The dynamic adsorption behavior of CO2 under both nonisothermal and nearly isothermal conditions in silica supported poly(ethylenimine) (PEI) hollow fiber sorbents (Torlon (R)-S-PEI) is investigated in a rapid temperature swing adsorption (RTSA) process. A maximum CO2 breakthrough capacity of 1.33 mmol/g-fiber (2.66 mmol/g-silica) is observed when the fibers are actively cooled by flowing cooling water in the fiber bores. Under dry CO2 adsorption conditions, heat released from the CO2-amine interaction increases the CO2 breakthrough capacity by reducing the severity of the diffusion resistance in the supported PEI. This internal resistance can also be alleviated by prehydrating the fiber sorbent with a humid N-2 feed. The CO2 breakthrough capacity of prehydrated fibers is adversely affected by the release of the adsorption enthalpy (unlike the dry fibers); however, active cooling of the fiber results in a constant CO2 breakthrough capacity even at high CO2 delivery rates (i.e., high adsorption enthalpy delivery rates). In full RTSA cycles, a purity of 50% CO2 is achieved and the adsorption enthalpy recovery rate can reach similar to 72%. Studies on the cyclic stability of uncooled fiber sorbents in the presence of SO2 and NO contaminants indicate that exposure to NO at 200 ppm over 120 cycles does not lead to a significant degradation of the sorbents, but SO2 exposure at a similar high concentration of 200 ppm causes 60% loss in CO2 breakthrough capacity after 120 cycles. A simple amine reinfusion technique is successfully demonstrated to recover the adsorption capacity in poisoned fiber sorbents after deactivation by exposure to impurities such SO2. (C) 2014 American Institute of Chemical Engineers