固载Cu(Ⅰ)的π络合MOF吸附剂用于乙烷/乙烯的选择性分离  

Immobilize Cu(Ⅰ)intoπ-complexed MOF adsorbent for selectivity separation of ethane/ethylene

作　　者：王涛虹 王超 李政 刘莹 田歌 常刚刚 阳晓宇 鲍宗必[2] WANG Taohong;WANG Chao;LI Zheng;LIU Ying;TIAN Ge;CHANG Ganggang;YANG Xiaoyu;BAO Zongbi(School of Chemistry,Chemical Engineering and Life Science,Wuhan University of Technology,Wuhan 430070,Hubei,China;College of Chemical and Biological Engineering,Zhejiang University,Hangzhou 310027,Zhejiang,China)

机构地区：[1]武汉理工大学化学化工与生命科学学院,湖北武汉430070 [2]浙江大学化学工程与生物工程学院,浙江杭州310027

出　　处：《化工学报》2024年第7期2565-2573,共9页CIESC Journal

基　　金：国家重点研发计划项目(2022YFB3806800);湖北省重点研发计划项目(2023BAB101);湖北省青年拔尖人才培养计划项目。

摘　　要：金属有机框架材料作为常见的吸附剂,已被广泛地应用于乙烷和乙烯气体混合物的分离,其中引入金属离子所产生π-络合作用可以显著提高MOFs对乙烯的吸附能力。在双羟基功能化后的UiO-66中负载Cu(Ⅰ),得到了优先吸附乙烯的Cu(Ⅰ)@UiO-66-(OH)_(2)吸附剂。羟基功能化的框架在增强极性的同时,可以与Cu(Ⅰ)产生协同效应,有效地提高了材料对乙烯/乙烷的吸附分离性能。得到的3%(质量分数)Cu(Ⅰ)@UiO-66-(OH)_(2)在298 K及1 bar(1 bar=0.1 MPa)条件下的C_(2)_H_(4)/C_(2)H_(6)IAST选择性为2.98,约为纯UiO-66-(OH)2的3倍。单组分吸附实验证明3%Cu(Ⅰ)@UiO-66-(OH)_(2)在整个压力范围下对乙烯的吸附容量均高于乙烷,并且其对乙烯的吸附热(42.81 kJ·mol-1)低于许多已报道的乙烯-选择性吸附剂。在模拟工业条件下对50/50(体积比)C_(2)_H_(4)/C_(2)H_(6)混合物进行穿透实验,进一步表明了3%Cu(Ⅰ)@UiO-66-(OH)_(2)吸附剂可以有效分离乙烷/乙烯混合物。As a common adsorbent,metal-organic frameworks(MOFs)has been widely researched in the separation of ethane and ethylene gas mixtures,and theπ-complexation generated by the introduction of metal ions can significantly improve the adsorption capacity of MOFs for ethylene.Cu(Ⅰ)was loaded into the dihydroxyl-functionalized UiO-66,and a Cu(Ⅰ)@UiO-66-(OH)_(2)adsorbent that preferentially adsorbed ethylene was obtained.The hydroxyl functionalized framework has a synergistic effect with Cu(Ⅰ)while enhancing the polarity,which can effectively improve the adsorption and separation performance of ethylene/ethane.The calculated C_(2)_H_(4)/C_(2)H_(6)IAST selectivity of 3%(mass)Cu(Ⅰ)@UiO-66-(OH)_(2)at 298 K and 1 bar is 2.98,which is approximately 3 times of the original UiO-66-(OH)_(2).Single-component adsorption experiments show that the adsorption capacity of 3%Cu(Ⅰ)@UiO-66-(OH)_(2)for ethylene is higher than that of ethane in the whole pressure range,and its adsorption heat of ethylene(42.81 kJ·mol^(-1))is lower than that of many reported ethylene-selective adsorbents.The breakthrough experiments of 50/50(volume ratio)C_(2)_H_(4)/C_(2)H_(6)mixture under simulated industrial conditions further demonstrate that the 3%Cu(Ⅰ)@UiO-66-(OH)_(2)adsorbent can effectively separate the ethane/ethylene mixture.

关 键 词：乙烷 乙烯 吸附 吸附剂 选择性 π-络合作用 

分 类 号：TQ028.1[化学工程]