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Research progress in carbon deposition resistance of nickel-basedcatalysts for carbon dioxide reforming of methane

2022 No. 05
777
755
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Authors:
MA Qingxiang
ZHANG Jing
WANG Yijie
LYU Linghui
FAN Hui
ZENG Chunyang
ZHAO Tiansheng
Unit:
State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering,Ningxia University;China Petroleum and Chemical Industry Federation
Abstract:

Global warming caused by the greenhouse effect poses a serious threat to the human living environment. Dry reforming of methane (DRM) reaction uses two major greenhouse gases as feedstock to produce syngas with H2/CO molar ratio close to 1 while consuming methane and carbon dioxide,making it an ideal feedstock for Fischer-Tropsch synthesis to produce liquid fuels or high value chemicals. Nickel-based catalysts are the most widely used catalysts for DRM reaction,but they are prone to deactivation due to sintering and carbon accumulation under high temperature,hindering their industrial application. In view of the inactivation of nickel-based catalysts due to carbon deposition,thermodynamics and reaction mechanisms of DRM reactions were reviewed,carbon deposition inactivation mechanisms was analysed,and catalyst active components,supports,auxiliaries and preparation methods were discussed. Thermodynamic analysis of DRM reaction shows that high temperature and low pressure favor a shift in equilibrium towards syngas production. Reverse water-gas shift reaction consumes CO2 from the feedstock to produce CO,so in general the CO2 conversion rate is higher than the CH4 conversion rate,and the H2/CO molar ratio is less than 1. At a reaction temperature of 557-700 ℃,the carbon deposition mainly comes from the carbon monoxide disproportionation reaction and the methane cracking reaction. Reaction temperature above 700 ℃ are not conducive to carbon monoxide disproportionation reactions and carbon deposition will mainly originate from methane cracking reaction. Amorphous carbon can be eliminated by hydrogen or oxygenated species at temperatures below 573 K. On the other hand,graphite carbon requires gasification at higher temperature to be eliminated and it is the main cause of catalyst deactivation. Increasing the CO2/CH4 molar ratio in the feed gas or adding water vapour or oxygen to the feed gas can reduce carbon deposition to some extent,but to solve the problem of carbon accumulation is the study of catalysts. Bimetallic nickel-based catalysts form alloys at certain ratios,which act synergistically in the activation of CH4 and the decarbonisation process. The limiting effect of the mesopore structure in support allows the nickel particles to be present in the catalyst pores as much as possible,which helps to reduce the size of nickel metal particles and to enhance the metal-support interaction to a certain extent,thus improving the catalytic activity and resistance to carbon depositionn in the DRM reaction. Supports with special redox properties and extraordinary oxygen storage capacity (OSC) can use oxygen vacancies to facilitate the activation and dissociation of CO2,reducing catalyst deactivation due to carbon deposition by oxidation of surface carbon to CO. The use of alkaline supports or auxiliaries can increase the catalyst alkalinity appropriately so that the carbon deposition rate of the methane cracking reaction is comparable to the carbon elimination reaction rate,thereby reducing carbon accumulation. New catalyst preparation methods,reaction process enhancement and reaction process coupling can all be effective in reducing and eliminating reaction carbon accumulation. Studies show that appropriate modifications to the composition and structure of catalyst can significantly improve the resistance of the catalyst to carbon accumulation in the DRM reaction.

Keywords:
methane
carbon dioxide
reforming
nickel-based catalyst
inactivation
carbon deposition resistance
Citation format:
马清祥(1980—),男,宁夏西吉人,研究员,硕士生导师。E-mail:maqx@nxu.edu.cn
通讯作者:赵天生(1968—),男,河南安阳人,教授,博士生导师,博士。E-mail:zhaots@nxu.edu.cn
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    SHI Yixiang
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