分步法分解硫化氢制氢和硫黄催化剂研究进展

doi:10.16085/j.issn.1000-6613.2022-1633

摘要/Abstract

摘要：

硫化氢（H₂S）不仅是一种剧毒且高腐蚀性气体，更是蕴含丰富氢能和硫元素的宝贵资源。在国家能源战略需求和双碳目标下，实现天然气藏中H₂S的低碳高值利用是天然气开发的必然发展趋势。分步法是一种可在较低温度区间将H₂S高值转化为H₂和硫黄的方法，具有H₂S分解效率高、能耗低的优点，但存在循环效率差、硫黄回收困难、反应过程机理认识浅薄等问题。为了深入了解分步法分解H₂S的研究现状和面临问题，本文主要综述了分步法的反应原理、发展历程、活性催化剂的研究进展，重点概述了金属硫化物和金属这两类催化剂的活性测试结果及具体反应过程，并对分步法分解H₂S所面临的关键问题进行了总结与展望。本文指出分步法最大问题在于催化剂硫化产氢和分解脱硫过程机理尚不明晰，使得催化剂的优化设计缺乏指导，从而导致分步法循环效率低。未来应当借助更多原位表征技术和理论模拟计算认识转化过程机理，同时加强相关实验设计以衡量不同催化剂优劣，开发出适用于分步法高效循环过程的催化剂。

关键词: 硫化氢, 分步法, 高值利用, 氢, 催化剂, 活性

Abstract:

Hydrogen sulfide (H₂S) is a highly toxic and corrosive gas, but it is also a rich resource of hydrogen and sulfur. Under the national energy demand and dual carbon goals, realizing the low-carbon and high-value utilization of H₂S in high-sulfur gas reservoirs becomes an important development trend of H₂S treatment. The two-step decomposition of H₂S could convert H₂S into high-valued hydrogen and sulfur efficiently at relatively low temperature. So, it has the advantages of high decomposition efficiency and low energy consumption. But the problems of poor circulation efficiency, difficulties in sulfur recycling, and unclear reaction mechanism still exist. To better understand the research status and problems of the two-step decomposition method, this paper reviewed the reaction principle and development history of two-step decomposition of H₂S, as well as the latest advances of relevant catalysts. In special, the activity and reaction process of metal sulfide and metal catalysts were summarized. Finally, the key problems of blind design of catalysts and hence inefficient decomposition of H₂S due to the unclear mechanism were pointed out. In the future, more in-situ characterization and theoretical calculations may be used to explore the mechanism, and relevant catalytic activity experiments should be carefully designed for rational comparison of different catalysts. This would help to develop efficient catalysts for the two-step decomposition of H₂S.

Key words: hydrogen sulfide, two-step method, high-value utilization, hydrogen, catalyst, reactivity

中图分类号:

于姗, 段元刚, 张怡欣, 唐春, 付梦瑶, 黄靖元, 周莹. 分步法分解硫化氢制氢和硫黄催化剂研究进展[J]. 化工进展, 2023, 42(7): 3780-3790.

YU Shan, DUAN Yuangang, ZHANG Yixin, TANG Chun, FU Mengyao, HUANG Jinyuan, ZHOU Ying. Research progress of catalysts for two-step hydrogen sulfide decomposition to produce hydrogen and sulfur[J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3780-3790.

图/表 8

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金属硫化物	产氢温度 /℃	脱硫温度 /℃	H₂S质量分数 /%	H₂产率 /%	年份	文献
Li₂S	400~800	—	99.5	0~7	1985	[39]
Na₂S	400~650	—	99.5	0~14
Na₂S₂	400~800	—	99.5	0~4
Na₂S₃	400~800	—	99.5	0~2
Na₂S₄	400~800	—	99.5	0~1.8
K₂S	400~700	—	99.5	0~18
K₂S₂	400~800	—	99.5	0~7.5
K₂S₃	400~800	—	99.5	0~4.5
K₂S₄	400~800	—	99.5	0~2.5

金属硫化物	产氢温度 /℃	脱硫温度 /℃	H₂S质量分数 /%	H₂产率 /%	年份	文献
Li₂S	400~800	—	99.5	0~7	1985	[39]
Na₂S	400~650	—	99.5	0~14
Na₂S₂	400~800	—	99.5	0~4
Na₂S₃	400~800	—	99.5	0~2
Na₂S₄	400~800	—	99.5	0~1.8
K₂S	400~700	—	99.5	0~18
K₂S₂	400~800	—	99.5	0~7.5
K₂S₃	400~800	—	99.5	0~4.5
K₂S₄	400~800	—	99.5	0~2.5

金属硫化物	产氢温度 /℃	脱硫温度 /℃	H₂S质量分数 /%	H₂产率 /%	年份	文献
ZrS₂	100~500	650	0.01	0~99	2022	[47]
VS	530~750	530~750	99.5	0~94	1987	[40]
V₂S₃	500~800	500~800	99.5	3.9~98	1987	[40]
V₂S₃/Al₂O₃	400~800	400~800	99.5	40	1987	[40]
V₂S₃/FeS	400~800	400~800	99.5	0~8	1987	[40]
V₂S₃/Cu₉S₅	400~800	400~800	99.5	9~80	1987	[40]
V₂S₃/Cu₉S₅/Al₂O₃	400~800	400~800	99.5	40	1987	[40]
V₂S₃/ZnS	400~800	400~800	99.5	0~8.5	1987	[40]
5%V₂S₃/Al₂O₃	450~600	450~600	—	0~61	1990	[42]
5%V₂O₅/Al₂O₃	450~600	450~600	—	0~68	1990	[42]
10%V₂O₅/Al₂O₃	450~600	450~600	—	0~69	1990	[42]
50%V₂O₅/Al₂O₃	450~600	450~600	—	0~66	1990	[42]
Cr₂S₃	400~800	400~800	99.5	1.5~7.5	1980	[35]
MoS₂	400~800	400~800	99.5	0.5~9	1980	[35]
MoS₂	530~800	530~800	99.5	1.5~80	1987	[40]
WS₂	400~800	400~800	99.5	0.5~8.5	1980	[35]

金属硫化物	产氢温度 /℃	脱硫温度 /℃	H₂S质量分数 /%	H₂产率 /%	年份	文献
ZrS₂	100~500	650	0.01	0~99	2022	[47]
VS	530~750	530~750	99.5	0~94	1987	[40]
V₂S₃	500~800	500~800	99.5	3.9~98	1987	[40]
V₂S₃/Al₂O₃	400~800	400~800	99.5	40	1987	[40]
V₂S₃/FeS	400~800	400~800	99.5	0~8	1987	[40]
V₂S₃/Cu₉S₅	400~800	400~800	99.5	9~80	1987	[40]
V₂S₃/Cu₉S₅/Al₂O₃	400~800	400~800	99.5	40	1987	[40]
V₂S₃/ZnS	400~800	400~800	99.5	0~8.5	1987	[40]
5%V₂S₃/Al₂O₃	450~600	450~600	—	0~61	1990	[42]
5%V₂O₅/Al₂O₃	450~600	450~600	—	0~68	1990	[42]
10%V₂O₅/Al₂O₃	450~600	450~600	—	0~69	1990	[42]
50%V₂O₅/Al₂O₃	450~600	450~600	—	0~66	1990	[42]
Cr₂S₃	400~800	400~800	99.5	1.5~7.5	1980	[35]
MoS₂	400~800	400~800	99.5	0.5~9	1980	[35]
MoS₂	530~800	530~800	99.5	1.5~80	1987	[40]
WS₂	400~800	400~800	99.5	0.5~8.5	1980	[35]

金属硫化物	实验温度/℃	脱硫温度/℃	H₂S质量分数/%	H₂S转化率/%	H₂产率/%	年份	文献
FeS	400~800	400~800	99.5	—	2~8.3	1980	[35]
FeS	550~600	750	—	—	3.5~33	1982	[36]
FeS	250~590	600	1.2~19.5	16.3^①	34^①	2021	[37]
FeS	200~400	900	0.9	38~100	—	2021	[46]
FeS₂	400~800	400~800	99.5	—	0.5~8	1980	[35]
Fe₇S₈	400~800	400~800	99.5	—	0.5~9	1980	[35]
FeS/Al₂O₃	22	600	1.04	0~100	—	2021	[37]
2%Mo-FeS	200~400	900	0.9	52~100	—	2021	[46]
CoS	400~800	400~800	99.5	—	2.5~7	1980	[35]
CoS	20	600	7.5	10.6^①	26^①	2021	[37]
CoS₂	400~800	400~800	99.5	—	0.5~6.5	1980	[35]
CoS_1.13-1.2	400~800	400~800	99.5	—	2~7.5	1980	[35]
Co₉S₈	550~850	850	—	—	0~55	1982	[36]
CoS/Al₂O₃	22~150	600	0.9	0~100	—	2021	[37]
CoMoS/Al₂O₃	21	600	1.05~19.7	0~100	0~0.6	2021	[37]
NiS	400~800	400~800	99.5	—	2.7~9.8	1980	[35]
NiS	20~400	600	1.2~19.5	2.8^①	32^①	2021	[37]
NiS₂	400~800	400~800	99.5	—	0.5~7	1980	[35]
NiS_1.2	400~800	400~800	99.5	—	0.3~7.6	1980	[35]
Ni₃S₂	550	750	—	—	35~97	1982	[36]
Ni₃S₂	300~700	800	—	—	0~50	1983	[44]
Ni₃S₂	200~500	500~800	0.01	80	—	2022	[47]
Ni₃S₂/MoS₂	400~500	800	—	—	40~85	1982	[36]
Ni₃S₂/MoS₂	300~700	800	—	—	0~79	1983	[44]
NiS/Al₂O₃	19~150	600	0.9	0~100	—	2021	[37]
Ni₃S₂/Al₂O₃	300~700	800	—	—	0~82	1983	[44]
Ni₃S₂/Al₂O₃	500~800	500~800	—	—	0~85	1984	[43]
NiMoS₄/Al₂O₃	22-300	400	0.9	0~100	0.3~15.7	2021	[37]