High‐Throughput Discovery of Ni(IN)₂for Ethane/Ethylene Separation

Abstract

Although ethylene (C2H4) is one of the most critical chemicals used as a feedstock in artificial plastic chemistry fields, it is challenging to obtain high‐purity C2H4 gas without any trace ethane (C2H6) by the oil cracking process. Adsorptive separation using C2H6‐selective adsorbents is beneficial because it directly produces high‐purity C2H4 in a single step. Herein, Ni(IN)2 (HIN = isonicotinic acid) is computationally discovered as a promising adsorbent with the assistance of the multiscale high‐throughput computational screening workflow and Computation‐Ready, Experimental (CoRE) metal–organic framework (MOF) 2019 database. Ni(IN)2 is subsequently synthesized and tested to show the ideal adsorbed solution theory (IAST) selectivity of 2.45 at 1 bar for a C2H6/C2H4 mixture (1:15), which is one of the top‐performing selectivity values reported for C2H6‐selective MOFs as well as excellent recyclability, suggesting that this material is a promising C2H6‐selective adsorbent. Process‐level simulation results based on experimental isotherms demonstrate that the material is one of the top materials reported to date for ethane/ethylene separation under the conditions considered in this work.

Improving Ethane/Ethylene Separation Performance of Isoreticular Metal–Organic Frameworks via Substituent Engineering

“…Remarkably, each one of them displayed an evidently higher uptake capacity toward C 2 H 6 than toward C 2 H 4 at the low-pressure region, despite comparable amounts being adsorbed at atmospheric pressure. A similar adsorption situation was also observed for the reported MOFs such as MAF-49, Co­(AIN) 2 , and Ni­(IN) 2 . At 298 K and the partial pressure of 0.1 atm typically encountered in actual mixed gas, the gravimetric uptake capacities of C 2 H 6 reach 51 cm 3 (STP) g –1 for NJU-Bai7 , 53 cm 3 (STP) g –1 for ZJNU-21 , 40 cm 3 (STP) g –1 for ZJNU-22 , and 49 cm 3 (STP) g –1 for ZJNU-23 , which surpass those of most C 2 H 6 -selective MOFs documented so far under identical conditions such as Ni­(bdc)­(ted) 0.5 [10.9 cm 3 (STP) g –1 ], DUT-52­(Hf) [17.2 cm 3 (STP) g –1 ], Dia-4-Ni [25.6 cm 3 (STP) g –1 ], and Fe 2 (BDP) 3 [26.2 cm 3 (STP) g –1 ], indicating their excellent performance for trapping low-concentration C 2 H 6 (Figure h).…”

“…A similar adsorption situation was also observed for the reported MOFs such as MAF-49, 29 Co(AIN) 2 , 30 and Ni(IN) 2 . 31 At 298 K and the partial pressure of 0.1 atm typically encountered in actual mixed gas, the gravimetric uptake capacities of C 2 H 6 reach 51 cm 3 (STP) g −1 for NJU-Bai7, 53 cm 3 (STP) g −1 for ZJNU-21, 40 cm 3 (STP) g −1 for ZJNU-22, and 49 cm 3 (STP) g −1 for ZJNU-23, which surpass those of most C 2 H 6 -selective MOFs documented so far under identical conditions such as Ni(bdc)(ted) 0.5 [10.9 cm 3 (STP) g −1 ], 32 DUT-52(Hf) [17.2 cm 3 (STP) g −1 ], 33 Dia-4-Ni [25.6 cm 3 (STP) g −1 ], 34 and Fe 2 (BDP) 3 [26.2 cm 3 (STP) g −1 ], 35 indicating their excellent performance for trapping lowconcentration C 2 H 6 (Figure 3h). At atmospheric pressure and 298 K, the amounts of C 2 H 6 adsorbed are 69.1, 72.7, 65.6, and 66.4 cm 3 (STP) g −1 for NJU-Bai7, ZJNU-21, ZJNU-22, and ZJNU-23, respectively.…”

A Robust Hydrogen-Bonded Metal–Organic Framework with Enhanced Ethane Uptake and Selectivity

“…Recently, separation potential has been reported as a combined metric of selectivity and adsorption capacity, which reflects the maximum productivity. Notably, Co­(AIN) 2 exhibited a superior separation potential (116.03 cm 3 g –1 ) for C 2 H 6 /C 2 H 4 (1:15, v/v) at 1 bar, exceeding those of even the most C 2 H 6 -selective MOFs, such as CPM-733 (100.76 cm 3 g –1 ), MIL-53­(Al)-FA (65.10 cm 3 g –1 ), MAF-49 (68.89 cm 3 g –1 ), MUF-15 (72.72 cm 3 g –1 ), Cu­(Qc) 2 (42.73 cm 3 g –1 ), Ni­(bdc)­(ted) 0.5 (39.76 cm 3 g –1 ), NIIC-20-Bu (80.57 cm 3 g –1 ), Ni­(IN) 2 (85.33 cm 3 g –1 ), and Ni1-a (71.64 cm 3 g –1 ). ,,,,− The separation potential and C 2 H 6 uptake amount at 62.5 mbar for C 2 H 6 -selective MOF adsorbents and Co­(AIN) 2 are displayed in Figure b. Thus, the recorded C 2 H 6 uptake of Co­(AIN) 2 under industrial pressure was exceptionally high and its separation potential was extremely competitive among the top-performing C 2 H 6 -selective MOFs, suggesting that Co­(AIN) 2 does indeed show considerable potential for the separation applications of actual gas mixtures.…”

A robust ethane-selective hypercrosslinked porous organic adsorbent with high ethane capacity

“…14,15 Indeed, as a result of the successful implementation of nonpolar pore properties by sophisticated design, C 2 H 6 -selective adsorbents based on MOFs, COFs, HOFs, and porous organic cages have been developed in recent years. 5–8,11,13,16–20 However, because they exhibit poor structural stability and problems with large-scale synthesis, it is necessary to develop a suitable porous material that lacks the shortcomings of existing materials.…”