Abstract
Since the 1950s, cellulose pyrolysis has been the subject of intense study, with kinetic analyses forming a major part of these studies. They represent useful tools for a better understanding of the physicochemical process and for the proper design of industrial pyrolysis units. Until recently, the methods most frequently used in these analyses were based on model-fitting, i.e. the fitting of the experimental data to a number of mathematical models. Nowadays, other methods, so-called “model-free” methods, are considered to be more suited. These are based on the principle that, at constant conversion, the reaction rate depends only on temperature. In its first part, this short review presents the particularities and drawbacks of the traditional model-fitting models. Subsequently, several main contributions in this field are listed and discussed. Finally, the more suited “model-free” (isoconversional) methods are explained and several main studies presented, as well as a comparison of this method with the model-fitting ones.
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References
Aboulkas, A., & El Harfi, K. (2008). Study of the kinetics and mechanisms of thermal decomposition of Moroccan Tarfaya oil shale and its kerogen. Oil Shale, 25, 426–443. DOI: 10.3176/oil.2008.4.04.
Alves, S. S., & Figueiredo, J. L. (1989). Kinetics of cellulose pyrolysis modelled by three consecutive first-order reactions. Journal of Analytical and Applied Pyrolysis, 17, 37–46. DOI: 10.1016/0165-2370(89)85004-1.
AGEE-Stat (2011). Renewable energy sources 2010. Bonn, Germany: Federal Ministry for the Environment, Nature Conservation and Nuclear Safety.
Agrawal, R. K. (1988). Kinetics of reactions involved in pyrolysis of cellulose. II. The modified Kilzer-Broido model. The Canadian Journal of Chemical Engineering, 66, 413–418. DOI: 10.1002/cjce.5450660310
Banyasz, J. L., Li, S., Lyons-Hart, J. L., & Shafer, K. H. (2001). Cellulose pyrolysis: the kinetics of hydroxyacetaldehyde evolution. Journal of Analytical and Applied Pyrolysis, 57, 223–248. DOI: 10.1016/s0165-2370(00)00135-2.
Barud, H. S., Ribeiro, C. A., Capela, J. M. V., Crespi, M. S., Ribeiro, S. J. L., & Messadeq, Y. (2011). Kinetic parameters for thermal decomposition of microcrystalline, vegetal, and bacterial cellulose. Journal of Thermal Analysis and Calorimetry, 105, 421–426. DOI: 10.1007/s10973-010-1118-9.
Blažek, J. (2005). Study of the reaction kinetics of the thermal degradation of polymer. Ph. D. thesis, Institut National Polytechnique de Toulouse, Toulouse, France.
Broido, A., Javier-Son, A. C., Ouano, A. C., Barrell, E. M., II (1973). Molecular weight decrease in the early pyrolysis of crystalline and amorphous cellulose. Journal of Applied Polymer Science, 17, 3627–3635. DOI: 10.1002/app.1973.070171207.
Broido, A., & Nelson, M. A. (1975). Char yield on pyrolysis of cellulose. Combustion and Flame, 24, 263–268. DOI: 10.1016/0010-2180(75)90156-x.
Broido, A. (1976). Kinetics of solid-phase cellulose pyrolysis. In F. Shafizadeh, K. V. Sarkanen, & D. A. Tillman (Eds.), Thermal uses and properties of carbohydrates and lignins (pp. 19–36). New York, NY, USA: Academic Press. DOI: 10.1016/b978-0-12-637750-7.50006-6.
Brown, M. E., Maciejewski, M., Vyazovkin, S., Nomen, R., Sempere, J., Burnham, A., Opfermann, J., Strey, R., Anderson, H. L., Kemmler, A., Keuleers, R., Janssens, J., Desseyn, H. O., Li, C. R., Tang, T. B., Roduit, B., Malek, J., & Mitsuhashi, T. (2000). Computational aspects of kinetic analysis. Part A: The ICTAC kinetics project-data, methods and results. Thermochimica Acta, 355, 125–143. DOI: 10.1016/s0040-6031(00)00443-3.
Budrugeac, P., & Segal, E. (2003). Prediction of the isothermal behavior of solid-gas systems from non-isothermal data. Journal of Thermal Analysis and Calorimetry, 72, 831–837. DOI: 10.1023/a:1025014114527.
Cabrales, L., & Abidi, N. (2010). On the thermal degradation of cellulose in cotton fibers. Journal of Thermal Analysis and Calorimetry, 102, 485–491. DOI: 10.1007/s10973-010-0911-9.
Capart, R., Khezami, L., & Burnham, A. K. (2004). Assessment of various kinetic models for the pyrolysis of a microgranular cellulose. Thermochimica Acta, 417, 79–89. DOI: 10.1016/j.tca.2004.01.029.
Chen, W. H., & Kuo, P. C. (2011). Isothermal torrefaction kinetics of hemicellulose, cellulose, lignin and xylan using thermogravimetric analysis. Energy, 36, 6451–6460. DOI: 10.1016/j.energy.2011.09.022.
Conesa, J. A., Caballero, J. A., Marcilla, A., & Font, R. (1995). Analysis of different kinetic models in the dynamic pyrolysis of cellulose. Thermochimica Acta, 254, 175–192. DOI: 10.1016/0040-6031(94)02102-t.
Di Blasi, C. (1993). Modeling and simulation of combustion processes of charring and non-charring solid fuels. Progress in Energy and Combustion Science, 19, 71–104. DOI: 10.1016/0360-1285(93)90022-7.
Di Blasi, C. (1996). Heat transfer mechanisms and multistep kinetics in the ablative pyrolysis of cellulose. Chemical Engineering Science, 51, 2211–2220. DOI: 10.1016/0009-2509(96)00078-4.
Di Blasi, C. (1998). Comparison of semi-global mechanisms for primary pyrolysis of lignocellulosic fuels. Journal of Analytical and Applied Pyrolysis, 47, 43–64. DOI: 10.1016/s0165-2370(98)00079-5.
Dickinson, C. F., & Heal, G. R. (2009a). A review of the ICTAC Kinetics Project, 2000. Part 1. Isothermal results. Thermochimica Acta, 494, 1–14. DOI: 10.1016/j.tca.2009.05.003.
Dickinson, C. F., & Heal, G. R. (2009b). A review of the ICTAC kinetics project, 2000. Part 2. Non-isothermal results. Thermochimica Acta, 494, 15–25. DOI: 10.1016/j.tca.2009.05.009.
Diebold, J. P. (1994). A unified, global model for the pyrolysis of cellulose. Biomass and Bioenergy, 7, 75–85. DOI: 10.1016/0961-9534(94)00039-v.
Evans, R. J., & Milne, T. A. (1987). Molecular characterization of the pyrolysis of biomass. 1. Fundamentals. Energy & Fuels, 1, 123–137. DOI: 10.1021/ef00002a001.
Fisher, T., Hajaligol, M., Waymack, B., & Kellogg, D. (2002). Pyrolysis behavior and kinetics of biomass derived materials. Journal of Analytical and Applied Pyrolysis, 62, 331–349. DOI: 10.1016/s0165-2370(01)00129-2.
Font, R., & García, A. N. (1995). Application of the transition state theory to the pyrolysis of biomass and tars. Journal of Analytical and Applied Pyrolysis, 35, 249–258. DOI: 10.1016/0165-2370(95)00916-8.
Galwey, A. K. (2004). Is the science of thermal analysis kinetics based on solid foundations? A literature appraisal. Thermochimica Acta, 413, 139–183. DOI: 10.1016/j.tca.2003.10.013.
Garcia-Perez, M. (2008). The formation of polyaromatic hydrocarbons and dioxins during pyrolysis: A review of the literature with descriptions of biomass composition, fast pyrolysis technologies and thermochemical reactions. Pullman, WA, USA: Washington State University. (WSUEEP08-010)
Gavillon, R. (2007). Préparation et caractérisation des matériaux cellulosiques ultra poreux. Ph. D. thesis, école des Mines de Paris, Paris, France. (in French)
Grønli, M., Antal, M. J., Jr., & Várhegyi, G. (1999). A roundrobin study of cellulose pyrolysis kinetics by thermogravimetry. Industrial & Engineering Chemistry Research, 38, 2238–2244. DOI: 10.1021/ie980601n.
Hopkins, M. W., DeJenga, C., & Antal, M. J., Jr. (1984). The flash pyrolysis of cellulosic materials using concentrated visible light. Solar Energy, 32, 547–551. DOI: 10.1016/0038-092x(84)90269-x.
Hu, S., Jess, A., & Xu, M. H. (2007). Kinetic study of Chinese biomass slow pyrolysis: Comparison of different kinetic models. Fuel, 86, 2778–2788. DOI: 10.1016/j.fuel.2007.02.031.
Huang, Y. F., Kuan, W. H., Chiueh, P. T., & Lo, S. L. (2011). A sequential method to analyze the kinetics of biomass pyrolysis. Bioresource Technology, 102, 9241–9246. DOI: 10.1016/j.biortech.2011.07.015.
Kim, S. D., & Eom, Y. J. (2006). Estimation of kinetic triplet of cellulose pyrolysis reaction from isothermal kinetic results. Korean Journal of Chemical Engineering, 23 (3), 409–414. DOI: 10.1007/bf02706742.
Kilzer, F. J., & Broido, A. (1965). Speculations on the nature of cellulose pyrolysis. Pyrodynamics, 2, 151–163.
Lédé, J. (2012). Cellulose pyrolysis kinetics: An historical review on the existence and role of intermediate active cellulose. Journal of Analytical and Applied Pyrolysis, 94, 17–32. DOI: 10.1016/j.jaap.2011.12.019.
Lewellen, P. C., Peters, W. A., & Howard, J. B. (1977). Cellulose pyrolysis kinetics and char formation mechanism. Symposium (International) on Combustion, 16, 1471–1480. DOI: 10.1016/s0082-0784(77)80429-3.
Li, C. R., & Tang, T. B. (1997). Dynamic thermal analysis of solid-state reactions. The ultimate method for data analysis? Journal of Thermal Analysis, 49, 1243–1248. DOI: 10.1007/bf01983680.
Li, C. R., & Tang, T. B. (1999). Isoconversional method for kinetic analysis of solid-state reactions from dynamics thermoanalytical data. Journal of Materials Science, 34, 3467–3470. DOI: 10.1023/a:1004605820783.
Liao, Y. F., Wang, S. R., & Ma, X. Q. (2004). Study of reaction mechanisms in cellulose pyrolysis. Preprints of Papers-American Chemical Society, Division of Fuel Chemistry, 49, 407–411.
Liu, Q., Wang, S. R., Wang, K. G., Guo, X. J., Luo, Z. Y., & Cen, K. F. (2008). Mechanism of formation and consequent evolution of active cellulose during cellulose pyrolysis. Acta Physico-Chimica Sinica, 24, 1957–1963. DOI: 10.1016/s1872-1508 (08)60078-9.
Mamleev, V., Bourbigot, S., & Yvon, J. (2007). Kinetic analysis of the thermal decomposition of cellulose: The change of the rate limitation. Journal of Analytical and Applied Pyrolysis, 80, 141–150. DOI: 10.1016/j.jaap.2007.01.012.
Mamleev, V., Bourbigot, S., Le Bras, M., & Yvon, J. (2009). The facts and hypotheses relating to phenomenological model of cellulose pyrolysis: Interdependence of the steps. Journal of Analytical and Applied Pyrolysis, 84, 1–17. DOI: 10.1016/j.jaap.2008.10.014.
Marra, F. (2009). Numerical analysis for kinetics and yield of wood biomass pyrolysis. In N. Mastorakis, & J. Sakellaris (Eds.), Advances in numerical methods (chapter 11, pp. 127–136). Heidelberg, Germany: Springer. DOI: 10.1007/978-0-387-76483-211.
Miller, R. S., & Bellan, J. (1997). A generalized biomass pyrolysis model based on superimposed cellulose, hemicellulose and lignin kinetics. Combustion Science and Technology, 126, 97–137. DOI: 10.1080/00102209708935670.
Ranzi, E., Cuoci, A., Faravelli, T., Frassoldati, A., Migliavacca, G., Pierucci, S., & Sommariva, S. (2008). Chemical kinetics of biomass pyrolysis. Energy & Fuels, 22, 4292–4300. DOI: 10.1021/ef800551t.
Reed, T. B., & Cowdery, C. D. (1987). Heat flux requirements for fast pyrolysis and a new method for generating biomass vapor. In 193rd National Meeting of the American Chemical Society, April 5–10, 1987. Denver, CO, USA: American Chemical Society Division of Petroleum Chemistry.
Sánchez-Jiménez, P. E., Pérez-Maqueda, L. A., Perejón, A., Pascual-Cosp, J., Benítez-Guerrero, M., & Criado, J. M. (2011). An improved model for the kinetic description of the thermal degradation of cellulose. Cellulose, 18, 1487–1498. DOI: 10.1007/s10570-011-9602-3.
Sbirrazzuoli, N., Vincent, L., Mija, A., & Guigo, N. (2009). Integral, differential and advanced isoconversional methods. Complex mechanisms and isothermal predicted conversiontime curves. Chemometrics and Intelligent Laboratory Systems, 96, 219–226. DOI: 10.1016/j.chemolab.2009.02.002.
Scott, D. S., Piskorz, J., & Radlein, D. (1989). Thermal conversion of biomass to liquids by the Waterloo fast pyrolysis process. In E. Mattucci, G. Grassi, & W. Palz (Eds.), Proceedings of Pyrolysis as a Basic Technology for Large Agro-Energy Projects, October 15–16, 1987 (pp. 115–124). Brussels, Belgium: Office for Official Publications of the European Communities.
Sewry, J. D., & Brown, M. E. (2002). “Model-free” kinetic analysis? Thermochimica Acta, 390, 217–225. DOI: 10.1016/s0040-6031(02)00083-7.
Shafizadeh, F. (1968). Pyrolysis and combustion of cellulosic materials. Advances in Carbohydrate Chemistry, 23, 419–474. DOI: 10.1016/s0096-5332(08)60173-3.
Shafizadeh, F., & Bradbury, A. G. W. (1979). Thermal degradation of cellulose in air and nitrogen at low temperatures. Journal of Applied Polymer Science, 23, 1431–1442. DOI: 10.1002/app.1979.070230513.
Shafizadeh, F. (1982). Introduction to pyrolysis of biomass. Journal of Analytical and Applied Pyrolysis, 3, 283–305. DOI: 10.1016/0165-2370(82)80017-x.
Šimon, P. (2005). Considerations on the single-step kinetics approximation. Journal of Thermal Analysis and Calorimetry, 82, 651–657. DOI: 10.1007/s10973-005-0945-6.
Sonobe, T., & Worasuwannarak, N. (2008). Kinetic analyses of biomass pyrolysis using the distributed activation energy model. Fuel, 87, 414–421. DOI: 10.1016/j.fuel.2007.05.004.
Stamm, A. J. (1956). Thermal degradation of wood and cellulose. Industrial & Engineering Chemistry, 48, 413–417. DOI: 10.1021/ie51398a022.
Tihay, V., Boulnois, C., & Gillard, P. (2011). Influence of oxygen concentration on the kinetics of cellulose wadding degradation. Thermochimica Acta, 525, 16–24. DOI: 10.1016/j.tca.2011.07.016.
Várhegyi, G., Antal, M. J., Jr., Szekely, T., & Szabó, P. (1989). Kinetics of the thermal decomposition of cellulose, hemicellulose, and sugarcane bagasse. Energy & Fuels, 3, 329–335. DOI: 10.1021/ef00015a012.
Várhegyi, G., Jakab, E., & Antal, M. J., Jr. (1994). Is the Broido-Shafizadeh model for cellulose pyrolysis true? Energy & Fuel, 8, 1345–1352. DOI: 10.1021/ef00048a025.
Várhegyi, G., Antal, M. J., Jr., Jakab, E., & Szabó, P. (1997). Kinetic modeling of biomass pyrolysis. Journal of Analytical and Applied Pyrolysis, 42, 73–87. DOI: 10.1016/s0165-2370(96)00971-0.
Völker, S., & Rieckmann, Th. (2002). Thermogravimetric investigation of cellulose pyrolysis — impact of initial and final mass on kinetic results. Journal of Analytical and Applied Pyrolysis, 62, 165–177. DOI: 10.1016/s0165-2370(01)00113-9.
Vyazovkin, S. (1996). A unified approach to kinetic processing of nonisothermal data. International Journal of Chemical Kinetics, 28(2), 95–101. DOI: 10.1002/(SICI)1097-4601(1996)28:2〈95::AID-KIN4〉3.0.CO;2-G.
Vyazovkin, S., & Dollimore, D. (1996). Linear and nonlinear procedures in isoconversional computations of the activation energy of nonisothermal reactions in solids. Journal of Chemical Information and Modeling, 36, 42–45. DOI: 10.1021/ci950062m.
Vyazovkin, S., & Wight, C. A. (1997). Kinetics in solids. Annual Review of Physical Chemistry, 48, 125–149. DOI: 10.1146/annurev.physchem.48.1.125.
White, J. E., Catallo, W. J., & Legendre, B. L. (2011). Biomass pyrolysis kinetics: A comparative critical review with relevant agricultural case studies. Journal of Analytical and Applied Pyrolysis, 91, 1–33. DOI: 10.1016/j.jaap.2011.01.004.
Zhu, G. Y., Zhu, X., Xiao, Z. B., & Yi, F. P. (2012). Study of cellulose pyrolysis using an in situ visualization technique and thermogravimetric analyzer. Journal of Analytical and Applied Pyrolysis, 94, 126–130. DOI: 10.1016/j.jaap.2011.11.016.
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Şerbănescu, C. Kinetic analysis of cellulose pyrolysis: a short review. Chem. Pap. 68, 847–860 (2014). https://doi.org/10.2478/s11696-013-0529-z
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DOI: https://doi.org/10.2478/s11696-013-0529-z