离子交换型分子筛在氧氩分离中的应用研究

    Application Research of Ion-Exchange Molecular Sieves in Oxygen-Argon Separation

    • 摘要: 惰性气体氩(Ar)在日常生活、工业生产及核环境监测等领域有着重要应用,将Ar从复杂气体组分中选择性地快速高效分离纯化是其应用的关键。然而,氧(O2)和Ar的分子尺寸及吸附扩散性质相似,并且O2和Ar的沸点十分接近,非低温条件下的O2/Ar分离十分困难。因此,O2与Ar的分离是其应用中必须攻克的难题。分子筛材料通过离子交换改性能够增强吸附质和吸附剂之间的相互作用,从而有效提高分子筛的O2/Ar分离能力。本文对离子交换型分子筛材料在O2/Ar吸附分离领域中的应用研究进行了系统总结和评述,结果发现碱土金属离子、Ce3+、Co2+等离子交换改性后的分子筛对O2具有较高的吸附能力和选择性,而Ag+交换分子筛即载银分子筛具有独特的Ar吸附选择性。目前,常压下离子交换型分子筛材料的O2/Ar分离系数均在2.0左右,这意味着常温常压下的O2/Ar高效分离仍然具有挑战性。开发新型高吸附容量、高吸附选择性的O2/Ar吸附分离材料仍然是未来的研究重点和趋势之一。

       

      Abstract: Inert gas argon has important applications in the fields of daily life, industrial manufacture and nuclear environmental monitoring. The key to its application is to selectively and efficiently separate and purify Ar from complex gas components. However, the separation of O2 and Ar at normal temperature is full of challenge due to their similar molecular sizes and adsorption properties as well as their close boiling point. In industry, high purity Ar is mainly produced by low temperature rectification, which is mature technology, but the equipment is large, high-energy consumption and explosive. Adsorption separation is a common method of gas separation. Molecular sieves are the most widely used material due to their huge specific surface area, aboudant pore structure and excellent adsorption properties. The silica tetrahedron in molecular sieve is electrically neutral, while the aluminum tetrahedron is electronegative, which makes it necessary to use H+ or Na+ outside the molecular sieve skeleton to maintain electrical neutrality. In actual application, the interaction between adsorbent and adsorbent can be enhanced by ion-exchange modification of molecular sieve material, so as to effectively improve the O2/Ar separation capacity of molecular sieve. In this paper, the application of ion-exchange modified molecular sieve materials in the field of O2/Ar adsorption separation was systematically summarized and reviewed. The results show that the O2/Ar separation coefficients of molecular sieves modified by alkaline earth metal ions like Ca2+, Sr2+ and Ba2+ can reach about 2.0, while that of Ce3+-exchanged X-type molecular sieve is as high as 5.9, it is an ideal adsorption material for O2/Ar separation. However, the high separation coefficient is limited to the range of low partial pressure, and the O2/Ar separation coefficient under normal pressure is below 2.0. The Ag+-exchanged molecular sieves, namely silver-loaded molecular sieves, have excellent Ar adsorption selectivity. At present, the O2/Ar separation coefficients of silver-loaded molecular sieve materials at atmospheric pressure are around 2.0, but the preparation cost of silver-loaded molecular sieves is high, and it is more suitable for small-scale separation applications, it means that the efficient separation of O2 and Ar at normal temperature and pressure is still challenging. The development of novel ion-exchange modified molecular sieve materials with high adsorption capacity and high adsorption selectivity for the separation of O2 and Ar is still one of the focuses and trends of future research projects.

       

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