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300 250 200 150 100 50 Liquid 0 °C Vapor Exp 0 °C Liquid Exp -40.3 °C Vapor -55 °C Vapor 0 °C Liquid -40.3 °C Vapor Exp -40.3 °C Liquid Exp -55 °C Liquid Exp 0 °C Vapor -40.3 °C Liquid -55 °C Vapor Exp -55 °C 0 0 0.2 0.4 0.6 0.8 1 Mole Fraction N2 Figure 6 Binary CO2-N2 thermodynamic data and non-ideal predictions. Data are from [24] The dew point and other lines are not quantitatively or even qualitatively accurate over the entire range of temperatures and pressures. That is, CO2 in light gases does not form an ideal system under these conditions. In the liquid region, the liquid that forms is a mixture of CO2 and light gases. More significantly, with 14% CO2 in nitrogen, no liquid forms under any conditions of temperature or pressure. Nonideal thermodynamics of the binary CO2-N2 system appear with measured data [24] in Figure 6 at three temperatures ranging from 0 °C to -55 °C, near the CO2 triple point. The data on the vapor and liquid branches of each curve represent corresponding endpoints of equilibrium tie lines in the two phases. No tie lines appear to avoid clutter. The data and predictions agree reasonably well over most of the region and represent a substantial improvement compared with the ideal predictions. As temperature decreases, the size of the two phase region increases. However, decreasing the temperature further forms solid rather than liquid CO2. At a nominal 14% CO2 in nitrogen (typical flue gas), no liquid forms at any temperature or pressure, in stark contrast to ideal behavior shown in Figure 5. That is, the frost/dew point line for typical flue gases (14% CO2) never enters the liquid-vapor region, unlike the Rault’s law estimates in the figure. This behavior presents some operational difficulties in that it requires solids handling. However, the formation of a solid represents a substantial thermodynamic and energy advantage since the solid that forms contains essentially no nitrogen or oxygen impurities and does not have to go through a subsequent distillation process. Liquid distillation in air separation units represents the largest energy demand, mostly associated with cooling for the condenser. The operational challenges associated with solids handling are discussed later. Pressure / barPDF Image | CC Pittsburgh Coal Conference
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