三种朝向链基有机骨架对天然气中C2~C3的分离

doi:10.16085/j.issn.1000-6613.2024-0773

摘要/Abstract

摘要：

利用硝酸铟和酰胺三酸配体H₃L，以硝酸作为模板剂，采用溶剂热法制备出三种朝向的链基有机骨架材料——3W-ROD-1。该材料具有永久孔隙结构，表现出较高比表面积达2742m²/g，孔体积为1.11cm³/g。由于其独特的结构特征，在298K、1bar条件下，研究了3W-ROD-1对丙烷、乙烷、甲烷的气体吸附。其中，3W-ROD-1对丙烷、乙烷、甲烷吸附量分别为8.74mmol/g、3.62mmol/g、0.44mmol/g，丙烷吸附量在同类材料中位居前列。通过理想吸附溶液理论（IAST）选择性计算得出，在298K、1bar条件下，C₃H₈/CH₄和C₂H₆/CH₄的吸附选择性分别为87.0（C₃H₈∶CH₄=15∶85）和9.5（C₂H₆∶CH₄=15∶85）。动态穿透分离实验进一步验证了其对丙烷/甲烷、乙烷/甲烷、丙烷/乙烷/甲烷混合体系具有良好的分离性能，在丙烷/乙烷/甲烷（体积比5∶10∶85）三组分分离中，丙烷、乙烷和甲烷的突破时间分别为50min、11.5min和3min。结果表明该材料在天然气纯化方面具有潜在的应用价值。

关键词: 链基有机金属骨架材料, 天然气, 分离, 甲烷

Abstract:

Three-way rod metal-organic framework—3W-ROD-1 was prepared by solvothermal method using In(NO₃)₃·4H₂O and H₃L, with nitric acid serving as the template. This material possessed a permanent pore structure and exhibited a relatively high specific surface area, reaching up to 2742m²/g,along with a pore volume of 1.11cm³/g. Owing to its unique structural characteristics, the adsorption capacity of 3W-ROD-1 for propane, ethane, and methane were 8.74mmol/g, 3.62mmol/g, and 0.44mmol/g, respectively. Notably, the adsorption capacity of propane ranked at the forefront among similar materials. Through IAST (ideal adsorption solution theory) selective calculation, the adsorption selectivities of C₃H₈/CH₄, C₂H₆/CH₄at 298K and 1bar were calculated to be 87.0 (C₃H₈∶CH₄=15∶85) and 9.5 (C₂H₆∶CH₄=15∶85), respectively. Dynamic breakthrough separation experiments further verified its excellent separation performance for the propane/methane, ethane/methane, and propane/ethane/methane mixed systems. In the three components separation of propane/ethane/methane (V/V/V=5/10/85), the breakthrough times were 50min, 11.5min and 3min, respectively. These findings convincingly demonstrated the potential application value of this material in the field of natural gas purification.

Key words: rod metal-organic framework, natural gas, separation, methane

中图分类号:

O614

张玉凤, 庞煜骞, 裴浩楠, 樊小青. 三种朝向链基有机骨架对天然气中C₂~C₃的分离[J]. 化工进展, 2024, 43(9): 5185-5192.

ZHANG Yufeng, PANG Yuqian, PEI Haonan, FAN Xiaoqing. Three-way rod metal-organic frameworks for purifying of C₂—C₃ from natural gas[J]. Chemical Industry and Engineering Progress, 2024, 43(9): 5185-5192.

图/表 7

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MOFs	比表面积/m²·g^-1	孔体积/cm³·g^-1	吸附量/mmol·g^-1			丙烷/甲烷选择性	乙烷/甲烷选择性	文献
MOFs	比表面积/m²·g^-1	孔体积/cm³·g^-1	丙烷	乙烷	甲烷	丙烷/甲烷选择性	乙烷/甲烷选择性	文献
PCN-224	2704	1.06	8.25	2.93	0.48	609	12	[31]
MFM-202a	2220	0.95	6.76	4.21	0.45	87	9.4	[34]
CTGU-15	3164	1.32	12.13	2.13	0.4	170	5.2	[21]
UTSA-35a	743	0.31	2.97	3.43	0.43	80	15	[38]
UiO-67	2591	0.94	9.5	4.26	0.56	73.7	8.1	[39]
InOF-1	982	0.39	4.25	4.14	0.64	90	17	[41]
Fe-MOF-74	—	0.63	5.67	5.00	0.77	7.4	20	[20]
JLU-Liu15	762	0.32	3.88	3.47	1.22	461.5	28.7	[37]
3W-ROD-1	2742	1.11	8.74	3.62	0.44	87.0	9.5	本研究

MOFs	比表面积/m²·g^-1	孔体积/cm³·g^-1	吸附量/mmol·g^-1			丙烷/甲烷选择性	乙烷/甲烷选择性	文献
MOFs	比表面积/m²·g^-1	孔体积/cm³·g^-1	丙烷	乙烷	甲烷	丙烷/甲烷选择性	乙烷/甲烷选择性	文献
PCN-224	2704	1.06	8.25	2.93	0.48	609	12	[31]
MFM-202a	2220	0.95	6.76	4.21	0.45	87	9.4	[34]
CTGU-15	3164	1.32	12.13	2.13	0.4	170	5.2	[21]
UTSA-35a	743	0.31	2.97	3.43	0.43	80	15	[38]
UiO-67	2591	0.94	9.5	4.26	0.56	73.7	8.1	[39]
InOF-1	982	0.39	4.25	4.14	0.64	90	17	[41]
Fe-MOF-74	—	0.63	5.67	5.00	0.77	7.4	20	[20]
JLU-Liu15	762	0.32	3.88	3.47	1.22	461.5	28.7	[37]
3W-ROD-1	2742	1.11	8.74	3.62	0.44	87.0	9.5	本研究

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三种朝向链基有机骨架对天然气中C₂~C₃的分离

Three-way rod metal-organic frameworks for purifying of C₂—C₃ from natural gas

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