Nitrate-promoted gas–solid reactions of H2 and CaCO3 for mid-temperature integrated CO2 capture and methanation

• Published in: Chemical engineering journal (Lausanne, Switzerland : 1996) Vol. 493; p. 152560
• Main Authors: Wei, Lifei, Han, Rui, Peng, Mingke, Li, Zhiyong, Zhang, Caidong, Liu, Qingling
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 01.08.2024
• Subjects: CaCO3 conversion; CaCO3 direct hydrogenation; Gas–solid reaction; Integrated CO2 capture and methanation; Nitrate promotion; Integrated CO2 capture and methanation; Nitrate promotion; CaCO3 conversion; Gas–solid reaction; CaCO3 direct hydrogenation
• ISSN: 1385-8947; 1873-3212
• DOI: 10.1016/j.cej.2024.152560

[Display omitted] •Molten KNO3 promotes direct CaCO3 hydrogenation.•Adding KNO3 increased the CaCO3 conversion of Ru/CeO2-CaO by 42% and the CH4 yield by 52% after 5 ICCM cycles.•Molten KNO3 can promote mass transfer in the diffusion-controlled stage of methanation.•The lower temperature is favorable for KNO3 to play a better promotional role. Integrated CO2 capture and methanation (ICCM) technology has attracted increasing attention for Carbon Neutrality. However, in the mid-temperature ICCM studies dominated by MgO, which involves the gas–gas catalytic pathway, the problems of high CO2 escape and low CH4 yield are common. Replacing MgO with CaO reduced CO2 escape because the reaction proceeded via the gas–solid pathway. However, the lower CaCO3 conversion rate limits its further applications. Here, we present an ICCM process with efficient CaCO3 conversion using alkali metal nitrates (KNO3, LiNO3, and (Li-K)NO3) to promote Ru/CeO2-CaO. The results showed that the doping of nitrates led to a decrease in the specific surface area of CaO, thus losing part of the CO2 capture performance. On the other hand, forming the molten liquid layer facilitated the gas–solid reaction between CaCO3 and H2, which improved the CaCO3 conversion. Compared with the Ru/CeO2-Neat CaO without nitrate promotion, the CaCO3 conversion of Ru/CeO2-KNO3/CaO was increased by 42% and CH4 yield by 52% after five ICCM cycles. Furthermore, kinetic analysis and in situ DRIFTS experiments demonstrated that molten KNO3 facilitated mass transfer in the diffusion-controlled stage of direct CaCO3 hydrogenation.