基于液氖液氮梯级蓄冷的液氢储能中冷能回收利用研究

doi:10.11949/0438-1157.20241053

摘要/Abstract

摘要：

为了解决液氢储能中能量时空错配问题及优先匹配合适应用场景，采用液氖、液氮、二氧化碳等工质联合梯级蓄冷的方法回收冷能，而后预冷旁路氢气再并入液化器补偿冷量以减小耗功。使用Aspen HYSYS软件建立蓄冷、释冷、冷能补偿等流程，并在优先回收低温区冷能的同时，从耦合跨临界CO₂燃料电池余热利用循环等方面进行优化。结果表明，无增压蓄冷更有利于直接补偿液化器，氢气出口温度可达到273.7 K，㶲效率为81.65%。增压后蓄冷更侧重于增加输出功，且膨胀产生更多高温区冷能，如在130 K膨胀时氢气出口温度为299 K，能量效率为86.07%，㶲效率为50.86%。对氦布雷顿两级膨胀和氢双压克劳特两种氢液化循环模拟计算均表明，补偿冷量可以有效降低液化耗功且提高㶲效率。

关键词: 氢, 液化, 冷能回收利用, 相变, 二氧化碳

Abstract:

To solve the problem of spatiotemporal mismatch of energy in liquid hydrogen energy storage and to preferentially match suitable application scenarios, the cold energy is recovered by the combined cascade storage of liquid neon, liquid nitrogen, carbon dioxide (CO₂), and other working substances, and then the pre-cooled bypass hydrogen is incorporated into the liquefier to compensate the cold capacity and reduce the power consumption. Aspen HYSYS software is used to establish the processes of cold storage, cold release, and cold energy compensation. While giving priority to recovering cold energy in the low temperature zone, optimization is carried out from aspects such as coupling the waste heat utilization cycle of transcritical CO₂ fuel cells. The results showed that the non-pressurized cold energy storage was better to directly compensate the liquefier, and the hydrogen outlet temperature reached 273.7 K, while exergy efficiency was 81.65%. After pressurization, it focused more on increasing output work, and expanders generated more cold energy at high-temperature zones. For example, under the condition of expansion at 130 K, the hydrogen outlet temperature was 299 K, while energy efficiency was 86.07% and exergy efficiency was 50.86%. The simulation of hydrogen liquefaction cycles of helium two-stage expansion Brayton cycle and hydrogen dual-pressure Claude cycle showed that compensating cold capacity could effectively reduce the energy consumption and increase the exergy efficiency.

Key words: hydrogen, liquefaction, cold energy recovery and utilization, phase change, carbon dioxide

中图分类号:

TK 91

张赵雪, 李正宇, 崔文慧, 王倩, 王志平, 龚领会. 基于液氖液氮梯级蓄冷的液氢储能中冷能回收利用研究[J]. 化工学报, 2025, 76(4): 1731-1741.

Zhaoxue ZHANG, Zhengyu LI, Wenhui CUI, Qian WANG, Zhiping WANG, Linghui GONG. Research on cascade recovery and utilization of cold energy in liquid hydrogen energy storage based on liquid neon - liquid nitrogen[J]. CIESC Journal, 2025, 76(4): 1731-1741.

图/表 15

图1 液氢储能系统流程示意图

Fig.1 Flow diagram of liquid hydrogen energy storage system

图2 蓄冷工质的潜热、显热分布及氢的㶲分布

Fig.2 Latent heat and sensible heat distribution of cold storage working medium and exergy distribution of hydrogen

表1 单位质量流量液氢的蓄冷流程计算结果

Table 1 Calculation results of cold energy storage flow of liquid hydrogen per unit mass flow

蓄冷流程	蓄冷工质输出流量/(kg/h)				氢气出口温度/K	㶲效率/%
蓄冷流程	LNe	HLNe	LN₂	CO₂	氢气出口温度/K	㶲效率/%
基本蓄冷流程	5.8	2.1	1		222.4	79.97
增加CO₂@2MPa	5.8	2.1	1	2.9	291.1	80.16
增加跨临界CO₂余热利用循环的蓄冷流程（增加CO₂循环@1 MPa）	5.8	2.1	1	2.2	273.7	81.65

图3 增加跨临界CO2余热利用循环的蓄冷流程

Fig.3 Cold energy storage process for increasing trans-critical CO2 waste heat utilization cycle

图4 蓄冷流程总换热复合曲线

Fig.4 Total heat transfer composite curve of cold storage process

图5 在298 K膨胀的跨临界CO2循环增压后蓄冷流程

Fig.5 Process of cold energy storage after pressurization with a trans-critical CO2 cycle expanding at 298 K

表2 增压后蓄冷的流程计算结果

Table 2 Calculation results of cold energy storage process after pressurization

流程	蓄冷工质流量/(kg/h)				氢气出口温度/K	㶲效率/%	能量效率/%
流程	HLNe	LN₂	CO₂	EG	氢气出口温度/K	㶲效率/%	能量效率/%
150 K膨胀 LCO₂@2 MPa	2.9	3.2	8.6		296.5	38.18	83.34
130 K膨胀 LCO₂@2 MPa	2.9	4	7		294.1	42.09	85.86
298 K膨胀 LCO₂@2 MPa	2.9	2.6	11	6	292.5	36.01	68.27
298 K膨胀CO₂循环@1 MPa（440 K高温燃料电池）	2.9	2.6	6.4	20	298.7	43.36	68.72
298 K膨胀CO₂循环@1 MPa （353 K燃料电池）	2.9	2.6	7.8	23	299.4	43.13	68.77
130 K膨胀 CO₂循环@1 MPa	2.9	4	7	5	299.0	50.86	86.07

图6 进入液化器之前的释冷预冷过程

Fig.6 Release process of cold energy to precool hydrogen before entering the liquefier

表3 释冷预冷流程输出冷氢气参数

Table 3 Output parameters of cold hydrogen in the cold energy release and precooling process

释冷流程	输入工质流量/(kg/h)			预冷氢气出口		㶲效率/%	蓄冷释冷总流程
释冷流程	LN₂	HLNe	LNe	温度/K	流量/(kg/h)	㶲效率/%	能量效率/%	㶲效率/%
无增压蓄冷	1	2.1	5.8	28.91	0.75	70.97	72.74	68.77
增压后蓄冷 150 K膨胀	3.2	2.9		51.89	0.64	63.14	52.70	37.94
298 K膨胀	2.6	2.9		50.04	0.58	65.98	48.16	35.01

图7 基于氦布雷顿循环的氢液化流程及冷能补偿

Fig.7 Hydrogen liquefaction process and cold energy compensation based on helium Brayton cycle

图8 基于氢克劳特循环的氢液化流程及冷能补偿

Fig.8 Hydrogen liquefaction process and cold energy compensation based on hydrogen Claude cycle

图9 氢气的T-s图

Fig.9 T-s diagram of hydrogen

图10 氢气最佳节流状态时压力与温度的关系

Fig.10 The relationship between pressure and temperature of hydrogen in the optimal throttling state

表4 冷能补偿液化循环的计算结果

Table 4 Calculation results of cold energy compensation to liquefaction cycle

液化及补偿流程	预冷氢流量/(kg/h)	液化耗功/(kWh/kg)	含液氮液化耗功	含液氮㶲效率/%
1.5 t氦循环		15.51	18.99	21.88
无增压蓄冷	+ 65	7.87	9.69	42.87
增压后蓄冷	+ 28	11.03	13.60	30.55
5 t氢循环		10.42	15.61	25.76
无增压蓄冷	+ 90	7.65	11.47	35.07
增压后蓄冷	+ 85	7.82	11.94	33.67

表5 冷能补偿液化循环的运行参数对比

Table 5 Comparison of operating parameters of cold energy compensation to liquefaction cycle

液化及补偿流程	分流比	透平做功/kW		节流前换热器		末级换热器
液化及补偿流程	分流比	一级	二级	负荷/kW	㶲效率/%	负荷/kW	㶲效率/%
1.5 t氦循环	0.7	11.36	14.22	42.24	83.20	3.23	83.30
无增压蓄冷						6.57	90.20
增压后蓄冷	0.52	18.17	10.57	40.45	95.11	4.67	89.63
5 t氢循环	0.12	41.41	48.08	14.60	74.09	9.93	85.59
无增压蓄冷				4.11	93.63	20.42	83.19
增压后蓄冷	0.14	35.29	40.98	9.44	90.24	20.11	85.05

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