In this paper, the yields and composition of solid and condensable products that were obtained by microwave-assisted torrefaction of softwood, wheat straw, and peat fuel pellets, defined as main- and side-stream torrefaction products, were studied. The torrefaction process, at temperatures varied in the range of 200–300 °C, was performed using a laboratory-scale torrefactor of original construction. Water-enriched fractions were distilled off from condensable products to isolate tar fractions, the fuel characteristics of which were compared with those of solid fractions. Py-GC/MS/FID, GC/MS/FID, thermal analysis, elemental analysis, and wet chemistry methods were used to characterize the main- and side-stream torrefaction products, with a focus on their valorization according to the biorefinery approach. The simultaneous development of the destruction and condensation processes in lignocarbohydrate complexes during microwave treatment leads to an increase in the relative portion of aromatic compounds in torrefied biomass, increasing the higher heating value (HHV) of the solid fractions. The increase up to 60% of the heat amount that was liberated due to the thermal oxidative conversion of solid fractions vs. that of the non-treated ones was established by DSC tests. The heat that was liberated by the combustion of the tar fractions was much lower than that of solid fractions, which was explained by the composition of tars, influencing their thermal conversion.
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