高稳定双金属MOF材料用于低浓度乙烷的高效分离

doi:10.11949/0438-1157.20200463

摘要/Abstract

摘要：

针对乙烷/乙烯分离过程中，缺乏高效稳定的乙烷选择吸附剂，采用溶剂热法合成了一种具有高稳定性的双金属微孔MOF材料MUV-10(Mn)，通过吸附分离的方式，实现了乙烯中低浓度乙烷的高效分离。采用XRD、SEM、TGA、比表面分析等表征手段对所制备材料的结构及形貌进行了确认和分析，详细测试了MUV-10(Mn)对乙烷和乙烯单组分气体的吸附性能，并进行了选择性和吸附热的计算。结果表明，MUV-10(Mn)在室温下的乙烷吸附量高于乙烯对于乙烷/乙烯混合气的选择性为1.42，且具有高的酸、碱和水蒸气稳定性。混合气体穿透实验表明，MUV-10(Mn)能够高效去除乙烯中的低浓度乙烷，得到高纯乙烯气体，在乙烯提纯方面显示出良好的应用前景。

关键词: 低碳烃, 乙烷, 乙烯, 吸附, 分离, 金属有机骨架材料

Abstract:

In view of lacking efficient ethane-selective adsorbent for ethane/ethylene separation, a highly stable microporous mixed metal-organic framework, termed as MUV-10(Mn), was synthesized by the solvothermal method and it could efficiently separate C₂H₆/C₂H₄mixture. The structure and morphology of synthesized material was confirmed by XRD, SEM, TGA and BET, etc. Selectivity and corresponding adsorption heat of C₂H₆ and C₂H₄were calculated based on single component adsorption results measured in details. The results show that MUV-10(Mn) features C₂H₆/C₂H₄ selectivity about 1.42 and can absorb more C₂H₆ than C₂H₄ at room temperature. And it has high acid, alkali and water vapor stability. Addtionally, dynamic breakthrough experiment showed MUV-10(Mn) could extracted low concentration of C₂H₆ from C₂H₆/C₂H₄mixture ( $V C 2 H 6 ? / ? V C 2 H 4$ =1∶9 and 1∶15) to collect C₂H₄ gas with high purity, which indicates the promising future of MUV-10(Mn) in C₂H₄purification.

Key words: light hydrocarbons, ethane, ethylene, adsorption, separation, metal-organic frameworks

中图分类号:

TQ 028.1

刘普旭, 贺朝辉, 李立博, 李晋平. 高稳定双金属MOF材料用于低浓度乙烷的高效分离[J]. 化工学报, 2020, 71(9): 4211-4218.

Puxu LIU, Chaohui HE, Libo LI, Jinping LI. Stable mixed metal-organic framework for efficient C₂H₆/C₂H₄ separation[J]. CIESC Journal, 2020, 71(9): 4211-4218.

图/表 5

图1 MUV-10(Mn)在[001]方向的结构图

Fig.1 The view of MUV-10(Mn) structure along [001] direction

图2 MUV-10(Mn)样品的XRD谱图(a)、TGA曲线(b)、N2吸附等温线(c)和SEM图片(d)

Fig.2 XRD pattern (a)，TGA curve (b)，N2 sorption isotherm (c) and SEM image (d) of MUV-10(Mn)

图3 C2H6和C2H4气体吸附等温线(a)，IAST选择性(b)，C2H6和C2H4吸附热(c)，单点Langmuir-Freundlich模型对298 K下C2H6和C2H4气体吸附等温线的拟合(d)

Fig.3 Adsorption isotherms of C2H6 and C2H4 (a), IAST selectivity (b), adsorption heat of C2H6 and C2H4 (c), fitting curves of C2H6 and C2H4 adsorption isotherms at 298 K based on the single-site Langmuir-Freundlich model (d)

图4 MUV-10(Mn)在298 K和105 Pa下C2H6和C2H4混合气的穿透实验曲线

Fig.4 Experimental breakthrough curves of MUV-10(Mn) for C2H6/C2H4 mixture at 298 K and 105 Pa

图5 MUV-10(Mn)在不同实验条件下的XRD图[(a)、(b)]及对应样品在298 K和105 Pa下的C2H6和C2H4循环吸附等温线[(c)~(e)]

Fig.5 XRD patterns[(a),(b)] and corresponding adsorption isotherms for C2H6 and C2H4 at 298 K and 105 Pa [(c)—(e)] of MUV-10(Mn) under different experimental conditions

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