FeTPPs-CuBTC协同强化低浓度煤层气吸附分离

doi:10.11949/0438-1157.20220362

摘要/Abstract

摘要：

高效分离CH₄/N₂混合物是实现低浓度煤层气利用的关键之一。基于原位封装策略采用一锅法将FeTPPs成功封装至CuBTC的孔隙中，通过两者的协同作用达到强化CH₄/N₂混合气体吸附分离的目的。实验结果显示，FeTPPs的封装增强了吸附剂与CH₄间的相互作用反而削弱了吸附剂与N₂间的相互作用，因此FeTPPs的封装有利于CH₄/N₂混合气体的吸附分离。基于理想吸附溶液理论(IAST)计算发现，在几乎不损失CH₄吸附量的情况下，常温常压下FeTPPs@CuBTC复合材料对CH₄/N₂混合气体的吸附选择性可达5.4，是CuBTC的1.28倍，也高于目前已报道的大部分zeotile和MOF材料。证实了FeTPPs封装策略在低浓度煤层气分离领域的应用潜力，也为新型吸附剂材料的开发提供了新的设计思路。

关键词: 低浓度煤层气, 二元混合物, 吸附, 分离, 金属卟啉, 金属-有机骨架, 协同强化

Abstract:

Efficient separation of CH₄/N₂ mixture is one of the keys to realize the utilization of low concentration coalbed methane. Based on the in-situ encapsulation strategy, FeTPPs were successfully encapsulated into the pores of CuBTC by one-pot method, and the purpose of enhancing the adsorption and separation of CH₄/N₂ mixed gas was achieved through the synergistic effect of the two. As a result, encapsulation of FeTPPs enhanced the interactions between CH₄ and adsorbent, while the interactions between N₂ and adsorbent were weakened. Therefore, the encapsulation of FeTPPs is beneficial for the CH₄/N₂ mixture separation. Based on the calculation of ideal adsorption solution theory (IAST), it was found that the selectivity of FeTPPs@CuBTC reached 5.4 under normal temperature and pressure without loss of CH₄ adsorption capacity, which is 1.28 times that of CuBTC and higher than most reported zeotile and MOFs. The study confirms the potential application of FeTPPs packaging strategy for low concentration coalbed methane, and also provides a new design idea for the development of new adsorbent materials.

Key words: low concentration coalbed methane, binary mixture, adsorption, separation, metalloporphyrin, metal-organic framework, synergistic effect

中图分类号:

TQ 028.2

席国君, 刘子涵, 雷广平. FeTPPs-CuBTC协同强化低浓度煤层气吸附分离[J]. 化工学报, 2022, 73(9): 3940-3949.

Guojun XI, Zihan LIU, Guangping LEI. Enhanced adsorption and separation of low concentration coalbed methane based on synergistic effect between FeTPPs and CuBTC[J]. CIESC Journal, 2022, 73(9): 3940-3949.

图/表 15

图1 CuBTC封装金属卟啉结构

Fig.1 Structure of CuBTC encapsulated metalloporphyrin

图2 CuBTC和FeTPPs@CuBTC的XRD谱图

Fig.2 XRD patterns of CuBTC and FeTPPs@CuBTC

图3 CuBTC和FeTPPs@CuBTC的SEM图

Fig.3 SEM images of CuBTC and FeTPPs@CuBTC

图4 CuBTC、FeTPPs和FeTPPs@CuBTC的红外光谱

Fig.4 IR spectra of CuBTC, FeTPPs and FeTPPs@CuBTC

表1 FeTPPs@CuBTC样品中Cu和Fe的含量

Table 1 Cu and Fe contents in FeTPPs@CuBTC samples

元素	含量/%（质量）
Cu	26.229
Fe	0.339

图5 CuBTC、FeTPPs和FeTPPs@CuBTC的热重曲线

Fig.5 TGA curves of CuBTC, FeTPPs and FeTPPs@CuBTC

图6 CuBTC和FeTPPs@CuBTC在77 K下N2吸脱附曲线（a）及孔径分布（b）

Fig.6 N2 adsorption isotherms at 77 K (a) and pore size distribution (b) of CuBTC and FeTPPs@CuBTC

图7 CuBTC和FeTPPs@CuBTC在0℃（a）和25℃（b）下的CH4、 N2等温吸附曲线；0℃(c)和25℃(d)下FeTPPs@CuBTC对比CuBTC的CH4、N2吸附量的变化程度

Fig.7 Isothermal adsorption curves of CH4 and N2 at 0℃ (a) and 25℃ (b) for CuBTC and FeTPPs@CuBTC; The change degree of CH4 and N2 adsorption capacity of FeTPPs@CuBTC compared with CuBTC at 0℃ (c)和25℃ (d)

图8 CuBTC和FeTPPs@CuBTC的CH4（a）和N2（b）吸附热

Fig.8 Adsorption heats for CH4 (a) and N2 (b) on CuBTC and FeTPPs@CuBTC

表2 CuBTC和FeTPPs@CuBTC 的 CH4、N2在25℃下等温吸附线的拟合参数

Table 2 Fitted parameters of CH4 and N2 at 25 ℃ for CuBTC and FeTPPs@CuBTC

样品	气体	q₁/(mmol/g)	q₂/(mmol/g)	a₁/kPa^-1	a₂/kPa^-1	k₁	k₂	R²
CuBTC	CH₄	0.035	3.21	0.095	0.003	0.801	1.024	0.99999
	N₂	0.03	0.805	0.051	9.89×10^-4	1.099	1.288	0.9999
FeTPPs@CuBTC	CH₄	0.4	0.369	1.19×10^-5	0.006	2.000	1.02	0.99997
	N₂	0.05	2.769	0.014	0.004	1.304	0.959	1

图9 CuBTC和FeTPPs@CuBTC对CH4/N2的各组分吸附量（a）和IAST吸附选择性（b）(CH4∶N2=50∶50, 25℃)(CH4∶N2= 50∶50 at 25℃)

Fig.9 Adsorption capacity (a) and IAST-predicted CH4/N2 selectivity (b) of CuBTC and FeTPPs@CuBTC for CH4/N2 mixture

图10 FeTPPs@CuBTC与文献[12,20-21,24,35-39]报道的部分吸附剂在CH4吸附容量和CH4/N2吸附选择性的对比(CH4∶N2=50∶50, 25℃)

Fig.10 Comparison between FeTPPs@CuBTC and some adsorbents reported in literatures[12,20-21,24,35-39] in CH4 adsorption capacity and CH4/N2 adsorption selectivity (CH4∶N2=50∶50, 25℃)

图11 CuBTC和FeTPPs@CuBTC对CH4/N2混合气（CH4∶N2=50∶50）的透过曲线

Fig.11 Breakthrough curves of CuBTC and FeTPPs@CuBTC to CH4/N2 mixed gas （CH4∶N2=50∶50）

图12 CuBTC（a）和FeTPPs@CuBTC（b）在潮湿空气中暴露后的XRD谱图

Fig.12 XRD patterns of CuBTC (a) and FeTPPs@CuBTC (b) after the exposure to moisture

图13 常温常压下五次吸附解吸过程中FeTPPs@CuBTC对N2吸附能力的变化

Fig.13 Change of N2 adsorption capacity of FeTPPs@CuBTC during the fifth adsorption and desorption process at 298 K and 100 kPa

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