基于流通式金属氢化物反应器的氢高效分离提纯实验研究

doi:10.11949/0438-1157.20240433

摘要/Abstract

摘要：

设计了一种填充LaNi_4.3Al_0.7的流通式金属氢化物反应器，用于从含0.1%CO和39.9%CO₂的混合气中分离提纯高纯氢，并系统实验研究了温度、压力等参数对装置分离纯化性能的影响。结果表明，吸氢过程中换热介质最佳温度约为120℃，旨在平衡高温下强抗中毒性和低温下强反应驱动力；混合气氢分压0.84 MPa被确定为较优工况。此外提出自产氢气吹扫以去除杂质并通过实验测试其性能，相比外加纯氢吹扫（主要通过黏性流促进杂质分离），自产氢气吹扫去除杂质效果更佳，其机理在于强化杂质表面脱附及分子扩散。通过自产氢气吹扫最终氢气纯度可达99.999%，氢气回收率达77.6%，展示了金属氢化物吸收分离法在氢分离提纯领域的广阔应用前景。

关键词: 金属氢化物, 氢气纯化, 中毒效应, 优化设计

Abstract:

The metal hydride (MH) method is viewed as one of the promising methods for hydrogen purification. The properties of MH materials will be significantly degenerated by the poisoning effect of impurity gases, especially for CO with strong effect. However, the present work in MH reactor level mainly focuses on some impurities with relatively insignificant effect yet, such as CH₄, CO₂, N₂, etc. To gain further insight into the reaction-separation behaviours of MH reactor running in by-product mixture, a flow-through type MH reactor filled with LaNi_4.3Al_0.7 is designed to separate hydrogen from mixture containing 0.1%CO and 39.9%CO₂. The effects of operating parameters such as temperature and pressure are systematically investigated for performance optimization. The optimum temperature of heat transfer fluids during hydrogen absorption process is found to be about 120℃, which keeps a balance between better anti-poisoning ability in high temperature and greater reaction driving force in low temperature. The experimental results also indicate that the optimum hydrogen partial pressure in the mixture gas should be about 0.84 MPa, due to the insignificant improvement of higher pressure. In addition, self-produce hydrogen purging is conducted to remove the impurity. The results of the experiment found clear support for the superiority of self-produce hydrogen purging for the MH reactor running in by-product mixture. Unexpectedly, purging the MH reactor with pure hydrogen for impurity replacement only leads to negligible improvement for impurity remove. A possible explanation is that molecular diffusion and desorption of impurities on the MH surface play a more important role for impurity transport and separation in MH reactor, rather than the viscous flow. The final hydrogen purity can reach 99.999% through self-produced hydrogen purge, and the hydrogen recovery rate can reach 77.6%, which shows the broad application prospects of metal hydride absorption separation method in the field of hydrogen separation and purification.

Key words: metal hydride, hydrogen purification, poisoning effect, performance optimization

中图分类号:

TK 91

郭磊磊, 吴震, 杨福胜, 张早校. 基于流通式金属氢化物反应器的氢高效分离提纯实验研究[J]. 化工学报, 2024, 75(12): 4576-4586.

Leilei GUO, Zhen WU, Fusheng YANG, Zaoxiao ZHANG. Experimental research on flow-through type metal hydride reactor running in by-product mixture for hydrogen purification[J]. CIESC Journal, 2024, 75(12): 4576-4586.

图/表 10

图1 金属氢化物吸收分离测试装置示意图1—气源;2—减压阀;3—流量控制器;4—压力变送器;5—阀门;6—MHAP反应器;7—换热装置;8—背压阀;9—真空泵;10—流量计;11—气相色谱仪;12—储氢罐

Fig.1 MH2P test equipment apparatus1—gas source;2—pressure regulator;3—flow controller;4—pressure transmitter;5—valve;6—MHAP reactor;7—heat transfer device;8—back pressure valve;9—vacuum pump;10—flow meter;11—gas chromatograph;12—hydrogen storage tank

图2 金属氢化物吸收分离测试装置实物图

Fig.2 MH2P test equipment

图3 金属氢化物吸收分离反应器

Fig.3 MH2P reactor

表1 MH2P测试装置中部分设备及参数

Table 1 Some equipment and parameters involved in this study

设备	参数
真空泵	抽气速率1 dm³/s，极限真空2 Pa
换热装置	温度范围-40~300℃，冷却功率1.2 kW，加热功率3.0 kW
背压阀	控制压力范围0~2.5 MPa
信号采集仪34970A	同时收集热电偶、直流/交流电压和电流信号
气相色谱仪GC2060	配置有高灵敏度热导检测器（TCD）和高稳定性氢火焰离子化检测器（FID）
温度传感器PT100	测量温度范围-200~850℃, 精度A级，输出0~5 V电压
压力变送器	测量压力范围-0.1~5 MPa，输出4~20 mA电流
流量控制器	控制流量范围0~0.56 dm³/s，精度0.5%

图4 MH2P反应器400 mm（a）、150 mm（b）处测点温度变化

Fig.4 Temperature evolution of measuring points at 400 mm (a) and 150 mm (b) in MH2P reactor

图5 流通式和封闭式MH2P反应器吸放氢过程温度变化

Fig.5 Temperature evolution of flow-through type MH2P reactor and discontinuous MH2P reactor in hydrogen absorption and desorption process

图6 110 mm（a）、150 mm（b）、180 mm（c）、240 mm（d）、310 mm（e）、400 mm（f）测点温度变化

Fig.6 Temperature evolution of measuring points at 110 mm (a), 150 mm (b), 180 mm (c), 240 mm (d)， 310 mm (e) and 400 mm (f) in MH2P reactor

图7 （a）换热介质温度120℃下MH2P反应器内各测点温度变化；（b）吸氢2000 s、换热介质60~150℃温度范围下MH2P反应器吸氢量

Fig.7 (a) Temperature evolution of measuring points in MH2P reactor at heat exchange medium temperature of 120℃; (b) Hydrogen absorption capacity of MH2P reactor at heat exchange medium temperature of 60—150℃ after 2000 s

图8 （a）换热介质温度120℃、混合气中氢分压0.48~1.20 MPa范围下MH2P反应器240 mm测点温度变化；（b）换热介质温度120℃、吸氢2000 s、混合气中氢分压0.48~1.08 MPa范围下MH2P反应器吸氢量

Fig.8 (a) Temperature evolution of 240 mm measuring point in MH2P reactor at heat exchange medium temperature of 120℃ and pressure of 0.48—1.20 MPa; (b) Hydrogen absorption capacity of MH2P reactor at heat exchange medium temperature of 120℃, pressure of 0.48—1.08 MPa after 2000 s

图9 不同平均放氢速率下的反应器出口氢气纯度

Fig.9 Hydrogen purity of off gas at different average hydrogen desorption rates

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