalysts and catalytic performance for slurry phase methanol synthesis were investigated. The characterization by XRD ，FT-IR ，DTG ，H 2-TPR and XPS showed that adding CO 2 helps to keep the mother liquor pH close to neutral ，and generates CO 32? ions ，thus to facilitate Zn 2+ precipitate and to promote Cu 2+ into Zn 5(CO 3)2(OH)6 lattice substitution of Zn 2+ formation the aurichalcite(Zn,Cu)5 (CO 3)2(OH)6，leading to the improvement of content in precursors. While the catalyst is calcined ，it exhibits a strong interaction between CuO and ZnO ，well dispersion of CuO crystal particles around ZnO surface ，and the best catalytic performance ，including the methanol space-time yield (STY) and the stability. While the volume flow of CO 2 was 40m L/min ，the methanol space-time yield (STY) and deactivation rate of the catalyst were 302.45g /(kg ?h) and 0.15%/d ，respectively. Compared with the catalyst prepared without adding CO 2 in the aging process ，the methanol STY and deactivation rate of the catalyst were increased and decreased by 7.36% and 28.57%，respectively 。

Key words ：CO 2 assisted aging ；slurry reactor ；CuO/ZnO/Al 2O 3 catalyst ；methanol synthesis

第一作者：陈雄（1988—），男，硕士研究生，从事一碳化学研究。E-mail chenxiong168@https://www.360docs.net/doc/474952338.html, 。联系人：李忠，教授，博士，主要从事催化和一碳化学研究。E-mail lizhong@https://www.360docs.net/doc/474952338.html, 。 收稿日期：2013-03-08；修改稿日期：2013-05-10。

基金项目：国家973计划（2012CB723105）及国家自然基金青年科学基金（21106092）项目。