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Hydrogen production from sorption enhanced aqueous phase reforming (APR) of biodiesel byproduct glycerol was studied by Ni-based monometallic and bimetallic catalysts supported on gelatinous MgO supports. Compared with Ni-based monometallic catalyst, the H 2 selectivity and glycerol conversion of the Cu–Ni bimetallic catalyst were found to be increased more than 3% and 30%, respectively. Meanwhile, higher reaction temperature was found to have higher H 2 yield with lower H 2 selectivity. The H 2 yield using the catalyst with gelatinous MgO support was 1.25 times higher than that of calcined support. Through in-situ CO 2 capture, the addition of CaO to the Cu–Ni bimetallic catalyst increased more than 58.3% and 14.4% of the H 2 yield and selectivity, respectively. An analysis about liquid product component indicate that the presence of CaO promote the further cleavage of the C–C bond, which further increased the conversion of glycerol. Furthermore, it was found that the presence of CaO could also improve the stability of the catalyst through the control experiments. [Display omitted] • Sorption enhanced APR to H 2 with in-situ CO 2 capture was studied. • Monometallic and bimetallic supported on MgO were developed. • Cu–Ni supported on gelatinous MgO exhibited good APR performance. • H2 yield by gelatinous MgO support was 1.25 times higher than that of calcined MgO. • Presence of CaO in APR improved conversion, selectivity, and stability. [ABSTRACT FROM AUTHOR]