电化学氢泵用于掺氢天然气氢气纯化与压缩研究进展

doi:10.19964/j.issn.1006-4990.2025-0017

摘要/Abstract

摘要：

氢能产业已成为全球能源转型的重要战略，为实现大规模、远距离和低成本氢能转运，利用天然气管网进行氢气混合输送具备规模化应用的可行性；但掺氢天然气中氢气含量通常较低，应用前需将氢气与天然气进行分离。电化学氢泵技术是以电为驱动力，以膜为质子传导和气体阻隔介质的氢气提纯与压缩技术，具有高选择性和氢源适应性，可同时实现氢气提纯与压缩，是掺氢输送并对接应用端的有效途径。对比氢气分离提纯的常用方法，主要介绍电化学氢泵的工作原理、主要功能、关键部件及其研究进展。重点分析核心部件的质子交换膜的研究进展，主要包括聚合物质子交换膜和混合基质型质子交换膜。对电化学氢泵用于掺氢天然气分离的前景和挑战进行展望。

关键词: 掺氢天然气, 分离, 电化学氢泵, 膜电极, 质子交换膜

Abstract:

Hydrogen energy has become an important strategy for global energy transformation.To achieve large-scale，long-distance，and low-cost hydrogen energy transportation，the use of natural gas pipelines for hydrogen mixed transportation has the feasibility of large-scale application.However，the hydrogen content in hydrogen doped natural gas is usually low，and hydrogen needs to be separated from natural gas before application.Electrochemical hydrogen pump technology is a hydrogen purification and compression technology that uses electricity as the driving force，membrane as the proton conduction and gas barrier medium.It has high selectivity and hydrogen source adaptability，and can simultaneously achieve hydrogen purification and compression.It is an effective way to transport hydrogen and connect with application ends.The common methods for hydrogen separation and purification were compared，and the working principle，main functions，key components，and research progress of electrochemical hydrogen pumps were introduced.The research progress of the core component proton exchange membrane was analyzed，mainly including polymer proton exchange membrane and mixed matrix proton exchange membrane.The prospects and challenges of using electrochemical hydrogen pumps for hydrogen doped natural gas separation were discussed.

Key words: hydrogen blend natural gasseparation, separation, electrochemical hydrogen pump, membrane electrode, proton exchange membrane

中图分类号:

TQ122

于广欣, 朱诗怡, 周铭浩, 吴洪, 陈赞, 纪钦洪, 姜忠义. 电化学氢泵用于掺氢天然气氢气纯化与压缩研究进展[J]. 无机盐工业, 2025, 57(12): 8-17.

YU Guangxin, ZHU Shiyi, ZHOU Minghao, WU Hong, CHEN Zan, JI Qinhong, JIANG Zhongyi. Research progress on electrochemical hydrogen pump technology for hydrogen purification and compression of hydrogen doped natural gas[J]. Inorganic Chemicals Industry, 2025, 57(12): 8-17.

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参考文献 75

[1]	国家能源局.氢能产业发展中长期规划（2021-2035年）［R/OL］.（2022-03-23）［2024-09-13］.
[2]	中华人民共和国国家发展和改革委员会.天然气利用管理办法［R/OL］.（2024-06-03）［2024-09-13］.
[3]	于广欣，纪钦洪，徐庆虎，等.电化学氢纯化与压缩技术现状及在氢能中的应用［J］.现代化工，2023，43（5）：6-10.
	YU Guangxin， JI Qinhong， XU Qinghu，et al.Status and application of electrochemical hydrogen purification and compression technologies［J］.Modern Chemical Industry，2023，43（5）：6-10.
[4]	ZHANG Donghui， KODAMA A， GOTO M，et al.Recovery of trace hydrogen by cryogenic adsorption［J］.Separation and Purification Technology，2004，35（2）：105-112.
[5]	张钢强，孙朋涛，刘书缘，等.变压吸附制氢的研究进展［J］.石油化工，2022，51（4）：498-502.
	ZHANG Gangqiang， SUN Pengtao， LIU Shuyuan，et al.Research progress of hydrogen production by pressure swing adsorption［J］.Petrochemical Technology，2022，51（4）：498-502.
[6]	AL-MUFACHI N A， REES N V， STEINBERGER-WILKENS R.Hydrogen selective membranes：A review of palladium-based dense metal membranes［J］.Renewable and Sustainable Energy Reviews，2015，47：540-551.
[7]	AHN S J， TAKAGAKI A， SUGAWARA T，et al.Permeation properties of silica-zirconia composite membranes supported on porous alumina substrates［J］.Journal of Membrane Science，2017，526：409-416.
[8]	谭遥，李琦，王捷，等.掺氢天然气分离工艺方案及经济性分析［J］.石油与天然气化工，2023，52（4）：41-47.
	TAN Yao， LI Qi， WANG Jie，et al.Scheme and economic analysis of hydrogen-blended natural gas separation［J］.Chemical Engineering of Oil & Gas，2023，52（4）：41-47.
[9]	NAYEBOSSADRI S， SPEIGHT J D， BOOK D.Hydrogen separation from blended natural gas and hydrogen by Pd-based membran-es［J］.International Journal of Hydrogen Energy，2019，44（55）：29092-29099.
[10]	NIU Xinpu， MORIYAMA N， NAGASAWA H，et al.Rational design of defect-free carbon-silica-zirconia ceramic membrane derived from crosslinked organic structure for highly efficient gas separation［J］.Journal of Membrane Science，2024，709：123112.
[11]	ROBESON L M.The upper bound revisited［J］.Journal of Membrane Science，2008，320（1/2）：390-400.
[12]	ZOU Jiexin， HAN Ning， YAN Jiangyan，et al.Electrochemical compression technologies for high-pressure hydrogen：Current status，challenges and perspective［J］.Electrochemical Energy Reviews，2020，3（4）：690-729.
[13]	ARUNAGIRI K， TURSSLINE J M， ARGES C G.Purifying hydrogen from dilute hydrogen-natural gas mixtures using HT-PEM electrochemical hydrogen pumps［J］.ACS Energy Letters，2024，9（6）：2912-2919.
[14]	ZONG Huajian， CHENG Andi， WANG Hao，et al.Multi-objective optimization of a hydrogen production process for polymer membrane coupled with electrochemical hydrogen pump from hydro-gen-doped natural gas by NSGA-Ⅱ［J］.Separation and Purification Technology，2024，349：127821.
[15]	JACKSON C， SMITH G， KUCERNAK A R.Deblending and purification of hydrogen from natural gas mixtures using the electrochemical hydrogen pump［J］.International Journal of Hydrogen Energy，2024，52：816-826.
[16]	RHANDI M， TRÉGARO M， DRUART F，et al.Electrochemical hydrogen compression and purification versus competing technologies：Part I.Pros and cons［J］.Chinese Journal of Catalysis，2020，41（5）：756-769.
[17]	GAO Zhong， FAN Chunyang， YIN Zhuoyu，et al.Electrochemical hydrogen Compression：Module design and membrane development［J］.Chemical Engineering Journal，2024，488：150733.
[18]	KIM J S， PARK J B， KIM Y M，et al.Fuel cell end plates：A review［J］.International Journal of Precision Engineering and Manu- facturing，2008，9（1）：33-46.
[19]	GAO Xin， CHEN Jiayi， XU Runjing，et al.Research progress and prospect of the materials of bipolar plates for proton exchange membrane fuel cells（PEMFCs）［J］.International Journal of Hydrogen Energy，2024，50：711-743.
[20]	XU Xiaozhi， GOU Yong， ZHAN Xin，et al.Investigation of the effect of the TaC/α-C coating process on the properties of stainless steel bipolar plates［J］.International Journal of Hydrogen Energy，2024，55：98-109.
[21]	SRIVASTAVA A， ROSS K A， SMITH C B.Coating developments towards enabling aluminum as a bipolar plate material for PEM fuel cells［J］.Journal of Power Sources，2023，582：233513.
[22]	SANJID A， ANISUR M R， SINGH RAMAN R K.Durable degradation resistance of graphene coated nickel and monel-400 as bi-polar plates for proton exchange membrane fuel cell［J］.Carbon，2019，151：68-75.
[23]	YAN Gaoxiang， ZHANG Xiang， WEI Lijuan，et al.Study on the effects of nano-copper addition on the properties of epoxy resin/graphite composite bipolar plates［J］.International Journal of Hydrogen Energy，2024，69：576-585.
[24]	MODANLOO V， TALEBI-GHADIKOLAEE H， ALIMIRZALOO V，et al.Fracture prediction in the stamping of titanium bipolar plate for PEM fuel cells［J］.International Journal of Hydrogen Energy，2021，46（7）：5729-5739.
[25]	WANG Fang， INOUE A， KONG Fanli，et al.Formation and ultrahigh mechanical strength of multicomponent co-based bulk glassy alloys［J］.Journal of Materials Research and Technology，2023，26：1050-1061.
[26]	CHANDA U K， PADHEE S P， PANDEY A K，et al.Electrodeposited Ni-Mo-Cr-P coatings for AISI 1020 steel bipolar plates［J］.International Journal of Hydrogen Energy，2020，45（41）：21892-21904.
[27]	AWIN Y， DUKHAN N.Experimental performance assessment of metal-foam flow fields for proton exchange membrane fuel cells［J］.Applied Energy，2019，252：113458.
[28]	LIU Gaoyang， SHAN Dongfang， FANG Baizeng，et al.Novel hybrid coating of TiN and carbon with improved corrosion resistance for bipolar plates of PEM water electrolysis［J］.International Journal of Hydrogen Energy，2023，48（50）：18996-19007.
[29]	KANG H E， KIM S H， CHOI J H，et al.Selective etching-induced surface modifications of FeCrAl alloy bipolar plates：Mechanisms for enhanced corrosion resistance and hydrophobicity［J］.Chemical Engineering Journal，2024，493：152409.
[30]	WAN Zhongmin， QUAN Wenxiang， YANG Chen，et al.Optimal design of a novel M-like channel in bipolar plates of proton exchange membrane fuel cell based on minimum entropy generati-on［J］.Energy Conversion and Management，2020，205：112386.
[31]	SHI Qitong， FENG Cong， MING Pingwen，et al.Compressive stress and its impact on the gas diffusion layer：A review［J］.International Journal of Hydrogen Energy，2022，47（6）：3994-4009.
[32]	GUO Hui， CHEN Lubing， ISMAIL S A，et al.Gas diffusion layer for proton exchange membrane fuel cells：A review［J］.Materials，2022，15（24）：8800.
[33]	MOYDIEN H， LEVECQUE P， SUSAC D.Experimental study of water management and performance of titanium fibre felts as versatile gas diffusions layers for PEMFCs［J］.International Journal of Hydrogen Energy，2023，48（84）：32968-32981.
[34]	ZHOU Ke， LI Tianya， HAN Yufen，et al.Optimizing the hydrophobicity of GDL to improve the fuel cell performance［J］.RSC Advances，2021，11（4）：2010-2019.
[35]	ATHANASAKI G， JAYAKUMAR A， KANNAN A M.Gas diffusion layers for PEM fuel cells：Materials，properties and manufacturing：A review［J］.International Journal of Hydrogen Energy，2023，48（6）：2294-2313.
[36]	GUO Yuqing， PAN Fengwen， CHEN Wenmiao，et al.The controllable design of catalyst inks to enhance PEMFC performance：A review［J］.Electrochemical Energy Reviews，2021，4（1）：67- 100.
[37]	SEDLAK J M， AUSTIN J F， LA-CONTI A B.Hydrogen recovery and purification using the solid polymer electrolyte electrolyte electrolysis cell［J］.International Journal of Hydrogen Energy，1981，6（1）：45-51.
[38]	ZHANG Qiaoqiao， GUAN Jingqi.Single-atom catalysts for electrocatalytic applications［J］.Advanced Functional Materials，2020，30（31）：2000768.
[39]	YANG Huimin， CHEN Yao， QIN Yong.Application of atomic layer deposition in fabricating high-efficiency electrocatalysts［J］.Chinese Journal of Catalysis，2020，41（2）：227-241.
[40]	FENG Ruixue， LI Dong， YANG Hongzhou，et al.Epitaxial ultrathin Pt atomic layers on CrN nanoparticle catalysts［J］.Advanced Materials，2024，36（9）：2309251.
[41]	VAN NGUYEN T， TEKALGNE M， NGUYEN T P，et al.Electrocatalysts based on MoS₂ and WS₂ for hydrogen evolution reaction：An overview［J］.Battery Energy，2023，2（3）：20220057.
[42]	JAYABAL S， SARANYA G， GENG Dongsheng，et al.Insight into the correlation of Pt-support interactions with electrocatalytic activity and durability in fuel cells［J］.Journal of Materials Chemistry A，2020，8（19）：9420-9446.
[43]	YEON J，WOO L， HWAN K，et al.Interplay of ligand and strain effects in CO adsorption on bimetallic Cu/M（M=Ni，Ir，Pd，and Pt） catalysts from first-principles：Effect of different facets on catalysis［J］.Catalysis Today，2021，359：57-64.
[44]	ZHANG Lei， WANG Qi， LI Lulu，et al.Single atom surface engineering：A new strategy to boost electrochemical activities of Pt catalysts［J］.Nano Energy，2022，93：106813.
[45]	VENUGOPALAN G， BHATTACHARYA D， ANDREWS E，et al.Electrochemical pumping for challenging hydrogen separatio- ns［J］.ACS Energy Letters，2022，7（4）：1322-1329.
[46]	NORDIO M， EGUARAS BARAIN M， RAYMAKERS L，et al.Effect of CO₂ on the performance of an electrochemical hydrogen compressor［J］.Chemical Engineering Journal，2020，392：123647.
[47]	CHENG Xuan， SHI Zheng， GLASS N，et al.A review of PEM hydrogen fuel cell contamination：Impacts，mechanisms，and mitigation［J］.Journal of Power Sources，2007，165（2）：739-756.
[48]	DONG Wenyan， XU Cong， ZHAO Wenhui，et al.Poisoning effects of H₂S，CS₂，and COS on hydrogen oxidation reaction over Pt/C catalysts［J］.ACS Applied Energy Materials，2022，5（10）：12640-12650.
[49]	AHMAD S， NAWAZ T，ALI A，et al.An overview of proton exchange membranes for fuel cells：Materials and manufacturing［J］.International Journal of Hydrogen Energy，2022，47（44）：19086-19131.
[50]	HOUCHINS C， KLEEN G J， SPENDELOW J S，et al.U.S.DOE progress towards developing low-cost，high performance，durable polymer electrolyte membranes for fuel cell applications［J］.Membranes，2012，2（4）：855-878.
[51]	YIN Chongshan， HE Chunqing， LIU Qicheng，et al.Effect of the orientation of sulfonated graphene oxide（SG） on the gas-barrier properties and proton conductivity of a SG/Nafion composite membrane［J］.Journal of Membrane Science，2021，625：119146.
[52]	CHEN Lei， CHEN Yanyu， TAO Wenquan.Schroeder′s paradox in proton exchange membrane fuel cells：A review［J］.Renewable and Sustainable Energy Reviews，2023，173：113050.
[53]	ELLIOTT J A， PADDISON S J.Modelling of morphology and proton transport in PFSA membranes［J］.Physical Chemistry Chemical Physics，2007，9（21）：2602-2618.
[54]	ESMAEILI N， GRAY E M， WEBB C J.Non-fluorinated polymer composite proton exchange membranes for fuel cell applications：A review［J］.ChemPhysChem，2019，20（16）：2016-2053.
[55]	WOLSKA J， WALKOWIAK-KULIKOWSKA J.On the sulfonation of fluorinated aromatic polymers：Synthesis，characterization and effect of fluorinated side groups on sulfonation degree［J］.European Polymer Journal，2020，129：109635.
[56]	PENG Jinwu， FU Xianzhu， LIU Dong，et al.An effective strategy to enhance dimensional-mechanical stability of phosphoric acid doped polybenzimidazole membranes by introducing in situ grown covalent organic frameworks［J］.Journal of Membrane Science，2022，655：120603.
[57]	FAN Yuting， ZHANG Yuqing， ZHANG Ailing，et al.Breaking the trade-off between proton conductivity and mechanical stability through liquid-crystal-modified aramid fibers in sulfonated polyether ether ketone membranes［J］.International Journal of Hydrogen Energy，2024，83：630-640.
[58]	EINSLA M L， KIM Y S， HAWLEY M，et al.Toward improved conductivity of sulfonated aromatic proton exchange membranes at low relative humidity［J］.Chemistry of Materials，2008，20（17）：5636-5642.
[59]	LI Nanwen， WANG Chenyi， LEE S Y，et al.Enhancement of proton transport by nanochannels in comb-shaped copoly（arylene ether sulfone）s［J］.Angewandte Chemie International Edition，2011，50（39）：9158-9161.
[60]	LI Nanwen， GUIVER M D.Ion transport by nanochannels in ion-containing aromatic copolymers［J］.Macromolecules，2014，47（7）：2175-2198.
[61]	LIU Bailing， HU Bo， DU Jing，et al.Precise molecular-level modification of nafion with bismuth oxide clusters for high-performance proton-exchange membranes［J］.Angewandte Chemie International Edition，2021，60（11）：6076-6085.
[62]	RICO-ZAVALA A， GURROLA M P， ARRIAGA L G，et al.Synthesis and characterization of composite membranes modified with Halloysite nanotubes and phosphotungstic acid for electrochemical hydrogen pumps［J］.Renewable Energy，2018，122：163-172.
[63]	RICO-ZAVALA A， MATERA F V， ARJONA N，et al.Nanocomposite membrane based on SPEEK as a perspectives application in electrochemical hydrogen compressor［J］.International Journal of Hydrogen Energy，2019，44（10）：4839-4850.
[64]	PENG Quan， LI Yan， QIU Ming，et al.Enhancing proton conductivity of sulfonated poly（ether ether ketone）-based membranes by incorporating phosphotungstic-acid-coupled graphene oxide［J］.Industrial & Engineering Chemistry Research，2021，60（11）：4460-4470.
[65]	WANG Sijia， ZHU Tianhao， SHI Benbing，et al.Porous organic polymer with high-density phosphoric acid groups as filler for hybrid proton exchange membranes［J］.Journal of Membrane Science，2023，666：121147.
[66]	LIU Ziwen， PANG Xiao， SHI Benbing，et al.Covalent organic frameworks with flexible side chains in hybrid PEMs enable highly efficient proton conductivity［J］.Materials Horizons，2024，11（1）：141-150.
[67]	SUN Pengzhan， MA Renzhi， SASAKI T.Recent progress on exploring exceptionally high and anisotropic H⁺/OH^- ion conduction in two-dimensional materials［J］.Chemical Science，2018，9（1）：33-43.
[68]	SAHOO R， MONDAL S， PAL S C，et al.Covalent-organic frameworks（COFs） as proton conductors［J］.Advanced Energy Materials，2021，11（39）：2102300.
[69]	TAN Chaoliang， CAO Xiehong， WU Xuejun，et al.Recent advances in ultrathin two-dimensional nanomaterials［J］.Chemical Reviews，2017，117（9）：6225-6331.
[70]	ZHAO Qiang， LEE D W， AHN B K，et al.Underwater contact adhesion and microarchitecture in polyelectrolyte complexes actuated by solvent exchange［J］.Nature Materials，2016，15（4）：407-412.
[71]	CHANDRA S， KUNDU T， DEY K，et al.Interplaying intrinsic and extrinsic proton conductivities in covalent organic frameworks［J］.Chemistry of Materials，2016，28（5）：1489-1494.
[72]	XING Na， PANG Xiao， MENG Qingrui，et al.Incorporating graphene oxide into COF membranes enables ultrahigh proton conductivity and ultralow H₂ crossover［J］.Journal of Membrane Science，2023，688：122103.
[73]	GAO Zhong， YIN Zhuoyu， KONG Yan，et al.Robust and highly proton conductive COF composite membranes for fuel cell and electrochemical hydrogen compression［J］.Chemical Engineering Journal，2024，490：151368.
[74]	MRUSEK S， BLASIUS M， MORGENROTH F，et al.Hydrogen extraction from methane-hydrogen mixtures from the natural gas grid by means of electrochemical hydrogen separation and compression［J］.International Journal of Hydrogen Energy，2024，50：526-538.
[75]	VAN ACHT S C J， LAYCOCK C， CARR S J W，et al.Simulation of integrated novel PSA/EHP/C process for high-pressure hydrogen recovery from Coke Oven Gas［J］.International Journal of Hydrogen Energy，2020，45（30）：15196-15212.

分离工艺	气体回收率/%	纯度要求/%	操作温度/℃	优点	缺点	分离纯度/％
低温精馏	80~95	20	213	连续分离多种组分	能耗高，预处理严格	90.000~99.000
变压吸附	60~95	50~90	20~30	分离纯度高，技术成熟	间歇操作，能耗较高	99.000~99.999
膜分离	85~95		25~500	能耗低，过程简单	处理能力较低，耐久性较低	90.000~99.999
电化学氢泵	85~99	1~99	20~80	分离纯度高；设备紧凑，无噪音	CO、H₂S等气体耐受性较差	99.999

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