Potassium (K) is an important element related to ash and fine-particle formation in biomass combustion processes. In situ measurements of gaseous atomic potassium, K(g), using robust optical absorption techniques can provide valuable insight into the K chemistry. However, for typical parts per billion K(g) concentrations in biomass flames and reactor gases, the product of atomic line strength and absorption path length can give rise to such high absorbance that the sample becomes opaque around the transition line center. We present a tunable diode laser atomic absorption spectroscopy (TDLAAS) methodology that enables accurate, calibration-free species quantification even under optically thick conditions, given that Beer-Lambert's law is valid. Analyte concentration and collisional line shape broadening are simultaneously determined by a least-squares fit of simulated to measured absorption profiles. Method validation measurements of K(g) concentrations in saturated potassium hydroxide vapor in the temperature range 950-1200 K showed excellent agreement with equilibrium calculations, and a dynamic range from 40 pptv cm to 40 ppmv cm. The applicability of the compact TDLAAS sensor is demonstrated by real-time detection of K(g) concentrations close to biomass pellets during atmospheric combustion in a laboratory reactor.
The use of small- and medium-scale combustion of biomass for energy utilization is expected to grow in the coming decades. To meet standards and legislation regarding particle emissions and to reduce corrosion and deposit formation, it is crucial to reduce the release of alkali species from the fuel. This can be achieved by capturing the volatile alkali in the residual bottom ash as more thermally stable compounds. In this work, we investigate the combination of primary measures, i.e., process parameters and fuel additives, for reduction of the release of K and Na from the fuel bed during fixed bed combustion. In addition, the influence of these combined measures on fine particle emissions was explored. The results showed a clear influence of the process parameters, herein bed temperature, and that a significant reduction of the alkali release and PM1 emissions can be achieved by correct settings. Furthermore, the application of additives (kaolin and diammonium sulfate) reduced both K and Na release even further. The observed effects on the release behavior was mainly explained by the formation of KAlSiO4 and K2SO4 during addition of kaolin and diammonium sulfate, respectively. This work therefore emphasizes the importance of good control over the fuel bed conditions, especially temperature, when these additives are applied. To reduce the potential deactivation (for kaolinite) and melting (for K2SO4), the control of bed temperature is vital. Thus, it was concluded that the release of volatile alkali species and related fine particle emissions in small- and medium-scale biomass heat and power plants using wood fuels could be significantly reduced by a correct combination of controlling the combustion parameters and the use of fuel additives.
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