Molecular simulation of adsorption separation of CO2/CH4 by MER-type zeolites

doi:10.16085/j.issn.1000-6613.2020-0220

Abstract

Abstract:

Adsorption separation of CO₂/CH₄ by MER-type zeolites has attracted widespread attentions because of its good industrial application prospect, but it is still lack of theoretical data. Cation-exchanged (Na⁺, K⁺, Cs⁺ and Ca²⁺) MER-type zeolites were first modeled, and then the adsorption behavior of CO₂ and CH₄ on the zeolites were simulated by Grand Canonical Monte Carlo (GCMC) simulation method, with the silicon MER-type zeolite as the reference. The results showed that the adsorption of CO₂ and CH₄ was consistent with the Langmuir-Freundlich adsorption isotherm model. The order of equilibrium adsorption capacities of CO₂and CH₄ on the zeolites is: Ca-MER＞Na-MER＞K-MER＞ Cs-MER, which is consistent with the orders of the free volume and specific surface area of the zeolites. The equilibrium adsorption capacity changed approximately linearly with the free volume and specific surface area of the zeolite. The MER-type zeolites with multivalent cation had a higher adsorption capacity for CO₂and CH₄. The probability density distribution results confirmed that CO₂ and CH₄ were mainly distributed in pau cage, and a small amount in d8R cage and ste cage in the MER-type zeolites. The adsorption selectivity of the cation-exchanged MER-type zeolites to CO₂/CH₄ mixture was up to more than 1000, which was attributed to the strong binding energy between the extra-framework cation and carbon dioxide as well as the unique octet ring window aperture. Na-MER and K-MER zeolites are excellent CO₂ adsorbents due to their high adsorption capacity, favorable adsorption heat and high adsorption selectivity. This study provides theoretical basis and experimental guidance for the adsorption separation of CO₂/CH₄ by cation-exchanged MER-type zeolites.

Key words: MER-type zeolite, adsorption, separation, carbon dioxide, molecular simulation

摘要：

MER型沸石在吸附分离CO₂/CH₄方面展现出良好的工业应用前景，受到广泛关注，但还缺乏理论基础数据。本文采用巨正则蒙特卡洛（GCMC）模拟方法，以全硅MER型沸石作为对照，模拟分析了CO₂/CH₄在Na⁺、K⁺、Cs⁺和Ca²⁺交换的MER型沸石中的吸附分离行为。结果表明：不同阳离子交换的MER型沸石对CO₂和CH₄的吸附符合Langmuir-Freundlich吸附等温线模型，平衡吸附量的大小顺序为：Ca-MER＞Na-MER＞K-MER＞Cs-MER，与沸石的自由体积和比表面积大小顺序一致，且近似成线性关系，选用高价阳离子MER型沸石可以提高吸附量；CO₂和CH₄主要分布在沸石的pau笼中，在d8R笼和ste笼中也有少量分布；骨架外阳离子与CO₂的强吸附作用和独特的八元环窗口孔径是MER型沸石对CO₂/CH₄混合组分表现出超高吸附选择性的原因，吸附选择性高达1000以上。综合吸附量、吸附热和吸附选择性分析指出，Na-MER和K-MER型沸石是优良的CO₂吸附剂。本研究为MER型沸石吸附分离CO₂/CH₄提供了理论依据和实验指导。

关键词: MER型沸石, 吸附, 分离, 二氧化碳, 分子模拟

CLC Number:

TQ021.4

Qin SHI, Jing XI, Fumin ZHANG. Molecular simulation of adsorption separation of CO₂/CH₄ by MER-type zeolites[J]. Chemical Industry and Engineering Progress, 2020, 39(11): 4408-4417.

石勤, 席静, 张富民. MER型沸石吸附分离CO₂/CH₄的分子模拟[J]. 化工进展, 2020, 39(11): 4408-4417.

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Molecular simulation of adsorption separation of CO₂/CH₄ by MER-type zeolites

MER型沸石吸附分离CO₂/CH₄的分子模拟

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