This work focuses on the optimization of cyclic adsorption processes to improve the performance of CO2 capture from flue gas, consisting of nitrogen and carbon dioxide. The adopted processes are the PSA (pressure swing adsorption) process and the FVPSA (fractionated vacuum pressure swing adsorption) process, modified from the FVSA (fractionated vacuum swing adsorption) process developed by Air Products and Chemicals, Inc. The system models are currently bench scale and adopt zeolite13X as an adsorbent. The high-temperature PSA is better for high purity of product (CO2) and the high-temperature FVPSA is much better than the normal-temperature PSA processes. The main goal of this study is to improve the purity and recovery of carbon dioxide. The Langmuir isotherm parameters were calculated from experimental data taken at National Energy Technology Laboratory (Siriwardane, R.; NETL, DOE, 2004). Moreover, efficient optimization strategies are essential to compare these processes. To perform optimization work more efficiently, we modified the previous optimization method by Ko et al. (Ind. Eng. Chem. Res. 2003, 42, 339-348) in a manner similar to that by Jiang et al. (AIChE J. 2003, 49, 11401157). This allows us to obtain optimization results with more accurate cyclic steady states (CSSs), better convergence, and faster computation. As a result, optimal conditions at CSS are found for these systems.