Catalytic co-pyrolysis of LDPE and PET with HZSM-5, H-beta, and HY: experiments and kinetic modelling

Okonsky, Sean Timothy; Krishna, J. V. Jayarama; Toraman, Hilal Ezgi

doi:10.1039/d2re00144f

Catalytic co-pyrolysis of LDPE and PET with HZSM-5, H-beta, and HY: experiments and kinetic modelling

Journal Article · Thu Jun 30 00:00:00 EDT 2022 · Reaction Chemistry & Engineering

DOI:https://doi.org/10.1039/d2re00144f· OSTI ID:1978907

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Pennsylvania State Univ., University Park, PA (United States); OSTI
Pennsylvania State Univ., University Park, PA (United States)

In this study, the catalytic pyrolysis of low-density polyethylene (LDPE), polyethylene terephthalate (PET) and their mixture (1 : 1 wt/wt) with three zeolite catalysts (HZSM-5, H-beta, HY) was investigated using a thermogravimetric analyzer (TGA) and a Pyroprobe® micro-reactor coupled to a gas chromatograph mass spectrometer (Py-GC/MS). The TGA results demonstrated that during pyrolysis at 10 °C min^–1, on average, zeolite catalysts decreased the maximum decomposition temperature by 149 °C for LDPE while only decreasing by 8 °C for PET. The derivative thermogravimetric (DTG) curve evidenced interactions when the two polymers were catalytically co-pyrolyzed for all the three catalysts. A lumped nth order reaction scheme was able to accurately model both non-catalytic and catalytic pyrolysis and co-pyrolysis by using the least squares fitting approach for determining the kinetic parameters. The kinetic model was able to model well the interaction effects observed during catalytic co-pyrolysis of LDPE and PET with HZSM-5, H-beta, and HY (Fit%_Wt% > 96%, Fit%_DTG > 94%). Py-GC/MS experiments for the catalytic fast pyrolysis of LDPE revealed that HZSM-5 resulted in the highest selectivity to aromatic hydrocarbons (31.6%) and HY resulted in the highest selectivity to gasoline range C₅–C₁₀ paraffins and olefins (40.9%). Catalytic fast pyrolysis of PET showed high selectivity to benzene for all the catalysts (>43%) and that HZSM-5 resulted in the highest selectivity to polyaromatic hydrocarbons (24.7%). Finally, the catalytic fast co-pyrolysis of LDPE and PET revealed interaction effects for all the three catalysts evidenced by a positive synergy% for alkylated benzenes (3–142%) and polyaromatics (105–187%) with a concomitant negative synergy% for benzene (24–36%) and C₅–C₁₀ paraffins and olefins (27–53%).

View Accepted Manuscript (DOE)

Research Organization:: Sustainable Manufacturing Innovation Alliance Corp., West Henrietta, NY (United States)

Sponsoring Organization:: USDOE; USDOE Office of Energy Efficiency and Renewable Energy (EERE)

Grant/Contract Number:: EE0007897

OSTI ID:: 1978907

Alternate ID(s):: OSTI ID: 1875713

Journal Information:: Reaction Chemistry & Engineering, Journal Name: Reaction Chemistry & Engineering Journal Issue: 10 Vol. 7; ISSN 2058-9883

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (62)

A review on thermal decomposition and combustion of thermoplastic polyesters Levchik, Sergei V.; Weil, Edward D. Polymers for Advanced Technologies, Vol. 15, Issue 12 https://doi.org/10.1002/pat.526	journal	December 2004
Determination of Integrated Molar Extinction Coefficients for Infrared Absorption Bands of Pyridine Adsorbed on Solid Acid Catalysts Emeis, C. A. Journal of Catalysis, Vol. 141, Issue 2 https://doi.org/10.1006/jcat.1993.1145	journal	June 1993
Alkylation of Benzene with Short-Chain Olefins over MCM-22 Zeolite: Catalytic Behaviour and Kinetic Mechanism Corma, A.; Martı́nez-Soria, V.; Schnoeveld, E. Journal of Catalysis, Vol. 192, Issue 1 https://doi.org/10.1006/jcat.2000.2849	journal	May 2000
Studies on pore systems in catalysts V. The t method Lippens, B. Journal of Catalysis, Vol. 4, Issue 3 https://doi.org/10.1016/0021-9517(65)90307-6	journal	June 1965
The pollution of the marine environment by plastic debris: a review Derraik, José G. B. Marine Pollution Bulletin, Vol. 44, Issue 9 https://doi.org/10.1016/S0025-326X(02)00220-5	journal	September 2002
Kinetic modeling of the thermal degradation of polyethylene and polystyrene mixtures Faravelli, Tiziano; Bozzano, Giulia; Colombo, Mauro Journal of Analytical and Applied Pyrolysis, Vol. 70, Issue 2 https://doi.org/10.1016/S0165-2370(03)00058-5	journal	December 2003
Fluidised bed pyrolysis of low density polyethylene to produce petrochemical feedstock Williams, Paul T.; Williams, Elizabeth A. Journal of Analytical and Applied Pyrolysis, Vol. 51, Issue 1-2 https://doi.org/10.1016/S0165-2370(99)00011-X	journal	July 1999
A global kinetic model as a tool to reproduce the deactivation behaviour of the HZSM-5 zeolite in the catalytic cracking of low-density polyethylene Marcilla, A.; Beltrán, M. I.; Gómez-Siurana, A. Applied Catalysis A: General, Vol. 328, Issue 2 https://doi.org/10.1016/j.apcata.2007.05.038	journal	September 2007
Effect of the acidity of the HZSM-5 zeolite catalyst on the cracking of high density polyethylene in a conical spouted bed reactor Elordi, G.; Olazar, M.; Artetxe, M. Applied Catalysis A: General, Vol. 415-416 https://doi.org/10.1016/j.apcata.2011.12.011	journal	February 2012
Improving the aromatic production in catalytic fast pyrolysis of cellulose by co-feeding low-density polyethylene Li, Xiangyu; Zhang, Haifeng; Li, Jian Applied Catalysis A: General, Vol. 455 https://doi.org/10.1016/j.apcata.2013.01.038	journal	March 2013
Deactivation of a Y-zeolite based catalyst with coke evolution during the catalytic pyrolysis of polyethylene for fuel oil Chen, Zezhou; Zhang, Xurui; Yang, Fan Applied Catalysis A: General, Vol. 609 https://doi.org/10.1016/j.apcata.2020.117873	journal	January 2021
Role of pore structure in the deactivation of zeolites (HZSM-5, Hβ and HY) by coke in the pyrolysis of polyethylene in a conical spouted bed reactor Elordi, G.; Olazar, M.; Lopez, G. Applied Catalysis B: Environmental, Vol. 102, Issue 1-2 https://doi.org/10.1016/j.apcatb.2010.12.002	journal	February 2011
Effect of precursor on the performance of alumina for the dehydration of methanol to dimethyl ether Osman, Ahmed I.; Abu-Dahrieh, Jehad K.; Rooney, David W. Applied Catalysis B: Environmental, Vol. 127 https://doi.org/10.1016/j.apcatb.2012.08.033	journal	October 2012
Pd-modified beta zeolite for modulated hydro-cracking of low-density polyethylene into a paraffinic-rich hydrocarbon fuel Pyra, Kamila; Tarach, Karolina A.; Śrębowata, Anna Applied Catalysis B: Environmental, Vol. 277 https://doi.org/10.1016/j.apcatb.2020.119070	journal	November 2020
Pyrolysis kinetics and synergistic effect in co-pyrolysis of Samanea saman seeds and polyethylene terephthalate using thermogravimetric analyser Mishra, Ranjeet Kumar; Sahoo, Abhisek; Mohanty, Kaustubha Bioresource Technology, Vol. 289 https://doi.org/10.1016/j.biortech.2019.121608	journal	October 2019
Selective synthesis of acetaldehyde from lactic acid on acid zeolites Sad, M. E.; González Peña, L. F.; Padró, C. L. Catalysis Today, Vol. 302 https://doi.org/10.1016/j.cattod.2017.03.024	journal	March 2018
Thermal degradation behaviors of polyethylene and polypropylene. Part I: Pyrolysis kinetics and mechanisms Aboulkas, A.; El harfi, K.; El Bouadili, A. Energy Conversion and Management, Vol. 51, Issue 7 https://doi.org/10.1016/j.enconman.2009.12.017	journal	July 2010
Effect of catalyst contact mode and gas atmosphere during catalytic pyrolysis of waste plastics Xue, Yuan; Johnston, Patrick; Bai, Xianglan Energy Conversion and Management, Vol. 142 https://doi.org/10.1016/j.enconman.2017.03.071	journal	June 2017
A hybrid kinetic and optimization approach for biomass pyrolysis: The hybrid scheme of the isoconversional methods, DAEM, and a parallel-reaction mechanism Liu, Hui; Ahmad, Muhammad Sajjad; Alhumade, Hesham Energy Conversion and Management, Vol. 208 https://doi.org/10.1016/j.enconman.2020.112531	journal	March 2020
Lumped-kinetic modeling and experiments on co-pyrolysis of palm kernel cake with polystyrene using a closed-tubing reactor to upgrade pyrolysis products Vo, Thuan Anh; Ly, Hoang Vu; Tran, Quoc Khanh Energy Conversion and Management, Vol. 249 https://doi.org/10.1016/j.enconman.2021.114879	journal	December 2021
How to determine consistent biomass pyrolysis kinetics in a parallel reaction scheme Anca-Couce, Andrés; Berger, Anka; Zobel, Nico Fuel, Vol. 123 https://doi.org/10.1016/j.fuel.2014.01.014	journal	May 2014
Conversion of low density polyethylene (LDPE) over ZSM-5 zeolite to liquid fuel Wong, S. L.; Ngadi, N.; Abdullah, T. A. T. Fuel, Vol. 192 https://doi.org/10.1016/j.fuel.2016.12.008	journal	March 2017
Catalytic cracking of low-density polyethylene over zeolite-containing hierarchical two-layered catalyst with different mesopore size using Curie point pyrolyzer Matsuura, Shinya; Hashimoto, Tadanori; Ishihara, Atsushi Fuel Processing Technology, Vol. 227 https://doi.org/10.1016/j.fuproc.2021.107106	journal	March 2022
Role of zeolite properties in bio-oil deoxygenation and hydrocarbons production by catalytic cracking Valle, Beatriz; Palos, Roberto; Bilbao, Javier Fuel Processing Technology, Vol. 227 https://doi.org/10.1016/j.fuproc.2021.107130	journal	March 2022
Influence of nanocrystalline HZSM-5 external surface on the catalytic cracking of polyolefins Serrano, D. P.; Aguado, J.; Escola, J. M. Journal of Analytical and Applied Pyrolysis, Vol. 74, Issue 1-2 https://doi.org/10.1016/j.jaap.2004.11.037	journal	August 2005
Binary mixture pyrolysis of polypropylene and polystyrene: A modeling and experimental study Kruse, Todd M.; Levine, Seth E.; Wong, Hsi-Wu Journal of Analytical and Applied Pyrolysis, Vol. 73, Issue 2 https://doi.org/10.1016/j.jaap.2005.03.006	journal	June 2005
Catalytic pyrolysis of HDPE in continuous mode over zeolite catalysts in a conical spouted bed reactor Elordi, G.; Olazar, M.; Lopez, G. Journal of Analytical and Applied Pyrolysis, Vol. 85, Issue 1-2 https://doi.org/10.1016/j.jaap.2008.10.015	journal	May 2009
Isothermal fast pyrolysis kinetics of synthetic polymers using analytical Pyroprobe Jayarama Krishna, J. V.; Korobeinichev, Oleg P.; Vinu, R. Journal of Analytical and Applied Pyrolysis, Vol. 139 https://doi.org/10.1016/j.jaap.2019.01.008	journal	May 2019
A review on kinetic study approach for pyrolysis of plastic wastes using thermogravimetric analysis Mortezaeikia, Vahid; Tavakoli, Omid; Khodaparasti, Mohammad Saleh Journal of Analytical and Applied Pyrolysis, Vol. 160 https://doi.org/10.1016/j.jaap.2021.105340	journal	November 2021
Pyrolysis of electronic waste and their mixtures: Kinetic and pyrolysate composition studies Krishna, J. V. Jayarama; Damir, Suyash S.; Vinu, R. Journal of Environmental Chemical Engineering, Vol. 9, Issue 4 https://doi.org/10.1016/j.jece.2021.105382	journal	August 2021
Heterogeneous Diels–Alder tandem catalysis for converting cellulose and polyethylene into BTX Wang, Jia; Jiang, Jianchun; Sun, Yunjuan Journal of Hazardous Materials, Vol. 414 https://doi.org/10.1016/j.jhazmat.2021.125418	journal	July 2021
Pyrolysis of poly(ethylene terephthalate) in a fluidised bed plant Yoshioka, Toshiaki; Grause, Guido; Eger, Christian Polymer Degradation and Stability, Vol. 86, Issue 3 https://doi.org/10.1016/j.polymdegradstab.2004.06.001	journal	December 2004
Catalytic cracking of low-density polyethylene over H-Beta and HZSM-5 zeolites: Influence of the external surface. Kinetic model Marcilla, A.; Gómez-Siurana, A.; Valdés, F. Polymer Degradation and Stability, Vol. 92, Issue 2 https://doi.org/10.1016/j.polymdegradstab.2006.11.007	journal	February 2007
Pyrolysis and combustion of polymer mixtures: Exploring additivity of the heat release rate Snegirev, A. Yu.; Handawy, M. Koraiem; Stepanov, V. V. Polymer Degradation and Stability, Vol. 161 https://doi.org/10.1016/j.polymdegradstab.2019.01.037	journal	March 2019
Catalytic pyrolysis of polyoleﬁn and multilayer packaging based waste plastics: A pilot scale study Sivagami, Krishnasamy; Divyapriya, Govindaraj; Selvaraj, Ramya Process Safety and Environmental Protection, Vol. 149 https://doi.org/10.1016/j.psep.2020.10.038	journal	May 2021
Thermochemical routes for the valorization of waste polyolefinic plastics to produce fuels and chemicals. A review Lopez, Gartzen; Artetxe, Maite; Amutio, Maider Renewable and Sustainable Energy Reviews, Vol. 73 https://doi.org/10.1016/j.rser.2017.01.142	journal	June 2017
Mechanical and chemical recycling of solid plastic waste Ragaert, Kim; Delva, Laurens; Van Geem, Kevin Waste Management, Vol. 69 https://doi.org/10.1016/j.wasman.2017.07.044	journal	November 2017
Plastic flexible films waste management – A state of art review Horodytska, O.; Valdés, F. J.; Fullana, A. Waste Management, Vol. 77 https://doi.org/10.1016/j.wasman.2018.04.023	journal	July 2018
Real time monitoring of slow pyrolysis of polyethylene terephthalate (PET) by different mass spectrometric techniques Dhahak, Asma; Grimmer, Christoph; Neumann, Anika Waste Management, Vol. 106 https://doi.org/10.1016/j.wasman.2020.03.028	journal	April 2020
Conversion of Polyethylene Terephthalate Based Waste Carpet to Benzene-Rich Oils through Thermal, Catalytic, and Catalytic Steam Pyrolysis Du, Shoucheng; Valla, Julia A.; Parnas, Richard S. ACS Sustainable Chemistry & Engineering, Vol. 4, Issue 5 https://doi.org/10.1021/acssuschemeng.6b00450	journal	April 2016
LESS BENZENE IN GASOLINE: AIR POLLUTION: EPA rule aims to cut toxic emissions from cars Hogue, Cheryl Chemical & Engineering News Archive, Vol. 85, Issue 8 https://doi.org/10.1021/cen-v085n008.p008a	journal	February 2007
Propane Dehydrogenation over Pt/TiO ₂ –Al ₂ O ₃ Catalysts Jiang, Feng; Zeng, Liang; Li, Shuirong ACS Catalysis, Vol. 5, Issue 1 https://doi.org/10.1021/cs501279v	journal	November 2014
Conceptual Frame Rationalizing the Self-Stabilization of H-USY Zeolites in Hot Liquid Water Ennaert, Thijs; Geboers, Jan; Gobechiya, Elena ACS Catalysis, Vol. 5, Issue 2 https://doi.org/10.1021/cs501559s	journal	December 2014
Influence of the Operating Variables on the Catalytic Conversion of a Polyolefin Mixture over HMCM-41 and Nanosized HZSM-5 Aguado, J.; Serrano, D. P.; Sotelo, J. L. Industrial & Engineering Chemistry Research, Vol. 40, Issue 24 https://doi.org/10.1021/ie010420c	journal	November 2001
Operating Conditions for the Pyrolysis of Poly-(ethylene terephthalate) in a Conical Spouted-Bed Reactor Artetxe, Maite; Lopez, Gartzen; Amutio, Maider Industrial & Engineering Chemistry Research, Vol. 49, Issue 5 https://doi.org/10.1021/ie900557c	journal	January 2010
Catalytic Degradation of High-Density Polyethylene over Different Zeolitic Structures Manos, George; Garforth, Arthur; Dwyer, John Industrial & Engineering Chemistry Research, Vol. 39, Issue 5 https://doi.org/10.1021/ie990512q	journal	March 2000
Chemistry of Polycyclic Aromatic Hydrocarbons Formation from Phenyl Radical Pyrolysis and Reaction of Phenyl and Acetylene Comandini, A.; Malewicki, T.; Brezinsky, K. The Journal of Physical Chemistry A, Vol. 116, Issue 10 https://doi.org/10.1021/jp207461a	journal	March 2012
Towards a better understanding of Lewis acidic aluminium in zeolites Ravi, Manoj; Sushkevich, Vitaly L.; van Bokhoven, Jeroen A. Nature Materials, Vol. 19, Issue 10 https://doi.org/10.1038/s41563-020-0751-3	journal	September 2020
Atomistics of pre-nucleation layering of liquid metals at the interface with poor nucleants Ma, Sida; Brown, Adam J.; Yan, Rui Communications Chemistry, Vol. 2, Issue 1 https://doi.org/10.1038/s42004-018-0104-1	journal	January 2019
Formation of 2- and 1-methyl-1,4-dihydronaphthalene isomers via the crossed beam reactions of phenyl radicals (C ₆ H ₅ ) with isoprene (CH ₂ C(CH ₃ )CHCH ₂ ) and 1,3-pentadiene (CH ₂ CHCHCHCH ₃ ) Yang, Tao; Muzangwa, Lloyd; Parker, Dorian S. N. Physical Chemistry Chemical Physics, Vol. 17, Issue 1 https://doi.org/10.1039/C4CP04612A	journal	January 2015
Conversion of methoxy and hydroxyl functionalities of phenolic monomers over zeolites Thilakaratne, Rajeeva; Tessonnier, Jean-Philippe; Brown, Robert C. Green Chemistry, Vol. 18, Issue 7 https://doi.org/10.1039/C5GC02548F	journal	January 2016
Synthesis of high-density jet fuel from plastics via catalytically integral processes Zhang, Xuesong; Lei, Hanwu RSC Advances, Vol. 6, Issue 8 https://doi.org/10.1039/C5RA25327F	journal	January 2016
Phenyl radical + propene: a prototypical reaction surface for aromatic-catalyzed 1,2-hydrogen-migration and subsequent resonance-stabilized radical formation Buras, Zachary J.; Chu, Te-Chun; Jamal, Adeel Physical Chemistry Chemical Physics, Vol. 20, Issue 19 https://doi.org/10.1039/C8CP01159A	journal	January 2018
Application of highly stable biochar catalysts for efficient pyrolysis of plastics: a readily accessible potential solution to a global waste crisis Wang, Chenxi; Lei, Hanwu; Qian, Moriko Sustainable Energy & Fuels, Vol. 4, Issue 9 https://doi.org/10.1039/D0SE00652A	journal	January 2020
Zeolite shape selectivity impact on LDPE and PP catalytic pyrolysis products and coke nature Hasan, Md M.; Batalha, Nuno; Fraga, Gabriel Sustainable Energy & Fuels, Vol. 6, Issue 6 https://doi.org/10.1039/D2SE00146B	journal	January 2022
Octane Rating of Gasoline and Octane Booster Additives Demirbas, A.; Balubaid, M. A.; Basahel, A. M. Petroleum Science and Technology, Vol. 33, Issue 11 https://doi.org/10.1080/10916466.2015.1050506	journal	June 2015
Pyrolysis of polyethylene terephthalate containing real waste plastics using Ni loaded zeolite catalysts Al-asadi, M.; Miskolczi, N. IOP Conference Series: Earth and Environmental Science, Vol. 154 https://doi.org/10.1088/1755-1315/154/1/012021	journal	May 2018
Production, use, and fate of all plastics ever made Geyer, Roland; Jambeck, Jenna R.; Law, Kara Lavender Science Advances, Vol. 3, Issue 7 https://doi.org/10.1126/sciadv.1700782	journal	July 2017
Catalytic pyrolysis of low density polyethylene over H-β, H-Y, H-Mordenite, and H-Ferrierite zeolite catalysts: Influence of acidity and structures Agullo, J.; Kumar, N.; Berenguer, D. Kinetics and Catalysis, Vol. 48, Issue 4 https://doi.org/10.1134/S002315840704009X	journal	July 2007
Catalytic Pyrolysis of Polyethylene Terephthalate Over Desilicated Beta Lee, Heejin; Kim, Young-Min; Jung, Sang-Chul Journal of Nanoscience and Nanotechnology, Vol. 20, Issue 9 https://doi.org/10.1166/jnn.2020.17636	journal	September 2020
Thermo-catalytic degradation of different consumer plastic wastes by zeolite a catalyst: A kinetic approach Patnaik, Sthitapragyan; Barick, Aruna Kumar; Panda, Achyut K. Progress in Rubber, Plastics and Recycling Technology, Vol. 37, Issue 2 https://doi.org/10.1177/1477760620972407	journal	November 2020
Catalytic Fast Pyrolysis of Poly (Ethylene Terephthalate) (PET) with Zeolite and Nickel Chloride Jia, Hang; Ben, Haoxi; Luo, Ying Polymers, Vol. 12, Issue 3 https://doi.org/10.3390/polym12030705	journal	March 2020

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