生物质催化制备甲烷的反应路径和催化剂研究进展

doi:10.3969/j.issn.0253-2417.2019.03.001

林产化学与工业 ›› 2019, Vol. 39 ›› Issue (3): 1-9.doi: 10.3969/j.issn.0253-2417.2019.03.001

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生物质催化制备甲烷的反应路径和催化剂研究进展

蔡炽柳^1,^2,³,朱长辉^1,^2,³,王海永^1,^2,³,王晨光^1,^2,³,刘琪英^1,^2,^3,*(),马隆龙^1,^2,³

1. 中国科学院广州能源研究所, 广东广州 510640
2. 中国科学院可再生能源重点实验室, 广东广州 510640
3. 广东省新能源和可再生能源研究开发与应用重点实验室, 广东广州 510640

收稿日期:2019-02-20 出版日期:2019-06-28 发布日期:2019-06-26
通讯作者: 刘琪英 E-mail:liuqy@ms.giec.ac.cn
作者简介:蔡炽柳(1982-),男,福建漳州人,副研究员,博士,从事生物质催化转化化学品的研究
基金资助:
国家自然科学基金资助项目(51576199);国家重点研发计划资助项目(2018YFB1501402);广东省自然科学基金资助项目(2017A030308010)

Research Progress of Reaction Path and Catalysts Used in Catalytic Conversion Process of Biomass to Methane

Chiliu CAI^1,^2,³,Changhui ZHU^1,^2,³,Haiyong WANG^1,^2,³,Chenguang WANG^1,^2,³,Qiying LIU^1,^2,^3,*(),Longlong MA^1,^2,³

1. Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, China
2. CAS Key Laboratory of Renewable Energy, Guangzhou 510640, China
3. Guangdong Provincial Key Laboratory of New and Renewable Energy Research and Development, Guangzhou 510640, China

Received:2019-02-20 Online:2019-06-28 Published:2019-06-26
Contact: Qiying LIU E-mail:liuqy@ms.giec.ac.cn
Supported by:
国家自然科学基金资助项目(51576199);国家重点研发计划资助项目(2018YFB1501402);广东省自然科学基金资助项目(2017A030308010)

摘要/Abstract

摘要：

甲烷是氢碳比最高的烃，也是一种具有较高燃烧热值的清洁能源。在生物质制备甲烷的方法中，生物质发酵法和生物质合成气发酵法因活性菌的温度敏感性而受到限制。因此，本文介绍了近年来生物质合成气催化制备甲烷的反应机理及相应的催化剂体系研究进展，重点讨论了合成气中CO甲烷化和CO₂甲烷化反应机理，以及催化剂中活性成分、载体、助剂对甲烷化的影响。同时，介绍了反应条件温和的生物质催化水热法，简述了反应路线及近年来的研究现状。最后，从技术的角度对该甲烷化的反应机理和高效、稳定的催化剂研究进行了展望。

关键词: 生物质, 甲烷, 催化水热法

Abstract:

Methane is the hydrocarbon with highest hydrogen-carbon ratio, and is a kind of clean energy with high combustion calorific value as well. During the preparation of methane from biomass, biomass fermentation and biomass syngas fermentation are limited by the temperature sensitivity of active bacteria. This paper introduces the research progress of reaction mechanism and corresponding catalyst system of biomass synthesis gas to methane by chemical catalysts. The reaction mechanism of CO methanation and CO₂ methanation in syngas, as well as the effects of active ingredients, supports and promoters in catalysts on methanation are mainly discussed. At the same time, the catalytic hydrothermal method of biomass with mild reaction conditions is also introduced. The reaction route and research progress in recent years are briefly described. Finally, methanation reaction mechanism and efficient, stable catalysts are perspective remarked from the technical point of view.

Key words: biomass, methane, catalytic hydrothermal method

中图分类号:

TQ35

蔡炽柳,朱长辉,王海永,王晨光,刘琪英,马隆龙. 生物质催化制备甲烷的反应路径和催化剂研究进展[J]. 林产化学与工业, 2019, 39(3): 1-9.

Chiliu CAI,Changhui ZHU,Haiyong WANG,Chenguang WANG,Qiying LIU,Longlong MA. Research Progress of Reaction Path and Catalysts Used in Catalytic Conversion Process of Biomass to Methane[J]. Chemistry and Industry of Forest Products, 2019, 39(3): 1-9.

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催化剂¹⁾ catalyst	制备方法 preparation method	温度/℃ temperature	压力/MPa pressure	空速/(mL·g^-1·h^-1) space velocity	CO转化率/% CO conversion	甲烷选择性/% CH₄ selectivity	文献来源 literature
40%Ni/Al₂O₃	溶胶-凝胶法sol-gel	230	1	8160	96.5	76.8	[13]
4.2%Ni/SiC	浸渍法impregnation	500	3	4006	96.7	100	[14]
20%Ni-Mg/Al₂O₃	浸渍法impregnation	400	0.1	30000	100	80	[15]
23%Ni-TiO₂	超声波法ultrasonic	280	0.1	38800 h^-1	52	95	[16]
10%Ni/MCM-41	浸渍法impregnation	450	1.5	20745	61.4	77.5	[17]
10%Ni/MCM-41	水热法hydrothermal	350	0.1	12000	97.9	88.2	[18]
10%Ni-Mo/MCM-41	浸渍法impregnation	280	0.1	12000	100	80	[19]
30%Ni-10%Fe/Al₂O₃-AX	溶胶-凝胶法sol-gel	230	1	8160	99.4	86.8	[20]

催化剂¹⁾ catalyst	制备方法 preparation method	温度/℃ temperature	压力/MPa pressure	空速/(mL·g^-1·h^-1) space velicity	CO₂转化率/% CO₂ conversion	甲烷选择性/% CH₄ selectivity	文献来源 literature
10%Ni/Al₂O₃	浸渍法impregnation	400	0.1	7200	57.8	94	[21]
Ni/MSN	溶胶-凝胶法sol-gel	300	0.1	50000	64.1	99.9	[22]
15%Ni-TiO₂	沉积沉淀法deposition-precipitation	218	0.1	2400	50	99	[23]
Ni/CeO₂	硬模板法hard template	360	0.1	45000	91.1	100	[24]
Ni-Ru/Al₂O₃	共沉淀法coprecipitation	350	0.1	9000	70	—	[25]
Ru-CeO₂/Al₂O₃	浸渍法impregnation	300	0.1	10000	60	99	[26]
Ni/MC γ-Al₂O₃	浸渍法impregnation	300	0.1	9000	74	100	[27]
2%La-10%Ni/ γ-Al₂O₃	浸渍法impregnation	450	0.15	7200	70	95	[28]
Co_0.4Ni/SiO₂	浸渍法impregnation	300	0.1	13200	58	—	[29]
Pt/Zr₆O₄(OH)₄	浸渍法-双溶剂法impregnation-double solvent	350	0.1	1650	50	36	[30]

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生物质催化制备甲烷的反应路径和催化剂研究进展

Research Progress of Reaction Path and Catalysts Used in Catalytic Conversion Process of Biomass to Methane

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