Thermodynamic analysis and optimization of 10 t/d hydrogen liquefaction process

doi:10.11949/0438-1157.20221084

Abstract

Abstract:

According to the requirements for the development of a 10 t/d hydrogen liquefaction unit, a continuous conversion dual-pressure Claude hydrogen liquefaction process with liquid nitrogen precooling was constructed. The hydrogen liquefaction process is based on a liquid-nitrogen-precooled dual pressure Claude cycle using continuous ortho-to-para hydrogen conversion method. The influence of key factors on process performance is analyzed, including expander isentropic efficiency, recuperator minimum approach and feed hydrogen pressure drop, etc. The thermodynamic parameter ranges of the liquefaction process and key equipment are provided, which could be a reference for the design of expanders and recuperators. Under the basic operation conditions (a severe operation condition for hydrogen expanders), the maximum liquid hydrogen output is 12.96 t/d with para-hydrogen concentration of 97%. The calculated overall specific power consumption is 10.50 kWh/kg LH₂ (the compression power of feed hydrogen is not included), with process exergy efficiency of 35.06%. The simulation methods and simulation results could be a reference for the development of continuous ortho-to-para conversion type large scale hydrogen liquefaction systems.

Key words: hydrogen, liquefaction, expander, thermodynamics process, process analysis

摘要：

针对10 t/d级氢液化装置研制要求，构建了液氮预冷的连续转化型双压Claude氢液化流程，并开展了氢物性计算方法筛选、连续转化热模型构建以及流程热力设计与参数优化，分析了膨胀机等熵效率、换热器窄点温差以及原料氢沿程阻力等因素对流程参数的影响，给出了不同工况下的流程性能及各关键部件的热力设计参数范围，可为膨胀机、换热器的研制提供设计热力输入参数。该氢液化流程在基础工况下（考虑较恶劣膨胀机运行条件）的最大理论液氢产量12.96 t/d，液氢产品仲氢含量97%；理论总氢液化比功耗为10.50 kWh/kg LH₂（不含原料氢增压），对应的流程㶲效率为35.06%；可为连续转化式大型氢膨胀液化装置的研制提供参考。

关键词: 氢, 液化, 膨胀机, 热力学过程, 流程分析

CLC Number:

TB 657.8

Haocheng WANG, Jingyao YANG, Xueqiang DONG, Hao GUO, Yanxing ZHAO, Maoqiong GONG. Thermodynamic analysis and optimization of 10 t/d hydrogen liquefaction process[J]. CIESC Journal, 2022, 73(11): 5106-5117.

王昊成, 杨敬瑶, 董学强, 郭浩, 赵延兴, 公茂琼. 10 t/d级氢液化装置流程热力分析与优化[J]. 化工学报, 2022, 73(11): 5106-5117.

Figures/Tables 19

Table 1 Comparison of several hydrogen liquefaction processes

流程构型	技术特点
L-H循环（节流循环）	用于早期或微小型液化装置，能耗较高，目前已少见应用
氦膨胀制冷循环	主要用于< 2.5 t/d的小型氢液化装置；能耗一般高于氢膨胀制冷
氢膨胀制冷循环	现有≥5 t/d大型氢液化装置的主流流程（双压Claude循环等）
新型循环（J-B循环等）	液体/两相膨胀机等技术尚未突破，设备初投资高、技术风险大，无实际应用

Fig.1 Typical expander arrangement methods in hydrogen expansion liquefaction processes

Table 2 Main parameter comparison of hydrogen expander units under typical operation conditions

参数	两组串联	两组并联
进口压力/bar	24.68	24.71
进口温度/K	65.05	75.74
出口压力/bar	18.50	13.84
出口温度/K	59.15	63.02
进出口焓降, Δh/(kJ/kg)	52.34	120.04
最大线速度, u/(m/s)	220.01	333.19
理论转速, ω/(r/min)	70031	106065

Fig.2 Typical ortho-to-para hydrogen conversion methods

Fig.3 10 t/d dual-pressure Claude hydrogen liquefaction process

Fig.4 cp of normal hydrogen calculated by MBWR and Refprop

Fig.5 cp of normal hydrogen and equilibrium hydrogen

Fig.6 Comparison of simulative heat source and actual ortho-to-para hydrogen conversion heat

Fig.7 Flow chart of complex optimization method

Table 3 Main thermodynamic parameters of 10 t/d hydrogen liquefaction process under basic operation conditions

流程参数	计算结果
最大液化量/（L/h）	7812.31
液氢质量流量/（g/s）	150.00
原料氢压力/bar	25.00
循环氢质量流量/（g/s）	845.40
总UA值/（kW/K）	617.63
液氮耗量/（L/h）	5810.12
氢循环理论功耗/kW	3347.00
氢循环理论比功耗/（kWh/kg LH₂）	6.20
预冷理论比功耗/（kWh/kg LH₂）	4.30
总理论比功耗/（kWh/kg LH₂）	10.50
流程㶲效率/%	35.06

Fig.8 Process performance under various expander isentropic efficiencies

Fig.9 Process exergy loss distribution under basic operation conditions

Table 4 Main parameter comparison of hydrogen expander units under typical operation conditions

文献	流程结构	设计产量/（t/d）	功耗/（kWh/kg）
[17]	液氮预冷的双压Claude流程（模拟值）	2.63	10.85
[15]	液氮预冷的氦气膨胀制冷流程（模拟值）	1.51	10.25
[19]	混合工质预冷的四级 J-B流程（模拟值）	100	5.91
[3]	液氮预冷的双压Claude流程（实测值）	5.00	11.90
[11]	液氮预冷的氦气膨胀制冷流程（实测值）	约1.5	约17
本文	液氮预冷的双压Claude流程（模拟值）	12.96	10.50

Fig.10 Key thermodynamic parameters of the compressor unit under various expander isentropic efficiencies

Fig.11 Key thermodynamic parameters of the expander unit under various expander isentropic efficiencies

Fig.12 T-Q plots of recuperators under basic conditions

Fig.13 Key thermodynamic parameters of recuperators under various expander isentropic efficiencies

Fig.14 Key thermodynamic parameters of recuperators under various minimum approaches (ΔTmin)

Fig.15 Key thermodynamic parameters of recuperators under various recuperator pressure drops (Δp)

References 36

1	Aasadnia M, Mehrpooya M. Large-scale liquid hydrogen production methods and approaches: a review[J]. Applied Energy, 2018, 212: 57-83.
2	Ohlig K, Decker L. The latest developments and outlook for hydrogen liquefaction technology[J]. AIP Conference Proceedings, 2014, 1573(1): 1311-1317.
3	Krasae-in S, Stang J H, Neksa P. Development of large-scale hydrogen liquefaction processes from 1898 to 2009[J]. International Journal of Hydrogen Energy, 2010, 35(10): 4524-4533.
4	唐璐, 邱利民, 姚蕾, 等. 氢液化系统的研究进展与展望[J]. 制冷学报, 2011, 32(6): 1-8.
	Tang L, Qiu L M, Yao L, et al. Review on research and developments of hydrogen liquefaction systems[J]. Journal of Refrigeration, 2011, 32(6): 1-8.
5	陈双涛, 周楷淼, 赖天伟, 等. 大规模氢液化方法与装置[J]. 真空与低温, 2020, 26(3): 173-178.
	Chen S T, Zhou K M, Lai T W, et al. Large-scale hydrogen liquefaction methods and devices[J]. Vacuum and Cryogenics, 2020, 26(3): 173-178.
6	Moradi R, Groth K M. Hydrogen storage and delivery: review of the state of the art technologies and risk and reliability analysis[J]. International Journal of Hydrogen Energy, 2019, 44(23): 12254-12269.
7	Ni M. An overview of hydrogen storage technologies [J]. Energy Exploration & Exploitation, 2006, 24(3): 197-209.
8	张祉祐. 低温技术原理与装置[M]. 北京:机械工业出版社, 1987.
	Zhang Z Y. Principle and Equipment of Cryogenic Technology[M]. Beijing: China Machine Press, 1987.
9	Garceau N M, Baik J H, Lim C M, et al. Development of a small-scale hydrogen liquefaction system[J]. International Journal of Hydrogen Energy, 2015, 40(35): 11872-11878.
10	曹学文, 杨健, 边江, 等. 新型双压Linde-Hampson氢液化工艺设计与分析[J]. 化工进展, 2021, 40(12): 6663-6669.
	Cao X W, Yang J, Bian J, et al. Design and analysis of a new type of dual-pressure Linde-Hampson hydrogen liquefaction process[J]. Chemical Industry and Engineering Progress, 2021, 40(12): 6663-6669.
11	吕翠, 王金阵, 朱伟平, 等. 氢液化技术研究进展及能耗分析[J]. 低温与超导, 2019, 47(7): 11-18.
	Lyu C, Wang J Z, Zhu W P, et al. Research progress and energy consumption analysis of hydrogen liquefaction technology[J]. Cryogenics ＆ Superconductivity, 2019, 47(7): 11-18.
12	殷靓, 巨永林. 氢液化流程设计和优化方法研究进展[J]. 制冷学报, 2020, 41(3): 1-10.
	Yin L, Ju Y L. Review on researches and developments of the design and optimization for hydrogen liquefaction processes[J]. Journal of Refrigeration, 2020, 41(3): 1-10.
13	Staats W L. Analysis of a supercritical hydrogen liquefaction cycle[D]. Cambridge: Massachusetts Institute of Technology, 2008.
14	Yuksel Y E, Ozturk M, Dincer I. Analysis and assessment of a novel hydrogen liquefaction process[J]. International Journal of Hydrogen Energy, 2017, 42(16): 11429-11438.
15	殷靓, 巨永林, 王刚. 1, 000 L/h氢液化装置工艺流程分析及优化[J]. 制冷技术, 2019, 39(1): 39-44.
	Yin L, Ju Y L, Wang G. Process analysis and optimization of 1, 000 L/h hydrogen liquefaction system[J]. Chinese Journal of Refrigeration Technology, 2019, 39(1): 39-44.
16	唐璐. 基于液氮预冷的氢液化流程设计及系统模拟[D]. 杭州: 浙江大学, 2012.
	Tang L. Design and simulation of a hydrogen liquefaction cycle based on liquid nitrogen precooling[D]. Hangzhou: Zhejiang University, 2012.
17	Baker C R, Shaner R L. A study of the efficiency of hydrogen liquefaction[J]. International Journal of Hydrogen Energy, 1978, 3(3): 321-334.
18	Stang J, Nekså P, Brendeng E. On the design of an efficient hydrogen liquefaction process[C]//Proceeding of the 16th World Hydrogen Energy Conference. 2006.
19	Krasae-in S, Stang J H, Neksa P. Simulation on a proposed large-scale liquid hydrogen plant using a multi-component refrigerant refrigeration system[J]. International Journal of Hydrogen Energy, 2010, 35(22): 12531-12544.
20	Ansarinasab H, Mehrpooya M, Mohammadi A. Advanced exergy and exergoeconomic analyses of a hydrogen liquefaction plant equipped with mixed refrigerant system[J]. Journal of Cleaner Production, 2017, 144: 248-259.
21	Kuendig A, Loehlein K, Kramer G J, et al. Large scale hydrogen liquefaction in combination with LNG re-gasification[C]//Proceedings of the 16th World Hydrogen Energy Conference. 2006: 3326-3333.
22	Cardella U, Decker L, Sundberg J, et al. Process optimization for large-scale hydrogen liquefaction[J]. International Journal of Hydrogen Energy, 2017, 42(17): 12339-12354.
23	Asadnia M, Mehrpooya M. A novel hydrogen liquefaction process configuration with combined mixed refrigerant systems[J]. International Journal of Hydrogen Energy, 2017, 42(23): 15564-15585.
24	Gross R, Otto W, Patzelt A, et al. Liquid hydrogen for Europe—the Linde plant at Ingolstadt [J]. Linde-Reports on Science and Technology, 1994, 54: 37-43.
25	Bracha M, Lorenz G, Patzelt A, et al. Large-scale hydrogen liquefaction in Germany[J]. International Journal of Hydrogen Energy, 1994, 19(1): 53-59.
26	Leachman J W, Jacobsen R T, Penoncello S G, et al. Fundamental equations of state for parahydrogen, normal hydrogen, and orthohydrogen[J]. Journal of Physical and Chemical Reference Data, 2009, 38(3): 721-748.
27	Zhuzhgov A V, Krivoruchko O P, Isupova L A, et al. Low-temperature conversion of ortho-hydrogen into liquid para-hydrogen: process and catalysts. Review[J]. Catalysis in Industry, 2018, 10(1):9-19.
28	杨晓阳, 杨昌乐. 正仲氢转化催化剂性能研究[J]. 化学推进剂与高分子材料, 2018, 16(3): 79-82.
	Yang X Y, Yang C L. Study on performance of orthohydrogen-parahydrogen converting catalyst[J]. Chemical Propellants ＆ Polymeric Materials, 2018, 16(3): 79-82.
29	Jacobsen R T, Stewart R B. Thermodynamic properties of nitrogen including liquid and vapor phases from[J]. Journal of Physical and Chemical Reference Data, 1973, 2(4): 757-922.
30	Lemmon E W, Huber M L, McLinden M O. NIST standard reference database 23: reference fluid thermodynamic and transport properties (REFPROP), version 9.0[DB]. Gaithersburg: National Institute of Standards and Technology, 2010.
31	Peng D Y, Robinson D B. A new two-constant equation of state[J]. Industrial & Engineering Chemistry Fundamentals, 1976, 15(1): 59-64.
32	Kwak T Y, Mansoori G A. van der Waals mixing rules for cubic equations of state. Applications for supercritical fluid extraction modelling[J]. Chemical Engineering Science, 1986, 41(5): 1303-1309.
33	Box M J. A new method of constrained optimization and a comparison with other methods[J]. The Computer Journal, 1965, 8(1): 42-52.
34	Linnhoff B, Hindmarsh E. The pinch design method for heat exchanger networks[J]. Chemical Engineering Science, 1983, 38(5): 745-763.
35	徐攀, 文键, 厉彦忠, 等. 氢正仲转化耦合流动换热板翅式换热器研究[J]. 西安交通大学学报, 2021, 55(12): 16-24.
	Xu P, Wen J, Li Y Z, et al. Study on hydrogen ortho-para conversion coupled with flow and heat transfer of the plate fin heat exchanger[J]. Journal of Xi’an Jiaotong University, 2021, 55(12): 16-24.
36	李启铭, 张磊, 徐攀, 等. 氢液化流程中催化换热一体化可行性研究[J]. 化学工程, 2021, 49(7): 26-30.
	Li Q M, Zhang L, Xu P, et al. Feasibility on integration of catalysis and heat transfer in hydrogen liquefaction process[J]. Chemical Engineering (China), 2021, 49(7): 26-30.

[1]	Xin YANG, Wen WANG, Kai XU, Fanhua MA. Simulation analysis of temperature characteristics of the high-pressure hydrogen refueling process [J]. CIESC Journal, 2023, 74(S1): 280-286.
[2]	Congqi HUANG, Yimei WU, Jianye CHEN, Shuangquan SHAO. Simulation study of thermal management system of alkaline water electrolysis device for hydrogen production [J]. CIESC Journal, 2023, 74(S1): 320-328.
[3]	Zehao MI, Er HUA. DFT and COSMO-RS theoretical analysis of SO₂ absorption by polyamines type ionic liquids [J]. CIESC Journal, 2023, 74(9): 3681-3696.
[4]	Ke LI, Jian WEN, Biping XIN. Study on influence mechanism of vacuum multi-layer insulation coupled with vapor-cooled shield on self-pressurization process of liquid hydrogen storage tank [J]. CIESC Journal, 2023, 74(9): 3786-3796.
[5]	Junfeng LU, Huaiyu SUN, Yanlei WANG, Hongyan HE. Molecular understanding of interfacial polarization and its effect on ionic liquid hydrogen bonds [J]. CIESC Journal, 2023, 74(9): 3665-3680.
[6]	Feifei YANG, Shixi ZHAO, Wei ZHOU, Zhonghai NI. Sn doped In₂O₃ catalyst for selective hydrogenation of CO₂ to methanol [J]. CIESC Journal, 2023, 74(8): 3366-3374.
[7]	Bin LI, Zhenghu XU, Shuang JIANG, Tianyong ZHANG. Clean and efficient synthesis of accelerator CBS by hydrogen peroxide catalytic oxidation method [J]. CIESC Journal, 2023, 74(7): 2919-2925.
[8]	Chao NIU, Shengqiang SHEN, Yan YANG, Bonian PAN, Yiqiao LI. Flow process calculation and performance analysis of methane BOG ejector [J]. CIESC Journal, 2023, 74(7): 2858-2868.
[9]	Xiaoyang LIU, Jianliang YU, Yujie HOU, Xingqing YAN, Zhenhua ZHANG, Xianshu LYU. Effect of spiral microchannel on detonation propagation of hydrogen-doped methane [J]. CIESC Journal, 2023, 74(7): 3139-3148.
[10]	Ming DONG, Jinliang XU, Guanglin LIU. Molecular dynamics study on heterogeneous characteristics of supercritical water [J]. CIESC Journal, 2023, 74(7): 2836-2847.
[11]	Xiaowen ZHOU, Jie DU, Zhanguo ZHANG, Guangwen XU. Study on the methane-pulsing reduction characteristics of Fe₂O₃-Al₂O₃ oxygen carrier [J]. CIESC Journal, 2023, 74(6): 2611-2623.
[12]	Yong LI, Jiaqi GAO, Chao DU, Yali ZHAO, Boqiong LI, Qianqian SHEN, Husheng JIA, Jinbo XUE. Construction of Ni@C@TiO₂ core-shell dual-heterojunctions for advanced photo-thermal catalytic hydrogen generation [J]. CIESC Journal, 2023, 74(6): 2458-2467.
[13]	Xueyan WEI, Yong QIAN. Experimental study on the low to medium temperature oxidation characteristics and kinetics of micro-size iron powder [J]. CIESC Journal, 2023, 74(6): 2624-2638.
[14]	Xiqing ZHANG, Yanting WANG, Yanhong XU, Shuling CHANG, Tingting SUN, Ding XUE, Lihong ZHANG. Effect of Mg content on isobutane dehydrogenation properties over nanosheets supported Pt-In catalysts [J]. CIESC Journal, 2023, 74(6): 2427-2435.
[15]	Tianhao BAI, Xiaowen WANG, Mengzi YANG, Xinwei DUAN, Jie MI, Mengmeng WU. Study on release and inhibition behavior of COS during high-temperature gas desulfurization process using Zn-based oxide derived from hydrotalcite [J]. CIESC Journal, 2023, 74(4): 1772-1780.