M2(&ITm&IT-dobdc) (M &DBLBOND; Mn, Fe, Co, Ni) Metal-Organic Frameworks as Highly Selective, High-Capacity Adsorbents for Olefin/Paraffin Separations

被引:199
作者
Bachman, Jonathan E. [1 ]
Kapelewski, Matthew T. [2 ]
Reed, Douglas A. [2 ]
Gonzalez, Miguel I. [2 ]
Long, Jeffrey R. [1 ,2 ,3 ]
机构
[1] Univ Calif Berkeley, Dept Chem & Biomol Engn, Berkeley, CA 94720 USA
[2] Univ Calif Berkeley, Dept Chem, Berkeley, CA 94720 USA
[3] Lawrence Berkeley Natl Lab, Div Mat Sci, Berkeley, CA 94720 USA
关键词
IRON(II) COORDINATION SITES; OLEFIN-PARAFFIN SEPARATION; PI-COMPLEXATION; HYDROCARBON SEPARATIONS; ADSORPTION; ETHYLENE; ETHANE; PROPYLENE; ZEOLITE; POLYMER;
D O I
10.1021/jacs.7b06397
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The metal-organic frameworks M-2(m-dobdc) (M = Mn, Fe, Co, Ni; m-dobdc(4-) = 4,6-dioxido-1,3-benzenedicarboxylate) were evaluated as adsorbents for separating olefins from paraffins. Using single-component and multicomponent equilibrium gas adsorption measurements, we show that the coordinatively unsaturated M2+ sites in these materials lead to superior performance for the physisorptive separation of ethylene from ethane and propylene from propane relative to any known adsorbent, including para-functionalized structural isomers of the type M-2(p-dobdc)(p-dobdc(4-) = 2,5-dioxido-1,4-benzenedicarboxylate). Notably, the M-2(m-dobdc) frameworks all exhibit an increased affinity for olefins over paraffins relative to their corresponding structural isomers, with the Fe, Co, and Ni variants showing more than double the selectivity. Among these frameworks, Fe-2(m-dobdc) displays the highest ethylene/ethane (>25 ) and propylene/propane (>55) selectivity under relevant conditions, together with olefin capacities exceeding 7 mmol/g. Differential enthalpy calculations in conjunction with structural characterization of ethylene binding in Co-2(m-dobdc) and Co-2(p-dobdc) via in situ single-crystal X-ray diffraction reveal that the vast improvement in selectivity arises from enhanced metal-olefin interactions induced by increased charge density at the metal site. Moderate olefin binding enthalpies, below 55 and 70 kJ/mol for ethylene and propylene, respectively, indicate that these adsorbents maintain sufficient reversibility under mild regeneration conditions. Additionally, transient adsorption experiments show fast kinetics, with more than 90% of ethylene adsorption occurring within 30 s after dosing. Breakthrough measurements further indicate that Co-2(m-dobdc) can produce high purity olefins without a temperature swing, an important test of process applicability. The excellent olefin/paraffin selectivity, high olefin capacity, rapid adsorption kinetics, and low raw materials cost make the M-2(m-dobdc) frameworks the materials of choice for adsorptive olefin/paraffin separations.
引用
收藏
页码:15363 / 15370
页数:8
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