Primary release and transformation of inorganic and organic sodium during fast pyrolysis of sodium-loaded lignin

This study employs a wire-mesh reactor (WMR) to understand the primary release and transformation of inorganic and organic sodium during fast pyrolysis of various sodium-loaded lignin samples at 300–800 °C. Due to the minimization of volatile-char interactions in WMR, the overall sodium release during lignin pyrolysis is relatively low, i.e., ∼9–11% and ∼7–14% for the inorganic and inorganic sodium loaded lignin, respectively. The presence of the inorganic sodium in the condensed volatiles (so-called oil) clearly indicates the important role of thermal ejection in the release of the inorganic sodium, since sodium salts are unlikely to evaporate under current conditions. While the release of the organic sodium into oil can be due to both thermal ejection of aerosols and evaporation of low carboxylates. Despite the low sodium release, significant transformation of the inorganic and organic sodium can take place during lignin pyrolysis. For the inorganic sodium loaded lignin, the inorganic sodium decreases continuously from ∼67% at 300 °C to ∼42% at 800 °C, accompanied by a steady increase in the organic sodium (i.e., the ion-exchangeable sodium) from ∼17% at 300 °C to ∼37% at 800 °C. While for the organic sodium loaded lignin, its transformation into the inorganic sodium is faster at higher temperatures, leading to a large increase in the inorganic sodium (i.e., carbonates) from ∼9% at 300 °C to ∼48% at 800 °C, as well as a reduction in the organic sodium from ∼79% at 300 °C to ∼28% at 800 °C. The data generated in this study will be important to understand the catalytic mechanism of sodium during thermochemical processing of alkali lignin for the production of bioenergy and biofuels.