Bayer red mud (RM) is an alumina refinery waste product rich in aluminum oxides and alkalis which are present primarily in the form of sodium hydro-aluminosilicate desilication product (DSP). A hydrothermal process was employed to recover alumina and alkali from "Fe-rich" and "Fe-lean" RM, the two representative species of RM produced in China. The hydrothermal process objective phase is andradite-grossular hydrogarnet characterized by the isomorphic substitution of Al and Fe. Batch experiments were used to evaluate the main factors influencing the recovery process, namely reaction temperature, caustic ratio (molar ratio of Na2O to Al2O3 in sodium solution), sodium concentration and residence time. The results revealed that the Na2O content of 0.5 wt% and A/S of 0.3 (mass ratio of Al2O3 to SiO2) in leached residue could be achieved with Fe-rich RM under optimal conditions. However, the hydrothermal treatment of Fe-lean RM proved less successful unless the reaction system was enriched with iron. Subsequent experiments examined the effects of the ferric compound's content and type on the substitution ratio. (C) 2011 Elsevier B.V. All rights reserved.