一维超微孔MOFs[M3(HCOO)6](M=Fe,Co,Ni)用于乙烯-丙烯混合物的分离

doi:10.16085/j.issn.1000-6613.2016-2136

化工进展 ›› 2017, Vol. 36 ›› Issue (08): 3019-3023.DOI: 10.16085/j.issn.1000-6613.2016-2136

一维超微孔MOFs[M₃(HCOO)₆](M=Fe,Co,Ni)用于乙烯-丙烯混合物的分离

李顺, 王勇, 李立博, 李晋平

太原理工大学化学化工学院精细化工研究所, 山西太原 030024

收稿日期:2016-11-21 修回日期:2017-03-27 出版日期:2017-08-05 发布日期:2017-08-05
通讯作者: 李立博,讲师,硕士生导师,从事新型多孔材料应用于气体吸附分离的研究。
作者简介:李顺(1992-),女,硕士研究生。E-mail:lishun0334@link.tyut.edu.cn。
基金资助:
山西省青年科技研究基金（201601D021042）及国家自然科学基金青年项目（21606163）。

One dimensional ultramicropore MOFs[M₃(HCOO)₆](M=Fe,Co,Ni) forethylene/propylene separation

LI Shun, WANG Yong, LI Libo, LI Jinping

Research Institute of Special Chemicals, College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024, Shanxi, China

Received:2016-11-21 Revised:2017-03-27 Online:2017-08-05 Published:2017-08-05

摘要/Abstract

摘要： 烯烃是重要的化工原料，其生产过程中存在分离提纯能耗过大的问题。本文通过溶剂热方法合成了超微孔[M₃（HCOO）₆]（M=Fe，Co，Ni）系列材料，利用XRD、N₂吸附、SEM等对其结构与形貌进行了表征，详细考察了[M₃（HCOO）₆]的不同孔道结构对于乙烯和丙烯吸附的影响。结合固定床气体分离装置，测试了[M₃（HCOO）₆]对于乙烯-丙烯气体混合物的动力学分离性能。结果表明：通过构建不同的中心金属，有效地控制了MOFs的孔径尺寸；较大的孔径尺寸会提高乙烯和丙烯的吸附量，但对丙烯/乙烯的吸附选择性不高，分离性能较低；较小的孔径有利于提高对丙烯的吸附强度，从而提高丙烯/乙烯的吸附选择性与分离性能。本文通过对[M₃（HCOO）₆]系列MOFs不同中心金属的替换，提高了其对于丙烯/乙烯混合物的分离性能，为实现低碳烃混合物的高效分离提供了思路。

关键词: 乙烯, 丙烯, 孔径, 吸附, 选择性, 气体, 分离

Abstract: Olefins are important industrial chemicals,but the energy consumption in their production is very large. In this work,[M₃(HCOO)₆](M=Fe,Co,Ni)were synthesized using solvothermal method and characterized by XRD,N₂-sorption,SEM. We studied the pore structure effect on their ethylene and propylene adsorption properties. In a fixed-bed gas separation apparatus,ethylene/propylene separation abilities of[M₃(HCOO)₆] series were studied under dynamic conditions. The results showed that the pore sizes in MOFs can be rationally tuned through metal substitution. Larger pore sizes will lead to higher ethylene and propylene adsorption capacities,but lower propylene/ethylene adsorption selectivity and separation efficiency. Smaller pore sizes will increase the propylene adsorption,thus improve their propylene/ethylene adsorption selectivity and separation ability. In this work,we show that metal substitution on[M₃(HCOO)₆] series can effectively increase the propylene/ethylene separation ability,and this strategy provides an idea for efficient separation of light hydrocarbons.

Key words: ethylene, propylene, pore sizes, adsorption, selectivity, gas, separation

中图分类号:

TQ028.1

李顺, 王勇, 李立博, 李晋平. 一维超微孔MOFs[M₃(HCOO)₆](M=Fe,Co,Ni)用于乙烯-丙烯混合物的分离[J]. 化工进展, 2017, 36(08): 3019-3023.

LI Shun, WANG Yong, LI Libo, LI Jinping. One dimensional ultramicropore MOFs[M₃(HCOO)₆](M=Fe,Co,Ni) forethylene/propylene separation[J]. Chemical Industry and Engineering Progress, 2017, 36(08): 3019-3023.

参考文献

[1] 张敬升,李东风.炼厂干气的回收和利用技术概述[J].化工进展,2015,34(9):3207-3215. ZHANG J S,LI D F.Overview on recovery technologies of refinery dry gas[J].Chemical Industry and Engineering Progree,2015,34(9):3207-3215.
[2] 王卅.我国丙烯下游产业产品市场情况[J].化工进展,2014,33(9):2517-2520. WANG S.Domestic markets in propylene downstream industries[J]. Chemical Industry and Engineering Progree,2014,33(9):2517-2520.
[3] 高重密.从丙烷到丙烯,路有多远?[N].中国化工报,2013-02-28. GAO C M.Domestic markets in propylene downstream industries[N].China Chemical Industry News,2013-02-28.
[4] 邹劲松.全球丙烯供需状况及其发展趋势分析[J].石油化工技术经济,2004,20(6):37-43. ZOU J S.Analysis on the global supply and demand situation of propylene and its developing trend[J].Techno-Economics in Petrochemicals,2004,20(6):37-43.
[5] ANSON A,WANG Y,LIN C C H,et al.Adsorption of ethane and ethylene on modified ETS-10[J].Chemical Engineering Science,2008,63(16):4171-4175.
[6] SHI M,LIN C C H,KUZNICKI T M,et al.Separation of a binary mixture of ethylene and ethane by adsorption on Na-ETS-10[J].Chemical Engineering Science,2010,65(11):3494-3498.
[7] 谢春雷,方义东.催化干气中乙烯的回收利用[J].石化技术,2005,12(3):63-67. XIE C L,FANG Y D.Recovery and application of ethylene from catalytic cracking dry gas[J].Petrochemical Industry Technology,2005,12(3):63-67.
[8] 王子宗.乙烯装置分离技术及国产化研究开发进展[J].化工进展,2014,33(3):523-537. WANG Z Z.Development of ethylene recovery technology and research on technology localization[J].Chemical Industry and Engineering Progree,2014,33(3):523-537.
[9] 杨雪萍.轻质烯烃-烷烃分离新工艺开发进展[J].化工进展,2005,24(4):367-371. YANG X P.Advances in light olefin-paraffin separation technology[J].Chemical Industry and Engineering Progree,2005,24(4):367-371.
[10] 张超军,赵阳.丙烯精馏塔制造技术[J].化学工程与装备,2015(8):111-113. ZHANG C J,ZHAO Y.Manufacturing technology of propylene distillation column[J].Chemical Engineering & Equipment,2015(8):111-113.
[11] 黄富,张杨,彭国峰,等.气体分馏装置优化运行技术措施[J].炼油技术与工程,2015,45(10):21-24. HUANG F,ZHANG Y,PENG G F,et al.Technical measures for optimized operation of gas fractionation unit[J].Petroleum Refinery Engineering,2015,45(10):21-24.
[12] 宋以常,杨远行,石培华.两段变压吸附及产品气净化技术在催化裂化干气提浓乙烯装置上的应用[J].炼油技术与工程,2012(7):34-38. SONG Y C,YANG Y X,SHI P H.Application of two-stage pressure swing absorption and product gas purification technologies in FCC dry gas enrichment ethylene plant[J]. Petroleum Refinery Engineering,2012(7):34-38.
[13] LI J R,SCULLEY J,ZHOU H C.Metal-organic frameworks for separations[J].Chemical Reviews,2011,112(2):869-932.
[14] FURUKAWA H,CORDOVA K E,O'KEEFFE M,et al.The chemistry and applications of metal-organic frameworks[J].Science,2013,341(6149):1230444.
[15] BLOCHE D,QUEEN W L,KRISHNA R,et al.Hydrocarbon separations in a metal-organic framework with open iron (Ⅱ) coordination sites[J].Science,2012,335(6076):1606-1610.
[16] LI L B,YANG J F,LI J P,et al.Separation of CO₂/CH₄ and CH₄/N₂ mixtures by M/DOBDC:a detailed dynamic comparison with MIL-100(Cr) and activated carbon[J].Microporous and Mesoporous Materials,2014,198:236-246.
[17] LI L B,WANG Y,YANG J F,et al.Targeted capture and pressure/temperature-responsive separation in flexible metal-organic frameworks[J].Journal of Materials Chemistry A,2015,3(45):22574-22583.
[18] LI L B,KRISHNA R,WANG Y,et al.Exploiting the gate opening effect in a flexible MOF for selective adsorption of propyne from C1/C2/C3 hydrocarbons[J].Journal of Materials Chemistry A,2016,4(3):751-755.
[19] HU J L,SUN T J,LIU X W,et al.Rationally tuning the separation performances of[M₃ (HCOO)₆] frameworks for CH₄/N₂ mixtures via metal substitution[J].Microporous and Mesoporous Materials,2016,225:456-464.
[20] REN X Y,SUN T J,HU J L,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.
[21] WANG Z M,ZHANG Y J,LIU T,et al.[Fe₃(HCOO) 6]:a permanent porous diamond framework displaying H₂/N₂ adsorption,guest inclusion,and guest-dependent magnetism[J].Advanced Functional Materials,2007,17(9):1523-1536.

一维超微孔MOFs[M₃(HCOO)₆](M=Fe,Co,Ni)用于乙烯-丙烯混合物的分离

One dimensional ultramicropore MOFs[M₃(HCOO)₆](M=Fe,Co,Ni) forethylene/propylene separation

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