镍基乙醇水汽重整催化剂:机理、失活与构效关系

doi:10.16085/j.issn.1000-6613.2017-0962

摘要/Abstract

摘要： 为了应对潜在的氢能利用需求，乙醇水汽重整反应受到了越来越多的关注。镍基催化剂因其高活性、高选择性以及成本优势而极具应用前景，同时在提高催化剂稳定性、降低反应温度、提高氢气收率等方面仍然有进一步发展的空间。更深入认识反应机理、失活机制和催化剂的构效关系是开发高效催化剂的关键。本文对近年来镍基乙醇重整催化剂的研究进展进行了整理总结，首先介绍了通过原位光谱、动力学以及理论计算等手段取得对反应中间物种与反应机理的新认识，分析了催化剂失活的主要原因，并且讨论了镍基催化剂的活性相、尺寸效应、助剂效应，双金属效应等问题，最后简单介绍了得益于基础研究进展的催化剂合成方面的成果，并提出对镍基乙醇水蒸气重整（ESR）剂未来发展的看法：在线/原位表征技术和理论计算将有助于真正理解镍基ESR催化剂的构效关系和反应机理，而新材料，如碳化钼的应用可能在提高催化剂反应性能方面起到作用。

关键词: 制氢, 乙醇水蒸气重整, 镍基催化剂, 反应机理, 失活, 双金属催化剂, 催化剂载体, 助剂

Abstract: According to the trend of hydrogen utilization, ethanol steam reforming reaction (ESR) have attracted more and more research interest. Nickel based ESR catalyst exhibits great potential for industrial application due to its high activity, selectivity and low cost. Nevertheless, there is still room for enhancing its stability, lowering the reaction temperature and increasing the yield of hydrogen. Comprehensive understanding of the reaction mechanism, deactivation mechanism and activitystructure relationship is necessary for preparing more efficient catalysts. Herein, the research progress of nickel based ESR catalyst has been reviewed. Firstly, new insights into reaction mechanism based on results of in-situ spectroscopy, kinetic analysis and theoretical calculation was introduced. Next, the reason for ESR catalyst deactivation was elucidated. Then we discussed the deactivation, active phase, size effect, promoter effect and bimetallic effect issues. Finally, the progress of novel catalysts arisen with the fundamental researches mentioned above was summarized in brief. Our perspective on the future development of nickel based ESR catalysts were presented. The operando/in-situ characterization methods are believed to bring in new understanding of the reaction mechanism and structure-activity relationship of nickel based catalysts, while the application of novel materials, such as molybdenum carbide, may prompt the catalytic properties of nickel based catalysts.

Key words: hydrogen production, ethanol steam reforming, nickel based catalyst, reaction mechanism, deactivation, bimetallic catalyst, catalyst support, promoter

中图分类号:

O643.3

赵华博, 李民, 罗刚. 镍基乙醇水汽重整催化剂:机理、失活与构效关系[J]. 化工进展, 2018, 37(02): 419-428.

ZHAO Huabo, LI Min, LUO Gang. Nickel based ethanol steam reforming catalysts: mechanism, deactivation and structure-activity relationship[J]. Chemical Industry and Engineering Progress, 2018, 37(02): 419-428.

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