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330 Y. Xie et al. / Applied Energy 136 (2014) 325–335 Table 3 Parameters used in the calculation of CO2 absorption enthalpy in imidazolium-based ILs. ILs [emim][BF4] [bmim][BF4] [hmim][BF4] [omim][BF4] [emim][PF6] [bmim][PF6] [hmim][PF6] [emim][Tf2N] [bmim][Tf2N] [hmim][Tf2N] [emim][FAP] [emim][TfO] [emim][DEP] [emim][MeSO3] [emim][EtSO4] [bmim][NO3] [bmim][DCA] [bmim][TfO] sð0Þ sð1Þ sð0Þ sð1Þ 12 12 21 21 c1 c2 c3 c4 0.0163 0.0079 0.0983 0.217 0.290 0.277 0.0528 0.141 0.0735 0.556 1.607 0.351 0.303 0.215 0.103 0.0662 0.279 0.250 25.91 9819.5 29.01 14,134 3.570 634.02 3.829 272.20 0.819 1214.9 0.665 982.75 12.93 3513.6 3.344 234.66 4.503 640.52 0.510 253.82 1.831 31.608 3.067 669.89 3.429 574.46 2.782 981.29 6.135 4317.3 3.203 181.04 4.016 447.43 2.884 487.43 1.048 66.10 0.075 0.548 4.353 3.342 0.704 1.505 0.822 1.581 1.407 6.802 0.286 6.586 3.493 2.842 1.015 6.306 756.11 10.1 11,758 8.63 331.20 7.28 649.05 6.69 1842.2 8.84 1506.55 8.32 156.56 8.03 923.12 7.41 715.34 6.83 433.01 6.52 857.48 6.43 1792.0 9.39 429.27 8.60 2410.6 10.1 1362.7 6.45 1317.3 8.56 742.24 7.40 1432.4 10.1 2479.0 123.7 2049.3 42.55 1659.6 53.58 1537.7 52.19 2131.2 3.080 2001.8 8.079 1920.3 73.51 1822.6 123.2 1695.1 220.5 1617.9 17.19 1589.9 0.996 2301.7 1.294 2097.0 1.681 2422.0 0.045 1258.3 5.199 1873.8 0.769 1668.8 12.73 2541.9 9.932 Fig. 5. CO2 dissolution enthalpy and excess enthalpy at 298 K in -j- [bmim][BF4], -d- [hmim][BF4], -N- [omim][BF4]. and [bmim]-based ILs at 298 K and at pressures up to 6 MPa. It can be seen that both the CO2 loading and the CO2 absorption enthal- pies strongly depend on the anion of ILs, the CO2 loadings are from 0 to 2.5 mol CO2/mol ILs, and the CO2 absorption enthalpies are in the range of 21 8 kJ/mol. As shown in Fig. 7(a), the CO2 loading in [emim]-based ILs increases in the order of [EtSO4] < [MeSO3] < [BF4] < [PF6] < [TfO] < [DEP] < [Tf2N] < [FAP] at 298.15 K. The magnitude of CO2 absorption enthalpies in [emim]-based ILs shows different orders at different pressures as shown in Fig. 7(b). For example, when the pressure is 0.1 MPa, the magnitude of CO2 absorption enthalpy in [emim]-based ILs decreases in the order of [BF4] > [MeSO3] > [TfO] > [PF6] > [DEP] > [Tf2N] > [FAP] > [EtSO4]. While at 3 MPa, the magnitude of CO2 absorption enthalpy in [emim]-based ILs decreases in the order of [MeSO3] > [BF4] > [TfO] > [DEP] > [PF6] > [Tf2N] > [FAP] > [EtSO4]. For [emim]-based ILs, the CO2 loading in [emim][FAP] and [emim][Tf2N] have the higher values than those in other ILs, while the magnitude of CO2 absorption enthalpy in [emim][FAP] and [emim][Tf2N] is small. For [emim][EtSO4], the CO2 loading is the lowest, while the magnitude of CO2 absorption enthalpy is the smallest. For [bmim]-based ILs, the CO2 loading increases in the order of [NO3] < [DCA] [BF4] < [PF6] < [TfO] < [Tf2N], as shown in Fig. 8(a). As shown in Fig. 8(b), the magnitude of CO2 absorption enthalpy in [bmim]-based ILs at 1MPa decreases in the order of [TfO] > [BF4] > [NO3] > [PF6] > [DCA] > [Tf2N]. In the investigated ILs, the CO2 loading in [bmim][Tf2N] have the highest value but with the lowest magnitude of CO2 absorption enthalpy. As discussed previously that with increasing chain length in cation, the CO2 loading increases and the magnitude of CO2 absorp- tion enthalpy decreases. Therefore, the effect of the chain length on Fig. 6. CO2 loading (a) and absorption enthalpy (b) at 298 K in -j- [bmim][BF4], -d- [hmim][BF4], -N- [omim][BF4].PDF Image | CO2 Separation with Ionic Liquids
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