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[Display omitted] • Electrolyzer and fuel cell integrated in an enhanced power-to-gas system. • No energy penalty for CO 2 capture, in a system with lower power requirements. • CO 2 separation exceeds 90 percent. This study outlines a concept for improving a power-to-gas (P2G) system through the implementation of highly efficient high-temperature electrolysis combined with a molten carbonate fuel cell (MCFC) as a CO 2 capture unit for a power plant. Laboratory scale experiments demonstrate that the MCFC could be used for CO 2 separation, opening the way to capture of CO 2 from flue gases at coal-fired power stations, while maintaining both high electric efficiency and a high CO 2 separation factor. Improved energy efficiency can be achieved by the lower electricity requirement of high temperature electrolysis compared to other technologies. Results obtained from experimental investigations show that a CO 2 separation rate in excess of 90 % is achievable through adjusting the cathode inlet flow. It should be noted that flue gas must be mixed with air before delivery to the MCFC. Controlled flow of inlet gases to the anode can raise electric efficiency to above 35 % for both laboratory-size and full-scale MCFC. The benefits of the concept are manifested by lower power consumption of the system and no energy penalty for the CO 2 capture process. Additionally, the system enjoys good thermal management because all devices run at elevated temperatures (Sabatier reactor at 300 °C, MCFC at 650 °C, solid oxide electrolyzer at 700–800 °C). The proposed improvements increase the system's competitiveness relative to alternative P2G systems and reduce the price of substitute natural gas. Secondly, it will eliminate the consumption of heat from the host coal-fired power plant. Thirdly, the entire system will be more straightforward, compact, and modular, allowing any future scale-up to be implemented without technological difficulties. Finally, the amount of energy required to produce hydrogen will decline by around 25 %. [ABSTRACT FROM AUTHOR]