金属有机框架材料HKUST-1吸附分离CH4/N2性能研究

›› 2018, Vol. 49 ›› Issue (5): 43-48.

金属有机框架材料HKUST-1吸附分离CH4/N2性能研究

韩素英¹,韩新华²,曹运祥¹,高荔¹,孙道峰¹,阎子峰¹

1. 中国石油大学（华东）重质油国家重点实验室
2. 科莱恩化工有限公司

收稿日期:2017-09-05 修回日期:2017-10-27 出版日期:2018-05-12 发布日期:2018-05-23
通讯作者: 阎子峰 E-mail:zifengy99@sina.com

ADSORPTION SEPARATION OF CH4/N2 OVER METAL ORGANIC FRAME MATERIAL HKUST-1

Han Suying,Han Xinhua,Cao Yunxiang,Gao Li,Sun Daofeng,Yan Zifeng

Received:2017-09-05 Revised:2017-10-27 Online:2018-05-12 Published:2018-05-23
Contact: Yan Zifeng E-mail:zifengy99@sina.com

摘要/Abstract

摘要： 以均苯三甲酸为配体，与金属离子Cu2+自组装得到稳定的金属有机框架材料（HKUST-1），并借助N2吸附-脱附、X射线粉末衍射、热重、SEM等对其结构进行表征，利用气体吸附仪测量了CH4和N2的吸附等温线，采用克-克（Clausius-Clapeyron）方程计算CH4的吸附热，并运用理想吸附溶液理论（ IAST）来计算HKUST-1对CH4/N2的分离因子。结果表明：在0℃、101.325 kPa和25℃、101.325 kPa的条件下，HKUST-1的CH4吸附量分别为25.1 cm3/g和15.2 cm3/g，N2吸附量分别为8.0 cm3/g和3.9 cm3/g，所制备的HKUST-1对CH4具有较好的吸附效果； HKUST-1对CH4/N2的选择性分离因子为6.8，对CH4/N2具有很好的分离效果； HKUST-1对CH4的吸附热为20 kJ/mol左右，与分子筛类吸附剂相比吸附热较小，易于再生。

关键词: HKUST-1, CH4/N2分离, 吸附等温线, 吸附热, 分离因子

Abstract: The HKUST-1 was obtained using trimesic acid self-assembly with Cu2+ and characterized by N2 adsorption，X-ray powder diffraction，TGA and SEM. Adsorption values of CH4 and N2 were measured by gas adsorption instrument. The Clausius-Clapeyron equation was used to calculate the adsorption heat of CH4. The separation coefficient of CH4/N2（SCH4/N2）was calculated by Ideal Adsorbed Solution Theory（IAST）. The results showed that HKUST-1 has a good adsorption effect on CH4. At conditions of 0 ℃，101.325 kPa and 25 ℃，101.325 kPa，the adsorption values of CH4 are 25.1 cm3/g and 15.2 cm3/g，the adsorption values of N2 are 8.0 cm3/g and 3.9 cm3/g，respectively. The selectivity factor for CH4 /N2 is 6.8，and the isosteric heat of adsorption of CH4 is about 20 kJ/mol. Compared with zeolite-like adsorbents，the isosteric heat was smaller，which meant a facile regeneration of adsorbents.

Key words: HKUST-1, separation of CH4/N2, adsorption isotherm, adsorption heat, separation coefficient

韩素英韩新华曹运祥高荔孙道峰阎子峰. 金属有机框架材料HKUST-1吸附分离CH4/N2性能研究[J]. , 2018, 49(5): 43-48.

Han Suying Han Xinhua Cao Yunxiang Gao Li Sun Daofeng Yan Zifeng. ADSORPTION SEPARATION OF CH4/N2 OVER METAL ORGANIC FRAME MATERIAL HKUST-1[J]. , 2018, 49(5): 43-48.

参考文献

[1]Champness N R, Schr?der M.Extended networks formed by coordination polymers in the solid state[J]. Solid State Mater. Sci., 1998, 3(4), 419-424.[J].Solid State Mater. Sci, 1998, 3(4):419-424 [2]于洋.以多类刚性有机配体为骨架的多孔MOFs的构建及其传感性质研究[D]. 山东师范大学, 2014. [3]秦勇, 袁亮, 胡千庭, 等.我国煤层气勘探与开发技术现状及发展方向[J].煤炭科学技术, 2012, 40(10):1-6 [4]申宝宏, 刘见中, 雷毅.我国煤矿区煤层气开发利用技术现状及展望[J].煤炭科学技术, 2015, 43(2):1-4 [5]杨江峰，赵强，于秋红，等.煤层气回收及分离材料的研究进展[J].化工进展, 2011, 30(4):793-800 [6]Mehra Y R.. Utilizing the Mehra process for processing and BTU upgrading of nitrogen-rich natural gas streams: U.S. Patent 4, 623, 371[P]. 1986-11-18. [7]Friesen D T, Babcock W C, et al.Liquid absorbent solutions for separating nitrogen from natural gas: U.S. Patent 6, 136, 222[P]. 2000-10-24. [8]Huang Y, Paul D.R. Effect of film thickness on the gas-permeation characteristics of glassy polymer membranes[J].Industrial & Engineering Chemistry Research, 2007, 46(8):2342-2347 [9]刘聪敏.吸附法浓缩煤层气甲烷研究[D]. 天津大学, 2010. [10]Yang R T.Adsorbents: fundamentals and applications[M]. John Wiley & Sons, 2003. [11]辜敏，鲜学福.变压吸附技术分离气体混合物[J].煤炭学报, 2002, 27(2):197-200 [12]胡江亮, 孙天军, 任新宇, 等.吸附剂上的吸附分离性能与热力学性质[J].燃料化学学报, 2013, 41(6):754-760 [13]聂明, 陆顺, 李庆, 等.溶剂热法制备金属有机框架-及其析氢性能[J].中国科学化学, 2016, 46(4):357-357 [14]欧阳少波，徐绍平，张俊杰，等.在吸附剂上的动态吸附特性[J].化工进展, 2014, 33(10):2546-2551 [15]Xu X L，Zhao X X，Sun L B，et al.Adsorption separation of carbon dioxide，methane，and nitrogen on Hβ and Na-exchanged β-zeolite[J].Journal of Natural Gas Chemistry, 2008, 17(4):391-396 [16]Ren X, Sun T, Hu J, et al.Highly enhanced selectivity for the separation of CH4 over N2 on two ultra-microporous frameworks with multiple coordination modes[J]. Microporous and Mesoporous Materials, 2014, 186: 137-145.[J].Microporous and Mesoporous Materials, 2014, 186(0):137-145 [17]孔祥明, 杨颖, 沈文龙, 等.在沸石-上的吸附平衡[J].化工学报, 2013, 64(6):2117-2124 [18]王鹏, 石耀琦, 马正飞, 等.CH4/N2在炭分子筛上的吸附平衡与扩散模型[J]. 高校化学工程学报, 2014(3):484-488.[J].高校化学工程学报, 2014, 3(0):484-488