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

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.