The multitude of biofuels in use and their widely different characteristics stress the need for improved characterisation of their chemical and physical properties. Industrial use of biofuels further demands rapid characterisation methods suitable for on-line measurements. The single most important property in biofuels is the calorific value. This is influenced by moisture and ash content as well as the chemical composition of the dry biomass. Near infrared (NIR) spectroscopy and bi-orthogonal partial least squares (BPLS) regression were used to model moisture and ash content as well as gross calorific value in ground samples of stem and branches wood. Samples from 16 individual trees of Norway spruce were artificially moistened into five classes (10, 20, 30, 40 and 50%). Three different models for decomposition of the spectral variation into structure and noise were applied. In total 16 BPLS models were used, all of which showed high accuracy in prediction for a test set and they explained 95.4-99.8% of the reference variable variation. The models for moisture content were spanned by the O-H and C-H overtones, i.e. between water and organic matter. The models for ash content appeared to be based on interactions in carbon chains. For calorific value the models was spanned by C-H stretching, by O-H stretching and bending and by combinations of O-H and C-O stretching. Also -C=C- bonds contributed in the prediction of calorific value. This study illustrates the possibility of using the NIR technique in combination with multivariate calibration to predict economically important properties of biofuels and to interpret models. This concept may also be applied for on-line prediction in processes to standardize biofuels or in biofuelled plants for process monitoring.
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