Abstract
A chemical reaction mechanism is proposed to describe the pyrolysis of scrap tire rubber based on the decomposition of their three main polymer compounds (natural, butadiene and styrene-butadiene rubbers). Samples of each polymer were tested separately using differential scanning calorimetry (DSC) at the same operating conditions (heating rate, temperature and atmosphere). The thermograms clearly show that the polymer decomposition takes place in two or three thermal steps. The comparison with the literature allowed associating these steps with depolymerization reactions. The DSC results also allowed determining the kinetic parameters for each reaction considered in the chemical mechanism proposed in this study. Consequently, these were included in a mathematical model developed for a fixed bed reactor (at laboratory-scale) considering mass and energy balances. The experimental conversion obtained in TGA at operating conditions of pyrolysis using scrap tire rubber as feedstock, were successful confronted with those simulated by the mathematical model obtaining a determination coefficient (R2) of 0.97. On the other hand, the mathematical model predicts correctly the influence of the temperature in the product yields, being this variable the most statistically significant in the process, being in agreement with ANOVA results ((p value < 0.001 at confidence level of 95%) allowing a good prediction of the product yields.
Similar content being viewed by others
References
Acosta, R., Tavera, C., Gauthier-Maradei, P., Nabarlatz, D.: Production of oil and char by intermediate pyrolysis of scrap tyres: influence on yield and product characteristics. Int. Chem. J. React. Eng. 13(2), 189–200 (2015)
Tang, Y., Curtis, C.W.: Thermal and catalytic coprocessing of waste tires with coal. Fuel Process Tech. 46(3), 195–215 (1996)
Saraf, S., Marsh, J. A., Cha, C. Y., Guffrey, F. D.: Reactive coprocessing of scrap tires and heavy oil. Resour. Conserv Recycl. 13(1), 1–13 (1995)
Narobe, M., Golob, J., Klinar, D., Francetic, V., Likozar, B.: Co-gasification of biomass and plastics: pyrolysis kinetics studies, experiments on 100 kW dual fluidized bed pilot plant and development of thermodynamic equilibrium model and balances. Bioresource Technol. 162, 21–29 (2014)
Pipilikaki, P., Katsioti, M., Papageorgiou, D., Fragoulis, D., Chaniatokis, E.: Use of tire derived fuel in clinker burning. Cem. Concr. Compos. 27(7–8), 843–847 (2005)
Ospina, J.A., Villada, S.: Methods to characterize liquid and gas combustibles obtain from the useless tyres throw the ASTM norms. Lámpsakos, 3(6), 23–31 (2011)
Conesa, J.A., Font, R., Fullana, A., Martín-Gullón, I., Aracil, I., Gálvez, A., Moltó, J., Gómez-Rico, M. F.: Comparison between emissions from the pyrolysis and combustion of different wastes. J. Anal. Appl. Pyrol. 84, 95–102 (2009)
Lah, B., Klinar, B., Likozar, B.: Pyrolysis of natural, butadiene, styrene–butadiene rubber and tyre components: modelling kinetics and transport phenomena at different heating rates and formulations. Chem. Eng. Sci. 87, 1–13 (2013)
Lee, Y. S., Lee, W., Seong-Gyu, C., Chan-Sik Ha, I.L. K.: Quantitative analysis of unknown compositions in ternary polymer blends: a model study on NR/SBR/BR systems. J. Anal. Appl. Pyrol. 78, 85–94 (2007)
Mancilla, M.A., Silva, L., Salgueiro, W., Marzocca, A., Somoza, A.: Thermal behavior in natural rubber/styrene butadiene rubber blends. a study using DSC. Anales AFA 22, 28–31 (2010)
Park, S., Gloyna, E. F.: Statistical-study-of-the-liquefaction-of-used-rubber-tyre-in-supercritical-water. Fuel 76(11), 999–1003 (1997)
Kyari, M., Cunliffe, A., Williams, P. T.: Characterization of oils, gases, and char in relation to the pyrolysis of different brands of scrap automotive tires. Energy Fuels 19, 1165–1173 (2005)
Aylón, E., Callen, M.S., López, J.M., Mastral, A.M., Murillo, R., Navarro, M.V., Stelmach, S.: Assessment of tire devolatilization kinetics. J. Anal. Appl. Pyrol. 74, 259–264 (2005)
Leung, D. Y. C., Wang, C. L.: Kinetic modeling of scrap tire pyrolysis. Energy Fuels 13(2), 421–427 (1999)
Quek, A., Balasubramanian, R.: An algorithm for the kinetics of tire pyrolysis under different heating rates. J. Hazard. Mater. 166(1), 126–132 (2009)
Wendlandt, W. W.: Thermal analysis, 3rd edn. Wiley, New York (1986)
Miranda, M., Pinto, F., Gulyurtu, I., Cabrita, I.: Pyrolysis of rubber tyre wastes: a kinetic study. Fuel 103, 542–552 (2013)
Lanteighne, J.-R., Laviolette, J.-P., Tremblay, G., Chaouki, J.: Predictive kinetics model for an industrial waste tire pyrolysis process. Energy Fuels 27, 1040–1049 (2013)
Lopez, G., Aguado, R., Olazar, M., Arabiourrutia, M., Bilbao, J.: Kinetics of scrap tyre pyrolysis under vacuum conditions. Waste Manag. 29, 2649–2655 (2009)
Seidelt, S., Muller-Hagedorn, M., Bockhorn, H.: Description of tire pyrolysis by thermal degradation behavior of main components. J. Anal. Appl. Pyrol. 75(1), 11–18 (2006)
Cheung, K.-Y., Lee, K.-L., Lam, K.-L., Lee, C.-W., Hui, C.-W.: Integrated kinetics and heat flow modeling to optimize waste tyre pyrolysis at different heating rates. Fuel Process. Technol. 92, 856–863 (2011)
Fernández, A. M., Barriocanal, C., Alvarez, R.: (2012). Pyrolysis of a Waste from the grinding of scrap tyres. J. Hazard. Mater. 203–204, 236–243
Martínez, O., Calvo, L. F., Morán, A.: Pyrolysis of tyres. Influence of the final temperature of the process on emissions and the calorific value of the products recovered. Waste Manag. 24(5), 463–469 (2004)
Conesa, J., Gullón, I. M., Font, R., Jauhiainen, J.: Complete study of the pyrolysis and gasification of scrap tires in a pilot plant reactor. Environ. Sci. Technol. 38(11), 3189–3194 (2004)
Acosta, R. A., Moncada, S. J., Gauthier-Maradei, P., Nabarlatz, D.: Estudio preliminar de la producción de aceite y carbón mediante pirólisis intermedia de caucho de llantas usadas. Rev. Investig. Univ. Quindío 24(1), 139–145 (2013)
Yang, J., Roy, C.: A new method for DTA measurement of enthalpy change during the pyrolysis of rubbers. Thermochim. Acta 288, 155–168 (1996)
Napoli, A., Soudais, Y., Lecomte, D., Castillo, S.: Scrap tire pyrolysis: experiment and modeling. J. Anal. Appl. Pyrol. 373, 40–41 (1997)
Pyle, D. L., Zaror, C.A.: Heat transfer and kinetics in the low temperature pyrolysis of solids. Chem. Eng. Sci. 39(1), 147–158 (1984)
Giwa, A., Giwa, S.O.: Application of Crank-Nicolson finite-difference method to the solution of the dynamic model of a reactor. Int. J. Adv. Sci. Tech. Res. 3(6), 613–623 (2013)
Gonzalez, J. F., Encinar, J. M., Canito, J. L., Rodríguez, J. J.: (2001). Pyrolysis of automobile tyre waste. Influence of operating variables and kinetics study. J. Anal. App. Pyrol. 58–59(3), 667–668
Murillo, R., Aylón, E., Navarro, M. V., Callén, M. S., Aranda, A., Mastral, A.M.: The application of thermal processes to valorise waste tyre. Fuel Process. Technol. 87, 143–147 (2006)
Michael, W.R.: Quality performance factors for tire-derived materials. In: De, S. K., Isayev, A.I., Khait, K. (eds.) Rubber recycling. Taylor & Francis Group, Boca Raton (2005)
Leung, D., Wang, C.: Kinetic study of scrap tyre pyrolysis and combustion. J. Anal. App. Pyrol. 45, 153–169 (1998)
Danon, B., Van der Gryp, P., Schwarz, C.E., Gogerns, J. F.: A review of dipentene (dl-limonene) production from waste tire pyrolysis. J. Anal. App. Pyrol. 112, 1–13 (2015)
Martínez, J. D., Puy, N., Murillo, R., García, T., Navarro, M. V., Mastral, A. M.: Waste tyre pyrolysis. A review. Renew. Sustain. Energ. Rev. 23, 179–213 (2013)
Chen, F., Qian, J.(: Studies on the thermal degradation of cis-1,4-polyisoprene. Fuel 81, 2071–2077 (2002)
Kar, Y.: Catalytic pyrolysis of car tire waste using expanded perlite. Waste Manag. 31, 1772–1782 (2011)
Danon, B., Görgens, J.: Determining rubber composition of waste tyres using devolatilization kinetics. Thermochim. Acta 621, 56–60 (2015)
Choi, S.-S.: Characteristics of the pyrolysis patterns of styrene-butadiene rubbers with differing microstructures. J. Anal. Appl. Pyrol. 62, 319–330 (2002)
Peterson, J. D., Vyazovkin, S., Wight, C. A.: Kinetics of the thermal and thermo-oxidative degradation of polystyrene, polyethylene and poly (propylene). Macromol. Chem. Phys. 202, 775–784 (2001)
Aguado, R., Olazar, M., Vélez, D., Arabiourrutia, M., Bilbao, J.: Kinetics of scrap tyre pyrolysis under fast heating conditions. J. Anal. Appl. Pyrol. 73, 290–298 (2005)
Danon, B., Mkhize, N.M., van der Gryp, P., Görgens, J.F.: Combined model-free and model-based devolatilization kinetics of tyre rubbers B. Thermochim. Acta 601, 45–53 (2015)
Conesa, J., Marcilla, A.: Kinetic study of the thermogravimetric behavior of different rubbers. J. Anal. Appl. Pyrol.. 37, 95–110 (1996)
Ucar, S., Karagoz, S., Ozkan, A. R., Yanik, J.: Evaluation of two different scrap tires as hydrocarbon source by pyrolysis. Fuel 84, 1884–1892 (2005)
Berrueco, C., Esperanza, E., Mastral, F.J., Ceamanos, J., García-Bacaicoa, P.: Pyrolysis of waste tyres in an atmospheric static-bed batch reactor: analysis of the gases obtained. J. Anal. Appl. Pyrol. 74, 245–253 (2005)
Williams, P.T.: Pyrolysis of waste tyres: a review. Waste Manag. 33, 1714–1728 (2013)
Acknowledgements
The authors are grateful to Vicerrectoría de Investigación y Extensión from Universidad Industrial de Santander for research funding (Grant number 5457). Y. Cely is grateful to Colciencias for the Young Researcher scholarship.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Gauthier-Maradei, P., Cely Valderrama, Y. & Nabarlatz, D. Mathematical Model of Scrap Tire Rubber Pyrolysis in a Non-isothermal Fixed Bed Reactor: Definition of a Chemical Mechanism and Determination of Kinetic Parameters. Waste Biomass Valor 10, 561–573 (2019). https://doi.org/10.1007/s12649-017-0079-7
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s12649-017-0079-7