Crystalline phase transformation of Sr-Fe based oxygen carriers modulate the cyclic performance for syngas and CO coproduction in chemical looping ethanol reforming coupled with CO2 splitting

Abstract

The chemical looping reforming coupled with CO2 splitting (CLR-CS) offers a promising solution for syngas production and simultaneous decomposition of CO2. In this study, the Sr-Fe based oxygen carriers (OCs) were evaluated in CLR-CS using ethanol as fuel. The presence of Sr significantly improved the oxidation performance of iron oxides. The Sr element in fresh Sr-Fe based OCs mainly formed two crystal phases, including SrFe12O19 and Sr4Fe6O13. Increasing the amount of Sr element made it easier to form Sr4Fe6O13 crystal phase. The Sr4Fe6O13 was favorable for syngas production, due to the higher surface oxygen vacancy formation energy with a range of 3.13–3.37 eV. However, the lower oxygen transfer capacity (OTC) of Sr4Fe6O13 resulted in a lower CO yield in the of stage of CO2 decomposition. Compared with Sr4Fe6O13, SrFe12O19 exhibited the higher OTC and the higher reactivity of lattice oxygen, which was preferable to produce more CO2 in the stage of ethanol reforming in fuel reactor. During the cycle tests, the crystalline phase of SrFe12O19 didn’t regenerate under the CO2 atmosphere but transformed into Sr4Fe6O13. It was attributed to the lower energy barrier of CO2 oxidation on the oxygen defect surface of Sr4Fe6O13. The phase transformation of SrFe12O19 accompanied the formation of Fe3O4. The excessive Fe3O4 had poor stability and inactivated easily due to sintering and agglomeration in Sr1Fe4 and Sr1Fe6 samples. The Sr1Fe2, namely the molar ratio of SrO to Fe2O3 of 1:2, exhibited the better performance for syngas (0.291 Nm3/kg OC) and CO (0.141 Nm3/kg OC) coproduction at 800 °C. Additionally, the Sr1Fe2 presented an excellent cyclic stability in 30 cycles due to the suitable proportion of Sr4Fe6O13 and iron oxides formed, which maintained a high syngas yield and avoided sintering of iron oxides. Overall, the Sr1Fe2 is a promising OC candidate in CLR-CS process.