Page 134 - 《精细化工》2021年第5期

第 38 卷第 5 期 精 细 化 工 Vol.38, No.5
202 1 年 5 月 FINE CHEMICALS May 2021

催化与分离提纯技术
水热法制备 Cu-ZnO 纳米催化剂用于乙酸乙酯加氢

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鲁 旖，吴浩飞，江志东
（上海交通大学 化学化工学院，上海 200240）

摘要：以六水合硝酸锌、三水合硝酸铜、尿素为原料，采用水热法制备了不同铜锌物质的量比 n（n=1/4、3/7、
2/3、1 和 3/2，对应铜摩尔分数分别为 20%、30%、40%、50%和 60%）的铜-氧化锌催化剂，用 SEM、XRD、
H 2 -TPR、BET 等方法对铜-氧化锌催化剂进行了结构表征。研究了铜摩尔分数对催化剂形貌及乙酸乙酯加氢反应
的影响。结果表明，水热法制得的铜-氧化锌催化剂均为纳米片自组装成的开放型纳米花结构。当铜摩尔分数为
40%时，纳米片厚度小于 50 nm，纳米花直径约 10 μm，乙酸乙酯转化率最高，铜摩尔分数过低或过高时加氢活
性下降。表征发现，铜摩尔分数为 40%的催化剂中铜与氧化锌的结合强度适中，活性位分散均匀。考察了水热
条件对催化性能的影响，在最优水热条件（130 ℃、10 h）下合成的催化剂乙酸乙酯转化率达到 94%〔加氢反
应条件为 220 ℃、氢气压力 3 MPa、氢气与乙酸乙酯物质的量比 20、液时空速 2.0 g 酯/(g 催化剂·h)〕。在催化剂
稳定性（300 h）测试中乙酸乙酯转化率保持在 92%以上。
关键词：乙酸乙酯；乙醇；催化加氢；铜-氧化锌催化剂；水热法；纳米花自组装；催化技术
中图分类号：TQ426.94 文献标识码：A 文章编号：1003-5214 (2021) 05-0988-06

Hydrothermal synthesis of Cu-ZnO catalysts for
hydrogenation of ethyl acetate

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LU Yi, WU Haofei, JIANG Zhidong
（School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China）

Abstract: Cu-ZnO catalysts with different Cu-Zn molar ratios (n=1/4, 3/7, 2/3, 1 and 3/2, corresponding to
copper molar fraction of 20%, 30%, 40%, 50% and 60%) were prepared by hydrothermal method using zinc
nitrate hexahydrate, copper nitrate trihydrate and urea. The structure of Cu-ZnO catalysts was characterized
by SEM, XRD, H 2-TPR and BET techniques. The effects of copper molar fraction on the morphology of
catalyst and hydrogenation of ethyl acetate were studied. The results showed that the prepared Cu-ZnO
catalysts were open nanometer flower structures which are self-assembled by nanometer sheets. When the
copper molar fraction was 40%, the thickness of the nanosheet was less than 50 nm, the diameter of the
nanoflower was about 10 μm, and ethyl acetate had the highest conversion rate. When the molar fraction of
copper was too high or too low, the hydrogenation activity of ethyl acetate decreased. It was found that the
binding strength of Cu and ZnO was moderate and the active sites were well dispersed in the catalyst with
copper molar fraction of 40%. The effects of hydrothermal conditions on the catalytic performance were
investigated. The optimal hydrothermal conditions for the preparation of were Cu-ZnO catalyst as follows:
temperature 130 ℃ and reaction time of 10 h. The conversion rate of ethyl acetate reached 94% under the
conditions of reaction temperature of 220 ℃, hydrogen pressure of 3 MPa, molar ratio of hydrogen to ethyl
acetate of 20, liquid hourly space velocity of 2.0 g ethyl acetate/(g catalyst·h). The conversion rate of ethyl
acetate remained above 92% in the stability test of catalyst (300 h).
Key words: ethyl acetate; ethanol; catalytic hydrogenation; Cu-ZnO catalysts; hydrothermal synthesis;
self-assembled nanoflowers; catalysis technology

收稿日期：2020-11-05; 定用日期：2020-12-25; DOI: 10.13550/j.jxhg.20201034
作者简介：鲁 旖（1995—），女，硕士生，E-mail：342636815@qq.com。联系人：江志东（1967—），男，副教授，E-mail：zdjiang@sjtu.edu.cn。