双金属MOF⁃74(Mg x Ni1-x )的制备及其对CO2/N2的吸附分离性能研究

doi:10.3969/j.issn.1672-6952.2022.06.001

摘要/Abstract

摘要：

以Mg、Ni为中心金属、十二烷基苯磺酸钠（SDBS）为模板剂，采用溶剂热法合成HP?MOF?74（Mg _x Ni_1-_x ）（x=0.25、0.50、0.75）样品，以烟道气中CO₂和N₂为吸附质，考察了HP?MOF?74（Mg _x Ni_1-_x ）样品在273 K和298 K下吸附分离CO₂/N₂的性能；通过静态容量法在273 K和298 K处测试了三种不同HP?MOF?74（Mg _x Ni_1-_x ）样品上CO₂和N₂的等温线，并使用双位点Langmuir?Freundlich（DSLF）和单位点Langmuir?Freundlich（SSLF）模型对获得的实验数据集进行了拟合；根据理想吸附溶液理论（IAST），估算了CO₂/N₂二元混合物的吸附选择性；使用Clausius–Clapeyron方程计算了等量吸附热（Q_st）。结果表明，在273 K和100 kPa的条件下，HP?MOF?74(Mg_0.50Ni_0.50)样品的CO₂吸附量为4.864 mmol/g；CO₂和N₂在HP?MOF?74(Mg_0.50Ni_0.50)样品上的吸附等温线分别与DSLF和SSLF模型十分吻合，说明CO₂的吸附行为是双孔位吸附，而N₂的吸附行为是单位点吸附；HP?MOF?74（Mg_0.25Ni_0.75）样品对CO₂的IAST吸附选择性为2 263，吸附量和选择性均优于传统吸附剂MOF?74材料；CO₂在HP?MOF?74（Mg _x Ni_1-_x ）样品上的等量吸附热均高于N₂，说明CO₂在HP?MOF?74（Mg _x Ni_1-_x ）样品上的表面自由结合能更高。

关键词: HP?MOF?74(Mg _x Ni_1-_x ), CO₂/N₂吸附分离, 吸附等温线, Henry选择性, 烟道气

Abstract:

HP?MOF?74(Mg _x Ni_1-_x ) (x=0.25, 0.50, 0.75) was synthesized by solvothermal method with Mg and Ni as central metals and sodium dodecylbenzene sulfonate (SDBS) as template. Using flue gas CO₂ and N₂ as adsorbents, the performance of HP?MOF?74(Mg _x Ni_1-_x ) in adsorption and separation of CO₂/N₂ at 273 K and 298 K was investigated, the isotherms of CO₂ and N₂ on three different HP?MOF?74(Mg _x Ni_1-_x ) materials were measured at 273 K and 298 K by static volumetric method, and the experimental data sets were fitted by Dual Site Langmuir Freundlich (DSLF) and Single Site Langmuir Freundlich (SSLF) models. The adsorption selectivity of CO₂/N₂ binary mixture was estimated according to the Ideal Adsorption Solution Theory (IAST). In addition, the isosteric heat of adsorption (Q_st) was calculated using the Clausius Clapeyron equation. The results show that the CO₂ adsorption capacity of HP?MOF?74(Mg_0.50Ni_0.50) sample is 4.864 mmol/g at 273 K and 100 kPa; the adsorption isotherms of CO₂ and N₂ on HP?MOF?74(Mg _x Ni_1-_x ) are in good agreement with Dual Site Langmuir Freundlich (DSLF) and Single Site Langmuir Freundlich (SSLF) models respectively, indicating that the adsorption behavior of CO₂ is double sites adsorption, while the adsorption behavior of N₂ is single site adsorption; at 273 K and 100 kPa, the IAST adsorption selectivity of HP?MOF?74(Mg_0.25Ni_0.75) for CO₂ is 2 263, and the adsorption capacity and selectivity are better than those of traditional adsorbent MOF?74; the CO₂ isosteric heat of adsorption on HP?MOF?74(Mg _x Ni_1-_x ) is higher than that of N₂, indicating that the surface free binding energy of CO₂ on HP?MOF?74(Mg _x Ni_1-_x ) is higher.

Key words: HP?MOF?74(Mg _x Ni_1-_x ), CO₂/N₂ adsorption separation, Adsorption isotherm, Henry selectivity, Flue gas

中图分类号:

O647

杨萍, 李有喜, 蔡武锋, 梁文博, 段林海. 双金属MOF⁃74(Mg _x Ni_1-_x )的制备及其对CO₂/N₂的吸附分离性能研究[J]. 辽宁石油化工大学学报, 2022, 42(6): 1-7.

Ping Yang, Youxi Li, Wufeng Cai, Wenbo Liang, Linhai Duan. Preparation of Bimetallic MOF⁃74(Mg _x Ni_1-_x ) and Its Adsorption and Separation Performance for CO₂/N₂[J]. Journal of Liaoning Petrochemical University, 2022, 42(6): 1-7.

图/表 8

参考文献 21

1	Adhikari A K， Lin K S. Synthesis， fine structural characterization， and CO₂ adsorption capacity of metal organic frameworks⁃74［J］. Journal of Nanoscience and Nanotechnology， 2014， 14（4）： 2709⁃2717.
2	王熙源. Mg⁃MOF⁃74的制备及对CO₂气体吸附的分子模拟研究［D］. 哈尔滨：哈尔滨工业大学， 2014.
3	吕璐，李宁，米铁，等. 烟道气二氧化碳吸附技术的研究进展［J］. 工业安全与环保， 2012， 38（12）： 16⁃18.
4	陈健. 金属⁃有机骨架MOF⁃74系列吸附捕集低浓度二氧化碳的研究［D］. 大连：大连理工大学， 2016.
5	Perumal S L， Hemalatha P， Alagara M， et al. Investigation of structural， optical and photocatalytic properties of Sr doped ZnO nanoparticles［J］. International Journal of Physical Sciences， 2015， 4： 1⁃13.
6	Bae T H， Long J R. CO₂/N₂ separations with mixed⁃matrix membranes containing Mg₂（dobdc） nanocrystals［J］. Energy & Environmental Science， 2013， 6（12）： 3565⁃3569.
7	Shen J N， Yu C C， Zeng G N， et al. Preparation of a facilitated transport membrane composed of carboxymethyl chitosan and polyethylenimine for CO₂/N₂ separation［J］. International Journal of Molecular Sciences， 2013， 14（2）： 3621⁃3638.
8	Zhang H， Diao R， Mostofi M， et al. Molecular simulation of enhanced CH₄ recovery and CO₂ storage by CO₂⁃N₂ mixture injection in deformable organic micropores［J］. Journal of Natural Gas Science and Engineering， 2020， 84： 103658.
9	张航. 多级孔金属⁃有机骨架材料的常温快速合成及机理研究［D］. 广州：华南理工大学， 2019.
10	李金清. 模板法合成多级孔Cu⁃BTC和多级孔ZIF⁃8［D］. 广州：华南理工大学， 2018.
11	刘江. MOF⁃74（Ni）的改性、其复合材料快速制备及其吸附烯烃烷烃和CO₂性能［D］. 广州：华南理工大学， 2016.
12	安晓银，鲁金明，刘毅，等. 双金属MOF⁃74的合成及其气体吸附分离性能研究［J］. 化工新型材料， 2020， 48（4）： 185⁃190.
13	杨家佳，丁玉栋，廖强，等. 合成前氨基改性Mg⁃MOF⁃74吸附分离CO₂性能研究［J］. 工程热物理学报， 2019， 40（2）： 435⁃441.
14	段崇雄. 多级孔金属⁃有机骨架材料的制备、形成机制及吸附性能研究［D］. 广州：华南理工大学， 2019.
15	武静. 聚离子液体多孔材料制备及其在CO₂捕集中的应用基础研究［D］. 北京：北京化工大学， 2015.
16	Tarafder A， Mazzotti M. A method for deriving explicit binary isotherms obeying the ideal adsorbed solution theory［J］. Chemical Engineering & Technology， 2012， 35（1）： 102⁃108.
17	Myers A L， Prausnitz J M. Thermodynamics of mixed⁃gas adsorption［J］. AIChE Journal， 1965， 11（1）： 121⁃127.
18	Mu B， Schoenecker P M， Walton K S. Gas adsorption study on mesoporous metal organic framework UMCM⁃1［J］. Journal of Physical Chemistry C， 2010， 114（14）： 6464⁃6471.
19	Karra J R， Walton K S. Molecular simulations and experimental studies of CO₂， CO， and N₂ adsorption in metal⁃organic frameworks［J］. Journal of Physical Chemistry C， 2010， 114（37）： 15735⁃15740.
20	Dong K， Tuy B， Ysb B， et al. Metal⁃organic framework MIL⁃101 loaded with polymethacrylamide with or without further reduction： Effective and selective CO₂ adsorption with amino or amide functionality［J］. Chemical Engineering Journal， 2020， 380： 122496.
21	Park J M， Dong K Y， Jhung S H. Selective CO₂ adsorption over functionalized Zr⁃based metal organic framework under atmospheric or lower pressure： Contribution of functional groups to adsorption［J］. Chemical Engineering Journal， 2020， 402： 126254.

吸附剂⁃吸附质	温度/K	参数						R²
吸附剂⁃吸附质	温度/K	q₁	b₁	n₁	q₂	b₂	n₂	R²
HP⁃MOF⁃74(Mg_0.25Ni_0.75)⁃CO₂	273	5.708 47	0.027 57	1.363 33	1.797 35	0.391 65	0.928 30	1.000 00
HP⁃MOF⁃74(Mg_0.50Ni_0.50)⁃CO₂	273	1.657 74	0.511 81	0.901 76	7.880 27	0.027 01	1.423 65	1.000 00
HP⁃MOF⁃74(Mg_0.75Ni_0.25)⁃CO₂	273	2.446 53	0.014 29	1.564 92	2.446 53	0.014 29	1.564 88	0.999 92
HP⁃MOF⁃74(Mg_0.25Ni_0.75)⁃CO₂	298	1.430 05	0.092 42	0.999 52	3.963 53	0.011 21	1.161 04	1.000 00
HP⁃MOF⁃74(Mg_0.50Ni_0.50)⁃CO₂	298	1.411 92	0.103 27	1.000 56	2.883 96	0.004 72	1.009 42	1.000 00
HP⁃MOF⁃74(Mg_0.75Ni_0.25)⁃CO₂	298	1.236 03	0.006 25	1.235 59	1.236 03	0.006 25	1.235 60	0.999 97
HP⁃MOF⁃74(Mg_0.25Ni_0.75)⁃N₂	273	1.151 43	0.001 74	1.004 71	—	—	—	0.999 93
HP⁃MOF⁃74(Mg_0.50Ni_0.50)⁃N₂	273	1.419 67	0.002 43	0.982 01	—	—	—	0.999 99
HP⁃MOF⁃74(Mg_0.75Ni_0.25)⁃N₂	273	3.107 95	0.002 72	1.001 27	—	—	—	0.999 99
HP⁃MOF⁃74(Mg_0.25Ni_0.75)⁃N₂	298	1.067 67	0.001 11	0.893 10	—	—	—	1.000 00
HP⁃MOF⁃74(Mg_0.50Ni_0.50)⁃N₂	298	2.250 93	0.001 04	0.948 21	—	—	—	0.999 96
HP⁃MOF⁃74(Mg_0.75Ni_0.25)⁃N₂	298	3.781 15	0.001 11	0.967 93	—	—	—	0.999 98

吸附剂⁃吸附质	温度/K	参数						R²
吸附剂⁃吸附质	温度/K	q₁	b₁	n₁	q₂	b₂	n₂	R²
HP⁃MOF⁃74(Mg_0.25Ni_0.75)⁃CO₂	273	5.708 47	0.027 57	1.363 33	1.797 35	0.391 65	0.928 30	1.000 00
HP⁃MOF⁃74(Mg_0.50Ni_0.50)⁃CO₂	273	1.657 74	0.511 81	0.901 76	7.880 27	0.027 01	1.423 65	1.000 00
HP⁃MOF⁃74(Mg_0.75Ni_0.25)⁃CO₂	273	2.446 53	0.014 29	1.564 92	2.446 53	0.014 29	1.564 88	0.999 92
HP⁃MOF⁃74(Mg_0.25Ni_0.75)⁃CO₂	298	1.430 05	0.092 42	0.999 52	3.963 53	0.011 21	1.161 04	1.000 00
HP⁃MOF⁃74(Mg_0.50Ni_0.50)⁃CO₂	298	1.411 92	0.103 27	1.000 56	2.883 96	0.004 72	1.009 42	1.000 00
HP⁃MOF⁃74(Mg_0.75Ni_0.25)⁃CO₂	298	1.236 03	0.006 25	1.235 59	1.236 03	0.006 25	1.235 60	0.999 97
HP⁃MOF⁃74(Mg_0.25Ni_0.75)⁃N₂	273	1.151 43	0.001 74	1.004 71	—	—	—	0.999 93
HP⁃MOF⁃74(Mg_0.50Ni_0.50)⁃N₂	273	1.419 67	0.002 43	0.982 01	—	—	—	0.999 99
HP⁃MOF⁃74(Mg_0.75Ni_0.25)⁃N₂	273	3.107 95	0.002 72	1.001 27	—	—	—	0.999 99
HP⁃MOF⁃74(Mg_0.25Ni_0.75)⁃N₂	298	1.067 67	0.001 11	0.893 10	—	—	—	1.000 00
HP⁃MOF⁃74(Mg_0.50Ni_0.50)⁃N₂	298	2.250 93	0.001 04	0.948 21	—	—	—	0.999 96
HP⁃MOF⁃74(Mg_0.75Ni_0.25)⁃N₂	298	3.781 15	0.001 11	0.967 93	—	—	—	0.999 98

双金属MOF⁃74(Mg _x Ni_1-_x )的制备及其对CO₂/N₂的吸附分离性能研究

Preparation of Bimetallic MOF⁃74(Mg _x Ni_1-_x ) and Its Adsorption and Separation Performance for CO₂/N₂

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