Carbon monoxide (CO), as an inevitable byproduct in the in-situ supercritical water–coal gasification process coupled with oxygen injection for temperature elevation and hydrogen production, becomes a critical component that must be suppressed and converted due to its low calorific value and toxicity. Based on a self-developed in-situ supercritical water-coal gasification cyclic continuous reaction system, cyclic continuous reaction experiments of CO under supercritical water-coal gasification conditions at different temperatures were conducted. In combination with reaction kinetics, the reaction behavior and kinetic characteristics of CO in the in-situ supercritical water-coal gasification system were systematically analyzed. The main research findings are as follows: Firstly, 450 °C is the threshold temperature that triggers the rapid consumption of CO and promotes the formation of H2, CO2, and CH4 through the water-gas shift reaction and other related reactions. With increasing temperature, CO consumption increasingly favors the formation of H2. Secondly, the rates of the water-gas shift reaction and the methanation reaction at different supercritical water-coal gasification temperatures directly determine the conversion rate and conversion pathway of CO. Thirdly, the supercritical water-coal gasification environment intrinsically promotes CO consumption and H2 formation, providing an advantageous medium for hydrogen production. Enhancing the forward rate of the water-gas shift reaction is essential not only for accelerating CO consumption but also for elevating H2 concentration, while accelerating the forward methanation reaction is critical for further reducing CO levels. Finally, after CO injection, the steady-state concentration of H2 is essentially unaffected by reaction temperature, whereas higher temperatures favor the overall reaction pathway toward the formation of high-calorific-value gases such as H2 and CH4. This study fills the existing gap regarding the reaction behavior and kinetic characteristics of CO in the in-situ supercritical water-coal gasification system. It provides essential theoretical guidance for effectively suppressing and converting CO, optimizing product composition, and enhancing hydrogenation efficiency within in-situ supercritical water-coal gasification processes.
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