An increase in demand for energy efficient processes for the separation of saturated and unsaturated light hydrocarbons mixtures drives the need of noncryogenic processes. The adsorptive separation using Metal-Organic Frameworks with coordinatively unsaturated metal sites may provide a cost-effective alternative due to the strong binding of the metal cation with the unsaturated hydrocarbons. Since experiments on adsorption equilibrium of gas mixtures are challenging, we propose classical force field based simulations to analyse the ability of MOF-74 with different metal substitutions for the separation of C2 and C3 olefin/paraffin binary mixtures. We parametrized the force field by fitting to available experimental single-component adsorption isotherms of ethane, ethene, propane, and propene in M–MOF-74 (M=Co, Fe, Mn, and Ni). The force field was validated for a variety of temperatures ranged from 273 K to 353 K. We then conducted Monte Carlo simulations in the Grand-Canonical ensemble to elucidate the adsorption mechanisms of the saturated/unsaturated hydrocarbon mixtures, at 318 K and 353 K. We computed the adsorption isotherms, and from these the adsorption selectivity, and addressed the variations of MOF properties with different metal cations. Fe-based MOF-74 appears the best option for both ethane/ethene and propane/propene separation applications. This finding partly agrees with previous work based on the Ideal Adsorbed Solution Theory.@en

Computing bubble-points of multicomponent mixtures using Monte Carlo simulations is a non-trivial task. A new method is used to compute gas compositions from a known temperature, bubble-point pressure, and liquid composition. Monte Carlo simulations are used to calculate the bubble-points of carbon dioxide (CO2) and methane (CH4) mixtures in the ionic liquids (ILs) 1-n-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [bmim][Tf2N] and 1-ethyl-3-methylimidazolium diethylphosphate [emim][dep]. The Continuous Fractional Component Monte Carlo (CFCMC) method in the osmotic ensemble has been used to compute the solubility of CO2/CH4 gas mixtures at different temperatures (T), pressures (P), and gas compositions (yi). The effect of T, P, and yi on the real CO2/CH4 selectivity (i.e., the selectivity of CO2 in the presence of CH4) is investigated. The real selectivity will differ from the ideal selectivity, which is defined as the ratio of the Henry's constants, if the solubility of CO2 is influenced by the presence of CH4. The computed real selectivities are compared with the experimentally obtained real and ideal selectivities. The real CO2/CH4 selectivity decreases with increasing temperature and pressure, while the gas phase composition has a minor effect. The real selectivity is approximately identical to the ideal selectivity for relatively low pressures and low solute concentrations in the liquid phase. The real selectivity deviates from the ideal selectivity as the solute concentration in the liquid phase increases.@en

Monte Carlo simulations are used to calculate the solubility of natural gas components in ionic liquids (ILs) and Selexol, which is a mixture of poly(ethylene glycol) dimethyl ethers. The solubility of the pure gases carbon dioxide (CO2), methane (CH4), ethane (C2H6), and sulfur dioxide (SO2) in the ILs 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([Cnmim][Tf2N], n = 4, 6), 1-ethyl-3-methylimidazolium diethylphosphate ([emim][dep]), and Selexol (CH3O[CH2CH2O]nCH3, n = 4, 6) have been computed at 313.15 K and several pressures. The gas solubility trend observed in the experiments and simulations is: SO2 > CO2 > C2H6 > CH4. Overall, the Monte Carlo simulation results are in quantitative agreement with existing experimental data. Molecular simulation is an excellent tool to predict gas solubilities in solvents and may be used as a screening tool to navigate through the large number of theoretically possible ILs.@en

The separation and purification of light hydrocarbons is challenging in the industry. Recently, a ZJNU-30 metal-organic framework (MOF) has been found to have the potential for adsorption-based separation of olefins and diolefins with four carbon atoms [H. M. Liu et al. Chem. - Eur. J. 2016, 22, 14988-14997]. Our study corroborates this finding but reveals Fe-MOF-74 as a more efficient candidate for the separation because of the open metal sites. We performed adsorption-based separation, transient breakthrough curves, and density functional theory calculations. This combination of techniques provides an extensive understanding of the studied system. Using this MOF, we propose a separation scheme to obtain a high-purity product.@en