Hydrocarbon Separations in a Metal-Organic Framework with Open Iron(II) Coordination Sites
Hydrocarbon Separations in a Metal-Organic Framework with Open Iron(II) Coordination Sites
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DOI：
10.1126/science.1217544
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发表时间：
2012-03-30
期刊：
影响因子：
56.9
通讯作者：
Long, Jeffrey R.
中科院分区：
文献类型：
--
作者：
Bloch, Eric D.;Queen, Wendy L.;Long, Jeffrey R.
通过开发在较高温度下运行的选择性固体吸附剂，有可能降低与低温蒸馏大规模工业分离轻烃相关的能源成本。在此，金属 - 有机框架Fe - 2(dobdc)（dobdc(4 - )：2,5 - 二氧代 - 1,4 - 苯二甲酸酯）被证明在318开尔文下对乙烯/乙烷和丙烯/丙烷混合物的分离表现出优异的性能特征。这些混合物的穿透数据为模拟提供了实验验证，模拟进而预测了该材料对甲烷/乙烷/乙烯/乙炔混合物的分馏、从乙烯中去除乙炔杂质以及基于膜的烯烃/石蜡分离的高选择性和高容量。中子粉末衍射数据证实了乙炔、乙烯和丙烯在铁(II)中心的侧向配位，同时也提供了乙烷和丙烷与金属之间弱得多的相互作用的固态结构表征。
The energy costs associated with large-scale industrial separation of light hydrocarbons by cryogenic distillation could potentially be lowered through development of selective solid adsorbents that operate at higher temperatures. Here, the metal-organic framework Fe-2(dobdc) (dobdc(4-): 2,5-dioxido-1,4-benzenedicarboxylate) is demonstrated to exhibit excellent performance characteristics for separation of ethylene/ethane and propylene/propane mixtures at 318 kelvin. Breakthrough data obtained for these mixtures provide experimental validation of simulations, which in turn predict high selectivities and capacities of this material for the fractionation of methane/ethane/ethylene/acetylene mixtures, removal of acetylene impurities from ethylene, and membrane-based olefin/paraffin separations. Neutron powder diffraction data confirm a side-on coordination of acetylene, ethylene, and propylene at the iron(II) centers, while also providing solid-state structural characterization of the much weaker interactions of ethane and propane with the metal.