Co-site substitution by Mn supported on biomass-derived active carbon for enhancing magnesia desulfurization

Abstract

Oxidation of magnesium sulfite (MgSO₃) is a crucial step for reclaiming the product in wet magnesia desulfurization processes. Here, for enhancing this reaction, a bimetallic catalyst was developed by loading CoO_x and MnO_x species on a biomass-derived active carbon (AC) support to minimize the costs and potential environmental risks during catalyst application. The substitution effect of Mn to Co sites was investigated, and a comparison of the catalyst with plain cobalt suggested that the ratio of Co/Mn must be greater than 3. A series of catalyst characterizations was performed to reveal the synergistic effect of Co and Mn in the bimetallic catalyst. The introduction of Mn species not only improved the dispersion of CoO_x-MnO_x mixed oxide but also generated abundant Co³⁺ species and surface-adsorbed oxygen, both of which acted as the main active sites for sulfite oxidation. Notably, in the bimetallic catalyst, the presence of Mn⁴⁺ species assisted regeneration of Co²⁺ to Co³⁺ species, further accelerating sulfite oxidation. Besides, the partial substitution of Co sites by Mn also suppressed the losing of Co species during reaction, favoring to decrease the environmental risk, as well as to save the cost of catalyst.

Keywords: Catalytic oxidation; Cobalt-sites substitution; Magnesium sulfite; Redox cycle; Synergistic effect.