Quantitative K-Cl-S chemistry in thermochemical conversion processes using in situ optical diagnostics

Abstract

The sulfation of gas-phase KOH and KCl was investigated in both oxidizing and reducing atmospheres at temperatures of 1120 K, 1260 K, 1390 K, and 1550 K. Well-defined gas environments were generated in a laminar flame burner fuelled with CH4/air/O2/N2. Atomized K2CO3 and KCl water solution fog and SO2 were introduced into the hot gas as sources of potassium, chlorine, and sulfur, respectively. The in situ concentrations of KOH, KCl, and OH radicals were measured using broadband UV absorption spectroscopy, and the concentration of K atom was measured using TDLAS at 769.9 nm and 404.4 nm. The nucleated and condensed K2SO4 aerosols were visualized as illuminated by a green laser sheet. With SO2 addition, reduced concentrations of KOH, KCl, and K atom were measured in the hot gas. The sulfation was more significant for the low temperature cases. KOH was sulfated more rapidly than KCl. K2SO4 aerosols, formed by homogeneous nucleation, were observed at temperatures below 1260 K. At 1390 K, no aerosols were formed, indicating that the consumed KOH was transformed into gaseous KHSO4 or K2SO4. K atoms formed in the hot flue gas with KOH addition enhanced the consumption of OH radicals except at the high-temperature case at 1550 K. At 1120 K and 1260 K, the sulfation of KOH with SO2 seeding reduced the concentration of K atom, resulting in less OH radical consumption. Studies were also conducted in a hot reducing environment at 1140 K, with the flame at an equivalence ratio of 1.31. Similar to the observation in the oxidizing atmosphere, the concentrations of KOH and K atom decreased dramatically with SO2 seeding. An unknown absorption spectrum observed was attributed to UV absorption by KOSO. The experimental results were used to evaluate a detailed K-Cl-S reaction mechanism, and a reasonable agreement was obtained.