低温耐硫甲烷化催化剂硫化过程

doi:10.11949/j.issn.0438-1157.20171143

化工学报 ›› 2018, Vol. 69 ›› Issue (1): 396-404.DOI: 10.11949/j.issn.0438-1157.20171143

• 催化、动力学与反应器 • 上一篇下一篇

低温耐硫甲烷化催化剂硫化过程

王玮涵, 张晓珊, 李振花, 王保伟, 马新宾

天津大学化工学院, 绿色合成与转化教育部重点实验室, 天津 300072

收稿日期:2017-08-20 修回日期:2017-10-12 出版日期:2018-01-05 发布日期:2018-01-05
通讯作者: 马新宾
基金资助:
国家高技术研究发展计划项目（2015AA050504）；国家自然科学基金项目（21606167，21576203）。

Sulfidation effect on low temperature sulfur-resistant methanation catalyst

WANG Weihan, ZHANG Xiaoshan, LI Zhenhua, WANG Baowei, MA Xinbin

Key Laboratory for Green Chemical Technology of Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China

Received:2017-08-20 Revised:2017-10-12 Online:2018-01-05 Published:2018-01-05
Contact: 10.11949/j.issn.0438-1157.20171143
Supported by:
supported by the National High Technology Research and Development Program (2015AA050504) and the National Natural Science Foundation of China (21606167, 21576203).

摘要/Abstract

摘要：

采用燃烧法制备MoO₃/ZrO₂催化剂，该催化剂由于具有比表面积大、粒径小的优点，表现出很高的低温耐硫甲烷化活性。通过考察硫化工艺条件的影响发现，硫化过程中硫化时间、硫化压力、硫化氢浓度的影响不大，而硫化温度的影响较明显，300℃下恒温硫化效果最佳，表征结果表明，300℃下恒温硫化可以使催化剂完全硫化，得到较多的MoS₂晶格条纹，有利于提高催化剂的甲烷化活性。恒温硫化时，硫化温度低于300℃时，催化剂硫化不完全，形成的MoS₂晶格条纹较少；硫化温度过高会导致催化剂过度硫化并发生团聚，从而导致催化剂的耐硫甲烷化活性降低。分步硫化时目标温度为400℃时效果最佳，且与300℃恒温硫化的效果接近，对于MoO₃/ZrO₂催化剂，可选择300℃恒温硫化，适宜的硫化条件为：硫化压力0.1 MPa，硫化温度300℃，硫化氢浓度3% H₂S/H₂，硫化时间4 h。

关键词: 低温, 硫化, 催化剂, 甲烷, 一氧化碳, 氧化钼

Abstract:

MoO₃/ZrO₂ catalyst, which prepared by solution combustion method, achieved the highest CO methanation activity due to its high surface area and effective MoO₃ dispersion on ZrO₂ support. By study of sulfidation process on methanantion activity, it was found that sulfidation pressure, time and H₂S concentration had little effect but sulfidation temperature had significant effect. For one-step constant temperature sulfidation process, the optimum sulfidation temperature was 300℃. Catalyst characterization showed that isothermal sulfidation at 300℃ produced catalyst with complete sulfidation and many MoS₂ crystalline, which is helpful to improve methanation activity. Isothermal sulfidation below 300℃ yielded catalyst with incomplete sulfidation and fewer amounts of MoS₂ crystalline while isothermal sulfidation above 300℃ resulted aggregation of MoS₂ crystalline, which will deteriorate MoO₃/ZrO₂ catalyst. For stepwise sulfidation process, the optimum sulfidation temperature was 400℃, which resulted catalyst with nearly same methanation activity as that of one-step isothermal sulfidation at 300℃. Therefore, the suitable sulfidation condition for MoO₃/ZrO₂ catalyst is determined as 0.1 MPa, isothermal 300℃, 3% H₂S/H₂, and time 4 h.

Key words: low temperature, sulfur-resistant, catalyst, methane, CO, MoO₃

中图分类号:

TQ221.1

王玮涵, 张晓珊, 李振花, 王保伟, 马新宾. 低温耐硫甲烷化催化剂硫化过程[J]. 化工学报, 2018, 69(1): 396-404.

WANG Weihan, ZHANG Xiaoshan, LI Zhenhua, WANG Baowei, MA Xinbin. Sulfidation effect on low temperature sulfur-resistant methanation catalyst[J]. CIESC Journal, 2018, 69(1): 396-404.

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低温耐硫甲烷化催化剂硫化过程

Sulfidation effect on low temperature sulfur-resistant methanation catalyst

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