Molten-Phase Unsaturation Enhanced Pyrolytic Upcycling of Polyolefins

Radhakrishnan, Harish; Cecon, Victor Sanfins; A., Lusi; Islam, Md Kaviul; Coffman, Isabel; Vorst, Keith; Bai, Xianglan

doi:10.1021/acs.energyfuels.4c02481

Molten-Phase Unsaturation Enhanced Pyrolytic Upcycling of Polyolefins

Journal Article · Thu Aug 15 00:00:00 EDT 2024 · Energy and Fuels

DOI:https://doi.org/10.1021/acs.energyfuels.4c02481· OSTI ID:3020474

^[1]; Cecon, Victor Sanfins ^[1]; ^[1]; Islam, Md Kaviul ^[1]; Coffman, Isabel ^[1]; Vorst, Keith ^[1]; ^[1]

Iowa State University, Ames, IA (United States)

Fast pyrolysis is a robust deconstruction technology for chemically upcycling waste plastics without losing significant carbon to noncondensable gases. However, fast pyrolysis of polyolefins often produces hydrocarbons with broad molecular weight distributions, mainly waxes, which can also negatively affect the commercial reactor operation and downstream upgrading of the products. We discovered that combining molten-phase thermal treatment with subsequent fast pyrolysis offers a facile method to enhance polyolefin pyrolysis and catalytic upgrading. The molten-phase thermal treatment increased unsaturated C–C bonds in the treated polyolefins. During subsequent pyrolysis, the preheated polyolefins significantly reduced wax range hydrocarbons in the condensable products without an increase in gas formation. Here, the wax yields from pyrolysis of high-density polyethylene (HDPE) preheated to 295 °C and low-density polyethylene (LDPE) preheated to 275 °C were 20.5% and 26.5%, respectively, compared to 38.6% and 46% produced from pyrolyzing untreated polyolefins. When catalytically pyrolyzed using a zeolite catalyst, the preheated polyolefins promoted higher yields of olefins during ex-situ catalytic pyrolysis and higher yields of aromatic hydrocarbons during in-situ catalytic pyrolysis. During ex-situ catalytic pyrolysis, ethylene yields were 23.3% and 24.7% for the preheated HDPE and LDPE compared to 16.7% and 9.3% for untreated HDPE and LDPE, respectively.

View Accepted Manuscript (DOE)

Research Organization:: Iowa State University, Ames, IA (United States); University of Wisconsin, Madison, WI (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Bioenergy Technologies Office (BETO)

Grant/Contract Number:: EE0009285

OSTI ID:: 3020474

Journal Information:: Energy and Fuels, Journal Name: Energy and Fuels Journal Issue: 17 Vol. 38; ISSN 1520-5029; ISSN 0887-0624

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (50)

Feedstock Recycling and Pyrolysis of Waste Plastics: Converting Waste Plastics into Diesel and Other Fuels Scheirs, John; Kaminsky, Walter https://doi.org/10.1002/0470021543	book	March 2006
Polyethylene Incorporating Diels–Alder Comonomers: A “Trojan Horse” Strategy for Chemically Recyclable Polyolefins Parke, Sarah M.; Lopez, Jaqueline C.; Cui, Shilin Angewandte Chemie International Edition, Vol. 62, Issue 30 https://doi.org/10.1002/anie.202301927	journal	June 2023
Thermal degradation of polyethylene in a nitrogen atmosphere of low oxygen content. II. Structural changes occuring in low-density polyethylene at an oxygen content less than 0.0005% Holmström, Arne; Sörvik, Erling M. Journal of Applied Polymer Science, Vol. 18, Issue 3 https://doi.org/10.1002/app.1974.070180314	journal	March 1974
The Chemistry and Kinetics of Polyethylene Pyrolysis: A Process to Produce Fuels and Chemicals Zhao, Dongting; Wang, Xianhua; Miller, James B. ChemSusChem, Vol. 13, Issue 7 https://doi.org/10.1002/cssc.201903434	journal	February 2020
The Effect of Polymer Structures on Complete Degradation: A First‐Principles Study Zhu, Yu; Zhang, Depeng; Zhang, Zhanwen ChemistryOpen, Vol. 7, Issue 6 https://doi.org/10.1002/open.201800078	journal	June 2018
Pyrolysis of polyolefins Wall, Leo A.; Straus, Sidney Journal of Polymer Science, Vol. 44, Issue 144 https://doi.org/10.1002/pol.1960.1204414404	journal	June 1960
Calculation of activation energy from fraction of bonds broken for thermal degradation of polyethylene Gao, Zhiming; Amasaki, Iwao; Kaneko, Tsuyoshi Polymer Degradation and Stability, Vol. 81, Issue 1 https://doi.org/10.1016/S0141-3910(03)00081-8	journal	January 2003
Thermal decomposition of cross-linked polybutadiene and its copolymers Jiang, David D.; Levchik, Galina F.; Levchik, Sergei V. Polymer Degradation and Stability, Vol. 65, Issue 3 https://doi.org/10.1016/S0141-3910(99)00027-0	journal	September 1999
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
Effect of the temperature in the nature and extension of the primary and secondary reactions in the thermal and HZSM-5 catalytic pyrolysis of HDPE Hernández, Ma del Remedio; Gómez, Amparo; García, Ángela N. Applied Catalysis A: General, Vol. 317, Issue 2 https://doi.org/10.1016/j.apcata.2006.10.017	journal	February 2007
Thermal and catalytic pyrolysis of polyethylene over HZSM5 and HUSY zeolites in a batch reactor under dynamic conditions Marcilla, A.; Beltrán, M. I.; Navarro, R. Applied Catalysis B: Environmental, Vol. 86, Issue 1-2 https://doi.org/10.1016/j.apcatb.2008.07.026	journal	February 2009
Catalytic conversion of model compounds of plastic pyrolysis oil over ZSM-5 Dong, Son; Li, Houqian; Bloede, Iris K. Applied Catalysis B: Environmental, Vol. 324 https://doi.org/10.1016/j.apcatb.2022.122219	journal	May 2023
Modelling plastic heating and melting in a semi-batch pyrolysis reactor Mazloum, Shawki; Awad, Sary; Allam, Nadine Applied Energy, Vol. 283 https://doi.org/10.1016/j.apenergy.2020.116375	journal	February 2021
Influence of time and temperature on pyrolysis of plastic wastes in a semi-batch reactor López, A.; de Marco, I.; Caballero, B. M. Chemical Engineering Journal, Vol. 173, Issue 1 https://doi.org/10.1016/j.cej.2011.07.037	journal	September 2011
A review on pyrolysis of plastic wastes Anuar Sharuddin, Shafferina Dayana; Abnisa, Faisal; Wan Daud, Wan Mohd Ashri Energy Conversion and Management, Vol. 115 https://doi.org/10.1016/j.enconman.2016.02.037	journal	May 2016
Parametric study on catalytic cracking of LDPE to liquid fuel over ZSM-5 zeolite Wong, S. L.; Tuan Abdullah, T. A.; Ngadi, N. Energy Conversion and Management, Vol. 122 https://doi.org/10.1016/j.enconman.2016.06.009	journal	August 2016
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
Pyrolysis of plastic wastes in a fountain confined conical spouted bed reactor: Determination of stable operating conditions Orozco, Santiago; Alvarez, Jon; Lopez, Gartzen Energy Conversion and Management, Vol. 229 https://doi.org/10.1016/j.enconman.2020.113768	journal	February 2021
The effect of thermal aging on the composition of pyrolysis oil fuel derived from typical waste plastics Song, Jiaxing; Sun, Kai; Huang, Qunxing Fuel Processing Technology, Vol. 218 https://doi.org/10.1016/j.fuproc.2021.106862	journal	July 2021
Thermal and catalytic pyrolysis of crosslinked polyethylene Marcilla, A.; Ruiz-Femenia, R.; Hernández, J. Journal of Analytical and Applied Pyrolysis, Vol. 76, Issue 1-2 https://doi.org/10.1016/j.jaap.2005.12.004	journal	June 2006
Catalytical and thermal pyrolysis of polyolefins Kaminsky, Walter; Zorriqueta, Ignacio-Javier Nuñez Journal of Analytical and Applied Pyrolysis, Vol. 79, Issue 1-2 https://doi.org/10.1016/j.jaap.2006.11.005	journal	May 2007
Characterization of the waxes obtained by the pyrolysis of polyolefin plastics in a conical spouted bed reactor Arabiourrutia, M.; Elordi, G.; Lopez, G. Journal of Analytical and Applied Pyrolysis, Vol. 94 https://doi.org/10.1016/j.jaap.2011.12.012	journal	March 2012
Pyrolysis of plastic waste: Opportunities and challenges Qureshi, Muhammad Saad; Oasmaa, Anja; Pihkola, Hanna Journal of Analytical and Applied Pyrolysis, Vol. 152 https://doi.org/10.1016/j.jaap.2020.104804	journal	November 2020
Gaseous products from primary reactions of fast plastic pyrolysis No authors listed Journal of Analytical and Applied Pyrolysis, Vol. 158 https://doi.org/10.1016/j.jaap.2021.105248	journal	September 2021
Liquid-fed waste plastic pyrolysis pilot plant: Effect of reactor volume on product yields Kulas, Daniel G.; Zolghadr, Ali; Shonnard, David R. Journal of Analytical and Applied Pyrolysis, Vol. 166 https://doi.org/10.1016/j.jaap.2022.105601	journal	September 2022
Pyrolysis of waste high density polyethylene (HDPE) and low density polyethylene (LDPE) plastics and production of epoxy composites with their pyrolysis chars Sogancioglu, Merve; Yel, Esra; Ahmetli, Gulnare Journal of Cleaner Production, Vol. 165 https://doi.org/10.1016/j.jclepro.2017.07.157	journal	November 2017
Conversion of low-density polyethylene into monocyclic aromatic hydrocarbons by catalytic pyrolysis: Comparison of HZSM-5, Hβ, HY and MCM-41 Tian, Xiaojie; Zeng, Zihong; Liu, Zhihao Journal of Cleaner Production, Vol. 358 https://doi.org/10.1016/j.jclepro.2022.131989	journal	July 2022
A review on thermal and catalytic pyrolysis of plastic solid waste (PSW) Al-Salem, S. M.; Antelava, A.; Constantinou, A. Journal of Environmental Management, Vol. 197 https://doi.org/10.1016/j.jenvman.2017.03.084	journal	July 2017
Challenges and opportunities of light olefin production via thermal and catalytic pyrolysis of end-of-life polyolefins: Towards full recyclability Abbas-Abadi, Mehrdad Seifali; Ureel, Yannick; Eschenbacher, Andreas Progress in Energy and Combustion Science, Vol. 96 https://doi.org/10.1016/j.pecs.2022.101046	journal	May 2023
Changes during the weathering of polyolefins Grause, Guido; Chien, Mei-Fang; Inoue, Chihiro Polymer Degradation and Stability, Vol. 181 https://doi.org/10.1016/j.polymdegradstab.2020.109364	journal	November 2020
The influence of the recycling stress history on LDPE waste pyrolysis Duque, João Vitor F.; Martins, Márcio F.; Debenest, Gérald Polymer Testing, Vol. 86 https://doi.org/10.1016/j.polymertesting.2020.106460	journal	June 2020
Catalytic pyrolysis of plastic waste: A review Miandad, R.; Barakat, M. A.; Aburiazaiza, Asad S. Process Safety and Environmental Protection, Vol. 102 https://doi.org/10.1016/j.psep.2016.06.022	journal	July 2016
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
Morphological characteristics of waste polyethylene/polypropylene plastics during pyrolysis and representative morphological signal characterizing pyrolysis stages Wang, H.; Chen, D.; Yuan, G. Waste Management, Vol. 33, Issue 2 https://doi.org/10.1016/j.wasman.2012.10.013	journal	February 2013
Wax Recovery from the Pyrolysis of Virgin and Waste Plastics Al-Salem, Sultan Majed; Dutta, Animesh Industrial & Engineering Chemistry Research, Vol. 60, Issue 22 https://doi.org/10.1021/acs.iecr.1c01176	journal	May 2021
Evaluation of Pyrolysis Wax as a Solvent in Polyolefin Pyrolysis Processing Zolghadr, Ali; Kulas, Daniel; Shonnard, David Industrial & Engineering Chemistry Research, Vol. 61, Issue 30 https://doi.org/10.1021/acs.iecr.2c01493	journal	July 2022
Effect of Temperature and Vapor Residence Time on the Micropyrolysis Products of Waste High Density Polyethylene Gracida-Alvarez, Ulises R.; Mitchell, Mary Kate; Sacramento-Rivero, Julio C. Industrial & Engineering Chemistry Research, Vol. 57, Issue 6 https://doi.org/10.1021/acs.iecr.7b04362	journal	February 2018
Homogeneous Catalysis in Plastic Waste Upcycling: A DFT Study on the Role of Imperfections in Polymer Chains Kolganov, Alexander A.; Sreenithya, A.; Pidko, Evgeny A. ACS Catalysis, Vol. 13, Issue 20 https://doi.org/10.1021/acscatal.3c03269	journal	October 2023
Study of the Viscosity and Thermal Characteristics of Polyolefins/Solvent Mixtures: Applications for Plastic Pyrolysis Zolghadr, Ali; Foroozandehfar, Azarnoosh; Kulas, Daniel G. ACS Omega, Vol. 6, Issue 48 https://doi.org/10.1021/acsomega.1c04809	journal	November 2021
Micropyrolysis of Polyethylene and Polypropylene Prior to Bioconversion: The Effect of Reactor Temperature and Vapor Residence Time on Product Distribution Kulas, Daniel G.; Zolghadr, Ali; Shonnard, David ACS Sustainable Chemistry & Engineering, Vol. 9, Issue 43 https://doi.org/10.1021/acssuschemeng.1c04705	journal	October 2021
Melt Processing Pretreatment Effects on Enzymatic Depolymerization of Poly(ethylene terephthalate) Patel, Akanksha; Chang, Allen C.; Perry, Sarah ACS Sustainable Chemistry & Engineering, Vol. 10, Issue 41 https://doi.org/10.1021/acssuschemeng.2c03142	journal	October 2022
Wax Formation in the Pyrolysis of Polyolefins in a Conical Spouted Bed Reactor Aguado, Roberto; Olazar, Martín; San José,, María J. Energy & Fuels, Vol. 16, Issue 6 https://doi.org/10.1021/ef020043w	journal	November 2002
Product Yields and Compositions in the Continuous Pyrolysis of High-Density Polyethylene in a Conical Spouted Bed Reactor Elordi, Gorka; Olazar, Martin; Lopez, Gartzen Industrial & Engineering Chemistry Research, Vol. 50, Issue 11 https://doi.org/10.1021/ie200186m	journal	April 2011
Cracking of High Density Polyethylene Pyrolysis Waxes on HZSM-5 Catalysts of Different Acidity Artetxe, Maite; Lopez, Gartzen; Amutio, Maider Industrial & Engineering Chemistry Research, Vol. 52, Issue 31 https://doi.org/10.1021/ie4014869	journal	July 2013
Chemically Recyclable Ester-Linked Polypropylene Kocen, Andrew L.; Cui, Shilin; Lin, Ting-Wei Journal of the American Chemical Society, Vol. 144, Issue 28 https://doi.org/10.1021/jacs.2c04499	journal	July 2022
Monomer recovery through advanced pyrolysis of waste high density polyethylene (HDPE) Diaz-Silvarrey, Laura S.; Zhang, Kui; Phan, Anh N. Green Chemistry, Vol. 20, Issue 8 https://doi.org/10.1039/C7GC03662K	journal	January 2018
Expanding plastics recycling technologies: chemical aspects, technology status and challenges Li, Houqian; Aguirre-Villegas, Horacio A.; Allen, Robert D. Green Chemistry, Vol. 24, Issue 23 https://doi.org/10.1039/D2GC02588D	journal	January 2022
Applications and societal benefits of plastics Andrady, Anthony L.; Neal, Mike A. Philosophical Transactions of the Royal Society B: Biological Sciences, Vol. 364, Issue 1526 https://doi.org/10.1098/rstb.2008.0304	journal	July 2009
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
Plastic waste inputs from land into the ocean Jambeck, J. R.; Geyer, R.; Wilcox, C. Science, Vol. 347, Issue 6223 https://doi.org/10.1126/science.1260352	journal	February 2015

Similar Records

Catalytic Upgrading of Pyrolysis Condensables from Postconsumer Polyolefins Using HZSM-5

Journal Article · Mon Oct 14 20:00:00 EDT 2024 · Energy and Fuels · OSTI ID:2510458

The Effects of Polyolefin Structure and Source on Pyrolysis-Derived Plastic Oil Composition

Journal Article · Tue Oct 29 20:00:00 EDT 2024 · Green Chemistry · OSTI ID:2475641

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

Journal Article · Wed Jun 29 20:00:00 EDT 2022 · Reaction Chemistry & Engineering · OSTI ID:1978907

Related Subjects

Aromatic compounds
Catalysts
Hydrocarbons
Plastics
Pyrolysis

Molten-Phase Unsaturation Enhanced Pyrolytic Upcycling of Polyolefins

Citation Formats

References (50)

Linked Research (1)

Similar Records

Related Subjects