醋酸或醋酸酯加氢制乙醇的热力学计算与分析

摘要

对醋酸、醋酸甲酯或醋酸乙酯加氢制乙醇进行了热力学计算和分析。计算了这3个反应的标准摩尔焓变和标准平衡常数，以及温度、压力和反应物配比对平衡转化率的影响。结果表明，3个反应的标准摩尔焓变都小于0，是放热反应；醋酸加氢反应的标准平衡常数较大，而醋酸甲酯加氢反应和醋酸乙酯加氢反应的标准平衡常数都小于0.7；醋酸加氢反应由于标准平衡常数较大，因此其平衡转化率受工艺条件影响较小，而醋酸甲酯加氢和醋酸乙酯加氢反应的平衡转化率受工艺条件的影响较大，醋酸酯加氢制乙醇反应适宜的温度为423~550 K，适宜的压力是2~3 MPa，适宜的氢酯比是10~20。

	Service

	把本文推荐给朋友
	加入我的书架
	加入引用管理器
	Email Alert
	RSS
	作者相关文章
	孙成伟
	郭翠梨
	叶陈良

关键词：醋酸；醋酸酯；加氢；乙醇；热力学

Abstract：

The thermodynamics of hydrogenation of acetic acid or acetic ester to ethanol had been analyzed. The enthalpy changes and the standard equilibrium constants of the three reactions were calculated. The effects of temperature, pressure and the molar ratio of reagents on the equilibrium conversion of acetic acid or acetic ester were researched. The result shows that all the enthalpy changes of the three reactions are less than 0, so the reactions are exothermic. The reaction conditions can not make a great influence on the conversion of acetic acid, because the standard equilibrium constant is comparatively large. However, the reaction conditions make a great effect on the conversion of acetic esters due to their small standard equilibrium constants. For the hydrogenation of acetic ester to ethanol, the suitable reaction temperature is 423-550 K and the suitable reaction pressure is 2-3 MPa and the suitable molar ratio of hydrogen and acetic ester is 10-20.

Keywords： acetic acid； acetic ester； hydrogenation； ethanol； thermodynamic

Received 2015-04-09;

Corresponding Authors: 郭翠梨,E-mail:gcl@tju.edu.cn。 Email: gcl@tju.edu.cn

About author: 孙成伟(1989-),男,硕士研究生,现从事多相催化反应的研究。

引用本文:

孙成伟, 郭翠梨, 叶陈良.醋酸或醋酸酯加氢制乙醇的热力学计算与分析[J]. 化学工业与工程, 2017,34(2): 45-49,95

Sun Chengwei, Guo Cuili, Ye Chenliang.Thermodynamic Calculation and Analysis of Hydrogenation of Acetic Acid or Acetic Ester to Ethanol[J]. Chemcial Industry and Engineering, 2017,34(2): 45-49,95

[1] 李振宇,黄格省,杨延翔,等. 燃料乙醇生产技术路线分析及产业发展建议[J]. 现代化工, 2011, 31(8):1-5 Li Zhenyu, Huang Gesheng, Yang Yanxiang, et al. Analysis and development proposal on fuel grade alcohol production technique process[J]. Modern Chemical Industry, 2011, 31(8):1-5(in Chinese)
[2] 孙陆晶. 燃料乙醇产业前景[J]. 化学工业, 2011, 29(1):8-11 Sun Lujing. Alcohol fuel industry prospect[J]. Chemical Industry, 2011, 29(1):8-11(in Chinese)
[3] 周颖霏, 钱伯章. 醋酸生产技术进展及市场分析[J]. 化学工业, 2010, 28(9):19-45 Zhou Yingfei, Qian Bozhang. Process technology of acetate acid and market analysis[J]. Chemical Industry, 2010, 28(9):19-45(inChinese)
[4] Claus P, Lucas M, Liicke B. Selective hydrogenolysis of methyl and ethyl acetate in the gas phase on copper and supported Group VIII metal catalysts[J]. Appl Catal A, 1991, 79(1):1-18
[5] Scheur F T V D, Staal L H. Effects of zinc addition to silica supported copper catalysts for the hydrogenolysis of esters[J]. Appl Catal A, 1994, 108(1):63-83
[6] Brands D S, Poels E K, Bliek A. Ester hydrogenolysis over promoted Cu/SiO₂catalysts[J]. Appl Catal A, 1999, 184(2):279-289
[7] 雷陈明, 顾顺超, 阎建民, 等. Cu/SiO₂的表征及其在乙酸乙酯加氢合成乙醇中的催化性能[J]. 石油化工, 2013, 42(6):615-619 Lei Chenming, Gu Shunchao, Yan Jianmin, et al. Characterization of Cu/SiO₂ catalyst and its performance in hydrogenation of ethyl acetate to ethanol[J]. Petrochemical Technology, 2013, 42(6):615-619(in Chinese)
[8] 尹安远,戴维林,范康年. 草酸二甲酯催化加氢合成乙二醇过程的热力学计算与分析[J]. 石油化工, 2008, 37(1):62-66 Yin Anyuan, Dai weilin, Fan Kangnian. Thermodynamics of ethylene glycol synthesis via hydrogenation of dimethyl oxalate[J]. Petrochemical Technology, 2008, 37(1):62-66(in Chinese)
[9] 左玉帮,刘永健,李江涛,等. 合成气甲烷化制替代天然气热力学分析[J]. 化学工业与工程, 2011, 28(6):47-53 Zuo Yubang, Liu Yongjian, LI Jiangtao, et al. Thermodynamic analysis for methanation of synthesis gas to substitute natural gas[J]. Chemcial Industry and Engineering, 2011, 28(6):47-53(in Chinese)
[10] Natal-Santiago M A, Sanchez-Castillo M A, Cortright R D, et al. Catalytic reduction of acetic acid, methyl acetate, and ethyl acetate over silica-supported copper[J]. Journal of Catalysis, 2000, 193(1):16-28
[10] 马沛生, 李永红. 化工热力学[M]. 第2版. 北京:化学工业出版社, 2009
[11] 刘业奎, 王黎, 侯栋, 等. 二氧化碳加氢合成低碳烯烃反应平衡体系热力学研究[J]. 催化学报, 2004, 25(3):210-218 Liu Yekui, Wang Li, Hou Dong, et al. Study on thermodynamics of balanceable reaction system for hydrogenation of carbon dioxide to light alkenes[J]. Chinese Journal of Catalysis, 2004, 25(3):210-218(in Chinese)
[12] 刘俊吉,周亚平,李松林. 物理化学[M]. 北京:高等教育出版社, 2009