Calcium looping method has been considered as one of the efficient options to capture CO2 in the combustion flue gas. CaO-based sorbent is the basis for application of calcium looping and should be subjected to the severe calcination condition so as to obtain the concentrated CO2 stream. In this research, CaO/CaZrO3 sorbents were synthesized using the sol–gel combustion synthesis(SGCS) method with urea as fuel. The cyclic reaction performance of the synthesized sorbents was evaluated on a lab-scaled reactor system through calcination at950 °C in a pure CO2 atmosphere and carbonation at 650 °C in the 15%(by volume) CO2. The mass ratio of CaO to CaZrO3 as 8:2(designated as Ca8Zr2) was screened as the best option among all the synthesized CaO sorbents for its high CO2 capture capacity and carbonation conversion at the initial cycle. And then a gradual decay in the CO2 capture capacity was observed at the following 10 successive cycles, but hereafter stabilized throughout the later cycles. Furthermore, structural evolution of the carbonated Ca8Zr2 over the looping cycles was investigated.With increasing looping cycles, the pore peak and mean grain size of the carbonated Ca8Zr2 sorbent shifted to the bigger direction but both the surface area(SA) ratio Φ and surface fractal dimension Dsdecreased. Finally,morphological transformation of the carbonated Ca8Zr2 was observed. Agglomeration and edge rounding of the newly formed CaCO3 grains were found as aggravated at the cyclic carbonation stage. As a result, carbonation of Ca8Zr2 with CO2was observed only confined to the external active CaO by the fast formation of the CaCO3 shell outside, which occluded the further carbonation of the unreacted CaO inside. Therefore, enough attention should be paid to the carbonation stage and more effective activation measures should be explored to ensure the unreacted active CaO fully carbonated over the extended looping cycles.
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.
