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This review considers problems related to design of efficient structured catalysts for natural gas and biofuels transformation into syngas. Their active components are comprised of fluorite, perovskite and spinel oxides or their nanocomposites (both bulk and supported on high surface area Mg-doped alumina or MgAl2O4) promoted by platinum group metals, nickel and their alloys. A complex of modern structural, spectroscopic and kinetic methods was applied to elucidate atomic-scale factors controlling their performance and stability to coking, such as dispersion of metals/alloys, strong metal-support interaction and oxygen mobility/reactivity as dependent upon their composition and synthesis procedures. Monolithic catalysts comprised of optimized active components loaded on structured substrates with a high thermal conductivity demonstrated high activity and stability to coking in processes of natural gas and biofuels reforming into syngas. A pilot-scale axial reactor equipped with the internal heat exchanger and such catalysts allowed to efficiently convert into syngas the mixture of natural gas, air and liquid biofuels in the autothermal reforming mode at low (~50–100 °C) inlet temperatures and GHSV up to 40,000 h−1.

Modern Trends in Design of Catalysts for Transformation of Biofuels into Syngas and Hydrogen: From Fundamental Bases to Performance in Real Feeds