Gallate-Based Metal–Organic Frameworks for Highly Efficient Removal of Trace Propyne from Propylene

Abstract

Purification of propylene from the propyne (C3H4)/propylene (C3H6) mixture is a significant and challenging process in the chemical industry. Nowadays, the removal of propyne from propylene mainly relies on the energy-intensive hydrogenation catalyzed by noble metals. We herein report three gallate-based metal–organic frameworks, namely, M­(II)-gallate (M = Ni, Mg, Co), which provide excellent performance in terms of removing propyne from the propyne/propylene mixture (1:99, v/v). The C3H4 uptake capacities of Mg-, Co-, and Ni-gallate can reach 3.75, 3.21, and 2.65 mmol/g, while the C3H6 uptake capacities are only 1.50, 1.49, and 0.9 mmol/g respectively, at ambient conditions. Particularly, the productivities of 99.9999% pure C3H6 in Co-gallate and Mg-gallate were 1580 and 1420 mL/g, respectively, outperforming the state-of-the-art material USTA-200 (1400 mL/g). The adsorption mechanism was further investigated by using the first-principle dispersion-corrected density functional theory calculations, revealing that the excellent C3H4/C3H6 separation ability of M-gallate originates from stronger supramolecular interactions and C–H···O interactions between the hydrogen atoms from C3H4 and oxygen atoms from M-gallate frameworks. Besides, the M-gallate materials also show excellent regeneration ability. Thus, this work demonstrates that the family of M-gallate materials shows industrially promising porous materials for propylene purification by the adsorption process.

Structural Evolution from Noninterpenetrated to Interpenetrated Thorium–Organic Frameworks Exhibiting High Propyne Storage

“…The Th(IV) atoms in Th-TFBPDC-i have the same coordination atoms with those in Th-TFBPDC (Figure S2b). Once again, the Th−O w bond distances of 2.702(8), 2.678(8), and 2.702 (17) Å are longer than other Th−O bond distances between 2.343 (7) and 2.533( 9) Å (Table S1).…”

“…In contrast, the previously reported MOFs showed low C 3 H 4 sorption amounts with typical values lower than 4 mmol g −1 at 298 K (Figure 5). For example, the C 3 H 4 capacity at 298 K is much higher than those of JXNU-6 (5.07 mmol g −1 ), 9 SIFSIX-2-Cu-i (4.46 mmol g −1 ), 16 Co-Gallate (3.75 mmol g −1 ), 17 GeFSIXdps-Cu (3.7 mmol g −1 ), 18 ZU-62 (3.64 mmol g −1 ), 19 UTSA- 200 (3.58 mmol g −1 ), 20 and NKMOF-1-Ni (3.5 mmol g −1 ). 21 The C 3 H 4 sorption amount of Th-TFBPDC is comparable to that of the top-performing SIFSIX-1-Cu (8.76 mmol g −1 ).…”

Separation of propyne, propadiene and propylene with carboxylate ionic liquids

“…丙烯是工业产量仅次于乙烯的重要烯烃原料， 主 要用作聚合单体生产如聚丙烯等下游产品， 被广泛用 于塑料、制药、纺织品、涂料等国民经济各个行业 [1][2][3][4] 。目前，丙烯生产主要通过蒸汽裂解的方式进行， 该技术会难以避免地引入少量丙炔和丙二烯等杂质 气体，严重影响后续的丙烯聚合过程，因此，实现丙 烯与丙炔和丙二烯有效分离是丙烯纯化过程中的关 键 [5,6] 。现有的丙炔/丙烯、丙二烯/丙烯分离技术主要 是选择性催化加氢， 通过将丙烯中的丙炔或丙二烯转 化为丙烯，从而达到丙烯纯化的效果，但该过程存在 丙烯过度加氢得到副产物丙烷的问题， 同时存在分离 能耗大、成本高等缺点，因此需要开发更为经济有效 的分离方法 [7,8] 。 近年来， 以离子液体作为溶剂的吸收分离技术受 到广泛关注 [9][10] 。 吸收分离技术流程简单， 处理量大， 同时离子液体具有极低的蒸气压、 良好的化学稳定性 和丰富的结构可设计性， 可以克服常规溶剂的局限性， 使吸收过程无溶剂损失，同时易于回收利用，无交叉 污染 [11][12] 。在气体分离领域，离子液体已被研究应用 于 CO2 捕集 [13][14][15][16] 、NH3 捕集 [17] 、H2S 和 SO2 脱除 [18][19][20] 以及低碳烃分离等方面 [21][22][23][24] 。其中，Kim 等人测定了 C2-C3 炔烃烯烃在几种咪唑类离子液体中的溶解度 [25] ， 其中 [ [26][27] ，有望与 丙炔和丙二烯分子发生相对较强的氢键相互作用， 获 得较高的溶解度 [28] ， 同时引入结构不对称的三丁基乙 基鏻阳离子([P4442] + )能显著降低离子液体粘度，且 合成的离子液体具备良好的热稳定性，分解温度在 580 K 左右 [29][30] [27][28] 进行溶解度测试前， 合成的离子液体经过 1 mbar [29][30]…”

Biological Metal–Organic Frameworks (Bio-MOFs) for CO2Capture

“…Others regard bio-MOFs as a subcategory of highly porous MOFs that are useful for biological and medical applications. 18,68 Bio-MOFs have several advantages, which are listed in Figure 4. 18 Bio-MOFs have been applied for H 2 O adsorption and desorption, selective CO 2 adsorption, catalysis, drug delivery, photostable sensor fabrication, O 2 antibacterial activity, and storage of various gases.…”

“…There is no clear definition of what constitutes a bio-MOF. − Some define a bio-MOF as an MOF in which one or more biomolecules function as organic ligands. Others regard bio-MOFs as a subcategory of highly porous MOFs that are useful for biological and medical applications. , Bio-MOFs have several advantages, which are listed in Figure …”