Pre-combustion capture of CO2 from shifted syngas is a major route for carbon capture and sequestration from integrated gasification combined cycle for coal as the fuel. Conventional Selexol absorption-based processes involve cooling the gas to near-ambient temperature. A novel cyclic 5-valve pressure swing membrane absorption (PSMAB) process is being developed for CO2 removal from lower-temperature shifted syngas at similar to 100 degrees C in hollow-fiber membrane contactors using ionic liquid (IL) absorbent, 1-butyl-3-methyl-imidazolium dicyanamide ([bmim][DCA]). Separation performance is considerably enhanced by adding nonvolatile polyamidoamine (PAMAM) dendrimer Generation 0 to the IL at higher temperatures for a 40% CO2, 60% He (surrogate for H-2) feed. Absorption performance in the cyclic process depends on selective sorption and other absorbent properties especially viscosity and hollow-fiber membrane contactor module design employing microporous hydrophobized polyether ether ketone (PEEK) hollow fiber-based membranes. Equilibrium CO2 solubility and CO2-He selectivity for IL, [bmim][DCA], has been compared with those for poly(ethylene glycol) (PEG) 400 which yields improved equilibrium CO2-He selectivity and CO2 absorption with/without 20 wt% PAMAM dendrimer over the temperature range 50-100 degrees C. The PSMAB process separation performance has been explored using PEG 400-based absorbent in two hollow-fiber membrane contactor modules with improved designs in series at temperatures up to 100 degrees C and feed-gas pressures up to 1720 kPag. This performance has been compared with that of the system using IL, [bmim][DCA]. The dendrimer-IL system performance for two modules-in-series with reduced dead volume considerably enhanced separation yielding >95% CO2 in the CO2-enriched product; further this performance exceeded easily that of the PEG 400-based system. (C) 2015 Elsevier B.V. All rights reserved.