Optical measurements of KOH, KCl and K for quantitative K-Cl chemistry in thermochemical conversion processes

Potassium and chlorine chemistry at high temperature is of great importance in biomass utilization through thermal conversion. In well-defined hot environments, we performed quantitative measurements of main potassium species, i.e., potassium hydroxide (KOH), potassium chloride (KCl) and K atoms, and the important radical OH. The concentrations of KOH, KCl and OH radicals were measured through a newly developed UV absorption spectroscopy technique. Quantitative measurements of potassium atoms were performed using tunable diode laser absorption spectroscopy at the wavelength of 404.4 and 769.9 nm to cover a wide concentration dynamic range. The reaction environment was provided by a laminar flame burner, covering a temperature range of 1120–1950 K and global fuel-oxygen equivalence ratios from 0.67 to 1.32. Potassium and chlorine were introduced into the combustion atmosphere by atomized K₂CO₃ or KCl water solution fog. The experimental results were compared to modeling predictions to evaluate a detailed K-Cl mechanism. For most cases, the experimental and simulation results were in reasonable agreement. However, the over-prediction of K atom concentration at low temperature fuel-rich condition and the overall under-prediction of KCl concentration call for further investigation. It was demonstrated that the optical methods and the well-defined hot environments could provide quantitative investigations widely applicable to different homogeneous reactions in thermochemical conversion processes, and in evaluation of corresponding reaction mechanisms with reliable data.