Sulfur evolution in chemical looping combustion of coal with MnFe2O4 oxygen carrier

Chemical looping combustion (CLC) of coal has gained increasing attention as a novel combustion technology for its advantages in CO2 capture. Sulfur evolution from coal causes great harm from either the CLC operational or environmental perspective. In this research, a combined MnFe2O4 oxygen carrier (OC) was synthesized and its reaction with a typical Chinese high sulfur coal, Liuzhi (LZ) bituminous coal, was performed in a thermogravimetric analyzer (TGA)-Fourier transform infrared (FT-IR) spectrometer. Evolution of sulfur species during reaction of LZ coal with MnFe2O4 OC was systematically investigated through experimental means combined with thermodynamic simulation. TGA-FTIR analysis of the LZ reaction with MnFe2O4 indicated MnFe2O4 exhibited the desired superior reactivity compared to the single reference oxides Mn3O4 or Fe2O3, and SO2 produced was mainly related to oxidization of H2S by MnFe2O4. Experimental analysis of the LZ coal reaction with MnFe2O4, including X-ray diffraction and X-ray photoelectron spectroscopy analysis, verified that the main reduced counterparts of MnFe2O4 were Fe3O4 and MnO, in good agreement with the related thermodynamic simulation. The obtained MnO was beneficial to stabilize the reduced MnFe2O4 and avoid serious sintering, although the oxygen in MnO was not fully utilized. Meanwhile, most sulfur present in LZ coal was converted to solid MnS during LZ reaction with MnFe2O4, which was further oxidized to MnSO4. Finally, the formation of both MnS and such manganese silicates as Mn2SiO4 and MnSiO3 should be addressed to ensure the full regeneration of the reduced MnFe2O4.