Abstract
A deeper understanding and quantification on the influence of inorganic species on the pyrolysis process, combined with the presence of heterogeneous secondary reactions, is pursued in this study. Both chemical controlled and transport limited regimes are considered. The former is achieved in a thermogravimetric analyser (TGA) with fine milled biomass in the mg range, while the latter is investigated in a particle level reactor with spherical particles of different sizes. To account for the influence of inorganics, wood particles were washed and doped with KCl aqueous solutions, resulting in K concentrations in the final wood of around 0.5% and 5% on dry basis. Gas species and condensable volatiles were measured online with Fourier transform infrared (FTIR) spectroscopy and a non-dispersive infrared (NDIR) gas analyzer. The removal of inorganic species delayed the pyrolysis reaction to higher temperatures and lowered char yields. The addition of inorganics (K) shifted the devolatilization process to lower temperatures, increased char and water yields, and reduced CO production among others. Higher heating rates and temperatures resulted in lower char, water, and light condensable yields, but significantly higher CH4 and other light hydrocarbons, as well as CO. The increase in these yields can be attributed, at least in part, to the gas phase cracking reactions of the produced volatiles. Larger particle size increased the formation of char, CH4 and other light hydrocarbons, and light condensables for low and high pyrolysis temperatures, while reduced the release of CO2 and H2O. This novel data set allows to quantify the influence of each parameter and can be used as basis for the development of detailed pyrolysis models which can include both the influence of inorganics and transport limitations when coupled into particle models.
