Research progress in the hydrogenation and dehydrogenation technology of polycyclic aromatic hydrocarbon liquid organic hydrogen carriers

doi:10.16085/j.issn.1000-6613.2022-0724

Abstract

Abstract:

The large-scale utilization mode of renewable energy based on "green electricity+green hydrogen" is an important measure to achieve the carbon neutrality. However, the current hydrogen storage and transportation technology cannot meet the large-scale and cross-temporal needs of this utilization mode. Hydrogen storage by liquid polycyclic aromatic hydrocarbons is considered to be the most likely technology to achieve large-scale safe and efficient off-site hydrogen storage and transportation. This article introduces the basic principle of polycyclic aromatic hydrocarbon liquid organic hydrogen storage technology and the physicochemical properties of common liquid organic hydrogen carriers, analyzes the key parameters of organic hydrogen carriers, explains the intra-ring and inter-ring dehydrogenation reaction mechanism of polycyclic aromatic hydrocarbons from the perspective of steric hindrance, and summarizes the further research progress on the dehydrogenation catalysts from the aspects of active component dispersion, surface charge effect, hydrogen overflow and low coordination number. The technical difficulties such as the high dehydrogenation temperature, low cyclic dehydrogenation rate and high catalyst cost and the future application scenarios and development directions such as the energy optimization and catalyst modification are prospected.

Key words: benzene, hydrogen, reaction, catalyst

摘要：

基于“绿电+绿氢”的可再生能源规模化利用模式是实现碳中和目标的重要措施，然而目前现有的氢储运技术无法满足该利用模式的大规模与跨时空需求。多环芳烃类有机液体氢载体储氢被认为是最有可能实现大规模且安全高效的异地氢储运技术。本文介绍了多环芳烃类不饱和有机液体储氢技术的基本原理与常用有机氢载体的物化性质，分析了作为有机氢载体的关键参数，在此基础上，从空间位阻效应的角度解释了多环芳烃类有机液体氢载体的环内与环间加脱氢反应机理，并进一步从活性组分分散度、表面电荷效应、氢溢流以及低配位数等方面对多环芳烃加脱氢催化剂的研究进展进行了总结。提出了目前多环芳烃类有机液体氢载体储氢的技术难点在于脱氢温度高、循环率低以及催化剂成本高，并对优化能量匹配、催化剂改性等未来的应用场景和发展方向进行了展望。

关键词: 苯, 氢, 反应, 催化剂

CLC Number:

TQ426

ZHOU Yiming, QI Suitao, ZHOU Yuliang, TAN Xiao, SHI Libin, YANG Bolun. Research progress in the hydrogenation and dehydrogenation technology of polycyclic aromatic hydrocarbon liquid organic hydrogen carriers[J]. Chemical Industry and Engineering Progress, 2023, 42(2): 1000-1007.

周一鸣, 齐随涛, 周宇亮, 谭潇, 石利斌, 杨伯伦. 多环芳烃类液体有机氢载体储放氢技术研究进展[J]. 化工进展, 2023, 42(2): 1000-1007.

Figures/Tables 8

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物化性质	甲苯	甲基环己烷	二苄基甲苯	全氢化二苄基甲苯	萘	十氢萘	苄基甲苯
外观与性状	无色液体	无色液体	微黄色液体	无色液体	无色有光泽晶体	无色液体	—
化学式	C₇H₈	C₇H₁₄	C₂₁H₂₀	C₂₁H₃₈	C₁₀H₈	C₁₀H₁₈	C₁₄H₁₄
结构式
分子量	92.14	98.19	272.38	290.38	128	138	182
闪点/℃	4	-3.9	200	—	78.89	58	—
熔点/℃	-94.9	-126.4	-39	-45	80.5	约-35	6.66
沸点/℃	110.6	101.2	390	354	217.9	约190	280.5
密度/g·cm^-3	0.87	0.77	1.04	0.91	1.162	0.9	—
引燃温度/℃	535	250	450	—	526.11	262	—
爆炸极限/%	1.2~7.0	1.2~6.7	—	—	0.9~5.9	0.4~4.9	—
毒性	低毒类	低毒类	低毒类	低毒类	低毒类	低毒类	低毒类
加氢温度/℃	约150	—	140	—	约250	—	—
脱氢温度/℃	—	约300	—	270	—	约340	—
价格/CNY·t^-1	8000	11000	14000	—	7900	75000	—

物化性质	甲苯	甲基环己烷	二苄基甲苯	全氢化二苄基甲苯	萘	十氢萘	苄基甲苯
外观与性状	无色液体	无色液体	微黄色液体	无色液体	无色有光泽晶体	无色液体	—
化学式	C₇H₈	C₇H₁₄	C₂₁H₂₀	C₂₁H₃₈	C₁₀H₈	C₁₀H₁₈	C₁₄H₁₄
结构式
分子量	92.14	98.19	272.38	290.38	128	138	182
闪点/℃	4	-3.9	200	—	78.89	58	—
熔点/℃	-94.9	-126.4	-39	-45	80.5	约-35	6.66
沸点/℃	110.6	101.2	390	354	217.9	约190	280.5
密度/g·cm^-3	0.87	0.77	1.04	0.91	1.162	0.9	—
引燃温度/℃	535	250	450	—	526.11	262	—
爆炸极限/%	1.2~7.0	1.2~6.7	—	—	0.9~5.9	0.4~4.9	—
毒性	低毒类	低毒类	低毒类	低毒类	低毒类	低毒类	低毒类
加氢温度/℃	约150	—	140	—	约250	—	—
脱氢温度/℃	—	约300	—	270	—	约340	—
价格/CNY·t^-1	8000	11000	14000	—	7900	75000	—

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