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第 36 卷第 5 期 精 细 化 工 Vol.36, No.5
201 9 年 5 月 FINE CHEMICALS May 2019

催化与分离提纯技术
活性形貌对 CuO/ZnO/Al O 催化加氢反应的影响
2
3

秦 霏 1,2 ，颜万鑫 1,2 ，纳 薇 1,2* ，叶海船 1,2 ，高文桂 1,2 ，王 华 1,2

（1.云南省复杂有色金属资源清洁利用国家重点实验室，云南 昆明 650093；2.昆明理工大学 冶金与能源
工程学院，云南 昆明 650093）

摘要：以硝酸铜、硝酸锌等为原料，采用沉淀-沉积法制备了载体是介孔 Al 2 O 3 的 CuO/ZnO/Al 2 O 3 催化剂，通过
改变焙烧时间可得到不同活性组分形貌（团簇球状和棒状）的催化剂，并用于 CO/CO 2 加氢反应。通过 XRD、
BET、N 2 吸附-脱附、TEM、H 2 -TPR、CO 2 -TPD、NH 3 -TPD 和 FTIR 对催化剂进行了表征与测试。结果表明，活
性组分（CuO/ZnO）形貌的改变影响了催化剂的 CuO 晶粒尺寸、比表面积、孔径及其还原性能，且对催化剂的
酸性位点和碱性位点的相对数量影响较大。团簇球状催化剂中活性组分的分散度高、易还原、碱性位多、酸性
位少，有利于甲醇的生成；而棒状催化剂中孔道不均匀、碱性位少、酸性位多，更有利于二甲醚（DME）的生
成。活性测试结果表明，团簇球状催化剂表现出高甲醇选择性（95.05%）和低 DME 选择性（4.18%）；棒状催
化剂的产物选择性与团簇球状相反，表现出高 DME 选择性（75.41%）和低甲醇选择性（12.81%）。
关键词：介孔 Al 2 O 3 ；CuO/ZnO/Al 2 O 3 催化剂；CO/CO 2 加氢反应；活性组分形貌；产物调控；催化技术
中图分类号：O643 文献标识码：A 文章编号：1003-5214 (2019) 05-0905-08

Effect of Active Morphology on Catalytic Hydrogenation of CuO/ZnO/Al 2O 3

1,2
1,2
1,2
1,2
1,2
QIN Fei , YAN Wan-xin , NA Wei 1,2* , YE Hai-chuan , GAO Wen-gui , WANG Hua
（1.State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization in Yunnan Province, Kunming
650093, Yunnan, China ；2.Faculty of Metallurgy and Energy Engineering, Kunming University of Science and
Technology, Kunming 650093, Yunnan, China）
Abstract: CuO/ZnO/Al 2O 3 catalysts with mesoporous Al 2O 3 as support were prepared by precipitation-
deposition method using cupric nitrate and zinc nitrate as raw materials. Catalysts possessing different
active component morphologies (globular clusters and rod-like structure) were obtained by changing
calcination time and used for CO/CO 2 hydrogenation reaction. The catalysts were characterized and tested
by XRD, BET, N 2 adsorption-desorption, TEM, H 2-TPR, CO 2-TPD, NH 3-TPD and FTIR. The results
showed that the morphology of the active components affects the CuO grain size, specific surface area, pore
size and reduction performance of the catalyst and has a great influence on the relative quantity of acid sites
and basic sites of the catalysts. The catalyst with globular clusters has high dispersion of active components,
easy to reduce, more basic sites and less acid sites, which is favorable for the formation of methanol. While
the rod-like catalyst has uneven pores, less basic sites and more acid sites, which is more conducive to the
formation of dimethyl ether (DME). The activity test results revealed that the catalyst with globular clusters
exhibited high methanol selectivity (95.05%) and low DME selectivity (4.18%). The rod-like catalyst
displayed the opposite trend with high DME selectivity (75.41%) and low methanol selectivity (12.81%).
Key words: mesoporous Al 2O 3; CuO/ZnO/Al 2O 3 catalysts; CO/CO 2 hydrogenation; morphology of active
component; product selective regulation; catalysis technology
Foundation items: National Natural Science Foundation of China (51404122, 51304099); National
Science and Technology Support Program (2011BAC01B03)

收稿日期：2018-09-16; 定用日期：2019-01-16; DOI: 10.13550/j.jxhg.20180690
基金项目：国家自然科学基金（51404122，51304099）；国家科技支撑计划（2011BAC01B03）
作者简介：秦 霏（1993—），女，硕士生。联系人：纳 薇（1981—），女，副教授，E-mail：weina＠kumst.edu.cn。