Thermodynamic optimization of syngas production via auto-thermal oxidative steam reforming of bio-oil

This contribution presented a detailed thermodynamic analysis and numerical optimization of auto-thermal oxidative steam reforming (ATR/OSR) of a typical bio-oil under various operating conditions. The objective was to achieve an H 2 /CO ratio of 2.15 while maximizing the generation of syngas and avoiding carbon formation. A thermodynamic equilibrium model coupled with response surface methodology (RSM) was applied to assess the effect of various operating parameters, including temperature, steam-to-bio-oil molar ratio, and equivalence ratio (ER), on the product distribution and syngas quality. The optimal condition was identified under an ER of 0.3, a steam-to-bio-oil molar ratio of 1.01, and an operating temperature of 924 K, yielding carbon-free syngas with H 2 /CO = 2.15, and a total syngas yield of 1.33 mol/mol C . A comparison of the optimum points with prior works validates the consistency of the thermodynamic and experimental data and highlights the feasibility of the proposed concept. This work therefore demonstrates a practical, carbon-negative, and energy-neutral route to generate FTS-ready syngas directly from bio-oil under moderate conditions. • A thermodynamic equilibrium model of real bio-oil was developed for auto-thermal oxidative steam reforming (ATR/OSR). • Multi-objective optimization via RSM determined the optimum at ER = 0.30, S/C = 1.01, and T = 924 K. • Maximum syngas yield of 1.33 mol.mol C −1 and a syngas ratio of H 2 /CO = 2.15 was attained under optimum conditions. • The process operated under thermoneutral conditions (ΔH ≈ 0 kJ mol −1 ) with zero carbon formation. • The study proposes a sustainable route to generate FTS-ready syngas from bio-oil without extra units.