Aqueous-phase reforming of Fischer-Tropsch alcohols over nickel-based catalysts to produce hydrogen: Product distribution and reaction pathways

[Display omitted] •The alcohols in Fischer-Tropsch derived wastewaters can converted into valuable products through catalytic aqueous-phase reforming (APR).•Hydrogen was one of the main products in the APR of C1-C3 alcohols over Ni-based catalysts that allowed alcohol conversions up to 60%.•Copper doping improved the stability of a nickel-copper catalyst; however, it limited the hydrogen yield.•The alcohol chain-length, the location of the hydroxyl group in the alcohol and the catalysts have a strong effect on the on the reaction pathway. Catalytic aqueous-phase reforming (APR) can be applied to process the organic compounds in the water fractions derived from the Fischer-Tropsch (FT) synthesis. This work aimed at finding an active nickel-based catalyst to convert organic compounds typically found in FT-derived waters, such as alcohols, into hydrogen. In addition, this work aimed at proposing potential reaction pathways that explain the product distribution resulting from the APR of C1–C3 alcohols. Solutions with 5% mass fraction of either methanol, ethanol, propan-1-ol or propan-2-ol in water were processed in APR at 230 °C and 3.2 MPa over different nickel-based catalysts in a continuous packed-bed reactor. Methanol was successfully reformed into hydrogen and carbon monoxide with conversions up to 60%. The conversion of C2–C3 alcohols achieved values in the range of 12% to 55%. The results obtained in the APR of C2–C3 alcohols suggest that in addition to reforming to hydrogen and carbon monoxide, the alcohols underwent dehydrogenation and decarbonylation. The most stable catalyst, nickel-copper supported on ceria-zirconia, reached feedstock conversions between 20% and 60% and high hydrogen selectivity. Monometallic nickel supported on ceria-zirconia catalysts reached higher H2 yields; however, the yield of side products, such as alkanes, was also higher over the monometallic catalysts. Accordingly, ceria-zirconia nickel-based supported catalysts constitute suitable candidates to process the alcohols in the water fractions derived from the FT synthesis.