The present work explored the constitution of the calorific values of biomass fuels and the mechanism by which basic chemical compositions affect the fuel calorific data. For the first time, an energy conversion model was developed for the functional groups stored in biomass fuels by combustion. Validation of the model was performed by testing with various types of substances. By analyzing the effect of mass increase of individual chemical species on the amount of heat released by a fuel, it was confirmed that for ligno-cellulosic fuels, the species containing C–H, C–C and C=C bonds positively affect the fuel calorific values, whereas the species containing O–H, C–N, C–O, and C=O bonds have negative role in the increase of the fuel calorific values. A ratio parameter was then developed to quantitatively evaluate the potential of individual chemical bonds to contribute to the calorific values of biomass fuels, which well explained the existing techniques for treating biomass as fuels. The outcomes of this work serve as a theoretical basis for improving the efficiency in energy utilization of biomass fuels.

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