Catalytic CO₂ gasification of rubber seed shell-derived hydrochar: reactivity and kinetic studies

In this study, hydrothermal carbonization (HTC) of a biomass was used as a means to improve the physicochemical properties of rubber seed shell (RSS) and enhance its reactivity in the char-CO₂ gasification reaction, known as the Boudouard reaction (C + CO₂ ↔ 2CO). Hydrochar samples were developed by hydrothermal treatment of RSS, without separating the solid residue from the liquid product, at 433, 473, 513, and 553 K under autogenous pressure. The CO₂ gasification reactivity of the developed hydrochars was then investigated at different heating rates (5, 10, 20, and 30 K/min) by the non-isothermal thermogravimetric method. The hydrochars revealed higher reactivity and improved gasification characteristics compared to the untreated biomass, while the hydrochar which was filtered from the liquid slurry showed lower reactivity compared to the untreated biomass. This was due to the chemical and structural evolutions of the biomass during hydrothermal treatment as indicated by various analyses. The gasification reactivity of the hydrochar was substantially enhanced by introduction of a catalyst (NaNO₃) during HTC. Kinetic analysis of the char-CO₂ gasification reaction was carried out by applying Flynn-Wall-Ozawa (FWO), Kissinger-Akahira-Sunose (KAS), and Starink isoconversional methods, and thermodynamic parameters were also determined. The activation energy of the Na-loaded RSS hydrochar in CO₂ gasification (120-154 kJ/mol) was considerably lower than that of the untreated biomass (153-172 kJ/mol). Thermodynamic studies also confirmed the promoting effect of hydrothermal treatment and catalyst impregnation on enhancement of reactivity of the virgin biomass and reduction of gasification temperature.