The pyrolysis process of various types of biomass (agricultural and wood by-products) in non-isothermal conditions using simultaneous thermal analyses (STA) was investigated. Devolatilization kinetics was implemented through combined application of model-free methods and DAEM (distributed activation energy model) using Gaussian distribution functions of activation energies. Results obtained were used in the curve prediction of the rate of mass loss against temperature at various heating rates by numerical optimization. The possible calculation of biomass samples behavior under pyrolytic conditions as the summation of their pseudo-components, hemicelluloses, cellulose, and lignin is also explored. The differences between experimental and calculated data are less than 3.20% offering a quality test of applicability of proposed model on the kinetic studies of a wide range of biomass samples. It seems that the most physically realistic model is the decomposition of biomass in three reactions, depending on the composition of the biomass regarding hemicelluloses, cellulose, and lignin. Kinetic model applied here may serve as a starting point to build more complex models capable of describing the thermal behavior of plant materials during thermochemical processing.
Agricultural waste is one of the main renewable energy resources available, especially in an agricultural country such as Serbia. Pyrolysis has already been considered as an attractive alternative for disposal of agricultural waste, since the technique can convert this special biomass resource into granular charcoal, non-condensable gases and pyrolysis oils, which could furnish profitable energy and chemical products owing to their high calorific value. In this regard, the development of thermochemical processes requires a good understanding of pyrolysis mechanisms. Experimental and some literature data on the pyrolysis characteristics of corn cob and several other agricultural residues under inert atmosphere were structured and analysed in order to obtain conversion behaviour patterns of agricultural residues during pyrolysis within the temperature range from 300 °C to 1000 °C. Based on experimental and literature data analysis, empirical relationships were derived, including relations between the temperature of the process and yields of charcoal, tar and gas (CO2, CO, H2 and CH4). An analytical semi-empirical model was then used as a tool to analyse the general trends of biomass pyrolysis. Although this semi-empirical model needs further refinement before application to all types of biomass, its prediction capability was in good agreement with results obtained by the literature review. The compact representation could be used in other applications, to conveniently extrapolate and interpolate these results to other temperatures and biomass types.
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