The thermal behaviours of a sewage sludge sample, woody (black locust, poplar and willow) and herbaceous (energy grass and wheat straw) biomass as well as mixed (sewage sludge and black locust in ratios 1:1 and 1:3) samples were compared under inert and oxidative atmosphere. The thermogravimetric experiments of each sample demonstrate that the beginning temperature of decomposition is similar in inert and oxidative atmospheres, i.e. the primary bond scissions are not affected by the atmosphere. Nevertheless, oxygen increases the decomposition rate and the volatile evolution of all samples at higher temperatures. Thermogravimetry/mass spectrometry (TG/MS) experiments have been performed to determine the mass loss of the samples and the formation of volatile products as a function of temperature in inert atmosphere. Wood and herbaceous biomass samples evolved various organic products (aldehydes, ketones, acids, furan derivatives, etc.) beside water and gaseous products. Sewage sludge released mainly water, carbon oxides, methane, hydrogen, hydrocarbons, ketones, acids as well as sulphur- and nitrogen-containing products. High heating value and low heating value of the samples have been determined by a bomb calorimeter. Principal component analysis (PCA) has been used to find statistical correlation between the data. The results unambiguously support the correlation between the thermogravimetric parameters (e.g. DTGmax) and the heating values of the samples.
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