氢气分离提纯用钯及钯合金膜的研究进展  

Progress in Pd and Pd Alloy Membranes for Hydrogen Separation and Purification

作　　者：殷朝辉 杨占兵[1] 李帅 Yin Zhaohui;Yang Zhanbing;Li Shuai(School of Metallurgical and Ecological Engineering,University of Science and Technology Beijing,Beijing 100083,China;National Engineering Research Center of Nonferrous Metals Materials and Products.for New Energy,GRINM Group Co,Ltd,Beijing 100088,China;GRIMAT Engineering Institute Co.,Ltd,Bejing 101407,China)

机构地区：[1]北京科技大学冶金与生态工程学院,北京100083 [2]有研科技集团有限公司,国家有色金属新能源材料与制品工程技术研究中心,北京100088 [3]有研工程技术研究有限公司,北京101407

出　　处：《稀有金属》2021年第2期226-239,共14页Chinese Journal of Rare Metals

基　　金：国家科技部ITER计划专项(2017YFE0301502);科技部国家重点研发计划项目(2019YFB1505000)资助。

摘　　要：伴随着煤、石油和天然气等传统化石能源在使用过程中产生的温室效应、能源危机等弊端,更清洁的氢能逐渐受到关注。氢能在能源、交通、工业等领域具有广阔的应用前景,尤其以燃料电池车为代表的交通领域是氢能初期应用的突破口与主要市场。而氢燃料电池对氢气浓度要求较高,氢气中即使微量的H2S和CO杂质也会严重降低电池性能。因此,需要对氢气进行分离纯化去除杂质气体。钯及钯合金膜由于对氢气具有极高的选择渗透性而应用于氢气的分离提纯,然而钯及钯合金膜的化学稳定性问题一直制约其广泛应用。本文介绍了纯Pd膜,Pd-Ag,Pd-Y,Pd-Pt,Pd-Cu和Pd-Au二元合金膜以及Pd-Ag-M,Pd-Cu-M三元合金膜氢渗透与抗杂质气体毒化方面的研究进展及存在问题。纯钯膜在低温下存在氢脆现象且易被杂质气体毒化;与纯钯膜相比,钯基二元合金膜成本较低,Pd-Ag,Pd-Y合金膜透氢性能较好而抗杂质气体毒化性能较差,Pd-Pt,Pd-Cu和Pd-Au合金膜则具有相反的特性;钯基三元合金膜在一定程度上提高了二元合金膜的透氢性能并改善了抗杂质气体毒化的性能,但仍存在合金元素偏析、各组元成分比例不易精确控制等问题,且钯基三元合金膜较之二元合金膜合成工艺更复杂、成本更高。最后,对钯合金膜未来的研究方向进行了展望。With the greenhouse effect and energy crisis caused by the use of traditional fossil energy,such as coal,oil and natural gas,cleaner hydrogen energy,especially high-purity hydrogen,has gradually attracted much attention.Hydrogen energy has wide application prospects in energy,transportation,industry,and other fields,especially the transportation field represented by fuel cell vehicles is the breakthrough and main market for the initial application of hydrogen energy.Hydrogen fuel cells have high requirements for hydrogen purity,and even traces of H2S and CO impurities in hydrogen will seriously deteriorate the performance of the cell.Therefore,it is essential to remove impurity gases to purify the hydrogen.Palladium and palladium alloy membranes have been used in the separation and purification of hydrogen due to their extremely high selective permeability to hydrogen,but the low chemical stability of palladium and palladium alloy membranes restricts their wide application.In the present paper,we reviewed the research progress and existing problems in hydrogen permeation and impurity gas poisoning resistance of pure Pd membranes,Pd-Ag,Pd-Y,Pd-Pt,Pd-Cu and Pd-Au binary alloy membranes,and Pd-Ag-M and Pd-Cu-M ternary alloy membranes,and forecasted the future research direction.Pure palladium membrane had good selective permeability to hydrogen,but its mechanical properties and chemical stability were poor.When the temperature was lower than 300℃,the transformation of a phase toβphase would cause the palladium membrane hydrogen embrittlement,and the membrane was easy to be poisoned by H2S,CO,etc.The competitive adsorption of H2S and CO on the membrane surface would occupy the dissociation site of hydrogen,thereby reducing the hydrogen permeability.Among them,the poisoning effect was more significant at low temperature and high CO concentration,but the poisoning effect was reversible.Compared with pure palladium membrane,the cost of palladium-based binary alloy membrane was lower.Pd-Ag and Pd-Y alloy membranes had

关 键 词：氢气 分离纯化 钯合金膜 抗毒化 

分 类 号：TK91[动力工程及工程热物理]