煤基合成气甲烷化用镍基催化剂失活热力学和抗失活预测

doi:10.16085/j.issn.1000-6613.2016.11.019

化工进展 ›› 2016, Vol. 35 ›› Issue (11): 3511-3518.DOI: 10.16085/j.issn.1000-6613.2016.11.019

煤基合成气甲烷化用镍基催化剂失活热力学和抗失活预测

张旭¹, 王子宗¹, 陈建峰²

1. 中国石化工程建设有限公司, 北京 100101;
2. 北京化工大学化学工程学院, 北京 100029

收稿日期:2016-01-25 修回日期:2016-03-27 出版日期:2016-11-05 发布日期:2016-11-05
通讯作者: 张旭(1983-),男,博士。E-mail:zx20032974@163.com。
作者简介:张旭(1983-),男,博士。E-mail:zx20032974@163.com。

Thermodynamic analysis of coal-based syngas methanation deactivation and anti-inactivation on nickel-based catalyst

ZHANG Xu¹, WANG Zizong¹, CHEN Jianfeng²

1. Sinopec Engineering Incorporation, Beijing 100101, China;
2. School of Chemical Engineering, Beijing University of Chemical Technology, Beijing 100029, China

Received:2016-01-25 Revised:2016-03-27 Online:2016-11-05 Published:2016-11-05

摘要/Abstract

摘要： 利用热力学数据对煤基合成气甲烷化用镍基催化剂硫中毒以及积炭热力学进行了详细的计算。计算发现，活性金属Ni、Mo在甲烷化反应条件下与H₂S、COS发生反应是自发进行的过程。10^-10数量级分压的H₂S含量、10^-14数量级分压的COS含量即可使镍金属活性组分生成硫化镍而使催化剂失活；当Mo作为助剂添加到Ni基催化剂时，硫含量不能超过10^-6数量级。不同温度区间发生的积炭反应类型不同，当温度为633.15～898.15K时，积炭反应主要以CO歧化反应、CO还原反应为主；898.15～983.15K时以CH₄裂解反应为主。另外，在0.1MPa下，添加摩尔分数为11.11%及以上含量水蒸气可以避免积炭。

关键词: 甲烷化反应, 热力学, 失活, 积炭, 催化剂, 抗中毒性

Abstract: Thermodynamics of sulfur poisoning and coking on nickel-based catalyst for coal-based synthesis gas methanation were systematically analyzed. It was found that the reactions of the active metal Ni, Mo with H₂S, COS were spontaneous under the methanation reaction condition. The Ni-based catalysts could be poisoned by H₂S, COS at a partial pressure magnitude of 10^-10 and 10^-14, respectively, and the sulfur content for Mo added catalysts could be no more than 10^-6. Different types of coking reactions occurred at different temperature ranges, and the carbon deposition was mainly from the CO disproportionation reaction and the CO reduction reaction when temperature was 633.15—898.15K, while that was mainly from CH₄cracking reaction when temperature was 898.15—983.15K. In addition, Ni-based catalysts could avoid carbon deposition at 0.1MPa by adding water vapor with the amount above 11.11% (mole fraction).

Key words: methanation, thermodynamics, deactivation, carbon deposition, catalysts, anti-inactivation

中图分类号:

张旭, 王子宗, 陈建峰. 煤基合成气甲烷化用镍基催化剂失活热力学和抗失活预测[J]. 化工进展, 2016, 35(11): 3511-3518.

ZHANG Xu, WANG Zizong, CHEN Jianfeng. Thermodynamic analysis of coal-based syngas methanation deactivation and anti-inactivation on nickel-based catalyst[J]. Chemical Industry and Engineering Progress, 2016, 35(11): 3511-3518.

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煤基合成气甲烷化用镍基催化剂失活热力学和抗失活预测

Thermodynamic analysis of coal-based syngas methanation deactivation and anti-inactivation on nickel-based catalyst

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