有机液体储氢技术催化脱氢过程强化研究进展

doi:10.16085/j.issn.1000-6613.2023-1265

化工进展 ›› 2024, Vol. 43 ›› Issue (1): 164-185.DOI: 10.16085/j.issn.1000-6613.2023-1265

• 专栏：化工过程强化 • 上一篇

有机液体储氢技术催化脱氢过程强化研究进展

盖宏伟¹(), 张辰君², 屈晶莹³, 孙怀禄³, 脱永笑¹(), 王斌⁴, 金旭², 张茜², 冯翔³(), CHEN De¹^,⁵

^1.中国石油大学(华东)新能源学院，山东青岛 266580
^2.中国石油天然气股份有限公司勘探开发研究院，北京 100083
^3.中国石油大学(华东)化学化工学院，山东青岛 266580
^4.西安交通大学化学工程与技术学院，陕西西安 710049
^5.挪威科技大学化学工程系，挪威特隆赫姆N -7491

收稿日期:2023-07-23 修回日期:2023-11-07 出版日期:2024-01-20 发布日期:2024-02-05
通讯作者: 脱永笑,冯翔
作者简介:盖宏伟（2000—），男，硕士研究生，研究方向为有机储氢介质催化脱氢过程强化。E-mail：2634617620@qq.com。
基金资助:
国家自然科学基金(22208374);山东省自然科学基金(ZR2020QB173);中国石油科技创新基金(2022DQ02-0607)

Research progress on catalytic dehydrogenation process intensification for liquid organic hydride carrier hydrogen storage

GAI Hongwei¹(), ZHANG Chenjun², QU Jingying³, SUN Huailu³, TUO Yongxiao¹(), WANG Bin⁴, JIN Xu², ZHANG Xi², FENG Xiang³(), CHEN De¹^,⁵

^1.College of New Energy, China University of Petroleum (East China), Qingdao 266580, Shangdong, China
^2.Research Institute of Petroleum Exploration & Development, China National Petroleum Corporation, Beijing 100083, China
^3.College of Chemistry and Chemical Engineering, China University of Petroleum (East China), Qingdao 266580, Shangdong, China
^4.College of Chemical Engineering and Technology, Xi'an Jiaotong University, Xi'an 710049, Shaanxi
^5.Department of Chemical Engineering, Norwegian University of Science and Technology, Trondheim N -7491, Norway

Received:2023-07-23 Revised:2023-11-07 Online:2024-01-20 Published:2024-02-05
Contact: TUO Yongxiao, FENG Xiang

摘要/Abstract

摘要：

氢能是实现化石能源清洁高效利用和支撑可再生能源大规模发展的理想互联媒介，然而氢的储运是制约氢能规模化应用的关键技术瓶颈。有机氢化物（LOHC）储氢技术具有成本低、储氢密度大、安全稳定等优势，可匹配现有化石能源输运架构，有望在大规模、长距离和分布式的氢储运场景中发挥重要作用。但是，在LOHC储氢循环中，相对于发展较为成熟的加氢技术，LOHC脱氢过程效率低、稳定性差，是制约该技术发展的关键。基于此，本文综述了LOHC储氢技术催化脱氢过程强化的研究进展和发展趋势，概述了LOHC储氢基本概念和催化脱氢反应基本原理，从催化过程强化、产物分离强化、能量效率强化等方面总结了脱氢过程强化策略，通过对比不同技术手段的特点，分析了LOHC储氢技术催化脱氢过程目前亟需解决的难题，即开发高效的脱氢催化剂、提高催化脱氢过程的传热传质效率以及降低脱氢过程能耗，这对LOHC储氢技术的实际应用具有重要的参考和借鉴意义。

关键词: 有机液体储氢, 传热, 传质, 催化剂, 催化剂载体

Abstract:

Hydrogen energy serves as an ideal intermediary for the clean and efficient utilization of fossil fuels and large-scale development of renewable energy. However, the storage and transportation of hydrogen are the key technical bottlenecks that limit the application of hydrogen energy. Liquid organic hydride carrier (LOHC) hydrogen storage technology, with its advantages of low cost, high hydrogen storage density, and safety, can be integrated into existing fossil fuel transport infrastructure, making it a promising solution for large-scale, long-distance, and distributed hydrogen storage and transportation scenarios. However, compared to more mature hydrogenation technologies, the efficiency and stability of LOHC dehydrogenation process are still not high enough in the storage cycle, which however is crucial for further development of LOHC storage technology. Herein, we provide a comprehensive review of the research progress and development trends in enhancing the catalytic dehydrogenation process for LOHC hydrogen storage technology. The review outlines the fundamental concepts of LOHC hydrogen storage and the principles of catalytic dehydrogenation reactions. It further summarizes the improvement strategies for the catalytic processes, product separation techniques, and energy efficiency. By analyzing the characteristics of different technical approaches, we point out the current challenges in the catalytic dehydrogenation process of LOHC hydrogen storage technology, including the development of dehydrogenation catalysts, enhancement of heat and mass transfer and optimization of energy efficiency, and highlight the research priorities and prospects in the future.

Key words: liquid organic hydride carrier (LOHC) hydrogen storage, heat transfer, mass transfer, catalyst, catalyst support

中图分类号:

TQ032

盖宏伟, 张辰君, 屈晶莹, 孙怀禄, 脱永笑, 王斌, 金旭, 张茜, 冯翔, CHEN De. 有机液体储氢技术催化脱氢过程强化研究进展[J]. 化工进展, 2024, 43(1): 164-185.

GAI Hongwei, ZHANG Chenjun, QU Jingying, SUN Huailu, TUO Yongxiao, WANG Bin, JIN Xu, ZHANG Xi, FENG Xiang, CHEN De. Research progress on catalytic dehydrogenation process intensification for liquid organic hydride carrier hydrogen storage[J]. Chemical Industry and Engineering Progress, 2024, 43(1): 164-185.

图/表 19

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LOHC	全氢化物熔点/℃	全氢化物沸点/℃	质量储氢密度（%） /体积储氢密度（kg/m³）	全氢化物脱氢温度/℃
苯	6.5	80.7	7.2/55.9	300~320
甲苯	-126.6	101	6.2/47.4	300~350
萘	-31	187	7.3/65.4	320~340
联苯	3	227	7.27/—	310~330
二苯基甲烷	-18.6	153	6.66/—	340~360
咔唑	65	124	6.7/—	150~170
N-乙基咔唑	-84.5	—	5.8/—	170~200
二苄基甲苯	-39	390	6.2/5.7	260~310

LOHC	全氢化物熔点/℃	全氢化物沸点/℃	质量储氢密度（%） /体积储氢密度（kg/m³）	全氢化物脱氢温度/℃
苯	6.5	80.7	7.2/55.9	300~320
甲苯	-126.6	101	6.2/47.4	300~350
萘	-31	187	7.3/65.4	320~340
联苯	3	227	7.27/—	310~330
二苯基甲烷	-18.6	153	6.66/—	340~360
咔唑	65	124	6.7/—	150~170
N-乙基咔唑	-84.5	—	5.8/—	170~200
二苄基甲苯	-39	390	6.2/5.7	260~310

催化剂载体	传质因子J_D	气相传质系数k_g/mm·s^-1	外扩散判据η_e·D_a	有效扩散系数D_e/mm²·g^-1	内扩散判据φ²·η_i
Ni-C₂H₆	3.50	7.07	9.07×10^-5	8.98	2.63×10^-7
Fe-CO	3.74	7.32	1.79×10^-4	8.46	7.18×10^-7
AC球-A	2.03	4.06	3.65×10^-3	1.37	0.02
AC球-B	2.04	4.04	5.94×10^-2	1.37	0.31

催化剂载体	传质因子J_D	气相传质系数k_g/mm·s^-1	外扩散判据η_e·D_a	有效扩散系数D_e/mm²·g^-1	内扩散判据φ²·η_i
Ni-C₂H₆	3.50	7.07	9.07×10^-5	8.98	2.63×10^-7
Fe-CO	3.74	7.32	1.79×10^-4	8.46	7.18×10^-7
AC球-A	2.03	4.06	3.65×10^-3	1.37	0.02
AC球-B	2.04	4.04	5.94×10^-2	1.37	0.31

强化策略	传热、传质性能	脱氢效率分析	评价
催化过程强化
液膜态/湿干多相态	催化剂表面经历湿干两相，催化剂表面温度较高，传递介质使用过热液体代替气体，传热和传质效率均提高	湿干多相态下，环己烷在375℃时脱氢反应速率可达3.8mol/g_Pt/min^[79]，是传统粉末Pt/Al₂O₃催化剂的3倍多	反应物与催化剂用量比例、喷雾条件等要求严格，难以应用于大规模制氢场景
微波耦合	催化剂由内向外发热，传热效率提高	微波加热至196℃，十氢萘^[84]脱氢速率可达0.07mol/(g_Pt·min)，在微波加热条件下，十氢萘的转化率是传统加热方式的2~3倍	加热更加均匀，传热效率提高，能耗降低且催化剂表面不易结焦
电场强化	质子扩散速率加强	在甲基环己烷脱氢时，施加电场降低了反应活化能25kJ/mol；448K时，甲基环己烷转化率可达约37%^[88]，超过传统加热的12%	电场强化加速了质子碰撞，降低了反应活化能，可以显著降低脱氢温度
规整结构催化剂及反应器	规整化的三维空间结构的催化剂载体具有特殊的流体流动、传热传质性能	在243℃下，2h内，十氢萘脱氢速率可达2.16mol/(g_Pt·min)，高于同种类型的粉末状催化剂脱氢速率（约2~3倍）^[91,99]	作为实验室向工业应用过渡的枢纽，是科学研究的重要方向
产物分离强化
膜分离	在反应过程中，将产物及时分离，避免产物带走过多热量，促使化学反应平衡向生成产物的方向移动，打破了热力学限制，传热以及传质速率均提高	使用膜分离反应器进行环己烷脱氢，转化率可达70%以上，渗透流H₂的纯度可达99.9%^[98]	膜分离反应器提高LOHC脱氢转化率以及H₂纯度
反应精馏	—	反应精馏相比于一般液相脱氢，其脱氢度提高约30%^[106]	—
能量效率强化
与燃料电池耦合	—	与燃料电池联合运行，氢气发电效率可达45%^[114]	将LOHC脱氢过程与燃料电池联合运行，将有效提高系统能量利用率，进一步节约能耗
加/脱氢一体化	—	使用双功能催化剂，二苄基甲苯的储氢效率可达84%^[119]	加氢放热和脱氢吸热的高效耦合，提高能量利用率；反应装置体积缩小，成本以及能耗降低

有机液体储氢技术催化脱氢过程强化研究进展

Research progress on catalytic dehydrogenation process intensification for liquid organic hydride carrier hydrogen storage

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