The steam reforming of the main biodiesel by-product, glycerol, has been catching up the interest of the scientific community in the last years. The use of glycerol for hydrogen production is an advantageous option not only because glycerol is renewable but also because it's use would lead to the decrease of the price of biodiesel, thus making it more competitive. Consequently, the use of biodiesel at large scale would significantly reduce CO2 emissions comparatively to fossil fuels. Moreover, hydrogen itself is seen as a very attractive clean fuel for transportation purposes.Therefore, the industrialization of the glycerol steam reforming (GSR) process would have a tremendous global environmental impact. In the last years, intensive research regarding GSR thermodynamics, catalysts, reaction mechanisms and kinetics, and innovative reactor configurations (sorption enhanced reactors (SERs) and membrane reactors (MRs)) has been done, aiming for improving the process effectiveness. In this review, the main challenges and strategies adopted for optimization of GSR process are addressed, namely the GSR thermodynamic aspects, the last developments on catalysis and kinetics, as well as the last advances on GSR performed in SERs and MRs.

A thermodynamic study of Glycerol Steam Reforming (GSR) for hydrogen production with in situ carbon dioxide and hydrogen (reaction products) simultaneous removal was performed. The sorption-enhanced membrane reactor (SEMR) was divided into multiple subGibbs reactors and the Gibbs free energy minimization method was employed. The effects of temperature (600-800 K), molar water-to-glycerol feed ratio (WGFR) (3-9), pressure (1-5 atm) and fraction of hydrogen and carbon dioxide removal ( , 0-0.99) on the GSR process were target of investigation. A hydrogen yield (total moles of hydrogen produced/mole of reacted glycerol) very close to the stoichiometric value of 7 was obtained at 700 K, WGFR of 9, 1 atm and for 2 = 0.99 and 2 = 0.80. This corresponds to an enhancement of 217%, 47% and 22% in terms of hydrogen yield comparatively to the traditional reactor (TR), sorption-enhanced reactor (SER) with carbon dioxide capture ( 2 = 0.99) and membrane reactor (MR) with hydrogen separation ( 2 = 0.80), respectively. In terms of coke, its formation was only observed under WGFRs below the stoichiometric value of 3.

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