Cu(I)NH4Y吸附剂的制备及其乙烯/乙烷吸附分离性能

Preparation of Cu(I)NH4Y zeolite for adsorption and separation of ethylene and ethane

  • 摘要: 本研究采用液相离子交换法,用不同浓度的CuCl2对NH4Y分子筛进行离子交换制得系列CuNH4Y-x分子筛吸附剂,并通过固定床吸附穿透实验及一系列表征手段探究了Cu的价态和负载量对乙烯/乙烷吸附分离性能的影响。吸附穿透实验结果表明,Cu(I)NH4Y0.10的乙烯吸附量明显高于Cu(II)NH4Y0.10,且Cu(I)NH4Y系列吸附剂的乙烯吸附量随着Cu负载量的增加呈现先增加后减小的趋势。H2-TPR和HRTEM表明,当Cu的负载量较低时,高度分散落位于Y分子筛超笼中的Cu(I)物种是乙烯有效吸附位点。然而,当Cu的负载量较高时,部分Cu物种发生团聚,造成对乙烯吸附能力的减弱。DFT密度泛函理论计算表明相比于Cu(II)NH4Y吸附剂,乙烯更容易吸附在Cu(I)NH4Y吸附剂上。该研究结果可为乙烯分离用高效Cu离子改性分子筛吸附剂的开发提供重要理论依据与指导。

     

    Abstract: In this work, a series of CuNH4Y-x zeolite adsorbents were prepared by ion exchange with different concentrations of CuCl2 and NH4Y zeolite. The effects of the valence and loading of Cu on the adsorption and separation of ethylene and ethane were investigated by fixed bed breakthrough adsorption experiment based on a series of characterization methods. The results of breakthrough adsorption experiments show that the ethylene adsorption capacity of Cu(I)NH4Y0.10 is significantly higher than that of Cu(II)NH4Y0.10, and the ethylene adsorption capacity of Cu(I)NH4Y series adsorbents increases first and then decreases with the increase of loading of Cu species. H2-TPR and HRTEM results show that monatomic Cu(I) species in the supercages of zeolite Y should be the effective active site when the loading amount of Cu is low. With the increase of Cu loading amount, the aggregation of Cu species results in the reduction of adsorption capacity of ethylene. The results of DFT calculation also confirm that the ethylene adsorption capacity of Cu(I)NH4Y adsorbent is significantly stronger than that of Cu(II)NH4Y adsorbent. These results can provide important theoretical basis and guidance for the development of high-efficiency Cu ion modified zeolite adsorbent for ethylene separation.

     

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