Production and purification of hydrogen by biogas combined reforming and steam-iron process

Cobalt ferrite and hematite with minor additives have been tested for production and purification of high purity hydrogen from a synthetic biogas by steam-iron process (SIP) in a fixed bed reactor. A catalyst based in nickel aluminate has been included in the bed of solids to enhance the rate of the reaction of methane dry reforming (MDR). The reductants resulting from MDR are responsible for reducing the oxides based on iron that will, in the following stage, be oxidized by steam to release hydrogen with less than 50 ppm of CO. Coke minimization along reduction stages forces to operate such reactors above 700 °C for reductions, and as low as 500 °C for oxidations to avoid coke gasification. To avoid problems such as reactor clogging by coke in reductions and/or contamination of hydrogen by gasification of coke along oxidations, steam in small proportions has been included in the feed with the aim of minimizing or even avoiding formation of carbonaceous depositions along the reduction stage of SIP. Since steam is an oxidant, it exerts an inhibiting effect upon reduction of the oxide, that slows down the efficiency of the process. It has been proved that co-feeding low proportions of steam with an equimolar mixture of CH₄ and CO₂ (simulating a poor heating value desulphurized biogas) is able to avoid coke deposition, allowing the operation of both, reductions and oxidations, in isothermal regime (700 °C). Empirical results have been contrasted with data found in literature for similar processes based in MDR and combined (or mixed) reforming process (CMR), concluding that the combination of MDR + SIP proposed in this work, taking apart economic aspects and complex engineering, shows similar yields towards hydrogen, but with the advantage of not requiring a subsequent purification process.