Low-temperature upcycling of polyolefins into liquid alkanes via tandem cracking-alkylation

Zhang, Wei; Kim, Sungmin; Wahl, Lennart; Khare, Rachit; Hale, Lillian; Hu, Jianzhi; Camaioni, Donald M.; Gutiérrez, Oliver Y.; Liu, Yue; Lercher, Johannes A.

doi:10.1126/science.ade7485

Low-temperature upcycling of polyolefins into liquid alkanes via tandem cracking-alkylation

Journal Article · Thu Feb 23 00:00:00 EST 2023 · Science

DOI:https://doi.org/10.1126/science.ade7485· OSTI ID:1964044

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Technische University, Garching (Germany)
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States). Institute for Integrated Catalysis
Technische University, Garching (Germany); East China Normal University (ECNU), Shanghai (China)
Technische University, Garching (Germany); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States). Institute for Integrated Catalysis

Selective upcycling of polyolefin waste has been hampered by the relatively high temperatures that are required to cleave the carbon-carbon (C–C) bonds at reasonably high rates. We present a distinctive approach that uses a highly ionic reaction environment to increase the polymer reactivity and lower the energy of ionic transition states. Combining endothermic cleavage of the polymer C–C bonds with exothermic alkylation reactions of the cracking products enables full conversion of polyethylene and polypropylene to liquid isoalkanes (C₆ to C₁₀) at temperatures below 100°C. Both reactions are catalyzed by a Lewis acidic species that is generated in a chloroaluminate ionic liquid. The alkylate product forms a separate phase and is easily separated from the reactant catalyst mixture. The process can convert unprocessed postconsumer items to high-quality liquid alkanes with high yields.

View Accepted Manuscript (DOE)

Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 1964044

Report Number(s):: PNNL-SA-179736

Journal Information:: Science, Journal Name: Science Journal Issue: 6634 Vol. 379; ISSN 0036-8075

Publisher:: AAASCopyright Statement

Country of Publication:: United States

Language:: English

References (46)

Ionic Liquid Analogs of AlCl ₃ with Urea Derivatives as Electrolytes for Aluminum Batteries Angell, Michael; Zhu, Guanzhou; Lin, Meng‐Chang Advanced Functional Materials, Vol. 30, Issue 4 https://doi.org/10.1002/adfm.201901928	journal	October 2019
Liquid Coordination Complexes Formed by the Heterolytic Cleavage of Metal Halides Coleman, Fergal; Srinivasan, Geetha; Swadźba-Kwaśny, Małgorzata Angewandte Chemie International Edition, Vol. 52, Issue 48 https://doi.org/10.1002/anie.201306267	journal	October 2013
Beyond Mechanical Recycling: Giving New Life to Plastic Waste Vollmer, Ina; Jenks, Michael J. F.; Roelands, Mark C. P. Angewandte Chemie International Edition, Vol. 59, Issue 36 https://doi.org/10.1002/anie.201915651	journal	June 2020
Influence of Intracrystalline Ionic Strength in MFI Zeolites on Aqueous Phase Dehydration of Methylcyclohexanols Milaković, Lara; Hintermeier, Peter H.; Liu, Yue Angewandte Chemie International Edition, Vol. 60, Issue 47 https://doi.org/10.1002/anie.202107947	journal	September 2021
Catalytic Hydrocracking-Mechanisms and Versatility of the Process Weitkamp, Jens ChemCatChem, Vol. 4, Issue 3 https://doi.org/10.1002/cctc.201100315	journal	February 2012
The Use of Heterogeneous Catalysis in the Chemical Valorization of Plastic Waste Mark, Lesli O.; Cendejas, Melissa C.; Hermans, Ive ChemSusChem, Vol. 13, Issue 22 https://doi.org/10.1002/cssc.202001905	journal	October 2020
Mechanical Recycling of Packaging Plastics: A Review Schyns, Zoé O. G.; Shaver, Michael P. Macromolecular Rapid Communications, Vol. 42, Issue 3 https://doi.org/10.1002/marc.202000415	journal	September 2020
ISOALKY™ Technology: Next-Generation Alkylate Gasoline Manufacturing Process Technology Using Ionic Liquid Catalyst Timken, Hye Kyung; Luo, Huping; Chang, Bong-Kyu Green Chemistry and Sustainable Technology https://doi.org/10.1007/978-3-030-35245-5_2	book	January 2020
Liquid-Phase Isobutane/Butene-Alkylation Using Promoted Lewis-Acidic IL-Catalysts Aschauer, Stephan; Schilder, Lisa; Korth, Wolfgang Catalysis Letters, Vol. 141, Issue 10 https://doi.org/10.1007/s10562-011-0675-2	journal	August 2011
Lewis Acidic Ionic Liquids Brown, Lucy C.; Hogg, James M.; Swadźba-Kwaśny, Małgorzata Topics in Current Chemistry, Vol. 375, Issue 5 https://doi.org/10.1007/s41061-017-0166-z	journal	August 2017
Alkylation of isobutane with 2-butene using 1-butyl-3-methylimidazolium chloride—aluminium chloride molten salts as catalysts Chauvin, Yves; Hirschauer, André; Olivier, Hélène Journal of Molecular Catalysis, Vol. 92, Issue 2 https://doi.org/10.1016/0304-5102(94)00065-4	journal	August 1994
Common mechanistic aspects of liquid and solid acid catalyzed alkylation of isobutane with n -butene Feller, Andreas; Zuazo, Iker; Guzman, Alexander Journal of Catalysis, Vol. 216, Issue 1-2 https://doi.org/10.1016/S0021-9517(02)00068-4	journal	May 2003
Chemistry and Technology of Isobutane/Alkene Alkylation Catalyzed by Liquid and Solid Acids Feller, Andreas; Lercher, Johannes A. Advances in Catalysis, Vol. 48, p. 229-295 https://doi.org/10.1016/S0360-0564(04)48003-1	book	July 2004
Catalytic processing of plastic waste on the rise Martín, Antonio J.; Mondelli, Cecilia; Jaydev, Shibashish D. Chem, Vol. 7, Issue 6 https://doi.org/10.1016/j.chempr.2020.12.006	journal	June 2021
Promotion of protolytic pentane conversion on H-MFI zeolite by proximity of extra-framework aluminum oxide and Brønsted acid sites Zhang, Yang; Zhao, Ruixue; Sanchez-Sanchez, Maricruz Journal of Catalysis, Vol. 370 https://doi.org/10.1016/j.jcat.2019.01.006	journal	February 2019
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
Variable Temperature and Pressure Operando MAS NMR for Catalysis Science and Related Materials Jaegers, Nicholas R.; Mueller, Karl T.; Wang, Yong Accounts of Chemical Research, Vol. 53, Issue 3 https://doi.org/10.1021/acs.accounts.9b00557	journal	January 2020
Acidic Ionic Liquids Amarasekara, Ananda S. Chemical Reviews, Vol. 116, Issue 10 https://doi.org/10.1021/acs.chemrev.5b00763	journal	May 2016
Characterization and Hydrogenation Removal of Acid-Soluble Oil in Ionic Liquid Catalysts for Isobutane Alkylation Li, Yaxing; Zhang, Rui; Meng, Xianghai Industrial & Engineering Chemistry Research, Vol. 60, Issue 38 https://doi.org/10.1021/acs.iecr.1c02376	journal	September 2021
Structural and Spectroscopic Characterizations of Amide–AlCl ₃ -Based Ionic Liquid Analogues Hu, Pengcheng; Zhang, Rui; Meng, Xianghai Inorganic Chemistry, Vol. 55, Issue 5 https://doi.org/10.1021/acs.inorgchem.5b02744	journal	February 2016
Group IIIA Halometallate Ionic Liquids: Speciation and Applications in Catalysis Kore, Rajkumar; Berton, Paula; Kelley, Steven P. ACS Catalysis, Vol. 7, Issue 10 https://doi.org/10.1021/acscatal.7b01793	journal	September 2017
Alkane Cross-Metathesis Reaction between Light and Heavy Linear Alkanes, on a Silica Supported Well-Defined Single-Site Catalyst Morlanés, Natalia; Kavitake, Santosh G.; Rosenfeld, Devon C. ACS Catalysis, Vol. 9, Issue 2 https://doi.org/10.1021/acscatal.8b02472	journal	December 2018
Upcycling Single-Use Polyethylene into High-Quality Liquid Products Celik, Gokhan; Kennedy, Robert M.; Hackler, Ryan A. ACS Central Science, Vol. 5, Issue 11 https://doi.org/10.1021/acscentsci.9b00722	journal	September 2019
Room-Temperature Ionic Liquids. Solvents for Synthesis and Catalysis Welton, Thomas Chemical Reviews, Vol. 99, Issue 8, p. 2071-2084 https://doi.org/10.1021/cr980032t	journal	August 1999
Developing Advanced Catalysts for the Conversion of Polyolefinic Waste Plastics into Fuels and Chemicals Serrano, D. P.; Aguado, J.; Escola, J. M. ACS Catalysis, Vol. 2, Issue 9 https://doi.org/10.1021/cs3003403	journal	August 2012
Conversion of Polyolefin Waste to Liquid Alkanes with Ru-Based Catalysts under Mild Conditions Rorrer, Julie E.; Beckham, Gregg T.; Román-Leshkov, Yuriy JACS Au, Vol. 1, Issue 1 https://doi.org/10.1021/jacsau.0c00041	journal	December 2020
Ultra-fast charging in aluminum-ion batteries: electric double layers on active anode Shen, Xuejing; Sun, Tao; Yang, Lei Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-21108-4	journal	February 2021
Chemical recycling to monomer for an ideal, circular polymer economy Coates, Geoffrey W.; Getzler, Yutan D. Y. L. Nature Reviews Materials, Vol. 5, Issue 7 https://doi.org/10.1038/s41578-020-0190-4	journal	April 2020
Catalytic upcycling of high-density polyethylene via a processive mechanism Tennakoon, Akalanka; Wu, Xun; Paterson, Alexander L. Nature Catalysis, Vol. 3, Issue 11 https://doi.org/10.1038/s41929-020-00519-4	journal	October 2020
Chemical and biological catalysis for plastics recycling and upcycling Ellis, Lucas D.; Rorrer, Nicholas A.; Sullivan, Kevin P. Nature Catalysis, Vol. 4, Issue 7 https://doi.org/10.1038/s41929-021-00648-4	journal	July 2021
Halometallate ionic liquids – revisited Estager, J.; Holbrey, J. D.; Swadźba-Kwaśny, M. Chem. Soc. Rev., Vol. 43, Issue 3 https://doi.org/10.1039/C3CS60310E	journal	January 2014
Sealed rotors for in situ high temperature high pressure MAS NMR Hu, Jian Zhi; Hu, Mary Y.; Zhao, Zhenchao Chemical Communications, Vol. 51, Issue 70 https://doi.org/10.1039/C5CC03910J	journal	January 2015
Mixed metal double salt ionic liquids comprised of [HN₂₂₂]₂[ZnCl₄] and AlCl₃ provide tunable Lewis acid catalysts related to the ionic environment Kore, Rajkumar; Kelley, Steven. P.; Aduri, Pavankumar Dalton Transactions, Vol. 47, Issue 23 https://doi.org/10.1039/C8DT00976G	journal	January 2018
Are ionic liquids and liquid coordination complexes really different? – Synthesis, characterization, and catalytic activity of AlCl₃/base catalysts Kore, Rajkumar; Kelley, Steven P.; Sawant, Anand D. Chemical Communications, Vol. 56, Issue 40 https://doi.org/10.1039/D0CC01452D	journal	January 2020
Catalytic methods for chemical recycling or upcycling of commercial polymers Kosloski-Oh, Sophia C.; Wood, Zachary A.; Manjarrez, Yvonne Materials Horizons, Vol. 8, Issue 4 https://doi.org/10.1039/D0MH01286F	journal	January 2021
Catalytic cracking reactions of polyethylene to light alkanes Adams, Christopher J.; Earle, Martyn J.; Seddon, Kenneth R. Green Chemistry, Vol. 2, Issue 1 https://doi.org/10.1039/a908167d	journal	January 2000
Chlorometallate(iii) ionic liquids as Lewis acidic catalysts – a quantitative study of acceptor properties Estager, Julien; Oliferenko, Alexander A.; Seddon, Kenneth R. Dalton Transactions, Vol. 39, Issue 47 https://doi.org/10.1039/c0dt00895h	journal	January 2010
Efficient and selective degradation of polyethylenes into liquid fuels and waxes under mild conditions Jia, Xiangqing; Qin, Chuan; Friedberger, Tobias Science Advances, Vol. 2, Issue 6 https://doi.org/10.1126/sciadv.1501591	journal	June 2016
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 to fuels by hydrocracking at mild conditions Liu, Sibao; Kots, Pavel A.; Vance, Brandon C. Science Advances, Vol. 7, Issue 17 https://doi.org/10.1126/sciadv.abf8283	journal	April 2021
The future of plastics recycling Garcia, Jeannette M.; Robertson, Megan L. Science, Vol. 358, Issue 6365 https://doi.org/10.1126/science.aaq0324	journal	November 2017
Polyethylene upcycling to long-chain alkylaromatics by tandem hydrogenolysis/aromatization Zhang, Fan; Zeng, Manhao; Yappert, Ryan D. Science, Vol. 370, Issue 6515 https://doi.org/10.1126/science.abc5441	journal	October 2020
Tandem In ₂ O ₃ -Pt/Al ₂ O ₃ catalyst for coupling of propane dehydrogenation to selective H ₂ combustion Yan, Huan; He, Kun; Samek, Izabela A. Science, Vol. 371, Issue 6535 https://doi.org/10.1126/science.abd4441	journal	March 2021
Role of the ionic environment in enhancing the activity of reacting molecules in zeolite pores Pfriem, Niklas; Hintermeier, Peter H.; Eckstein, Sebastian Science, Vol. 372, Issue 6545 https://doi.org/10.1126/science.abh3418	journal	May 2021
Chloroaluminate Ionic Liquids: from their Structural Properties to their Applications in Process Intensification Gilbert, B.; Olivier-Bourbigou, H.; Favre, F. Oil & Gas Science and Technology - Revue de l'IFP, Vol. 62, Issue 6 https://doi.org/10.2516/ogst:2007068	journal	November 2007
Electrodeposition of Aluminum in the 1-Ethyl-3-Methylimidazolium Tetrachloroaluminate Ionic Liquid Shi, Meng; Jiang, Junhua; Zhao, Haiyan Electrochem, Vol. 2, Issue 2 https://doi.org/10.3390/electrochem2020013	journal	March 2021

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