
天然气提质过程中可有效回收丙烷和乙烷的高工业应用潜力金属有机框架材料
Shikai Xian, Junjie Peng, Haardik Pandey, Timo Thonhauser, Hao Wang, Jing Li
工程(英文) ›› 2023, Vol. 23 ›› Issue (4) : 56-63.
天然气提质过程中可有效回收丙烷和乙烷的高工业应用潜力金属有机框架材料
Robust Metal–Organic Frameworks with High Industrial Applicability in Efficient Recovery C3H8 and C2H6 from Natural Gas Upgrading
开发具有高吸收和选择性的高效吸附剂用于从天然气中分离和回收C2H6和C3H8是一项重要但具有挑战性的任务。在这项工作中,我们证明了高表面极性和合适孔径是协同提高分离性能的两个关键因素,例如,金属有机框架(MOF)-303 和MIL-160(MIL:拉瓦锡材料研究所)都具有一维(1D)开放通道,其具有高密度杂原子和所需的孔径(5~7 Å)。值得注意的是,MOF-303 在298 K和5 kPa 下对C3H8的吸收高达3.38 mmol∙g−1,C3H8/CH4 (5:85, V/V)理想吸附溶液理论(IAST)选择性为5114,在所有已报道的MOF中创下新高。此外,MOF-303 也显示出很高的C2H6吸收能力(在10 kPa 时)和C2H6/CH4 (10:85, V/V)选择性,分别达到1.59 mmol∙g−1和26。与MOF-303 相比,MIL-160 的孔径更大,1D通道内杂原子密度更低,因此其具有明显较低的吸收和选择性,但其值超过了大多数报道的MOF。密度泛函理论(DFT)的计算结果表明,高表面极性和合适的孔径能协同增强框架对C3H8和C2H6的亲和力,从而产生了对C3H8和C2H6的高负载能力和选择性。在95%的相对湿度(RH)下暴露一个月后,两种MOF均具有显著的湿度稳定性,且结构没有变化。此外,这两种化合物的合成都可以很容易地通过一锅反应来放大规模,从而获得约5 g 的高结晶度样品。最后,通过三元突破性实验、再生试验和循环评价,证明了MOF-303 和MIL-160 作为先进的吸附剂在高效分离C3H8/C2H6/CH4方面的巨大潜力。其优异的分离性能、高稳定性、低成本和良好的可扩展性,是天然气净化和回收C2H6和C3H8的理想吸附剂。
Developing efficient adsorbents with high uptake and selectivity for separation and recovery of C2H6 and C3H8 from natural gas is an important but challenging task. In this work, we demonstrate that high surface polarity and suitable pore diameter are two key factors that can synergistically enhance the separation performance, exemplified by metal–organic framework (MOF)-303 and Matériaux de l'Institut Lavoisier (MIL)-160, both possessing one-dimensional (1D) open channels with high density of heteroatoms and desired pore size (5–7 Å). Significantly, the uptake of MOF-303 for C3H8 is up to 3.38 mmol∙g−1 at 298 K and 5 kPa with a record-high C3H8/CH4 (5:85, v/v) ideal adsorbed solution theory (IAST) selectivity of 5114 among all reported MOFs. In addition, MOF-303 also displays high C2H6 uptake capacity (at 10 kPa) and C2H6/CH4 (10:85, v/v) selectivity, reaching 1.59 mmol∙g−1 and 26, respectively. Owing to the larger pore diameter and lower density of heteroatoms within its 1D channels, MIL-160 shows apparently lower uptake and selectivity compared to those of MOF-303, though the values exceed those of majority of reported MOFs. Density functional theory (DFT) calculations verify that the high surface polarity and the suitable pore diameter synergistically enhance the affinity of the frameworks toward C3H8 and C2H6, giving rise to the high loading capacity and selectivity for C3H8 and C2H6. Both MOFs feature remarkable moisture stability without structural change upon exposure to 95% relative humidity (RH) for a month. In addition, synthesis of both compounds can be readily scaled up through one-pot reactions to afford about 5 g samples with high crystallinity. Finally, the substantial potential of MOF-303 and MIL-160 as advanced adsorbents for efficient separation of C3H8/C2H6/CH4 has been demonstrated by ternary breakthrough experiments, regeneration tests, and cyclic evaluation. The excellent separation performance, high stability, low cost, and good scalability endow both MOFs promising adsorbents for natural gas purification and recovery of C2H6 and C3H8.
金属-有机框架,烃类吸附和分离,选择性,稳定性,放大合成 /
Metal–organic framework / Hydrocarbon adsorption and separation / Selectivity / Stability / Scale-up synthesis
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