Production of a hydrogen-rich gas from fast pyrolysis bio-oils: Comparison between homogeneous and catalytic steam reforming routes

The aim of the present work is to produce hydrogen from biomass through bio-oil. Two possible upgrading routes are compared: catalytic and non-catalytic steam reforming of bio-oils. The main originality of the paper is to cover all the steps involved in both routes: the fast pyrolysis step to produce the bio-oils, the water extraction for obtaining the bio-oil aqueous fractions and the final steam reforming of the liquids. Two reactors were used in the first pyrolysis step to produce bio-oils from the same wood feedstock: a fluidized bed and a spouted bed. The mass balances and the compositions of both batches of bio-oils and aqueous fractions were in good agreement between both processes. Carboxylic acids, alcohols, aldehydes, ketones, furans, sugars and aromatics were the main compounds detected and quantified. In the steam reforming experiments, catalytic and non-catalytic processes were tested and compared to produce a hydrogen-rich gas from the bio-oils and the aqueous fractions. Moreover, two different catalytic reactors were tested in the catalytic process (a fixed and a fluidized bed). Under the experimental conditions tested, the H₂ yields were as follows: catalytic steam reforming of the aqueous fractions in fixed bed (0.17 g H₂/g organics) > non-catalytic steam reforming of the bio-oils (0.14 g H₂/g organics) > non-catalytic steam reforming of the aqueous fractions (0.13 g H₂/g organics) > catalytic steam reforming of the aqueous fractions in fluidized bed (0.07 g H₂/g organics). These different H₂ yields are a consequence of the different temperatures used in the reforming processes (650 °C and 1400 °C for the catalytic and the non-catalytic, respectively) as well as the high spatial velocity employed in the catalytic tests, which was not sufficiently low to reach equilibrium in the fluidized bed reactor.