Hydrogen Production through Autothermal Reforming of Ethanol: Enhancement of Ni Catalyst Performance via Promotion

Autothermal reforming of bioethanol (ATR of C2H5OH) over promoted Ni/Ce0.8La0.2O1.9 catalysts was studied to develop carbon-neutral technologies for hydrogen production. The regulation of the functional properties of the catalysts was attained by adjusting their nanostructure and reducibility by introducing various types and content of M promoters (M = Pt, Pd, Rh, Re; molar ratio M/Ni = 0.003–0.012). The composition–characteristics–activity correlation was determined using catalyst testing in ATR of C2H5OH, thermal analysis, N2 adsorption, X-ray diffraction, transmission electron microscopy, and EDX analysis. It was shown that the type and content of the promoter, as well as the preparation mode (combined or sequential impregnation methods), determine the redox properties of catalysts and influence the textural and structural characteristics of the samples. The reducibility of catalysts improves in the following sequence of promoters: Re < Rh < Pd < Pt, with an increase in their content, and when using the co-impregnation method. It was found that in ATR of C2H5OH over bimetallic Ni-M/Ce0.8La0.2O1.9 catalysts at 600 °C, the hydrogen yield increased in the following row of promoters: Pt < Rh < Pd < Re at 100% conversion of ethanol. The introduction of M leads to the formation of a NiM alloy under reaction conditions and affects the resistance of the catalyst to oxidation, sintering, and coking. It was found that for enhancing Ni catalyst performance in H2 production through ATR of C2H5OH, the most effective promotion is with Re: at 600 °C over the optimum 10Ni-0.4Re/Ce0.8La0.2O1.9 catalyst the highest hydrogen yield 65% was observed.