炭材料在CH4-CO2重整反应中的研究进展Research progress on carbon materials in CH4-CO2 reforming
郭硕闻,孙映晖,李媖,许瞳,张国杰,张永发,白杰
GUO Shuowen,SUN Yinghui,LI Ying,XU Tong,ZHANG Guojie,ZHANG Yongfa,BAI Jie
摘要(Abstract):
双碳时代,CO_2的转化与利用成为研究热点。CH_4-CO_2重整反应在催化诱导合成气(CO和H_2)时同时利用这2种温室气体,并能通过费托合成解决气体燃料固有的存储和运输问题。CH_4-CO_2重整反应原料中,CH_4分子构型为正四面体,不易分解;CO_2是最小的非极性分子,■键断裂需较高能量。因此CH_4-CO_2重整反应需使用催化剂,且使用廉价、高效率的催化剂一直是研究重点。与无法兼具催化活性和稳定性的非贵金属相比,炭材料发达的孔隙结构能对活性金属进行分散和固定,部分生物质材料含有丰富的官能团,能提高反应气体的吸附和活化,从而提高催化剂的稳定性和抗积碳能力。总结了炭材料在CH_4-CO_2重整反应中的应用,分析了不同炭材料在提高催化剂抗烧结和抗积碳性能方面的作用机制。炭材料单独作催化剂时活性并不理想,将炭材料用作载体或对炭材料进行改性尤为重要。通过负载活性金属及助剂将炭材料的结构性质与金属的高活性相结合,而改性是通过不同化学试剂和方法丰富炭材料表面结构,优化炭材料的理化性质。杂原子掺杂改性能扩大炭材料孔隙优势、提高炭材料表面官能团含量。这2种方法结合得到改性炭材料载体,是当前炭材料催化剂研究热点。对炭材料改性既有利于金属的分散和锚固,又提高了载体与反应气体吸附和活化速率。本研究能够为催化CH_4-CO_2重整反应和炭质催化剂使用研究方向提供参考。
In dual carbon era, carbon dioxide emission reduction and conversion projects have been a current research hotspot. Methane carbon dioxide reforming is a catalytically induced syngas production process that utilizes both greenhouse gases simultaneously and converts them into syngas(carbon monoxide and hydrogen). The syngas produced by this reaction can be synthesized by Fischer-Tropsch to solve the inherent storage and transportation problems of gaseous fuels. Among the raw materials for the methane-carbon dioxide reforming reaction, the methane molecule has a regular tetrahedral configuration, which is not easy to decompose. Carbon dioxide is the smallest non-polar molecule, and high energy is required for ■ bond cleavage. Therefore, the methane carbon dioxide reforming reaction requires catalyst, and the use of inexpensive catalysts for reforming reactions that maximize synthesis gas production has been a focus of research. Non-precious metals are the best choices in current catalytic materials, but they cannot combine the activity and stability of catalysts. Different from metal catalysts, carbon materials have well-developed pore structures and some biomass materials contain rich functional groups, which can improve the adsorption and activation of reactive gases, and can also disperse and fix active metals, thereby improving the stability and anti-cokingability of catalysts. The application of carbon materials in CH_4-CO_2 reforming reaction was summarized, and the mechanism of different carbon materials in improving the anti-sintering and anti-coking properties of catalysts was analyzed. The activity of carbon material alone as a catalyst is not ideal, and the use of carbon material as a carrier or modification of carbon material can improve the catalytic performance of carbon material catalyst. When the carbon material is used as a carrier, the structural properties of the carbon material can be combined with the high activity of the metal by loading active metals and additives, and the activity and stability of the catalyst can be improved at the same time. Carbon material modification is to enrich the surface structure of carbon materials and optimize the physical properties of carbon materials through different chemical reagents and methods. Heteroatom doping modification can improve the catalytic performance of carbonaceous catalysts by expanding the pore advantage of carbon materials and increasing the content of functional groups on the surface of carbon materials. Combining these two methods to obtain a modified carbon material carrier is the latest research stage of carbon material catalyst, which is not only conducive to metal dispersion and anchoring, but also improves the adsorption and activation rate of the carrier and the reaction gases. The review can provide a reference for the research direction of catalytic methane dry reforming and the use of carbon catalysts.
关键词(KeyWords):
甲烷;二氧化碳;重整;炭材料;改性炭材料;碳转化;CO_2利用
methane;carbon dioxide(CO_2);reforming;carbon material;modified carbon material;carbon conversion;CO_2 utilization
基金项目(Foundation): 国家自然科学基金资助项目(21878200);; 内蒙古自然科学基金资助项目(2021BS02010);; 内蒙古教育厅资助项目(JY20220150);; 内蒙古工业大学校基金资助项目(ZZ202009,BS2021026)
作者(Author):
郭硕闻,孙映晖,李媖,许瞳,张国杰,张永发,白杰
GUO Shuowen,SUN Yinghui,LI Ying,XU Tong,ZHANG Guojie,ZHANG Yongfa,BAI Jie
DOI: 10.13226/j.issn.1006-6772.CH22052201
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- 甲烷
- 二氧化碳
- 重整
- 炭材料
- 改性炭材料
- 碳转化
- CO_2利用
methane - carbon dioxide(CO_2)
- reforming
- carbon material
- modified carbon material
- carbon conversion
- CO_2 utilization