This work attempts to address the quest of removing carbon dioxide from flue gas streams to help preserve the environment. It is based on a model that is able to describe the solid-liquid-vapour and solid-vapour phase equilibria for the ternary system of N2-O2-CO2 at pressures from 5 to 130 bar and over a wide range of temperature (140 to 220 K). Furthermore, a corresponding state-of-the art solid-vapor (SV) CO2 capture/separation unit is developed and introduced in this work. The SV unit was modeled using the Aspen Custom Modeler software by implementing the thermodynamic model developed before. It was then simulated using the Aspen Plus simulator; its performance was studied and analyzed. Moreover, the performance of the unit was optimized and compared to the most conventional corresponding technology used by the industry (i.e., amine-scrubbing). Results proved that for the same output clean gas composition, which contains only 0.3% CO2, the developed state-of-the-art SV unit consumes almost half of the energy required by the conventional process. Other advantages of the novel SV separation unit include the lower requirement of capital equipment, no need of additional agents (such as solvents) and the avoidance of product contamination with such additional agents.