Hydrogen production and reduction of Ni-based oxygen carriers during chemical looping steam reforming of ethanol in a fixed-bed reactor

Abstract

Hydrogen production and reduction of Ni-based oxygen carriers (OCs) during chemical looping steam reforming (CLSR) of ethanol were studied in a fixed-bed reactor using four OCs with different supports including NiO/SBA-15, NiO/MCM-41, NiO/MMT and NiO/Al2O3. The OCs prepared were characterized by N2 adsorption-desorption, TPR, TPO, XRD, TEM, FTIR and TGA-DSC. The results demonstrated that NiO component in all the OCs was first reduced by ethanol and the reduced OCs were responsible of catalytic steam reforming and water gas shift for hydrogen production. Mesoporous NiO/SBA-15 presented increasing conversion of NiO reduction and the highest selectivity of hydrogen production. The conversion of ethanol increased with reactions proceeding until the highest value is reached after about ∼300s, and the negative steam conversion obtained was resulted from H2O formation from ethanol oxidation by OCs. Compared with MMT and Al2O3 supports, the oxidization of NiO with MCM-41 and SBA-15 supports was very fast and less carbon was formed and deposited. Enhancement in hydrogen production from CLSR process was achieved by in-situ CO2 removal. Shrinking Core model (SCM) based on the constant pattern model for fixed-bed reactor indicated the rates of OCs reduction with ethanol were mainly controlled by surface chemical reaction and product layer diffusion. The reduction process was found to undergo three different rate-limiting stages, and the critical times for changes in the rate-limiting steps were determined.