化石燃料的使用，导致大量CO2温室气体排放，由此引起了一系列环境和气候问题。主要温室气体CO2和CH4的处理和利用已迫在眉睫。CH4-CO2干重整 (DRM) 将CO2和CH4转化为工业原料气合成气，可以实现2种温室气体的利用。贵金属催化剂对DRM反应表现出优异的催化活性和抗积碳性能，但由于资源有限、价格高，限制了其应用。非贵金属Ni基催化剂的催化活性不仅可以与贵金属相媲美，且来源丰富、价格低，是最有可能被产业化的催化剂之一。但Ni基催化剂存在易烧结和积碳的问题。研究者对Ni基催化剂进行了大量改性工作以提高其催化活性、抗烧结能力和抗积碳能力。为更全面深入认识DRM反应及其Ni基催化剂，首先综述了CH4-CO2重整反应的热力学、反应机理和动力学。热力学研究表明，高温低压有利于DRM反应进行；但至今没有适合于所有催化剂统一的反应机理，不同催化剂的反应机理和速控步骤不同。进一步对影响Ni基催化剂性能的载体、助剂、制备方法和焙烧温度主要因素进行分析，结果发现载体、助剂、制备方法和焙烧温度对催化剂活性组分的分散度、载体与活性组分的相互作用力和表面酸碱性有显著影响，进而影响催化剂的活性和稳定性。介绍了新型结构的Ni基干重整催化剂进展，发现新型结构催化剂的限域效应可以有效提高催化剂的抗烧结和抗积碳能力。最后，对Ni基DRM催化剂未来的研究方向进行了展望，为未来新型高效催化剂的设计和开发提供新的思路。

The use of fossil fuels leads to a large amount of CO2 greenhouse gas emissions,which has caused a series of environmental and climate problems. The treatment and utilization of the major greenhouse gases CO2 and CH4 have become urgent. CH4-CO2 dry reforming (DRM) converts CO2 and CH4 into syngas,an industrial feed gas,enabling the utilization of both greenhouse gases. Precious metal catalysts exhibit excellent catalytic activity and anti-coking performance for DRM reactions,but their applications are limited due to limited resources and high prices. The catalytic activity of non-precious metal Ni-based catalysts is not only comparable to that of noble metals,but also has abundant sources and low prices.It is one of the most likely to be industrialized catalysts. However,Ni-based catalysts have the problems of easy sintering and carbon deposition. Researchers have carried out a lot of modification work on Ni-based catalysts to improve their catalytic activity,anti-sintering ability and anti-carbon deposition ability. In order to gain a more comprehensive understanding of the DRM reaction and its Ni-based catalysts,the thermodynamics,reaction mechanism and kinetics of the CH4-CO2 reforming reaction were reviewed. Thermodynamic studies have shown that high temperature and low pressure are favorable for the DRM reaction;but so far there is no unified reaction mechanism suitable for all catalysts,and different catalysts have different reaction mechanisms and rate control steps. The main factors affecting the performance of Ni-based catalysts,such as carriers,additives,preparation methods and calcination temperature,were further analyzed. The interaction force and surface acidity and alkalinity have a significant effect,which in turn affects the activity and stability of the catalyst. The progress of Ni-based dry reforming catalysts with new structures was introduced. It is found that the confinement effect of the catalysts with new structures could effectively improve the anti-sintering and anti-coking abilities of the catalysts. Finally,the future research direction of Ni-based DRM catalysts was prospected.It provides new ideas for the design and development of new efficient catalysts in the future.

0 引言

1 DRM反应热力学

2 DRM反应动力学和机理研究

3 Ni基催化剂性能的影响因素

   3.1 载体的影响

   3.2 助剂的影响

   3.3 制备方法的影响

   3.4 焙烧温度的影响

4 新型催化材料结构对Ni基干重整催化剂性能的影响

5 结语与展望