Utilizing Limestone Alone for Integrated CO2 Capture and Reverse Water-Gas Reaction in a Fixed Bed Reactor: Employing Mass and Gas Signal Analysis

Abstract

The integrated CO2 capture and utilization coupled with the reverse water-gas shift reaction (ICCU-RWGS) presents an alternative pathway for converting captured CO2 into CO in situ. This study investigates the effectiveness of three calcium-based materials (natural limestone, sol-gel CaCO3, and commercial CaCO3) as dual-functional materials (DFMs) for the ICCU-RWGS process at intermediate temperatures (650–750 °C). Our approach involves a fixed-bed reactor coupled with mass spectrometry and in situ Fourier transform infrared (FTIR) measurements to examine cyclic CO2 capture behavior, detailed physical and chemical properties, and morphology. The in situ FTIR results revealed the dominance of the RWGS route and exhibited self-catalytic activity across all calcium-based materials. Particularly, the natural limestone demonstrated a CO yield of 12.7 mmol g−1 with 100% CO selectivity and 81% CO2 conversion. Over the 20th cycle, a decrease in CO2 capture capacity was observed: sol-gel CaCO3, natural limestone, and commercial CaCO3 showed reductions of 44%, 61%, and 59%, respectively. This suggests inevitable deactivation during cyclic reactions in the ICCU-RWGS process, while the skeleton structure effectively prevents agglomeration in Ca-based materials, particularly in sol-gel CaCO3. These insights, coupled with the cost-effectiveness of CaO-alone DFMs, offer promising avenues for efficient and economically viable ICCU-RWGS processes.