Research progress and application scenarios of storage and transportation technology with liquid organic hydrogen carrier

doi:10.19799/j.cnki.2095-4239.2023.0523

Abstract

Abstract:

Under the "dual-carbon" strategic goal, the hydrogen energy industry has undergone rapid and extensive development. The upstream hydrogen production resources are abundant, and the downstream hydrogen market is expansive. However, the cross-regional imbalance in hydrogen energy supply and demand has led to a critical bottleneck in midstream hydrogen energy storage and transportation, hindering the further progress of the hydrogen energy industry. In response to this challenge, liquid organic hydrogen-carrying (LOHC) storage and transportation technology was developed. This method, employing a chemical hydrogen storage approach, perfectly overcomes the defects of physical hydrogen storage methods, such as high-pressure gas hydrogen storage and low-temperature liquid and metal solid methods. Compared with other hydrogen energy storage and transportation technologies, LOHC has outstanding advantages in safety, cost, technology, efficiency, and other aspects. It is expected to address the shortcomings in hydrogen energy storage and transportation, thus enhancing the hydrogen energy industry chain. Herein, three main LOHC storage and transportation technologies, namely methylcyclohexane, N-ethylcarbazole, and dibenzyltoluene, are compared and analyzed from the aspects of process principle, hydrogen storage carrier, comprehensive cost, and research and development. The analysis suggests that these three LOHC technologies, having completed theoretical research, experimental verification, and pilot scale, are poised for industrial popularization and application. In the future perspective, the new application scenarios of two LOHC storage and transportation technologies, including large-scale hydrogen energy storage and transportation bases and distributed dehydrogenation and hydrogenation integrated stations, are analyzed. The challenges and research directions of LOHC storage and transportation technology are summarized while providing hopeful suggestions for the future.

Key words: hydrogen energy, liquid organic hydrogen carrier (LOHC), storage and transportation, application scenarios

CLC Number:

TQ116.2

Chengzhi XING, Ming ZHAO, Chao SHANG, Sijing ZHANG, Zili ZHANG, Yang LIU. Research progress and application scenarios of storage and transportation technology with liquid organic hydrogen carrier[J]. Energy Storage Science and Technology, 2024, 13(2): 643-651.

Figures/Tables 7

Table 1

The summery for comprehensive comparison of hydrogen energy storage and transportation technologies[3-9]"

指标	高压气态	液态		固态
指标	高压气态	低温液态	有机液体	金属氢化物	碳材料物理吸附
技术原理	将氢气压缩于高压容器中，储氢密度与储存压力、储存容器类型相关	低温(20 K)条件下对氢液化，并低温保冷储运，实现氢的高密度储运	利用可循环有机液体的不饱和共价键作为载体进行加氢、脱氢，实现氢能储运	利用合金不同金属组分与氢原子结合形成金属氢化物，实现氢的储存和释放	采用高比表面积碳吸附剂(活性炭或纳米碳材料分子筛)通过物理吸附解析，实现氢储运
体积储氢密度（容器）	13 g/L(20 MPa) 24 g/L(35 MPa)	60～71 g/L	51～62 g/L	50～55 g/L	50～55 g/L
质量储氢密度（容器）	4%(Ⅲ型瓶) 5.5%～6%(Ⅳ型瓶)	5%～20%	5.5%	1%~2%	2.5%～8.25%
运输工具及经济距离	长管拖车 ≤150 km	液氢槽罐车 ≥200 km	槽罐车 ≥200 km	固体货车 ≥200 km	固体货车 ≥200 km
优点	技术成熟、加氢放氢便捷，氢能储运产业链完善	液氢体积密度最高，释放氢气纯度高	储氢密度高、安全性能高、储运便捷、经济、可实现远距离运输	安全性能高，储存压力低，运输方便	压力适中，储存容器自重轻，形状多样化，安全性高
缺点	储氢密度低，容器耐压要求高，储运安全性差，运输成本高(1 kg H₂ 100 km、200 km的运费为7～8元、20～25元)，无法完成中运距离运输	产业链不完善，液化能耗高(12～17 kWh/kg H₂)，冷能利用率低，容器绝热性要求高，储运保冷能耗高，汽化及泄压排放损耗大	产业链不完善，加氢、脱氢涉及化学可逆反应平衡，技术控制相对复杂，释放的氢气需净化处理，有机液体循环过程存在损耗	产业链尚未形成，价格高，寿命短、储存释放条件苛刻	产业链尚未形成，价格高，寿命短、储存释放难以控制
技术进展	发展成熟，广泛用于车用氢能领域	国外已有多年液氢运输经验，国内氢液化及液氢储运技术仍需进一步提升	已完成技术研发，处于工业化推广应用阶段	处于研发阶段，距离商业化大规模应用较远	处于研发阶段，距离商业化大规模应用较远

Table 1

Fig. 1

Table 2

Table 3

Table 4

Fig. 2

Fig. 3

References 23

1	中国氢能联盟. 中国氢能源及燃料电池产业白皮书(2020版)[R]. 2020.
2	TEICHMANN D, ARLT W, WASSERSCHEID P. Liquid organic hydrogen carriers as an efficient vector for the transport and storage of renewable energy[J]. International Journal of Hydrogen Energy, 2012, 37(23): 18118-18132.
3	王尔德, 雷正龙, 于振兴. 镁基储氢材料的研究进展[J]. 粉末冶金技术, 2003, 21(1): 31-36.
	WANG E D, LEI Z L, YU Z X. A review on the development of Mg-based hydrogen storage materials[J]. Powder Metallurgy Technology, 2003, 21(1): 31-36.
4	李志宝, 孙立贤, 张莹洁, 等. MgH₂储氢热力学研究进展[J]. 中国科学: 化学, 2014, 44(6): 964-972.
	LI Z B, SUN L X, ZHANG Y J, et al. Progress on hydrogen storage thermodynamic of MgH₂[J]. Scientia Sinica Chimica), 2014, 44(6: 964-972.
5	李袁庆, 刘志远, 杨松恋. 储氢材料的研究进展[J]. 化工管理, 2013(16): 207.
	LI Y Q, LIU Z Y, YANG S L. Research progress of hydrogen storage materials[J]. Chemical Enterprise Management, 2013(16): 207.
6	杨明, 王圣平, 张运丰, 等. 储氢材料的研究现状与发展趋势[J]. 硅酸盐学报, 2011, 39(7): 1053-1060.
	YANG M, WANG S P, ZHANG Y F, et al. Current status and future prospects of research on hydrogen storage materials[J]. Journal of the Chinese Ceramic Society, 2011, 39(7): 1053-1060.
7	龚金明, 刘道平, 谢应明. 储氢材料的研究概况与发展方向[J]. 天然气化工(C1化学与化工), 2010, 35(5): 71-78.
	GONG J M, LIU D P, XIE Y M. Progress on hydrogen storage materials[J]. Natural Gas Chemical Industry, 2010, 35(5): 71-78.
8	SREEDHAR I, KAMANI K M, KAMANI B M, et al. A Bird's Eye view on process and engineering aspects of hydrogen storage[J]. Renewable and Sustainable Energy Reviews, 2018, 91: 838-860.
9	AZIZ M, ODA T, KASHIWAGI T. Comparison of liquid hydrogen, methylcyclohexane and ammonia on energy efficiency and economy[J]. Energy Procedia, 2019, 158: 4086-4091.
10	蔡卫权, 张光旭, 陈进富, 等. 有机氢载体低温高效脱氢催化剂的研究进展[J]. 石油化工, 2007, 36(7): 744-749.
	CAI W Q, ZHANG G X, CHEN J F, et al. Development of dehydrogenation catalyst for reversible hydrogen storage based on organic hydrides[J]. Petrochemical Technology, 2007, 36(7): 744-749.
11	EYPASCH M, SCHIMPE M, KANWAR A, et al. Model-based techno-economic evaluation of an electricity storage system based on liquid organic hydrogen carriers[J]. Applied Energy, 2017, 185: 320-330.
12	Wulf C, Zapp P. Assessment of system variations for hydrogen transportation by LOHCs[J]. Int J Hydrogen Energy, 2018, 43: 11884-11895.
13	JIANG Z, PAN Q, XU J, et al. Current situation and prospect of hydrogen storage technology with new organic liquid[J]. International Journal of Hydrogen Energy, 2014, 39(30): 17442-17451.
14	BINIWALE R B, RAYALU S, DEVOTTA S, et al. Chemical hydrides: A solution to high capacity hydrogen storage and supply[J]. International Journal of Hydrogen Energy, 2008, 33(1): 360-365.
15	袁胜楠, 张龙龙, 赵宁, 等. 液态有机物储氢技术发展历程与问题分析[J]. 太阳能, 2022(9): 5-14.
	YUAN S N, ZHANG L L, ZHAO N, et al. Development history and problem analysis of liquid organic hydrogen carrier technology[J]. Solar Energy, 2022(9): 5-14.
16	HE T, PEI Q J, CHEN P. Liquid organic hydrogen carriers[J]. Journal of Energy Chemistry, 2015, 24(5): 587-594.
17	姜召, 徐杰, 方涛. 新型有机液体储氢技术现状与展望[J]. 化工进展, 2012, 31(S1): 315-322.
	JIANG Z, XU J, FANG T. Current situation and prospect for hydrogen storage technology with new organic liquid[J]. Chemical Industry and Engineering Progress, 2012, 31(S1): 315-322.
18	万超, 安越, 孔文静, 等. 十二氢乙基咔唑的催化脱氢性能研究[J]. 太阳能学报, 2014, 35(3): 439-442.
	WAN C, AN Y, KONG W J, et al. A study of catalytic dehydrogenation from dodecahydro-n-ethylcarbazole over a catalyst[J]. Acta Energiae Solaris Sinica, 2014, 35(3): 439-442.
19	吴富英. 新型有机液体储氢剂乙基咔唑的加氢催化剂研究[D]. 杭州: 浙江大学, 2014.
	WU F Y. Study on the hydrogenation effect of catalyst on new liquid hydrogen storage material N-ethylcarbazole[D]. Hangzhou: Zhejiang University, 2014.
20	孔文静. 咔唑加脱氢性能研究[D]. 杭州: 浙江大学, 2012.
	KONG W J. Study on the hydrogen uptake and release performance of carbazole[D]. Hangzhou: Zhejiang University, 2012.
21	BP statistical review of world energy 2020[R]. https://www.bp.com/content/dam/bp/country-sites/zh_cn/ china/home/reports/statistical-review-of-world-energy/2019/2019srbook.pdf.
22	薛景文, 于鹏飞, 张彦康, 等. 液态有机氢载体储氢系统脱氢反应器研究进展[J]. 热力发电, 2022, 51(11): 1-10.
	XUE J W, YU P F, ZHANG Y K, et al. Review on advances of dehydrogenation reactor for hydrogen storage system using liquid organic hydrogen carrier[J]. Thermal Power Generation, 2022, 51(11): 1-10.
23	NAKAYAMA J, MISONO H, SAKAMOTO J, et al. Simulation-based safety investigation of a hydrogen fueling station with an on-site hydrogen production system involving methylcyclohexane[J]. International Journal of Hydrogen Energy, 2017, 42(15): 10636-10644.

储氢介质	N-乙基咔唑(H0-NEC)	甲苯(TOL)	二苄基甲苯(H0-DBT)
加氢后有机物	全氢-乙基咔唑(H12-NEC)	甲基环己烷(MCH)	全氢二苄基甲苯(H18-DBT)
反应焓 △H/(kcal/mol H₂)	-11.8	-16.3	-16.0
加氢压力	8 MPa	4 MPa	6.0 MPa
脱氢压力	0.3 MPa	0.4 MPa	0.3 MPa
加氢方式	气(氢气)+液(H0-NEC)两相同时催化反应，加氢反应器流场复杂，需设液体分离器	气化温度较低，先将液体(TOL)加热气化，气相反应，加氢反应器流场简单，容易控制	气(氢气)+液(H0-DBT)两相同时催化反应，加氢反应器流场复杂，需设液体分离器
加氢温度	140～150 ℃，放热反应，副产140～150 ℃饱和蒸汽	130～200 ℃，放热反应，副产130～200 ℃饱和蒸汽	130～200 ℃，放热反应，副产130～200 ℃饱和蒸汽
加氢催化剂	镍系催化剂、钯及铂系催化剂、钌系催化剂和铑系催化剂
脱氢方式	气(氢气)+液(H12-NEC)两相同时催化反应，加氢反应器流场复杂，需设液体分离器	气化温度较低，先将液体(MCH)加热气化，气相反应，加氢反应器流场简单，容易控制	气(氢气)+液(H18-DBT)两相同时催化反应，加氢反应器流场复杂，需设液体分离器
脱氢催化剂	微量的贵金属	贵金属(Pt/Ir/Pd)	贵金属(Pt)
脱氢温度/℃	＞200	＞350	＞320
脱氢速度	20 L/(min·kW)	0.2 L/(min·kW)	0.7 L/(min·kW)

储氢介质	N-乙基咔唑(H0-NEC)	甲苯(TOL)	二苄基甲苯(H0-DBT)
分子结构
熔点	H0-NEC 70 ℃	TOL -95 ℃	DBT -34 ℃
熔点	H12-NEC -85 ℃	MCH -126 ℃	H18-DBT -50 ℃
沸点	H0-NEC 220 ℃	TOL 111 ℃	H0-DBT 390 ℃
沸点	H12-NEC 280 ℃	MCH 101 ℃	H18-DBT 371 ℃
液态温度范围	-85～280 ℃ (需加入一定溶剂，乙基咔唑才可在常温常压下保持液态)	-95～101 ℃ (常温常压下稳定液态)	-34～371 ℃ (常温常压下稳定液态)
质量储氢密度/%	5.8	6.12	6.23
体积储氢密度/(g/L)	58	47.4	59
闪点	186 ℃	闪点(闭杯) 4.4 ℃	200 ℃
火灾危险性	丙B 可燃	甲易燃易爆	丙B 可燃
爆炸极限/%	挥发性弱，无爆炸极限	1.2～7.0	挥发性弱，无爆炸极限
毒性	无毒	低毒	无毒
加氢催化剂	镍系催化剂、钯及铂系催化剂、钌系催化剂和铑系催化剂
加氢效率	＞95%	＞95%	＞95%
脱氢效率	＞95%	＞95%	＞95%
储氢载体成本	50000元/吨，量化生产可降至30000元/吨	市场大宗类危险化学品，市场价约8000元/吨	市场价格约25000元/吨
安全性能	普通化学品(不在《危险化学品名录(2015 版)》内)，储运不受危险化学品限制	第三类危险化学品，储运受到危险化学品限制	普通化学品(不在《危险化学品名录(2015 版)》内)，储运不受危险化学品限制

项目	N-乙基咔唑装置	甲苯装置	二苄基甲苯装置	备注
氢气/(元/kg H₂)	8.44	8.44	8.44
加氢/(元/kg H₂)	0.96	2.75	2.51	生产成本，不考虑载体损耗
储氢载体运输/(元/kg H₂)	4.10	4.50	4.20
脱氢/(元/kg H₂)(按导热油加热)	7.00	13.98	12.80
气氢运输/(元/kg H₂)	7.00	7.00	7.00	城市短途管束车运氢费用
加氢站到站氢价/(元/kg H₂)	27.54	36.27	34.95

[1]	Qili LIN, Hongxun QI, Jingjing HUANG, Bingcheng ZHANG, Zhen CHEN, Zhenkun XIAO. Levelized cost of combined hydrogen production by water electrolysis with alkaline-proton exchange membrane [J]. Energy Storage Science and Technology, 2023, 12(11): 3572-3580.
[2]	Jin XU, Xian DING, Yongli GONG, Guangli HE, Ting HU. Economic analysis of hydrogen production plant with water electrolysis [J]. Energy Storage Science and Technology, 2022, 11(7): 2374-2385.
[3]	Wei LIU, Yanming WAN, Yalin XIONG, Jian LIU. Outlook of low carbon and clean hydrogen in China under the goal of "carbon peak and neutrality" [J]. Energy Storage Science and Technology, 2022, 11(2): 635-642.
[4]	Yalin XIONG, Wei LIU, Pengbo GAO, Binqi DONG, Mingsheng ZHAO. Research on the hydrogen energy demand and carbon-reduction path in China's synthetic ammonia industry to achieve the “carbon peak” and “carbon neutrality” goals [J]. Energy Storage Science and Technology, 2022, 11(12): 4048-4058.
[5]	Jiamin LU, Junhui XU, Weidong WANG, Hao WANG, Zijun XU, Liuping CHEN. Development of large-scale underground hydrogen storage technology [J]. Energy Storage Science and Technology, 2022, 11(11): 3699-3707.
[6]	Yanming WAN, Yalin XIONG, Xueying WANG. Strategic analysis of hydrogen energy development in major countries [J]. Energy Storage Science and Technology, 2022, 11(10): 3401-3410.
[7]	Xiaoyuan WU, Zhelun ZUO, Shiyu GUO, Ru WANG, Jianhui HE. Evaluation on city application readiness of fuel cell logistics vehicles [J]. Energy Storage Science and Technology, 2020, 9(5): 1574-1584.
[8]	ZHAO Yuejing, HE Guangli, MIAO Ping, XU Zhuang, YANG Kang, TIAN Zhonghui, DONG Wenping, XIONG Yalin. Study on comprehensive evaluation of 35 MPa/70 MPa hydrogen dispenser refueling performance [J]. Energy Storage Science and Technology, 2020, 9(3): 702-706.
[9]	LI Luling, FAN Shuanshi, CHEN Qiuxiong, YANG Guang, WEN Yonggang. Hydrogen storage technology: Current status and prospects [J]. Energy Storage Science and Technology, 2018, 7(4): 586-594.
[10]	WANG Shuo1,2, ZHANG Jun3 . Research on patent status and process route of hydrogen production in China [J]. Energy Storage Science and Technology, 2018, 7(2): 353-362.
[11]	HUO Xianxu, WANG Jing, JIANG Ling, XU Qingshan. Review on key technologies and applications of hydrogen energy storage system [J]. Energy Storage Science and Technology, 2016, 5(2): 197-203.
[12]	CHEN Jun, CHEN Qiuxiong, CHEN Yunwen, FAN Shuanshi, WANG Yanhong, YANG Liang, LANG Xuemei, ZHANG Wenxiang, HUANG Yi, XIONG Wentao, WEN Yonggang. Current status of energy storage using hydrates [J]. Energy Storage Science and Technology, 2015, 4(2): 131-140.