Hydrogen storage and release performances of N-heterocyclic hydrogen storage carriers

doi:10.16085/j.issn.1000-6613.2024-1319

Abstract

Abstract:

N-heterocycles are considered to be the most promising liquid organic hydrogen carriers due to the relatively low dehydrogenation reaction enthalpy. In this study, the hydrogen storage and release properties of five common N-heterocyclic hydrogen storage carriers were investigated using commercial catalysts. A commercial Ru/Al₂O₃ catalyst was used to evaluate the hydrogenation performance of poor hydrogen N-heterocycles, while a commercial Pd/Al₂O₃ catalyst was used to assess the dehydrogenation performance of perhydro-N-heterocycles. During the dehydrogenation process at 180℃ for 6h, the conversion rates of 12H-N-ethylcarbazole, 8H-indole, and 8H-N-methylindole were 96.54%, 61.98%, and 75.11%, and dehydrogenation rates of 79.88%, 30.15%, and 54.47%, respectively. After reaction 6h at 200℃, the conversion rates of 10H-quinoline and 10H-2-methylquinoline were 4.92% and 44.42%, with dehydrogenation rates of 3.22% and 35.35%, respectively. The results indicate that the N-ethylcarbazole system exhibits excellent dehydrogenation efficiency, while the N-methylindole system shows good hydrogen storage and release activity, and all materials remain liquid at room temperature, which is favorable for practical applications. The quinoline system has a high hydrogen storage density, but its storage and release conditions are relatively harsh and require further research and optimization. This study provides a reference for the selection of N-heterocyclic hydrogen storage carriers and an evaluation method for hydrogen storage and release performance.

Key words: N-heterocycle, liquid organic hydrogen carrier, hydrogenation, dehydrogenation, palladium alumina, catalyst

摘要：

N-杂环有机物因其较低的脱氢反应焓而被认为是最具潜力的有机液态储氢载体。本文基于5种常见N-杂环储氢载体，使用商业催化剂考察各自的储放氢性能：商业Ru/Al₂O₃催化剂被用于评估贫氢-N-杂环储氢载体的储氢性能，而商业Pd/Al₂O₃催化剂被用于评价富氢-N-杂环储氢载体的放氢性能。在180℃反应6h的脱氢过程中，12H-N-乙基咔唑、8H-吲哚和8H-N-甲基吲哚的转化率分别为96.54%、61.98%和75.11%，脱氢率分别为79.88%、30.15%和54.47%；200℃反应6h后，10H-喹啉和10H-2-甲基喹啉的转化率分别为4.92%和44.42%，脱氢率为3.22%和35.35%。结果表明，N-乙基咔唑体系在放氢效率方面表现优异，而N-甲基吲哚体系储放氢活性均表现良好，且其所有物料在常温下均为液态，具有实际应用优势。喹啉体系储氢密度高，但其储放氢条件较为苛刻，仍需进一步研究优化。本文结果为N-杂环储氢载体的选择提供了可参考的依据和储放氢性能评价方法。

关键词: N-杂环, 有机液态储氢载体, 加氢, 脱氢, 钯氧化铝, 催化剂

CLC Number:

TK91

LI Peiya, YANG Fusheng, WANG Bin, FANG Tao. Hydrogen storage and release performances of N-heterocyclic hydrogen storage carriers[J]. Chemical Industry and Engineering Progress, 2025, 44(10): 5689-5696.

李培雅, 杨福胜, 王斌, 方涛. N-杂环储氢载体的储放氢性能[J]. 化工进展, 2025, 44(10): 5689-5696.

Figures/Tables 9

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储氢体系	熔点/℃	沸点/℃	加氢温度/℃	脱氢温度/℃	储氢量(质量分数)/%	反应焓/kJ·mol^-1	价格/CNY·kg^-1
苯/环己烷	6/7	80/81	约150	>300	7.13	-68.8	约6
甲苯/甲基环己烷	-95/-126	111/101	约150	300~350	6.12	-68.3	约8
二苄基甲苯/全氢二苄基甲苯	-39/-45	390/354	约150	260~310	6.21	-65.4	约40
苄基甲苯/全氢苄基甲苯	-30/<-30	280/270	约150	250~270	6.18	-63.5	约30
萘/十氢萘	80/-30	218/187	约200	320~340	7.25	-66.3	约8

储氢体系	熔点/℃	沸点/℃	加氢温度/℃	脱氢温度/℃	储氢量(质量分数)/%	反应焓/kJ·mol^-1	价格/CNY·kg^-1
苯/环己烷	6/7	80/81	约150	>300	7.13	-68.8	约6
甲苯/甲基环己烷	-95/-126	111/101	约150	300~350	6.12	-68.3	约8
二苄基甲苯/全氢二苄基甲苯	-39/-45	390/354	约150	260~310	6.21	-65.4	约40
苄基甲苯/全氢苄基甲苯	-30/<-30	280/270	约150	250~270	6.18	-63.5	约30
萘/十氢萘	80/-30	218/187	约200	320~340	7.25	-66.3	约8

储氢体系	熔点/℃	沸点/℃	加氢反应条件	脱氢温度/℃	储氢量(质量分数)/%	反应焓/kJ·mol^-1	价格/CNY·kg^-1
咔唑/12H-咔唑	248/58	352/267	150~180℃，6~8MPa	170~200	6.70	-52.57	约80
N-乙基咔唑/12H-N-乙基咔唑	68/-13	270/245	150~180℃，6~8MPa	140~180	5.79	-50.5	约200
吲哚/8H-吲哚	54/<0	254/186	180~200℃，8~10MPa	约180	6.39	-58.48	约80
N-甲基吲哚/8H-N-甲基吲哚	4/-20	238/185	130~150℃，6~8MPa	150~180	5.76	-53.5	约500
喹啉/10H-喹啉	-16/45	237/200	150~180℃，6~8MPa	>200	7.20	-61.5	约90
2-甲基喹啉/10H-2-甲基喹啉	-2/35	248/225	250~300℃，8~10MPa	约200	6.53	-59.5	约300
吩嗪/14H-吩嗪	175/97	360/305	250~300℃，8~12MPa	约200	7.20	-61.3	约800

储氢体系	熔点/℃	沸点/℃	加氢反应条件	脱氢温度/℃	储氢量(质量分数)/%	反应焓/kJ·mol^-1	价格/CNY·kg^-1
咔唑/12H-咔唑	248/58	352/267	150~180℃，6~8MPa	170~200	6.70	-52.57	约80
N-乙基咔唑/12H-N-乙基咔唑	68/-13	270/245	150~180℃，6~8MPa	140~180	5.79	-50.5	约200
吲哚/8H-吲哚	54/<0	254/186	180~200℃，8~10MPa	约180	6.39	-58.48	约80
N-甲基吲哚/8H-N-甲基吲哚	4/-20	238/185	130~150℃，6~8MPa	150~180	5.76	-53.5	约500
喹啉/10H-喹啉	-16/45	237/200	150~180℃，6~8MPa	>200	7.20	-61.5	约90
2-甲基喹啉/10H-2-甲基喹啉	-2/35	248/225	250~300℃，8~10MPa	约200	6.53	-59.5	约300
吩嗪/14H-吩嗪	175/97	360/305	250~300℃，8~12MPa	约200	7.20	-61.3	约800

催化剂	金属负载量（质量分数）/%	比表面积/m²·g^-1	孔径/nm	孔容/cm³·g^-1	平均颗粒直径/μm	活性金属平均粒径/nm
Ru/Al₂O₃	5.00	156.88	9.17	0.36	70	—
Pd/Al₂O₃	5.00	155.08	8.72	0.33	28~34	4.95