弱极性超微孔Sc/In-CPM-66A用于CH4/N2吸附分离性能的研究

doi:10.11949/0438-1157.20240323

摘要/Abstract

摘要：

低浓度煤层气的提质利用对缓解国内天然气不足的现状具有重要意义，然而煤层气中存在的氮气杂质限制了该类资源的进一步应用，因此进行低浓度煤层气中CH₄/N₂混合物的分离至关重要。本文制备了两种具有弱极性超微孔的金属有机框架材料，Sc-CPM-66A和In-CPM-66A，研究了材料从CH₄/N₂混合物中富集CH₄的性能。利用PXRD、77 K N₂吸附、TGA和FTIR光谱对材料的结构进行了表征。IAST 选择性计算表明In-CPM-66A和Sc-CPM-66A的CH₄/N₂ 选择性达到6.0。受益于材料表面存在的大量的甲基基团，两种材料对CH₄的吸附热低于被报道的大部分材料，材料与甲烷分子之间弱的相互作用有利于吸附剂的脱附再生。穿透实验进一步表明CPM-66A可以实现动态条件下CH₄/N₂混合物的分离，循环穿透实验显示该类材料具有良好的可重复性。

关键词: 天然气, CH₄/N₂, 弱极性, CPM-66A, 选择性, 吸附剂

Abstract:

The enrichment of low-concentration coalbed methane is of great significance to alleviate the current situation of the shortage of natural gas in China. However, the nitrogen impurities in coalbed methane greatly limit the further application of this resource. Therefore, it is very important to separate the CH₄/N₂ gas mixture in low concentration coalbed methane. Two low-polar ultra-microporous metal-organic framework materials, Sc-CPM-66A and In-CPM-66A, were prepared to study the performance of the materials in enriching CH₄ from CH₄/N₂ mixture. The structure of the materials was characterized by PXRD, 77 K N₂ adsorption, TGA and FTIR spectra. IAST selectivity calculations showed that the CH₄/N₂ selectivity of Sc-CPM-66A and In-CPM-66A reached 6.0. Benefiting from the large number of methyl groups on the surface of the materials, the adsorption heat of the two materials for CH₄ was lower than that of most reported materials. The weak interaction between the materials and methane molecules was conducive to the desorption and regeneration of the adsorbent in industrial applications. The breakthrough experiments further proved that CPM-66A could achieve the separation of CH₄/N₂ mixture under dynamic conditions. The cyclic breakthrough experiments showed that the materials had good repeatability.

Key words: natural gas, CH₄/N₂, low-polar, CPM-66A, selectivity, sorbents

中图分类号:

TQ 028.8

唐宇昊, 张迎迎, 赵智伟, 鲁梦悦, 张飞飞, 王小青, 杨江峰. 弱极性超微孔Sc/In-CPM-66A用于CH₄/N₂吸附分离性能的研究[J]. 化工学报, DOI: 10.11949/0438-1157.20240323.

Yuhao TANG, Yingying ZHANG, Zhiwei ZHAO, Mengyue LU, Feifei ZHANG, Xiaoqing WANG, Jiangfeng YANG. Ultra-microporous Sc/In-CPM-66A with low-polar pore surfaces for efficient separation of CH₄/N₂[J]. CIESC Journal, DOI: 10.11949/0438-1157.20240323.

图/表 10

图1 CPM-66A的结构示意图

Fig.1 Structure diagram of CPM-66A

图2（a） In-CPM-66A和 Sc-CPM-66A的PXRD图谱;（b）In-CPM-66A和 Sc-CPM-66A的水蒸气稳定性PXRD图谱；（c）In-CPM-66A在造粒/吸附/穿透后的PXRD图谱；（d）Sc-CPM-66A在造粒/吸附/穿透后的PXRD图谱

Fig.2 (a)PXRD patterns of In-CPM-66A and Sc-CPM-66A;(b) PXRD patterns of water vapor stability of In-CPM-66A and Sc-CPM-66A;(c) In-CPM-66A after as shaped/multiple adsorption tests/ multiple breakthrough tests;(d) Sc-CPM-66A after as shaped/multiple adsorption tests/multiple breakthrough tests

图3 （a-d）Sc-CPM-66A和In-CPM-66A的SEM图像

Fig.3 (a-d) SEM images of Sc-CPM-66A and In-CPM-66A

图4（a） Sc-CPM-66A和In-CPM-66A在195 K下的CO2吸脱附等温线；（b）In-CPM-66A和Sc-CPM-66A的孔径分布图

Fig. 4 (a) CO2 absorption and desorption isotherms of In-CPM-66A and Sc-CPM-66A at 195 K; (b) Pore size distribution of In-CPM-66A and Sc-CPM-66A

图5（a） In-CPM-66A 和 Sc-CPM-66A的热重曲线；（b）Sc-CPM-66A的质谱曲线

Fig.5(a) Thermogravimetric curves of In-CPM-66A and Sc-CPM-66A;(b) Mass spectrum curve of Sc-CPM-66A

图6 In-CPM-66A和Sc-CPM-66A的红外光谱

Fig.6 Infrared spectra of In-CPM-66A and Sc-CPM-66A

图7（a） 298 K下In-CPM-66A和Sc-CPM-66A的CH4/N2吸脱附等温线；（b）273 K下In-CPM-66A和Sc-CPM-66A的CH4/N2吸脱附等温线

Fig.7 (a) CH4/N2 adsorption isotherms of In-CPM-66A and Sc-CPM-66A at 298 K;(b) CH4/N2 adsorption isotherms of In-CPM-66A and Sc-CPM-66A at 273 K

图8（a） 298 K下CH4/N2（50/50，v/v）的IAST选择性；（b）273 K下CH4/N2（50/50，v/v）的IAST选择性；（c）在298 K和1 bar下，一些典型MOF的CH4和N2的吸附容量和选择性对比

Fig.8 (a) IAST selectivity of CH4/N2 (50/50, v/v) at 298 K; (b) IAST selectivity of CH4/N2 (50/50, v/v) at 273 K; (c) Comparison of adsorption capacity and selectivity of CH4 and N2 in some typical MOF at 298 K and 1 bar

图9（a） 298 K下Sc-CPM-66A的CH4/N2吸附热;（b）298 K下In-CPM-66A的CH4/N2吸附热;（c）CH4选择性材料吸附热对比

Fig.9 (a) CH4/N2 adsorption heat of Sc-CPM-66A at 298 K;(b) CH4/N2 adsorption heat of In-CPM-66A at 298 K; (c)Comparison of the CH4 adsorption heat of some previously reported CH4 selective materials

图10（a） In-CPM-66A的CH4/N2（20/80，v/v）穿透曲线；（b）In-CPM-66A的CH4/N2（50/50，v/v）穿透曲线；（c）In-CPM-66A的CH4/N2（50/50，v/v）穿透循环曲线；（d）Sc-CPM-66A的CH4/N2（20/80，v/v）穿透曲线；（e）Sc-CPM-66A的CH4/N2（50/50，v/v）穿透曲线；（f）Sc-CPM-66A的CH4/N2（50/50，v/v）穿透循环曲线

Fig.10 (a) The breakthrough curve of In-CPM-66A for CH4/N2 (20/80, v/v); (b) The breakthrough curve of In-CPM-66A for CH4/N2 (50/50, v/v); (c) The breakthrough cycle curves of In-CPM-66A for CH4/N2 (50/50, v/v); (d) The breakthroughcurve of Sc-CPM-66A for CH4/N2 (20/80, v/v); (e) The breakthrough curve of Sc-CPM-66A forCH4/N2 (50/50, v/v); (f) The breakthrough cycle curves of Sc-CPM-66A for CH4/N2 (50/50, v/v)

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弱极性超微孔Sc/In-CPM-66A用于CH₄/N₂吸附分离性能的研究

Ultra-microporous Sc/In-CPM-66A with low-polar pore surfaces for efficient separation of CH₄/N₂

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