Insight into the role of SO2 on selenium conversion during adsorption by CaO: Theoretical calculation and experimental study

SO2 can noticeably impact the control of high toxic selenium emissions from flue gas by CaO. Surprisingly, our experiments showed that under certain conditions, SO2 can promote selenium capture by CaO, rather than hinder it. To elucidate the underlying mechanism, a combination of theoretical calculations and experiments was conducted. Thermodynamic equilibrium analysis revealed that gaseous SO2 and solid Ca-S reaction products can promote SeO2 converting to SeO/Se0. The Ca-S products facilitated greater SeO2 conversion compared to SO2. Experimental results demonstrated that selenium adsorption capacity of incompletely sulfurized CaO (CaO with pre-adsorbed SO2) was higher than that of completely sulfurized CaO (Ca-S products), highlighting the importance of adsorption sites of CaO. Density functional theory calculations showed that the pre-adsorbed SO2 hardly affected selenium adsorption energy on the SO2/CaO surface, while completely sulfurized CaO had low selenium adsorption energy, explaining the experimental phenomenon and proving necessary of CaO. Additionally, SeO/Se0 had higher adsorption energy on CaO than SeO2. Overall, the promotion of SO2 on selenium adsorption was primarily affected by two factors: 1) sulfur facilitating SeO2 conversion to SeO/Se0 which can be adsorbed more easily by CaO; 2) sufficient adsorption sites on CaO surface existing for SeO/Se0 adsorption, despite co-adsorption with sulfur.