European Journal of Chemistry

Fuel oil production from thermal decomposition of the model and waste polystyrene: Comparative kinetics and product distribution

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Published: Mar 31, 2023
DOI: https://doi.org/10.5155/eurjchem.14.1.80-89.2374
Keywords:
Fuel oil, Kinetic models, Pyrolysis GC/MS, Products distribution, Arrhenius parameters, Thermokinetic analysis
Section
Research Article
Issue
Vol. 14 No. 1 (2023): March 2023
Dates
Received 2022-11-30
Accepted 2023-01-14
Published 2023-03-31
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Ghulam Ali
National Centre of Excellence in Physical Chemistry, University of Peshawar, 25120, Peshawar, Pakistan
https://orcid.org/0000-0002-7995-3925
Jan Nisar
National Centre of Excellence in Physical Chemistry, University of Peshawar, 25120, Peshawar, Pakistan
https://orcid.org/0000-0002-6072-6255
Muhammad Arshad
Bio/Chem Lab, Government Institute Kacha Mali Khel Dera Ismail Khan, Peshawar 25120, Pakistan
https://orcid.org/0000-0002-8896-9814

Abstract

The thermal degradation of model polystyrene (MPS) and waste polystyrene (WPS) was performed in a thermobalance system at four heating rates (β) i.e., 5, 10, 15 and 20 °C/min  in an inert atmosphere. The apparent activation energy (Ea) and frequency factor (A) for the MPS and the WPS were calculated using Ozawa-Flynn-Wall (OFW), Kissinger-Akahira-Sunose (KAS), and Augis-Bennetis (AB) methods. It has been determined that Ea and A vary according to fraction conversion, heating rates, and applied models. The activation energy determined for MPS was found to be in the range of 91-106, 90-105, and 114-133 kJ/mol, while, for WPS, Ea was determined in the range of 82-160, 79-159 and 102-202 kJ/mol by applying OFW, KAS, and AB models, respectively. From the results obtained, it was concluded that the Ea determined by all of these methods increases with fraction conversion, indicating that the decomposition of polystyrene follows a complex mechanism of the solid-state reaction. Hence, the kinetic parameters, i.e., Ea and A, seem to play a key role in investigating the mechanism of solid-state reactions and will provide an opportunity to develop the mechanism of the industrial decomposition reactions. The results show that the MPS has a lower activation energy compared to WPS. This high Ea of WPS may be due to the additives used in the manufacturing of different polystyrene products. Pyrolysis GC/MS of WPS indicates that the main components of pyrolysis oil are 1-hydroxy-2-propanone, styrene, α-methyl styrene, toluene, and 1,2-dimethyl benzene. The presence of some oxygenated compounds in the fuel oil of WPS may be due to contamination or additives used during polystyrene processing, as the WPS samples were collected from a garbage dump near a local market. WPS can be utilized as fuel if the fuel oil collected from the pyrolysis of WPS is properly upgraded to make it equivalent to commercial fuel oil.


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Ali, G.; Nisar, J.; Arshad, M. Fuel Oil Production from Thermal Decomposition of the Model and Waste Polystyrene: Comparative Kinetics and Product Distribution. Eur. J. Chem. 2023, 14, 80-89.

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References

[1]. Ali, G.; Nisar, J. Kinetics and thermodynamics of the pyrolysis of waste polystyrene over natural clay. Adv. Environ. Eng. Res. 2022, 03, 1-40.
https://doi.org/10.21926/aeer.2204044

[2]. Karagöz, S.; Karayildirim, T.; Uçar, S.; Yuksel, M.; Yanik, J. Liquefaction of municipal waste plastics in VGO over acidic and non-acidic catalysts☆. Fuel (Lond.) 2003, 82, 415-423.
https://doi.org/10.1016/S0016-2361(02)00250-8

[3]. Ohta, M.; Oshima, S.; Osawa, N.; Iwasa, T.; Nakamura, T. Formation of PCDDs and PCDFs during the combustion of polyvinylidene chloride and other polymers in the presence of HCl. Chemosphere 2004, 54, 1521-1531.
https://doi.org/10.1016/j.chemosphere.2003.07.002

[4]. Woo, O. S.; Ayala, N.; Broadbelt, L. J. Mechanistic interpretation of base-catalyzed depolymerization of polystyrene. Catal. Today 2000, 55, 161-171.
https://doi.org/10.1016/S0920-5861(99)00235-7

[5]. Ali, G.; Nisar, J.; Shah, A.; Farooqi, Z. H.; Iqbal, M.; Shah, M. R.; Ahmad, H. B. Production of liquid fuel from polystyrene waste: Process optimization and characterization of pyrolyzates. Combust. Sci. Technol. 2021, 1-14.
https://doi.org/10.1080/00102202.2021.1985481

[6]. Ukei, H.; Hirose, T.; Horikawa, S.; Takai, Y.; Taka, M.; Azuma, N.; Ueno, A. Catalytic degradation of polystyrene into styrene and a design of recyclable polystyrene with dispersed catalysts. Catal. Today 2000, 62, 67-75.
https://doi.org/10.1016/S0920-5861(00)00409-0

[7]. Nisar, J.; Nasir, U.; Ali, G.; Shah, A.; Farooqi, Z. H.; Iqbal, M.; Shah, M. R. Kinetics of pyrolysis of sugarcane bagasse: effect of catalyst on activation energy and yield of pyrolysis products. Cellulose 2021, 28, 7593-7607.
https://doi.org/10.1007/s10570-021-04015-1

[8]. Šimon, P. Isoconversional methods. J. Therm. Anal. Calorim. 2004, 76, 123-132.
https://doi.org/10.1023/B:JTAN.0000027811.80036.6c

[9]. Khawam, A.; Flanagan, D. R. Complementary use of model-free and modelistic methods in the analysis of solid-state kinetics. J. Phys. Chem. B 2005, 109, 10073-10080.
https://doi.org/10.1021/jp050589u

[10]. Opfermann, J. R.; Kaisersberger, E.; Flammersheim, H. J. Model-free analysis of thermoanalytical data-advantages and limitations. Thermochim. Acta 2002, 391, 119-127.
https://doi.org/10.1016/S0040-6031(02)00169-7

[11]. Zhou, D.; Schmitt, E. A.; Zhang, G. G.; Law, D.; Vyazovkin, S.; Wight, C. A.; Grant, D. J. W. Crystallization kinetics of amorphous nifedipine studied by model-fitting and model-free approaches. J. Pharm. Sci. 2003, 92, 1779-1792.
https://doi.org/10.1002/jps.10425

[12]. Nisar, J.; Ali, G.; Shah, A.; Iqbal, M.; Khan, R. A.; Sirajuddin; Anwar, F.; Ullah, R.; Akhter, M. S. Fuel production from waste polystyrene via pyrolysis: Kinetics and products distribution. Waste Manag. 2019, 88, 236-247.
https://doi.org/10.1016/j.wasman.2019.03.035

[13]. Nisar, J.; Ali, G.; Shah, A.; Shah, M. R.; Iqbal, M.; Ashiq, M. N.; Bhatti, H. N. Pyrolysis of expanded waste polystyrene: Influence of nickel-doped copper oxide on kinetics, thermodynamics, and product distribution. Energy Fuels 2019, 33, 12666-12678.
https://doi.org/10.1021/acs.energyfuels.9b03004

[14]. Peterson, J. D.; Vyazovkin, S.; Wight, C. A. Kinetics of the Thermal and Thermo-Oxidative Degradation of Polystyrene, Polyethylene and Poly(propylene). Macromolecular Chemistry and Physics 2001, 202, 775-784.
https://doi.org/10.1002/1521-3935(20010301)202:6<775::AID-MACP775>3.0.CO;2-G

[15]. Balakrishnan, R. K.; Guria, C. Thermal degradation of polystyrene in the presence of hydrogen by catalyst in solution. Polym. Degrad. Stab. 2007, 92, 1583-1591.
https://doi.org/10.1016/j.polymdegradstab.2007.04.014

[16]. Aboulkas, A.; El harfi, K.; El Bouadili, A. Thermal degradation behaviors of polyethylene and polypropylene. Part I: Pyrolysis kinetics and mechanisms. Energy Convers. Manag. 2010, 51, 1363-1369.
https://doi.org/10.1016/j.enconman.2009.12.017

[17]. Mumbach, G. D.; Alves, J. L. F.; Da Silva, J. C. G.; De Sena, R. F.; Marangoni, C.; Machado, R. A. F.; Bolzan, A. Thermal investigation of plastic solid waste pyrolysis via the deconvolution technique using the asymmetric double sigmoidal function: Determination of the kinetic triplet, thermodynamic parameters, thermal lifetime and pyrolytic oil composition for clean energy recovery. Energy Convers. Manag. 2019, 200, 112031.
https://doi.org/10.1016/j.enconman.2019.112031

[18]. Flynn, J. H.; Wall, L. A. A quick, direct method for the determination of activation energy from thermogravimetric data. J. Polym. Sci. B 1966, 4, 323-328.
https://doi.org/10.1002/pol.1966.110040504

[19]. Ali, G.; Nisar, J.; Iqbal, M.; Shah, A.; Abbas, M.; Shah, M. R.; Rashid, U.; Bhatti, I. A.; Khan, R. A.; Shah, F. Thermo-catalytic decomposition of polystyrene waste: Comparative analysis using different kinetic models. Waste Manag. Res. 2020, 38, 202-212.
https://doi.org/10.1177/0734242X19865339

[20]. Kissinger, H. E. Variation of peak temperature with heating rate in differential thermal analysis. J. Res. Natl. Bur. Stand. (1934) 1956, 57, 217.
https://doi.org/10.6028/jres.057.026

[21]. Nisar, J.; Khan, M. A.; Ali, G.; Iqbal, M.; Din, M. I.; Hussain, Z.; Bhatti, I. A.; Al-Kadhi, N. S.; Alamro, F. S. Polypropylene pyrolysis kinetics under isothermal and non-isothermal conditions: a comparative analysis. Z. Phys. Chem. (N F) 2022, 236, 1163-1172.
https://doi.org/10.1515/zpch-2022-0005

[22]. Chrissafis, K. Kinetics of thermal degradation of polymers: Complementary use of isoconversional and model-fitting methods. J. Therm. Anal. Calorim. 2009, 95, 273-283.
https://doi.org/10.1007/s10973-008-9041-z

[23]. Westerhout, R. W. J.; Waanders, J.; Kuipers, J. A. M.; van Swaaij, W. P. M. Kinetics of the low-temperature pyrolysis of polyethene, polypropene, and polystyrene modeling, experimental determination, and comparison with literature models and data. Ind. Eng. Chem. Res. 1997, 36, 1955-1964.
https://doi.org/10.1021/ie960501m

[24]. Wu, C.-H.; Chang, C.-Y.; Hor, J.-L.; Shih, S.-M.; Chen, L.-W.; Chang, F.-W. On the thermal treatment of plastic mixtures of MSW: Pyrolysis kinetics. Waste Manag. 1993, 13, 221-235.
https://doi.org/10.1016/0956-053X(93)90046-Y

[25]. Encinar, J. M.; González, J. F. Pyrolysis of synthetic polymers and plastic wastes. Kinetic study. Fuel Process. Technol. 2008, 89, 678-686.
https://doi.org/10.1016/j.fuproc.2007.12.011

[26]. Şenocak, A.; Alkan, C.; Karadağ, A. Thermal decomposition and a kinetic study of poly(para-substituted styrene)s. Am. J. Analyt. Chem. 2016, 07, 246-253.
https://doi.org/10.4236/ajac.2016.73021

[27]. Aguado, R. Kinetics of polystyrene pyrolysis in a conical spouted bed reactor. Chem. Eng. J. 2003, 92, 91-99.
https://doi.org/10.1016/S1385-8947(02)00119-5

[28]. Sørum, L.; Grønli, M. G.; Hustad, J. E. Pyrolysis characteristics and kinetics of municipal solid wastes. Fuel (Lond.) 2001, 80, 1217-1227.
https://doi.org/10.1016/S0016-2361(00)00218-0

[29]. Heydari, M.; Rahman, M.; Gupta, R. Kinetic study and thermal decomposition behavior of lignite coal. Int. J. Chem. Eng. 2015, 2015, 1-9.
https://doi.org/10.1155/2015/481739

[30]. Nisar, J.; Ali, G.; Shah, A.; Farooqi, Z. H.; Khan, R. A.; Iqbal, M.; Gul, M. Pyrolysis of waste tire rubber: a comparative kinetic study using different models. Energy Sources Recovery Util. Environ. Eff. 2020, 1-11.
https://doi.org/10.1080/15567036.2020.1823530

[31]. Blanco, I.; Abate, L.; Antonelli, M. L. The regression of isothermal thermogravimetric data to evaluate degradation Ea values of polymers: A comparison with literature methods and an evaluation of lifetime prediction reliability. Polym. Degrad. Stab. 2011, 96, 1947-1954.
https://doi.org/10.1016/j.polymdegradstab.2011.08.005

[32]. Marcilla, A.; Beltrán, M. Kinetic study of the thermal decomposition of polystyrene and polyethylene-vinyl acetate graft copolymers by thermogravimetric analysis. Polym. Degrad. Stab. 1995, 50, 117-124.
https://doi.org/10.1016/0141-3910(95)00138-C

[33]. Vyazovkin, S. Evaluation of activation energy of thermally stimulated solid-state reactions under arbitrary variation of temperature. J. Comput. Chem. 1997, 18, 393-402.
https://doi.org/10.1002/(SICI)1096-987X(199702)18:3<393::AID-JCC9>3.0.CO;2-P

[34]. Vyazovkin, S. Kinetic concepts of thermally stimulated reactions in solids: A view from a historical perspective. Int. Rev. Phys. Chem. 2000, 19, 45-60.
https://doi.org/10.1080/014423500229855

[35]. Nisar, J.; Ali, G.; Shah, A.; Farooqi, Z. H.; Iqbal, M.; Khan, S.; Sherazi, S. T. H.; Sirajuddin Production of fuel oil and combustible gases from pyrolysis of polystyrene waste: Kinetics and thermodynamics interpretation. Environ. Technol. Innov. 2021, 24, 101996.
https://doi.org/10.1016/j.eti.2021.101996

[36]. Cheng, J.; Pan, Y.; Yao, J.; Wang, X.; Pan, F.; Jiang, J. Mechanisms and kinetics studies on the thermal decomposition of micron Poly (methyl methacrylate) and polystyrene. J. Loss Prev. Process Ind. 2016, 40, 139-146.
https://doi.org/10.1016/j.jlp.2015.12.017

[37]. Özsin, G.; Pütün, A. E. Insights into pyrolysis and co-pyrolysis of biomass and polystyrene: Thermochemical behaviors, kinetics and evolved gas analysis. Energy Convers. Manag. 2017, 149, 675-685.
https://doi.org/10.1016/j.enconman.2017.07.059

[38]. Aljabri, N. M.; Lai, Z.; Hadjichristidis, N.; Huang, K.-W. Renewable aromatics from the degradation of polystyrene under mild conditions. J. Saudi Chem. Soc. 2017, 21, 983-989.
https://doi.org/10.1016/j.jscs.2017.05.005

[39]. Undri, A.; Frediani, M.; Rosi, L.; Frediani, P. Reverse polymerization of waste polystyrene through microwave assisted pyrolysis. J. Anal. Appl. Pyrolysis 2014, 105, 35-42.
https://doi.org/10.1016/j.jaap.2013.10.001

[40]. Ma, C.; Yu, J.; Wang, B.; Song, Z.; Xiang, J.; Hu, S.; Su, S.; Sun, L. Catalytic pyrolysis of flame retarded high impact polystyrene over various solid acid catalysts. Fuel Process. Technol. 2017, 155, 32-41.
https://doi.org/10.1016/j.fuproc.2016.01.018

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Higher Education Commission of Pakistan, Pakistan.
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