Selective adsorption of ethylene over ethane and propylene over propane in the metal-organic frameworks M2(dobdc) (M = Mg, Mn, Fe, Co, Ni, Zn)
Selective adsorption of ethylene over ethane and propylene over propane in the metal-organic frameworks M2(dobdc) (M = Mg, Mn, Fe, Co, Ni, Zn)
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DOI：
10.1039/c3sc00032j
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发表时间：
2013-01-01
期刊：
影响因子：
8.4
通讯作者：
Long, Jeffrey R.
中科院分区：
文献类型：
--
作者：
Geier, Stephen J.;Mason, Jarad A.;Long, Jeffrey R.
通过使用在较高温度下操作的选择性固体吸附剂，可以显着降低与乙烯-乙烷和丙烯-丙烷混合物的低温分离相关的能源成本。金属有机框架 M-2(dobdc)（M = Mg、Mn、Fe、Co、Ni、Zn；dobdc(4-) = 2,5-二氧化-1,4-苯二甲酸）在该应用中特别令人感兴趣，因为它们具有高密度的配位不饱和 M2+ 阳离子位点，可以选择性地与不饱和烃相互作用。在这里，我们提供了整个系列在 45、60 和 80 摄氏度下乙烯、乙烷、丙烯和丙烷的气体吸附数据。人们发现样品制备和活化的方法对于实现高分离选择性和容量非常重要。虽然所有研究的化合物都表现出良好的性能特征，但 Fe-2(dobdc) 和 Mn-2(dobdc) 分别对乙烯-乙烷和丙烯-丙烷混合物的分离表现出最高的选择性。中子粉末衍射数据确定的晶体结构阐明了乙烷、乙烯和丙烯在 Mn2(dobdc) 和 Co-2(dobdc) 中的结合。
A significant reduction in the energy costs associated with the cryogenic separation of ethylene-ethane and propylene-propane mixtures could potentially be realized through the use of selective solid adsorbents that operate at higher temperatures. The metal-organic frameworks M-2(dobdc) (M = Mg, Mn, Fe, Co, Ni, Zn; dobdc(4-) = 2,5-dioxido-1,4-benzenedicarboxylate) are of particular interest for this application, owing to their high density of coordinatively unsaturated M2+ cation sites that can selectively interact with unsaturated hydrocarbons. Here, we present gas adsorption data for ethylene, ethane, propylene, and propane at 45, 60, and 80 degrees C for the entire series. The means of sample preparation and activation is found to be important for achieving high separation selectivities and capacities. While all of the compounds investigated show good performance characteristics, Fe-2(dobdc) and Mn-2(dobdc) exhibit the highest selectivities for the separation of ethylene-ethane and propylene-propane mixtures, respectively. Crystal structures determined from neutron powder diffraction data elucidate the binding of ethane, ethylene, and propylene in Mn2(dobdc) and Co-2(dobdc).