化工进展 ›› 2015, Vol. 34 ›› Issue (10): 3644-3649,3736.DOI: 10.16085/j.issn.1000-6613.2015.10.019

• 能源加工与技术 • 上一篇    下一篇

铜基催化剂催化乙酸甲酯加氢制燃料乙醇实验研究

李洪1,2,3, 黄伟进1, 肖财春1, 从海峰1, 高鑫1,2,3, 李鑫钢1,2,3   

  1. 1 天津大学化工学院, 天津 300072;
    2 精馏技术国家工程研究中心, 天津 300072;
    3 天津化学化工协同创新 中心, 天津 300072
  • 收稿日期:2015-03-06 修回日期:2015-03-23 出版日期:2015-10-05 发布日期:2015-10-05
  • 通讯作者: 高鑫,副教授。E-mailgaoxin@tju.edu.cn。
  • 作者简介:李洪(1980—),副研究员。E-maillihong.tju@163.com。
  • 基金资助:

    国家高技术研究发展计划(2015AA030501)及国家自然科学基金(21336007)项目。

Experimental study on hydrogenation of methyl acetate to fuel ethanol with copper-based catalyst

LI Hong1,2,3, HUANG Weijin1, XIAO Caichun1, CONG Haifeng1, GAO Xin1,2,3, LI Xingang1,2,3   

  1. 1 School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China;
    2 National Engineering Research Centre of Distillation Technology, Tianjin 300072, China;
    3 Collaborative Innovation Center of Chemical Science and Engineering Tianjin, Tianjin 300072, China
  • Received:2015-03-06 Revised:2015-03-23 Online:2015-10-05 Published:2015-10-05

摘要: 研究考察了实验室制备的铜基催化剂对乙酸甲酯(MeOAc)催化加氢的催化性能,结果表明Cu/ZnO催化剂效果较差,而添加Al元素的Cu-ZnO/Al2O3催化剂效果较好。同时采用单管反应器研究了MeOAc催化加氢制乙醇的反应性能,采用30~60目Cu-ZnO/Al2O3(Ⅱ)催化剂,通过实验考察了温度、空速、进料配比和压力4个因素对反应活性和选择性的影响。结果表明,反应温度230℃,高H2/MeOAc配比和低空速有利于反应,考察的压力范围对反应影响不显著,获得的最高转化率达0.954,对应的选择性为0.974,而获得的最高选择性达0.989,对应的转化率为0.920,具有工业开发价值。对于难分离的甲醇和乙酸乙酯,提出了低温分离的气相色谱方法,具有很好的基线分离效果。

关键词: 乙酸甲酯, 燃料乙醇, 铜基催化剂, 加氢, 色谱分析

Abstract: Different copper-based catalysts manufactured in laboratory were evaluated in hydrogenation of methyl acetate to ethanol. The Cu-ZnO/Al2O3 catalyst was good but the Cu/ZnO catalyst was not. Methyl acetate hydrogenation over Cu-ZnO/Al2O3(Ⅱ)(30~60 mesh) was studied in a tubular reactor, and the influences of reaction temperature, space velocity, feed molar ratio and pressure factor were studied through orthogonal experiments. Reaction temperature of 230℃, higher ratio of H2/methyl acetate, lower space velocity were beneficial to the reaction, the effect of reaction pressure in the range of investigation was not significant. The highest conversion was up to 0.954, its corresponding selectivity was 0.974, while the highest selectivity was up to 0.989, and its corresponding conversion was 0.920. Gas chromatography at low temperature was used to analyze methanol and ethyl acetate, which were difficult to separate, and achieved perfect baseline separation.

Key words: methyl acetate, fuel ethanol, copper-based catayst, hydrogenation, chromatographic analysis

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