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

参考文献 48

1	Tsai W T . The decomposition products of sulfur hexafluoride (SF₆): reviews of environmental and health risk analysis[J]. Fluorine Chem., 2007, 128: 1345-1352.
2	Kim M B , Lee S J , Lee C Y , et al . High SF₆ selectivities and capacities in isostructural metal-organic frameworks with proper pore sizes and highly dense unsaturated metal sites[J]. Micropor. Mesopor. Mat., 2014, 190: 356-361.
3	Christophorou L G , Vanbrunt R J . SF₆/N₂ mixtures - basic and HV insulation properties[J]. IEEE Trans. Dielectr. Electr. Insul., 1995, 2: 952-1003.
4	Yamamoto O , Takuma T , Kinouchi M . Recovery of SF₆ from N₂/SF₆ gas mixtures by using a polymer membrane[J]. IEEE Electr. Insul. Mag., 2002, 18: 32-37.
5	Imai T , Inohara T , Toyoda M . Use of zeolite filter in portable equipment for recovering SF₆ in SF₆/N₂ mixtures[J]. IEEE Trans. Dielectr. Electr. Insul., 2004, 11: 166-173.
6	Toyoda M , Murase H , Imai T , et al . SF₆ reclaimer from SF₆/N₂ mixtures by gas separation with molecular sieving effect[J]. IEEE Trans. Power Deliv., 2003, 18: 442-448.
7	Senkovska I , Barea E , Navarro J A R , et al . Adsorptive capturing and storing greenhouse gases such as sulfur hexafluoride and carbon tetrafluoride using metal-organic frameworks[J]. Micropor. Mesopor. Mat., 2012, 156: 115-120.
8	Lee E K , Lee J D , Lee H J , et al . Pure SF₆ and SF₆ -N₂ mixture gas hydrates equilibrium and kinetic characteristics[J]. Environ. Sci. Technol., 2009, 43: 7723-7727.
9	Cha I , Lee S , Lee J D , et al . Separation of SF₆ from gas mixtures using gas hydrate formation[J]. Environ. Sci. Technol., 2010, 44: 6117-6122.
10	Skarmoutsos I , Eddaoudi M , Maurin G . Highly tunable sulfur hexafluoride separation by interpenetration control in metal organic frameworks[J]. Micropor. Mesopor. Mat., 2019, 281: 44-49.
11	Chuah C Y , Goh K L , Bae T H . Hierarchically structured HKUST‑1 nanocrystals for enhanced SF₆ capture and recovery[J]. J. Phys. Chem. C, 2017, 121： 6748-6755.
12	Skarmoutsos I , Tamiolakis G , Froudakis G E . Highly selective separation and adsorption-induced phase transition of SF₆ -N₂ fluid mixtures in three-dimensional carbon nanotube networks[J]. J. Supercrit. Fluids, 2016, 113: 89-95.
13	Takase A , Kanoh H , Ohba T . Wide carbon nanopores as efficient sites for the separation of SF₆ from N₂ [J]. Sci. Rep., 2015, 5: 11994.
14	Kim P J , You Y W , Park H , et al . Separation of SF₆ from SF₆/N₂ mixture using metal-organic framework MIL-100(Fe) granule[J]. Chem. Eng. J., 2015, 262: 683-690.
15	Kim M B , Kim K M , Kim T H , et al . Highly selective adsorption of SF₆ over N₂ in a bromine-functionalized zirconium-based metal-organic framework[J]. Chem. Eng. J., 2018, 339: 223-229.
16	Kim M B , Yoon T U , Hong D Y , et al . High SF₆/N₂ selectivity in a hydrothermally stable zirconium-based metal-organic framework[J]. Chem. Eng. J., 2015, 276: 315-321.
17	Sun R , Tai C W , Strømme M , et al . Hierarchical porous carbon synthesized from novel porous amorphous calcium or magnesium citrate with enhanced SF₆ uptake and SF₆/N₂ selectivity[J]. ACS Appl. Nano Mater., 2019, 2: 778-789.
18	Hasell T , Miklitz M , Stephenson A , et al . Porous organic cages for sulfur hexafluoride separation[J]. J. Am. Chem. Soc., 2016, 138: 1653-1659.
19	Fang X K , Hu X , Maenhout G J , et al . Sulfur hexafluoride (SF₆) emission estimates for china: an inventory for 1990—2010 and a projection to 2020[J]. Environ. Sci. Technol., 2013, 47: 3848-3855.
20	Chiang Y C , Wu P Y . Adsorption equilibrium of sulfur hexafluoride on multi-walled carbon nanotubes[J]. J. Hazard. Mater., 2010, 178: 729-738.
21	Mohindra V , Chae H , Sawin H H , et al . Abatement of perfluorocompounds (PFC’s) in a microwave tubular reactor using O as an additive gas[J]. IEEE Trans. Plasma Sci., 1997, 10: 399-407.
22	Ravishankara A R , Solomon S , Turnipseed A A , et al . Atmospheric lifetimes of long-lived halogenated species[J]. Science, 1993, 259:194-199.
23	Builes S , Roussel T , Vega L F . Optimization of the separation of sulfur hexafluoride and nitrogen by selective adsorption using Monte Carlo simulations[J]. AIChE J. 2011, 57: 962-974.
24	Kim D H , Ko Y H , Kim T H , et al . Separation of N₂/SF₆ binary mixtures using polyethersulfone (PESf) hollow fiber membrane[J]. Korean J. Chem. Eng., 2012, 29: 1081-1085.
25	Cho W S , Lee K H , Chang H J , et al . Evaluation of pressure-temperature swing adsorption for sulfur hexafluoride (SF₆) recovery from SF₆ and N₂ gas mixture[J]. Korean J. Chem. Eng., 2011, 28: 2196-2201.
26	Ho M T , Allinson G W , Wiley D E . Reducing the cost of CO₂ capture from flue gases using pressure swing adsorption[J]. Ind. Eng. Chem. Res., 2008, 47: 4883-4890.
27	Wiersum A D , Chang J S , Serre C , et al . An adsorbent performance indicator as a first step evaluation of novel sorbents for gas separations: application to metal-organic frameworks[J]. Langmuir, 2013, 29: 3301-3309.
28	Tong M M , Lan Y S , Yang Q Y , et al . Exploring the structure-property relationships of covalent organic frameworks for noble gas separations[J]. Chem. Eng. Sci., 2017, 168: 456-464.
29	Cui X L , Chen K J , Xing H B , et al . Pore chemistry and size control in hybrid porous materials for acetylene capture from ethylene[J]. Science, 2016, 353:141-144.
30	Li B , Cui X L , O’Nolan D , et al . An ideal molecular sieve for acetylene removal from ethylene with record selectivity and productivity[J]. Adv. Mater., 2017, 29: 1704210.
31	Yang L F , Cui X L , Yang Q W , et al . A single-molecule propyne trap: highly efficient removal of propyne from propylene with anion-pillared ultramicroporous materials[J]. Adv. Mater., 2018, 30: 1705374.
32	Li L B , Wen H M , He C H , et al . A metal-organic framework with suitable pore size and specific functional sites for the removal of trace propyne from propylene[J]. Angew. Chem. Int. Ed., 2018, 57: 15183-15188.
33	Furukawa H , Cordova K E , O’Keeffe M , et al . The chemistry and application of metal-organic frameworks[J]. Science, 2013, 341: 974-986.
34	Mueller U , Schubert M , Teich F , et al . Metal-organic frameworks-prospective industrial applications[J]. J. Mater. Chem., 2006, 16: 626-636.
35	Bae Y S , Snurr R Q . Development and evaluation of porous materials for carbon dioxide separation and capture[J]. Angew. Chem. Int. Ed., 2011, 50: 11586-11596.
36	Biswas S , Vanpoucke D E P , Verstraelen T , et al . New functionalized metal-organic frameworks MIL-47-X (X = —Cl, —Br, —CH₃, —CF₃, —OH, —OCH₃): synthesis, characterization, and CO₂ adsorption properties[J]. J. Phys. Chem. C, 2013, 117: 22784-22796.
37	Au V K M , Nakayashiki K , Huang H B , et al . Stepwise expansion of layered metal-organic frameworks for nonstochastic exfoliation into porous nanosheets[J]. J. Am. Chem. Soc., 2019, 141: 53-57.
38	Bachman J E , Reed D A , Kapelewski M T , et al . Enabling alternative ethylene production through its selective adsorption in the metal-organic framework Mn₂(m-dobdc)[J]. Energy Environ. Sci., 2018, 11: 2423-2431.
39	Wang K K , Huang H L , Liu D H , et al . Covalent triazine-based frameworks with ultramicropores and high nitrogen contents for highly selective CO₂ capture[J]. Environ. Sci. Technol., 2016, 50; 4869-4876.
40	Breneman C M , Wiberg K B . Determining atom-centered monopoles from molecular electrostatic potentials: the need for high sampling density in formamide conformational analysis[J]. J. Comput. Chem., 1990, 11: 361-373.
41	Dellis D , Samios J . Molecular force field investigation for sulfur hexafluoride: a computer simulation study[J]. Fluid Phase Equilibria, 2010, 291: 81-89.
42	Potoff J J , Siepmann J I . Vapor-liquid equilibria of mixtures containing alkanes, carbon dioxide, and nitrogen[J]. AIChE J., 2001, 47: 1676-1682.
43	Rappé A K , Casewit C J , Colwell K S , et al . UFF, a full periodic table force field for molecular mechanics and molecular dynamics simulations[J]. J. Am. Chem. Soc., 1992, 114: 10024-10035.
44	Vlugt T J H , García P E , Dubbeldam D , et al . Computing the heat of adsorption using molecular simulations: the effect of strong coulombic interactions[J]. J. Chem. Theory Comput., 2008, 4: 1107-1118.
45	Chen Y J , Li P , Modica J A , et al . Acid-resistant mesoporous metal-organic framework toward oral insulin delivery: protein encapsulation, protection, and release[J]. J. Am. Chem. Soc., 2018, 140: 5678-5681
46	Li L Y , Yang L F , Wang J W , et al . Highly efficient separation of methane from nitrogen on a squarate-based metal-organic framework[J]. AIChE J., 2018, 64: 3681-3689.
47	Hu J L , Sun T J , Liu X W , et al . Separation of CH₄ /N₂ mixtures in metal-organic frameworks with 1D micro-channels[J]. RSC Adv., 2016, 6: 64039-64046.
48	Lin R B , Wu H , Li L B , et al . Boosting ethane/ethylene separation within isoreticular ultramicroporous metal-organic frameworks[J]. J. Am. Chem. Soc., 2018, 140: 12940-12946.

[1]	赵亚欣, 张雪芹, 王荣柱, 孙国, 姚善泾, 林东强. 流穿模式离子交换层析去除单抗聚集体[J]. 化工学报, 2023, 74(9): 3879-3887.
[2]	刘爽, 张霖宙, 许志明, 赵锁奇. 渣油及其组分黏度的分子层次组成关联研究[J]. 化工学报, 2023, 74(8): 3226-3241.
[3]	邢雷, 苗春雨, 蒋明虎, 赵立新, 李新亚. 井下微型气液旋流分离器优化设计与性能分析[J]. 化工学报, 2023, 74(8): 3394-3406.
[4]	张佳怡, 何佳莉, 谢江鹏, 王健, 赵鹬, 张栋强. 渗透汽化技术用于锂电池生产中N-甲基吡咯烷酮回收的研究进展[J]. 化工学报, 2023, 74(8): 3203-3215.
[5]	张瑞航, 曹潘, 杨锋, 李昆, 肖朋, 邓春, 刘蓓, 孙长宇, 陈光进. ZIF-8纳米流体天然气乙烷回收工艺的产品纯度关键影响因素分析[J]. 化工学报, 2023, 74(8): 3386-3393.
[6]	张缘良, 栾昕奇, 苏伟格, 李畅浩, 赵钟兴, 周利琴, 陈健民, 黄艳, 赵祯霞. 离子液体复合萃取剂选择性萃取尼古丁的研究及DFT计算[J]. 化工学报, 2023, 74(7): 2947-2956.
[7]	高金明, 郭玉娇, 鄂承林, 卢春喜. 一种封闭罩内顺流多旋臂气液分离器的分离特性研究[J]. 化工学报, 2023, 74(7): 2957-2966.
[8]	文兆伦, 李沛睿, 张忠林, 杜晓, 侯起旺, 刘叶刚, 郝晓刚, 官国清. 基于自热再生的隔壁塔深冷空分工艺设计及优化[J]. 化工学报, 2023, 74(7): 2988-2998.
[9]	韩奎奎, 谭湘龙, 李金芝, 杨婷, 张春, 张永汾, 刘洪全, 于中伟, 顾学红. 四通道中空纤维MFI分子筛膜用于二甲苯异构体分离[J]. 化工学报, 2023, 74(6): 2468-2476.
[10]	朱兴驰, 郭志远, 纪志永, 汪婧, 张盼盼, 刘杰, 赵颖颖, 袁俊生. 选择性电渗析镁锂分离过程模拟优化[J]. 化工学报, 2023, 74(6): 2477-2485.
[11]	王蕾, 王磊, 白云龙, 何柳柳. SA膜状锂离子筛的制备及其锂吸附性能[J]. 化工学报, 2023, 74(5): 2046-2056.
[12]	蔺彩虹, 王丽, 吴瑜, 刘鹏, 杨江峰, 李晋平. 沸石中碱金属阳离子对CO₂/N₂O吸附分离性能的影响[J]. 化工学报, 2023, 74(5): 2013-2021.
[13]	孙永尧, 高秋英, 曾文广, 王佳铭, 陈艺飞, 周永哲, 贺高红, 阮雪华. 面向含氮油田伴生气提质利用的膜耦合分离工艺设计优化[J]. 化工学报, 2023, 74(5): 2034-2045.
[14]	张正, 何永平, 孙海东, 张荣子, 孙正平, 陈金兰, 郑一璇, 杜晓, 郝晓刚. 蛇形流场电控离子交换装置用于选择性提锂[J]. 化工学报, 2023, 74(5): 2022-2033.
[15]	王荣, 王永洪, 张新儒, 李晋平. 6FDA型聚酰亚胺炭分子筛气体分离膜的构筑及其应用[J]. 化工学报, 2023, 74(4): 1433-1445.

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

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 13

参考文献 48

相关文章 15

编辑推荐

Metrics

本文评价