Page 151 - 《精细化工》2021年第10期

第 38 卷第 10 期 精 细 化 工 Vol.38, No.10
2021 年 10 月 FINE CHEMICALS Oct. 2021

催化与分离提纯技术
共沉淀法制备 Cu-Mn-Al 尖晶石催化剂

用于甲醇水蒸气重整制氢


吴浩飞，江志东 ，马紫峰

（上海交通大学 化学化工院，上海 200240）

摘要：以硝酸铜、硝酸铝和硝酸锰为原料，用共沉淀法制备了 Cu-Mn-Al 尖晶石固溶体催化剂，用于甲醇水蒸
气重整制氢反应。采用 BET、H 2 -TPR、XRD、SEM、XPS 等方法对催化剂进行了表征，考察了 Mn 的添加比例
（CuMn x Al 4–x , x=0~0.5）对催化剂物理化学性质、形貌及催化性能的影响。结果表明，Mn 添加比例不同，催化
剂的比表面积、还原性能以及表面化学性质发生改变，随着 Mn 比例从 0 增大到 0.5（以 Cu 的物质的量为基准，
下同），CuAl 尖晶石粒径增大、比表面积下降，并且更难被还原。催化剂的催化性能在 x=0.25 时最佳，在 260 ℃、
0.3 MPa、n（H 2 O）∶n（CH 3 OH）=1∶1、质量空速（WHSV）为 3.0 g-feed/(g-cat·h)的反应条件下，最高甲醇
转化率为 91.7%，连续运行 150 h 后甲醇转化率降至 78.8%，均明显高于未含 Mn 的 CuAl 尖晶石催化剂。
关键词：共沉淀法；甲醇水蒸气重整；Cu-Mn-Al 尖晶石；制氢；催化技术
中图分类号：TQ116.2；TQ426 文献标识码：A 文章编号：1003-5214 (2021) 10-2081-08

Preparation of Cu-Mn-Al spinel catalysts by co-precipitation method
for hydrogen preparation from methanol steam reforming


WU Haofei, JIANG Zhidong , MA Zifeng
（School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China）

Abstract: Cu-Mn-Al spinel solid solution catalysts were prepared by coprecipitation method using copper
nitrate, aluminum nitrate and manganese nitrate, and tested in methanol steam reforming reaction for the
preparation of hydrogen. The catalysts were characterized by BET, H 2-TPR, XRD, SEM, XPS, etc. The
effects of addition ratio of Mn (CuMn x Al 4–x , x = 0~0.5) on the catalyst physicochemical properties,
morphology and catalytic performance were investigated. The results showed that the specific surface area,
reduction properties and surface chemistry of catalyst samples were altered with the addition ratio of Mn.
With the increase of Mn proportion from 0 to 0.5 (based on the molar of Cu, the same below), the particle
size of spinel particles increased, the specific surface area decreased, and it became more difficult to be
reduced. The catalytic performance of catalyst CuMn 0.25Al 3.75 was the best. Under the reaction conditions
of 260 ℃, 0.3 MPa, n(H 2O)∶n(CH 3OH) =1∶1, weight hourly space velocity (WHSV) 3.0 g-feed/(g-cat·h),
the highest methanol conversion rate was 91.7% and dropped to 78.8% after 150 h running, which were
obviously higher than that of CuAl spinel catalyst without Mn.
Key words: coprecipitation method; methanol steam reforming; Cu-Mn-Al spinel; hydrogen preparation;
catalysis technology

20 世纪 70 年代，“氢经济”的概念被提出，其 但 H 2 本质是二次能源，难以从自然环境中直接获
[1]
核心就是以 H 2 作为燃料 。H 2 作为有希望替代化石 取。H 2 的制取方法包括化石燃料制氢、电解水制氢
燃料的一种绿色新能源，近年来得到了广泛研究 [2-3] 。 和生物质制氢等 [4-6] 。化石燃料制氢是传统的制氢方

收稿日期：2021-04-18; 定用日期：2021-06-17; DOI: 10.13550/j.jxhg.20210403
作者简介：吴浩飞（1997—），男，硕士生，E-mail：975598174@qq.com。联系人：江志东（1967—），男，副教授，E-mail：zdjiang@sjtu.
edu.cn。