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where Hij(T,p) is the Henry’s constant of gas i in the pure solvent j at the system temperature and pressure, Hij(T) is the Henry’s constant of gas i in the pure solvent j at zero pressure, Vij∞ is the infinite dilution partial volume of gas i in the pure solvent j, and Aij, Bij, Cij and Dij are parameters. The Henry’s constant of gas i in the mixed solvent (Hi,mix ) was calculated from those in the pure solvents 43: (11) Hi,mix Hij T ln( ) wln j i,mix j ij x V j ij wj kx V 2/3 k 2/3 where ∞i,mix is the infinite dilution activity coefficient of gas i in the mixed solvent, ∞i,j is the infinite dilution activity coefficient of gas i in the pure solvent j, and wj is the weighting factor. Vij∞ was calculated from the Brelvi-O’Connell model 44 with the characteristic volumes for the gas i (ViBO) and solvent j (VjBO), respectively. The general form of the Brelvi-O’Connell model is: BO BO l Vij fcn Vi ,Vj ,Vj (12) where Vjl is the liquid molar volume of solvent j. For the components other than ChCl/Urea (1:2), the characteristic volumes were taken from the Aspen databank as listed in Table S2 (Supporting information) in this work. For ChCl/Urea (1:2), as recommended in Aspen Plus, its critical volume was used as the characteristic volume. Due to the extremely low vapor pressure of ChCl/Urea (1:2), it can be assumed that ChCl/Urea (1:2) only exists in the liquid phase. Therefore, for the system studied in this work, H2O is the only solvent involved in vapor-liquid phase equilibrium. The vapor-liquid phase equilibrium for H2O can be expressed as: py v psx (13) ww www where pws is the vapor pressure of water, and the subscript w represents the properties of H2O. 2.2.2. Parameters for calculating phase equilibrium. The parameters for calculating (a) the phase equilibrium of pure water, (b) the fugacity coefficient with RK equation and (c) the solubility of CO2, CH4, N2, or O2 in pure water were taken from the Aspen databank or estimated using the Property Constant Estimation System (PCES) embedded in Aspen Plus. Due to the low solubility of N2 or O2 in ChCl/Urea (1:2) and their trace contents in the raw biogas, their solubilities in ChCl/Urea (1:2) were assumed to be zero 16. For other systems, the model parameters for calculating the Henry’s constant and the binary interaction parameters in NRTL for calculating activity coefficient were obtained from the fitting of the experimental data. The fitting results and discussion were briefly described in the following sections. 2.2.3. Solubility of CO2 in ChCl/Urea (1:2). The CO2 solubility in ChCl/Urea (1:2) has been determined by several research groups. Li et al.23 reported the CO2 solubility in ChCl/Urea (1:2) from 1 to 13 MPa with mole ratios of choline chloride to urea at 1:1.5, 1:2.0, and 1:2.5. Leron et al. 24 measured the CO2 solubility in ChCl/Urea (1:2) with a mole ratio of choline chloride to urea at 1:2 in a wide 9 ikPDF Image | CO2 Separation with Ionic Liquids
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