用于甲醇蒸汽重整制氢的钯合金膜反应器的研究与进展  

Research and Development of Palladium Alloy Membrane Reactor for Hydrogen Production by Steam Reforming of Methanol

作　　者：韩力 杨占兵[1] 张婧[2] 李帅 Han Li;Yang Zhanbing;Zhang Jing;Li Shuai(School of Metallurgical and Ecological Engineering,University of Science and Technology Beijing,Beijing 100083,China;School of Materials and Metallurgy,Inner Mongolia University of Science and Technology,Baotou 014010,China;National Engineering Research Center of Nonferrous Metals Materials and Products for New Energy,China GRINM Group Co.,Ltd.,Beijing 100088,China;GRIMAT Engineering Institute Co.,Ltd.,Beijing 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]内蒙古科技大学材料与冶金学院,内蒙古包头014010 [3]中国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 [4]有研工程技术研究有限公司,北京101407

出　　处：《稀有金属》2023年第10期1412-1426,共15页Chinese Journal of Rare Metals

基　　金：国家重点研发计划项目(2019YFB1505000);北京市自然科学基金项目(2212039)资助。

摘　　要：氢气的储运安全与成本问题限制了氢的规模使用。利用甲醇蒸汽重整(MSR)可以实施现场规模化制氢且反应条件温和,可避免以上限制。其中在钯合金膜反应器进行MSR制氢工艺流程简单、制氢效率高和能耗低,应用前景广阔。但在MSR制氢过程中,反应中间体和催化剂以及CO等多种杂质气体共存时会严重降低钯合金膜的透氢性能和抗毒化性能,大大降低了钯合金膜反应器的制氢效率和寿命。介绍了在MSR反应中操作条件和钯合金膜性能对膜反应器性能和寿命的影响。阐述了钯合金膜常用的基体和制备方法,并从钯合金膜透氢性和抗毒化性两方面进行讨论和比较。此外,综述了在MSR反应下常用的Pd-Ag, Pd-Cu和Pd-Au二元钯合金膜在膜反应器中氢渗透和抗杂质气体毒化方面的研究进展,分析了存在的问题和可能的解决方法。最后对钯合金膜应用在MSR制氢膜反应器未来研究方向进行了展望。With the deterioration of energy crisis and environmental pollution, the development and utilization of abundant, clean and safe renewable energy becomes an urgent need for the rapid development of society. The production process of hydrogen is relatively mature. As a carrier of clean energy, hydrogen only emits water after combustion, and it has better combustion characteristics in traditional combustion systems. In recent years, it has attracted much attention in fields such as fuel cells. Among them, the proton exchange membrane fuel cell(PEMFC) has the advantages of low pollution, high power density and fast start-up, and has become the most potential fuel cell at this stage. However, the safety and cost of hydrogen storage and transportation limit the large-scale application of hydrogen. Methanol, liquid ammonia and other hydrogen storage media are liquid at normal temperature and pressure, with high hydrogen storage density, good safety, mature technology and low cost, which can meet the application of hydrogen in many aspects. Among them, the H/C ratio(molratio) of methanol is high, and the methanol steam reforming(MSR) reaction temperature is low(200~350 ℃), which can realize large-scale hydrogen production. The traditional methanol reforming hydrogen production process has the disadvantages of large volume and high energy consumption, and it is difficult to apply in small scale hydrogen production. As a new type of hydrogen production device, membrane reactor has the advantages of high selectivity, high energy efficiency and small size, and can be used in small hydrogen production devices. Palladium and its alloy membranes have complete hydrogen selectivity and are promising for membrane reactors. However, under MSR reaction conditions, the coexistence of intermediates, catalysts and various impurity gases such as CO affects the hydrogen permeability and poisoning resistance of palladium alloy membranes, which limits the wide application of membrane reactors. This paper introduced the research status a

关 键 词：氢气 甲醇蒸汽重整(MSR) 膜反应器 钯合金膜 

分 类 号：TK91[动力工程及工程热物理]