Recently progress of Ni and Co-based catalysts for hydrogen production from ethanol

doi:10.16085/j.issn.1000-6613.2020-1733

Abstract

Abstract:

Hydrogen production from ethanol has the advantages of environmental friendliness, cleanliness, and sustainability. The key to this technology is the appropriate catalyst. Compared with noble metal catalysts, the Ni-based and Co-based catalysts have advantages of low cost and high activity and have become a research hotspot in recent years. However, there are still some problems in the process of ethanol steam reforming with the Ni-based and Co-based catalysts, such as poor stability, low catalytic activity at low temperature and short life time. Therefore, this paper firstly introduces the mechanism of hydrogen production from ethanol. Based on the types of support and the alloying modification of active catalyst nanoparticles, we then reviews the recent research results of Ni-based and Co-based catalysts for hydrogen production from ethanol steam reforming. Thereafter the methods to improve the performance of the catalysts are summarized. Finally, the future development direction of Ni-based and Co-based catalysts is prospected, which provides ideas for the preparation of Ni-based and Co-based catalysts with small particle size, high low-temperature catalytic activity and good stability.

Key words: ethanol, hydrogen production, nickel, cobalt, catalyst, support

摘要：

乙醇制氢具有环保、清洁、可持续等优点，其关键在于选择合适的催化剂。相较于贵金属催化剂而言，Ni与Co基催化剂因其具有成本低且活性高的优点，近年来在乙醇催化制氢中逐渐成为研究热点。然而Ni与Co基催化剂在催化乙醇水蒸气重整制氢的过程中仍存在着稳定性较差、低温催化活性低和使用寿命较短等问题。本文介绍了乙醇制氢的机理，围绕载体的类型及催化剂活性纳米颗粒的合金化改性，综述了近年来Ni与Co基催化剂催化乙醇水蒸气重整制氢的研究现状，总结了提高催化剂性能的方法及措施，并展望了Ni与Co基催化剂未来的发展方向，为颗粒尺寸小且低温催化活性高、稳定性好的Ni与Co基催化剂的制备提供思路。

关键词: 乙醇, 制氢, 镍, 钴, 催化剂, 载体

CLC Number:

O643.3

GUO Junyan, ZHANG Haijun, DUAN Hongjuan, LI Xiaojian, LIU Xin, HAN Lei. Recently progress of Ni and Co-based catalysts for hydrogen production from ethanol[J]. Chemical Industry and Engineering Progress, 2021, 40(7): 3772-3784.

郭俊艳, 张海军, 段红娟, 李孝建, 刘鑫, 韩磊. Ni与Co催化乙醇制氢研究进展[J]. 化工进展, 2021, 40(7): 3772-3784.

Figures/Tables 7

化学反应	反应方程式		编号
乙醇脱氢反应	C₂H₅OH $→$ CH₃CHO+H₂	? $H r, 298 ?$ =68.9kJ/mol	（4）
乙醇分解反应	C₂H₅OH $→$ H₂+CO+CH₄	? $H r, 298 ?$ =49.6kJ/mol	（5）
乙醛水蒸气重整	CH₃CHO+H₂O $→$ 2CO+3H₂	? $H r, 298 ?$ =186.8kJ/mol	（6）
水煤气变换反应	CO+H₂O $→$ CO₂+H₂	? $H r, 298 ?$ =-41.4kJ/mol	（7）
甲烷水蒸气重整	CH₄+H₂O $→$ CO+3H₂	? $H r, 298 ?$ =206.1kJ/mol	（8）
乙醇脱水反应	C₂H₅OH $→$ C₂H₄+H₂O	? $H r, 298 ?$ =45.5kJ/mol	（9）
乙醛分解反应	CH₃CHO $→$ CO+CH₄	? $H r, 298 ?$ =-19.3kJ/mol	（10）
乙醛羟醛缩合反应	2CH₃CHO $→$ CH₃COCH₃+CO+H₂	? $H r, 298 ?$ =4.1kJ/mol	（11）
一氧化碳甲烷化反应	CO+3H₂ $→$ CH₄+H₂O	? $H r, 298 ?$ =-206.1kJ/mol	（12）
二氧化碳甲烷化反应	CO₂+4H₂ $→$ CH₄+2H₂O	? $H r, 298 ?$ =-164.8kJ/mol	（13）
乙烯分解反应	C₂H₄ $→$ 2C+2H₂	? $H r, 298 ?$ =-52.3kJ/mol	（14）
甲烷分解反应	CH₄ $→$ C+2H₂	? $H r, 298 ?$ =74.9kJ/mol	（15）
一氧化碳歧化反应	2CO $→$ C+CO₂	? $H r, 298 ?$ =-172.6kJ/mol	（16）

化学反应	反应方程式		编号
乙醇脱氢反应	C₂H₅OH $→$ CH₃CHO+H₂	? $H r, 298 ?$ =68.9kJ/mol	（4）
乙醇分解反应	C₂H₅OH $→$ H₂+CO+CH₄	? $H r, 298 ?$ =49.6kJ/mol	（5）
乙醛水蒸气重整	CH₃CHO+H₂O $→$ 2CO+3H₂	? $H r, 298 ?$ =186.8kJ/mol	（6）
水煤气变换反应	CO+H₂O $→$ CO₂+H₂	? $H r, 298 ?$ =-41.4kJ/mol	（7）
甲烷水蒸气重整	CH₄+H₂O $→$ CO+3H₂	? $H r, 298 ?$ =206.1kJ/mol	（8）
乙醇脱水反应	C₂H₅OH $→$ C₂H₄+H₂O	? $H r, 298 ?$ =45.5kJ/mol	（9）
乙醛分解反应	CH₃CHO $→$ CO+CH₄	? $H r, 298 ?$ =-19.3kJ/mol	（10）
乙醛羟醛缩合反应	2CH₃CHO $→$ CH₃COCH₃+CO+H₂	? $H r, 298 ?$ =4.1kJ/mol	（11）
一氧化碳甲烷化反应	CO+3H₂ $→$ CH₄+H₂O	? $H r, 298 ?$ =-206.1kJ/mol	（12）
二氧化碳甲烷化反应	CO₂+4H₂ $→$ CH₄+2H₂O	? $H r, 298 ?$ =-164.8kJ/mol	（13）
乙烯分解反应	C₂H₄ $→$ 2C+2H₂	? $H r, 298 ?$ =-52.3kJ/mol	（14）
甲烷分解反应	CH₄ $→$ C+2H₂	? $H r, 298 ?$ =74.9kJ/mol	（15）
一氧化碳歧化反应	2CO $→$ C+CO₂	? $H r, 298 ?$ =-172.6kJ/mol	（16）

催化剂	制备方法	金属负载量（质量分数）/%	乙醇转化率/%	H₂产率/%	反应条件	参考文献
Ni/多孔SiO₂	浸渍法	10	95	47	T=873K、S/E^①=9、 W/F^②=18g·h·mol^-1	［14］
Ni/SiO₂纤维	浸渍法	10	100	55
Ni/SiO₂纤维	共沉淀法	10	100	60
Ni/SiO₂纤维	静电吸附法	10	100	65
Ni/SBA-15	浸渍法	6	100	82.5	T=823K、S/E=3、 $F H 2 O + E t O H ③ = 0.02 m L · ??? m i n - 1$	［15］
Ni/β沸石	溶胶-凝胶等体积浸渍法	15	100	78	T=823K、S/E = 6、 WHSV^④=30h^-1	［16］
Ni/Al₂O₃-TiO₂	一步法	10	93	88	T=773K、S/E=3、 WHSV=2773h^-1	［17］
Ni/La₂O₃-α-Al₂O₃	浸渍法	10	100	82	T=873K、S/E=6、 W/F=0.35g·h·g^-1	［18］
Ni/La₂O₃-α-Al₂O₃	浸渍法	15	100	62	T=723K、S/E=3、 GHSV^⑤=23140mL·g^-1·h^-1	［19］
Ni/La₂O₃-CeO₂	浸渍法	8	100	70	T=823K、S/E=6、 $F H 2 O + E t O H = 0.615 m o l · ??? h - 1$	［20］
Ni/La₂O₃-CeO₂-ZrO₂	浸渍法	10	90	85	T=773K、S/E =3、 GHSV=64.8h^-1	［21］
Ni/凹凸棒石	共沉淀法	20	95	78	T=873K、S/E = 1.5、 WHSV=12.6h^-1	［22］
Ni/Mg-凹凸棒石	共沉淀法	20	100	96.7	T=973K、S/E=1.5、 GHSV=19200~19400h^-1	［23］
Au-Ni/CaO-CeO₂	浸渍法	10	100	75	T=773K、S/E=3、 $F H 2 O + E t O H = 0.02 m L · ??? m i n - 1$	［24］
Ni/水滑石	浸渍法	10	75	68	T=673K、S/E=9、 GHSV=2700mL·g^-1·h^-1	［25］
Cu-Ni-Co/水滑石	浸渍法	10	85	83	T=673K、S/E=9、 GHSV=2700mL·g^-1·h^-1	［25］
Ni/CeO₂	浸渍法	10	100	60	T=873K、S/E=3、 $F H 2 O + E t O H = 1 m L · ??? h - 1$	［26］
Ni/CeO₂	浸渍法	10	100	68	T=693K、S/E=12、 GHSV=60000mL·g^-1·h^-1	［27］
K-Ni/CeO₂	浸渍法	10	100	85	T=693K、S/E=12、 GHSV=60000mL·g^-1·h^-1	［27］
Ni/CeO₂	浸渍法	13	89	71	T=873K、S/E=6、 GHSV=20000mL·g^-1·h^-1	［28］
4Cu-Ni/CeO₂			99	73
4Co-Ni/CeO₂			91	73
4Mg-Ni/CeO₂			96	74
Ni/La₂O₃-CeO₂	浸渍法	10	100	88	T=733K、S/E=12、 GHSV=60000mL·g^-1·h^-1	［29］
Ni/Ce_0.5Zr_0.5O₂	浸渍法	10	100	73	T=723K、S/E=13、 GHSV=22000h^-1	［30］
Ni/Ce_0.5Zr_0.5O₂	共沉淀法	10	100	89
B-Ni/Ce_0.5Zr_0.5O₂	共沉淀法	10	100	92
Ni/MgO-CaO	共沉淀法	5	100	97.2	T=873K、S/E=4、 GHSV=2620mL·g^-1·h^-1	［31］
Ni/脱铝β沸石	浸渍法	10	100	75	T=773K、S/E = 12、 WHSV=9.5h^-1	［32］
Ce-Ni/SBA-15	表面活性剂辅助等容浸渍法	3	100	97	T=923K、S/E=4、 W/F=1.7g·h·mol^-1	［33］
Ce-Ni/蒙脱石	超声波辅助阳离子交换浸渍法	10	97.3	88.5	T=923K、S/E=4、 $F H 2 O + E t O H = 3.8 g · ??? h - 1$	［34］
Fe-Cu-Ni/β沸石	浸渍法	10	100	72.1	T=773K、S/E=8、 WHSV=7.35h^-1	［35］
Rh-Ni/La₂O₃-CeO₂-Al₂O₃	浸渍法	10	100	69	T=773K、S/E=3、 GHSV=26000h^-1	［36］

催化剂	制备方法	金属负载量（质量分数）/%	乙醇转化率/%	H₂产率/%	反应条件	参考文献
Ni/多孔SiO₂	浸渍法	10	95	47	T=873K、S/E^①=9、 W/F^②=18g·h·mol^-1	［14］
Ni/SiO₂纤维	浸渍法	10	100	55
Ni/SiO₂纤维	共沉淀法	10	100	60
Ni/SiO₂纤维	静电吸附法	10	100	65
Ni/SBA-15	浸渍法	6	100	82.5	T=823K、S/E=3、 $F H 2 O + E t O H ③ = 0.02 m L · ??? m i n - 1$	［15］
Ni/β沸石	溶胶-凝胶等体积浸渍法	15	100	78	T=823K、S/E = 6、 WHSV^④=30h^-1	［16］
Ni/Al₂O₃-TiO₂	一步法	10	93	88	T=773K、S/E=3、 WHSV=2773h^-1	［17］
Ni/La₂O₃-α-Al₂O₃	浸渍法	10	100	82	T=873K、S/E=6、 W/F=0.35g·h·g^-1	［18］
Ni/La₂O₃-α-Al₂O₃	浸渍法	15	100	62	T=723K、S/E=3、 GHSV^⑤=23140mL·g^-1·h^-1	［19］
Ni/La₂O₃-CeO₂	浸渍法	8	100	70	T=823K、S/E=6、 $F H 2 O + E t O H = 0.615 m o l · ??? h - 1$	［20］
Ni/La₂O₃-CeO₂-ZrO₂	浸渍法	10	90	85	T=773K、S/E =3、 GHSV=64.8h^-1	［21］
Ni/凹凸棒石	共沉淀法	20	95	78	T=873K、S/E = 1.5、 WHSV=12.6h^-1	［22］
Ni/Mg-凹凸棒石	共沉淀法	20	100	96.7	T=973K、S/E=1.5、 GHSV=19200~19400h^-1	［23］
Au-Ni/CaO-CeO₂	浸渍法	10	100	75	T=773K、S/E=3、 $F H 2 O + E t O H = 0.02 m L · ??? m i n - 1$	［24］
Ni/水滑石	浸渍法	10	75	68	T=673K、S/E=9、 GHSV=2700mL·g^-1·h^-1	［25］
Cu-Ni-Co/水滑石	浸渍法	10	85	83	T=673K、S/E=9、 GHSV=2700mL·g^-1·h^-1	［25］
Ni/CeO₂	浸渍法	10	100	60	T=873K、S/E=3、 $F H 2 O + E t O H = 1 m L · ??? h - 1$	［26］
Ni/CeO₂	浸渍法	10	100	68	T=693K、S/E=12、 GHSV=60000mL·g^-1·h^-1	［27］
K-Ni/CeO₂	浸渍法	10	100	85	T=693K、S/E=12、 GHSV=60000mL·g^-1·h^-1	［27］
Ni/CeO₂	浸渍法	13	89	71	T=873K、S/E=6、 GHSV=20000mL·g^-1·h^-1	［28］
4Cu-Ni/CeO₂			99	73
4Co-Ni/CeO₂			91	73
4Mg-Ni/CeO₂			96	74
Ni/La₂O₃-CeO₂	浸渍法	10	100	88	T=733K、S/E=12、 GHSV=60000mL·g^-1·h^-1	［29］
Ni/Ce_0.5Zr_0.5O₂	浸渍法	10	100	73	T=723K、S/E=13、 GHSV=22000h^-1	［30］
Ni/Ce_0.5Zr_0.5O₂	共沉淀法	10	100	89
B-Ni/Ce_0.5Zr_0.5O₂	共沉淀法	10	100	92
Ni/MgO-CaO	共沉淀法	5	100	97.2	T=873K、S/E=4、 GHSV=2620mL·g^-1·h^-1	［31］
Ni/脱铝β沸石	浸渍法	10	100	75	T=773K、S/E = 12、 WHSV=9.5h^-1	［32］
Ce-Ni/SBA-15	表面活性剂辅助等容浸渍法	3	100	97	T=923K、S/E=4、 W/F=1.7g·h·mol^-1	［33］
Ce-Ni/蒙脱石	超声波辅助阳离子交换浸渍法	10	97.3	88.5	T=923K、S/E=4、 $F H 2 O + E t O H = 3.8 g · ??? h - 1$	［34］
Fe-Cu-Ni/β沸石	浸渍法	10	100	72.1	T=773K、S/E=8、 WHSV=7.35h^-1	［35］
Rh-Ni/La₂O₃-CeO₂-Al₂O₃	浸渍法	10	100	69	T=773K、S/E=3、 GHSV=26000h^-1	［36］

催化剂	制备方法	金属负载量（质量分数）/%	乙醇转化率/%	H₂产率/%	反应条件	参考文献
Co/SiO₂	浸渍法	20	100	75	T=873K、S/E=6、 GHSV=51700h^-1	［49］
Co/CeO₂	浸渍法	10	97.1	93.3	T=723K、S/E=10、 WHSV=0.19~2.88g·g^-1·h^-1	［50］
Co/Al₂O₃	浸渍法	15	100	80	T=873K、S/E=5、 $F H 2 O + E t O H = 0.09 m L · ??? m i n - 1$	［51］
Na-Co/Al₂O₃			100	90
K-Co/Al₂O₃			100	90
Ce-Co/Al₂O₃			100	86
Ni-Co/Al₂O₃		15Co 5Ni	100	88
Co/CaO-Al₂O₃	浸渍法	15	100	74.6	T=723K、S/E=3、 GHSV=23139mL·g^-1·h^-1	［52］
Co-Ce/海泡石	表面活性剂辅助共沉淀法	10	96.2	77.9	T=873K、S/E=3、 WHSV=21h^-1	［53］
Co-Ce/海泡石	共沉淀法	10	90.8	69.1	T=873K、S/E=3、 WHSV=21.5h^-1	［54］
Ru-Co/活性炭	一步法	1	99	77	T=823K、S/E=3、 GHSV=89.4h^-1	［55］
Ni-Co/CeO₂	浸渍法	10Ni 10Co	95	59	T=773K、S/E=6、 W/F=0.12g·h·mol^-1	［56］
Ni-Co/CeO₂	反相微乳液共沉淀法	10Ni 10Co	85	56	T=773K、S/E=6、 W/F=0.12g·h·mol^-1	［56］
Ni-Co/MCM-41	浸渍法	9Ni 1Co	90	80	T=763K、S/E=5、 $F H 2 O + E t O H = 0.6 m L · ??? m i n - 1$	［57］
MC-Ni-Co/Zr	软模板水热法及浸渍法	—	95	65	T=648K、S/E=12、 GHSV=15L·g^-1·h^-1	［58］
OMC-Ni-Co/Zr	软模板水热法及浸渍法	—	83	68.2	T=648K、S/E=12、 GHSV=15L·g^-1·h^-1	［59］
Co/Al₂O₃	浸渍法	10	99.5	86.1	T=823K、S/E=3、 WHSV=8.0h^-1	［60］
Co/CeO₂	共沉淀法	29	100	96	T=773K、S/E=12、 GHSV=60000mL·g^-1·h^-1	［61］
Co/CeO₂	浸渍法	10	100	84.6	T=693K、S/E=3、 $F H 2 O + E t O H = 3 m L · ??? m i n - 1$	［62］
K-Co/CeO₂	浸渍法	10	100	98.5	T=693K、S/E=3、 $F H 2 O + E t O H = 3 m L · ??? m i n - 1$	［62］
Ce-Co/CeO₂	浸渍法	10	100	86	T=813K、S/E=4、 GHSV=60000mL·g^-1·h^-1	［63］
Co/La₂O₃–CeO₂	浸渍法	10	100	94	T=773K、S/E=12、 GHSV=60000mL·g^-1·h^-1	［29］
Co/Y₂O₃-ZrO₂	浸渍法	3	100	70	T=773K、S/E=13、 GHSV=4500h^-1	［64］
La-Co/Y₂O₃-ZrO₂	浸渍法	3	99	73	T=773K、S/E=13、 GHSV=4500h^-1	［64］
Co/Zn-Al水滑石衍生物	共沉淀法	20	100	73.7	T=773K、S/E=10、 GHSV=4700h^-1	［65］
La-Co/Zn-Al水滑石衍生物	共沉淀法	20	100	75.5	T=773K、S/E=10、 GHSV=4700h^-1	［65］
Ni-Co/Al₂O₃	浸渍法	7.5Ni 7.5Co	97.2	88.9	T=823K、S/E=13、 LHSV^①=7.5h^-1	［66］
Ni-Co/SBA-15	共沉淀法	8Ni 2Co	85.6	62.4	T=773K、S/E=3.7、 $F H 2 O + E t O H = 0.02 m L · ??? m i n - 1$	［67］
LaNi_0.7Co_0.3O₃/ZrO₂	柠檬酸盐络合法	—	100	75	T=673K、S/E=3、 GHSV=66000mL·g^-1·h^-1	［68］

催化剂	制备方法	金属负载量（质量分数）/%	乙醇转化率/%	H₂产率/%	反应条件	参考文献
Co/SiO₂	浸渍法	20	100	75	T=873K、S/E=6、 GHSV=51700h^-1	［49］
Co/CeO₂	浸渍法	10	97.1	93.3	T=723K、S/E=10、 WHSV=0.19~2.88g·g^-1·h^-1	［50］
Co/Al₂O₃	浸渍法	15	100	80	T=873K、S/E=5、 $F H 2 O + E t O H = 0.09 m L · ??? m i n - 1$	［51］
Na-Co/Al₂O₃			100	90
K-Co/Al₂O₃			100	90
Ce-Co/Al₂O₃			100	86
Ni-Co/Al₂O₃		15Co 5Ni	100	88
Co/CaO-Al₂O₃	浸渍法	15	100	74.6	T=723K、S/E=3、 GHSV=23139mL·g^-1·h^-1	［52］
Co-Ce/海泡石	表面活性剂辅助共沉淀法	10	96.2	77.9	T=873K、S/E=3、 WHSV=21h^-1	［53］
Co-Ce/海泡石	共沉淀法	10	90.8	69.1	T=873K、S/E=3、 WHSV=21.5h^-1	［54］
Ru-Co/活性炭	一步法	1	99	77	T=823K、S/E=3、 GHSV=89.4h^-1	［55］
Ni-Co/CeO₂	浸渍法	10Ni 10Co	95	59	T=773K、S/E=6、 W/F=0.12g·h·mol^-1	［56］
Ni-Co/CeO₂	反相微乳液共沉淀法	10Ni 10Co	85	56	T=773K、S/E=6、 W/F=0.12g·h·mol^-1	［56］
Ni-Co/MCM-41	浸渍法	9Ni 1Co	90	80	T=763K、S/E=5、 $F H 2 O + E t O H = 0.6 m L · ??? m i n - 1$	［57］
MC-Ni-Co/Zr	软模板水热法及浸渍法	—	95	65	T=648K、S/E=12、 GHSV=15L·g^-1·h^-1	［58］
OMC-Ni-Co/Zr	软模板水热法及浸渍法	—	83	68.2	T=648K、S/E=12、 GHSV=15L·g^-1·h^-1	［59］
Co/Al₂O₃	浸渍法	10	99.5	86.1	T=823K、S/E=3、 WHSV=8.0h^-1	［60］
Co/CeO₂	共沉淀法	29	100	96	T=773K、S/E=12、 GHSV=60000mL·g^-1·h^-1	［61］
Co/CeO₂	浸渍法	10	100	84.6	T=693K、S/E=3、 $F H 2 O + E t O H = 3 m L · ??? m i n - 1$	［62］
K-Co/CeO₂	浸渍法	10	100	98.5	T=693K、S/E=3、 $F H 2 O + E t O H = 3 m L · ??? m i n - 1$	［62］
Ce-Co/CeO₂	浸渍法	10	100	86	T=813K、S/E=4、 GHSV=60000mL·g^-1·h^-1	［63］
Co/La₂O₃–CeO₂	浸渍法	10	100	94	T=773K、S/E=12、 GHSV=60000mL·g^-1·h^-1	［29］
Co/Y₂O₃-ZrO₂	浸渍法	3	100	70	T=773K、S/E=13、 GHSV=4500h^-1	［64］
La-Co/Y₂O₃-ZrO₂	浸渍法	3	99	73	T=773K、S/E=13、 GHSV=4500h^-1	［64］
Co/Zn-Al水滑石衍生物	共沉淀法	20	100	73.7	T=773K、S/E=10、 GHSV=4700h^-1	［65］
La-Co/Zn-Al水滑石衍生物	共沉淀法	20	100	75.5	T=773K、S/E=10、 GHSV=4700h^-1	［65］
Ni-Co/Al₂O₃	浸渍法	7.5Ni 7.5Co	97.2	88.9	T=823K、S/E=13、 LHSV^①=7.5h^-1	［66］
Ni-Co/SBA-15	共沉淀法	8Ni 2Co	85.6	62.4	T=773K、S/E=3.7、 $F H 2 O + E t O H = 0.02 m L · ??? m i n - 1$	［67］
LaNi_0.7Co_0.3O₃/ZrO₂	柠檬酸盐络合法	—	100	75	T=673K、S/E=3、 GHSV=66000mL·g^-1·h^-1	［68］

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