The objective of this study was to discuss the applicability of isoconversional models in estimating the activation energy and pre-exponential factor for biomass pyrolysis. Thermogravimetry and derivative thermogravimetry experiments of tucumã endocarp were performed at the heating rates of 5, 10, and 20 °C min−1 in an atmosphere of nitrogen. The isoconversional models of Ozawa–Flynn–Wall, modified Coats–Redfern, Friedman, and Vyazovkin were applied to the experimental data, considering first-order rate law, resulting in activation energies of 147.25, 144.64, 160.47, and 144.96 kJ mol−1, respectively. The pre-exponential factor varied from 9.75 to 11.95 log s−1. As isoconversional models consider the solid decomposition to be represented by a single reaction, described by only one peak in the derivative thermogravimetry data, only a satisfactory agreement between experimental and theoretical data was observed. The fit was verified by simulating curves of conversion as a function of temperature, in which the kinetic parameters obtained with Ozawa–Flynn–Wall and Vyazovkin models generated the lowest relative deviations (9.05 and 9.3 %, respectively). In consequence, the use of isoconversional models is attractive because this kind of model is easy to apply, generating satisfactory approximations for the actual kinetic parameters.
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Lora ES, Andrade RV. Biomass as energy source in Brazil. Renew Sustain Energy Rev. 2009;13:777–88.
Van de Velden M, Baeyens J, Brems A, Janssens B, Dewil R. Fundamentals, kinetics and endothermicity of the biomass pyrolysis reaction. Renew Energy. 2010;35:232–42.
Basu P. Biomass gasification and pyrolysis—practical design. Oxford: Academic Press; 2010. p. 23–92.
Anca-Couce A, Berger A, Zobel N. How to determine consistent biomass pyrolysis kinetics in a parallel reaction scheme. Fuel. 2014;123:230–40.
Cardoso CR, Miranda MR, Santos KG, Ataíde CH. Determination of kinetic parameters and analytical pyrolysis of tobacco waste and sorghum bagasse. J Anal Appl Pyrolysis. 2011;92:392–400.
Mohan D, Pittman CU, Steele PH. Pyrolysis of wood/biomass for bio-oil: a critical review. Energy Fuels. 2006;20:848–89.
White JE, Catallo WJ, Legendre BL. Biomass pyrolysis kinetics: a comparative critical review with relevant agricultural residue case studies. J Anal Appl Pyrolysis. 2011;91:1–33.
Gómez MF, Silveira S. Rural electrification of the Brazilian Amazon—achievements and lessons. Energy Policy. 2010;38:6251–60.
Vyazovkin S, Burnham AK, Criado JM, Pérez-Maqueda LA, Popescu C, Sbirrazzuoli N. ICTAC Kinetics Committee recommendations for performing kinetic computations on thermal analysis data. Thermochim Acta. 2011;520:1–19.
Flynn JH, Wall LA. General treatment of the thermogravimetry of polymers. J Res Natl Bur Stand. 1934;1966(70):487–523.
Braun RL, Burnham AK, Reynolds JG, Clarkson JE. Pyrolysis kinetics for lacustrine and marine source rocks by programmed micropyrolysis. Energy Fuels. 1991;5:192–204.
Ceylan S, Topçu Y. Pyrolysis kinetics of hazelnut husk using thermogravimetric analysis. Bioresour Technol. 2014;156C:182–8.
Friedman HL. Kinetics of thermal degradation of char-forming plastics from thermogravimetry. Application to a phenolic plastic. J Polym Sci Part C Polym Symp. 1964;6:183–95.
Nascimento VF. Caracterização de biomassas amazônicas—ouriço de castanha-do-brasil, ouriço de sapucaia e caroço do fruto do tucumã—visando sua utilização em processos de termoconversão. Master’s Dissertation, University of Campinas. 2012, p. 148.
Ozawa T. A new method of analyzing thermogravimetric data. Bull Chem Soc Jpn. 1965;707:1881–6.
Cai J, Wu W, Liu R, Huber GW. A distributed activation energy model for the pyrolysis of lignocellulosic biomass. Green Chem. 2013;15:1331.
ASTM—American Society for Testing and Materials Standard D240. Standard test method for heat of combustion of liquid hydrocarbon fuels by bomb calorimeter. West Conshohocken: ASTM International; 2009. doi:10.1520/D0240-09.
Tannous K, Silva FS. Particles and geometric shapes analyzer APOGEO. In: Khosrow-Pour M, editor. Encyclopedia of information science and technology. 3rd ed. doi:10.4018/978-1-4666-5888-2.ch349.
ASTM Standard Standard E1755, 2001. Standard test method for ash in biomass. West Conshohocken: ASTM International; 2007. doi:10.1520/E1755-01R07.
ASTM Standard E871, 1982. Standard test method for moisture analysis of particulate wood fuels. West Conshohocken: ASTM International; 2006. doi:10.1520/E0871-82R06.
ASTM Standard E872, 1982. Standard test method for volatile matter in the analysis of particulate wood fuels. West Conshohocken: ASTM International; 2006. doi:10.1520/E0872-82R06.
Sánchez C. Caracterização das biomassas. In: SÁNCHEZ C (Org.). Tecnologia da gaseificação de biomassa. Campinas, Sao Paulo, Brazil: Editora Átomo, pp. 200–209, 2010.
Mendeleev DI. Compositions (collection of works). Reports from the Science Academy of Union of Soviet Socialist Republics: Moscow, vol. 15, p. 115–118, 1949.
Vyazovkin S, Wight CA. Isothermal and nonisothermal reaction kinetics in solids: in search of ways toward consensus. J Phys Chem. 1997;5639:8279–84.
Senum GI, Yang RT. Rational approximations of the integral of Arrhenius function. J Therm Anal. 1977;11:445–7.
Coats AW, Redfern JP. Kinetic parameters from thermogravimetric data II. J Polym Sci Part B Polym Lett. 1965;3:917–20.
Órfão JJM, Antunes FJA, Figueiredo JL. Pyrolysis kinetics of lignocellulosic materials—three independent reactions model. Fuel. 1999;78:349–58.
Raveendran K, Ganesh A, Khilar KC. Pyrolysis characteristics of biomass and biomass components. Fuel. 1996;75:987–98.
Di Blasi C. Modeling chemical and physical processes of wood and biomass pyrolysis. Prog Energy Combust Sci. 2008;34:47–90.
Shen J, Wang XS, Garcia-Perez M, Mourant D, Rhodes MJ, Li CZ. Effects of particle size on the fast pyrolysis of oil mallee woody biomass. Fuel. 2009;88:1810–7.
Biagini E, Fantei A, Tognotti L. Effect of the heating rate on the devolatilization of biomass residues. Thermochim Acta. 2008;472:55–63.
Mishra G, Bhaskar T. Non isothermal model free kinetics for pyrolysis of rice straw. Bioresour Technol. 2014;169:614–21.
The authors are thankful for the financial support received from the Coordination for the Improvement of Higher Education Personnel (CAPES), Brazil.
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Baroni, É.G., Tannous, K., Rueda-Ordóñez, Y.J. et al. The applicability of isoconversional models in estimating the kinetic parameters of biomass pyrolysis. J Therm Anal Calorim 123, 909–917 (2016). https://doi.org/10.1007/s10973-015-4707-9