化工进展 ›› 2022, Vol. 41 ›› Issue (11): 5870-5878.DOI: 10.16085/j.issn.1000-6613.2022-0026

• 工业催化 • 上一篇    下一篇

有序介孔CuCoZr催化剂的制备及其催化合成气制乙醇及高级醇性能

刘瑞琴1(), 孟凡会1(), 王立言2, 张鹏1, 张俊峰2, 谭猗生2, 李忠1()   

  1. 1.太原理工大学省部共建煤基能源清洁高效利用国家重点实验室, 山西 太原 030024
    2.中国科学院山西煤炭化学研究所煤转化国家重点实验室, 山西 太原 030001
  • 收稿日期:2022-01-05 修回日期:2022-03-10 出版日期:2022-11-25 发布日期:2022-11-28
  • 通讯作者: 孟凡会,李忠
  • 作者简介:刘瑞琴(1995—),女,硕士研究生,研究方向为合成气催化转化。E-mail: liuruiqin333@163.com
  • 基金资助:
    国家自然科学基金重点项目(U1510203);山西省自然科学基金(202103021224073);山西省重点研发计划项目(国际科技合作)(201803D421011)

Preparation of ordered mesoporous CuCoZr catalyst and its catalytic performance for syngas to ethanol and higher alcohols

LIU Ruiqin1(), MENG Fanhui1(), WANG Liyan2, ZHANG Peng1, ZHANG Junfeng2, TAN Yisheng2, LI Zhong1()   

  1. 1.State Key Laboratory of Clean and Efficient Coal Utilization, Taiyuan University of Technology, Taiyuan 030024, Shanxi, China
    2.State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, Shanxi, China
  • Received:2022-01-05 Revised:2022-03-10 Online:2022-11-25 Published:2022-11-28
  • Contact: MENG Fanhui, LI Zhong

摘要:

改性费托合成催化剂(尤其是CuCo催化剂)在合成气制乙醇及高级醇反应中具有高的催化活性和总醇选择性,被认为是潜在的工业催化剂。采用蒸发诱导自组装(EISA)法和共沉淀(CP)法制备了一系列CuCoZr催化剂,考察了制备方法及EISA法制备的催化剂Cu/Co原子比对合成气制乙醇及高级醇性能的影响。采用N2物理吸附-脱附、小角X射线衍射(XRD)原位XRD、透射电镜(TEM)、H2-程序升温还原(TPR)、CO-程序升温脱附(TPD)和原位红外漫反射光谱(DRIFT)对催化剂进行表征,分析了合成气在Cu/Co原子比为3∶1的Cu3Co1Zr催化剂表面的反应路径。结果表明,EISA法制备的CuCoZr催化剂为有序介孔结构,比表面积随Cu/Co原子比的增加先增大后减小,其中Cu3Co1Zr催化剂比表面积和CO吸附量均为最大,分别为143m2/g和0.33mmol/g,催化剂的Cu晶粒尺寸仅为9.1nm。在催化合成气制醇的反应中CO转化率达到74.9%,总醇中的高级醇时空收率达到75.2mg/(gcat·h),乙醇物质的量分数为31.0%,明显优于共沉淀法制备的组成相同的CuCoZr-CP催化剂。

关键词: 合成气, 加氢, 乙醇, 高级醇, 催化剂, 制备方法, 介孔结构

Abstract:

Modified Fischer-Tropsch catalysts, especially the CuCo catalyst, are potential industrial catalysts for ethanol and higher alcohols production from syngas, due to their high catalytic activity and total alcohols selectivity. A series of CuCoZr catalysts were prepared by evaporation-induced self-assembly (EISA) and co-precipitation (CP) method. The effect of preparation method and Cu/Co atomic ratio of EISA catalyst on its catalytic performance of ethanol and higher alcohols synthesis from syngas were investigated. The catalysts were characterized by N2 physical adsorption-desorption, small-angle XRD, in-situ XRD, TEM, H2-TPR, CO-TPD and in-situ DRIFT, and the reaction path of syngas on Cu3Co1Zr catalyst with Cu/Co atomic ratio of 3∶1 was analyzed. The results showed that CuCoZr catalyst prepared by EISA method possessed ordered mesoporous structure, and the specific surface area increased firstly and then decreased as the Cu/Co ratio. Cu3Co1Zr catalyst showed the largest specific surface area and CO adsorption capacity, which were 143m2/g and 0.33mmol/g, respectively. Moreover, the crystalline size of Cu was only 9.1nm. During the catalytic reaction, Cu3Co1Zr catalyst gave a CO conversion of 74.9% and a higher alcohol yield of 75.2mg/(gcat·h) with ethanol mole fraction of 31.0%, much better than those given by the co-precipitated CuCoZr-CP catalyst with the same composition.

Key words: syngas, hydrogenation, ethanol, higher alcohols, catalyst, preparation method, mesoporous structure

中图分类号: 

京ICP备12046843号-2;京公网安备 11010102001994号
版权所有 © 《化工进展》编辑部
地址:北京市东城区青年湖南街13号 邮编:100011
电子信箱:hgjz@cip.com.cn
本系统由北京玛格泰克科技发展有限公司设计开发 技术支持:support@magtech.com.cn