水热稳定金属-有机骨架材料用于高效分离SF6/N2混合物的研究

doi:10.11949/0438-1157.20191133

摘要/Abstract

摘要：

SF₆/N₂混合物的高效分离，对SF₆气体的回收与减弱其直接排放所导致的温室效应，具有重要的实际意义。合成了一种具有不同性质孔道结构的金属-有机骨架材料，Cu-MOF-OMe。该材料具有含不饱和配位金属位点和甲氧基双功能化的特征，且表现出良好的水热稳定性和再生性能。该材料表现出优异的综合分离性能，298 K和10⁵ Pa下的分离选择性（361）和吸附剂选择性参数 (SSP) 值 (780)均远高于文献报道值。理论计算发现，亲水性孔道中的不饱和金属位和疏水性孔道中丰富的甲氧基的协同作用，为该MOF材料具有优异SF₆/N₂分离性能的主要原因。研究结果可为SF₆/N₂高效分离材料的设计与开发提供参考依据。

关键词: 金属-有机骨架材料, 不饱和金属位点, 六氟化硫, 氮气, 分离

Abstract:

The efficient separation of the SF₆/N₂ mixture has important practical significance for the recovery of SF₆ gas and the reduction of the greenhouse effect caused by its direct discharge. In this work, a metal–organic framework (Cu-MOF-OMe) was prepared with two different types and properties of pores. It possesses dually-functionalized characteristics of coordinatively unsaturated metal sites and methoxy groups, which exhibit good hydrothermal stability and adsorptive regenerability. This material also shows excellent separation performance for SF₆/N₂ mixture. At 298 K and 10⁵ Pa, the observed adsorption selectivity (361) and sorbent selection parameter (SSP) value (780) are highest compared to various porous materials reported so far. Theoretical calculation results indicated that the underlying reason of such excellent separation properties is attributed to the cooperative effects of the open Cu sites in the hydrophilic pores and the abundant methoxy groups in the hydrophobic pores. The findings may provide valuable foundation for developing highly efficient materials for practical of SF₆/N₂ separation.

Key words: metal-organic frameworks, unsaturated metal sites, sulfur hexafluoride, nitrogen, separation

中图分类号:

TQ 028.8

常苗, 刘磊, 阳庆元, 刘大欢, 仲崇立. 水热稳定金属-有机骨架材料用于高效分离SF₆/N₂混合物的研究[J]. 化工学报, 2020, 71(1): 320-328.

Miao CHANG, Lei LIU, Qingyuan YANG, Dahuan LIU, Chongli ZHONG. Study on efficient separation of SF₆/N₂ mixture using a hydrothermally stable metal-organic framework[J]. CIESC Journal, 2020, 71(1): 320-328.

图/表 13

图1 Cu-MOF-OMe的晶体结构图

Fig.1 Crystal structure of Cu-MOF-OMe

图2 Cu-MOF-OMe的PXRD谱图（a）和热重曲线（b）

Fig.2 Powder X-ray diffraction patterns (a) and TGA curve (b) of Cu-MOF-OMe

图3 Cu-MOF-OMe的77 K N2吸附-脱附等温线（a），FT-IR谱图（b）和SEM图（c）

Fig.3 N2 adsorption- desorption isotherms at 77 K (a), FT-IR curve (b) and SEM image (c) of Cu-MOF-OMe

图4 Cu-MOF-OMe在298 K下的 SF6和N2吸附-脱附等温线（a）和IAST理想选择性（b）

Fig.4 Adsorption-desorption isotherms of SF6 and N2 at 298 K (a) and IAST selectivities (b) in Cu-MOF-OMe

表1 298 K下Cu-MOF-OMe的SF6和N2吸附数据的拟合参数

Table 1 Fitted parameters of SF6 and N2 sorption data of Cu-MOF-OMe at 298 K

Parameter	SF₆	N₂
q _satA/(cm³/g)	24.065	0.256
b _A/Pa^-1	221729.490	1739.130
q _satB/(cm³/g)	30.910	25266.260
b _B/Pa^-1	956.938	0.0835
R ²	0.9992	0.9997

图5 298 K下Cu-MOF-OMe的SF6和N2吸附等温线的Dual-Sites Langmuir模型拟合

Fig.5 Dual-Sites Langmuir model for fitting SF6 and N2 isotherms of Cu-MOF-OMe at 298 K

表2 298 K和1 bar条件下不同材料的选择性、SF6吸附量、SSP数值、SF6和N2吸附热的对比

Table 2 Comparison of IAST selectivity, uptake capacity of SF6, SSP values, adsorption heat of SF6 and N2 in different materials at 298 K and 1 bar

Adsorbents	Selectivity for SF₆/N₂ mixture (0.1∶0.9)	SF₆ uptake at 1.0 bar/(cm³/g)	SSP	Q _st for SF₆/ (kJ/mol)	Q _st for N₂/ (kJ/mol)	Ref.
Mg-MOF-74	18	143.8	95	32.0		[2]
Co-MOF-74	34	119.6	253	40.0		[2]
Zn-MOF-74	46	82.2	447	27.0		[2]
Ca-A	28.5	50.4	434	37.0		[6]
KKUST-1	65	115.6	446	25.0		[11]
activated carbon	30	54.2	120	5.0		[11]
CNHs^①	44	83.3				[13]
MIL-100-Fe	24	37.1	100	21.0	13.0	[14]
UIO-66-2Br	220	17.9	45	40.6		[15]
UIO-66	74	32.5	156	33.8	14.0	[16]
Zeolite-13X	44	39.4	162	29.5	28.0	[16]
PC-CaCit	30	80.9	66	30.0		[17]
PC-MgCit	30	74.8	133	24.6		[17]
CC3α	74	50.4	434	37.0		[18]
Cu-MOF-OMe	361	38	780	57.8	18.0	this work

图6 273 K下Cu-MOF-OMe的SF6和N2吸附等温线

Fig.6 SF6 and N2 adsorption isotherms of Cu-MOF-OMe at 273 K

图7 SF6/N2分离性能比较

Fig.7 Comparison of separation performance of SF6/N2

图8 Cu-MOF-OMe的再生实验

Fig.8 Regeneration experiment of Cu-MOF-OMe

图9 298 K下GCMC模拟吸附等温线与实验结果对比

Fig.9 Comparison of GCMC simulated isotherms and experimental data at 298 K

表3 SF6和N2的力场参数

Table 3 Force field information of SF6 and N2

吸附分子	σ/ ?	(ε/k _b)/K	电荷 /e
SF₆	4.615	238.89	—
N₂_N	3.32	36.4	-0.482
N₂_com	—	—	0.964

图10 通过DFT计算SF6和N2在Cu - MOF-OMe亲水性孔和疏水性孔中的吸附结合位点

Fig.10 SF6 and N2 adsorption binding sites in hydrophilic and hydrophobic pores of Cu-MOF-OMe by DFT calculation

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水热稳定金属-有机骨架材料用于高效分离SF₆/N₂混合物的研究

Study on efficient separation of SF₆/N₂ mixture using a hydrothermally stable metal-organic framework

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