Low-temperature dechlorination of polyvinyl chloride (PVC) for production of H2 and carbon materials using liquid metal catalysts

Polo-Garzon, Felipe; Wu, Zili; Li, Yuanyuan; Zhang, Junyan; Yu, Xinbin; Toups, Elena; Lopez-Honorato, Eddie; Damron, Joshua T.; Foster, Jeffrey C.; Cheng, Yongqiang; Daemen, Luke L.; Ramirez-Cuesta, Anibal J.; Meyer III, Harry M.

doi:10.1126/sciadv.adm9963

Low-temperature dechlorination of polyvinyl chloride (PVC) for production of H₂ and carbon materials using liquid metal catalysts

Journal Article · Wed Jul 24 00:00:00 EDT 2024 · Science Advances

DOI:https://doi.org/10.1126/sciadv.adm9963· OSTI ID:2426028

^[1]; ^[2]; ^[1]; Zhang, Junyan ^[1]; Yu, Xinbin ^[1]; ^[3]; ^[1]; ^[1]; ^[1]; ^[1]; Daemen, Luke L. ^[1]; ^[1]; ^[1]

Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
University of New Orleans, LA (United States)

Polyvinyl chloride (PVC) is ubiquitous in everyday life; however, it is not recycled because it degrades uncontrollably into toxic products above 250°C. Therefore, it is of interest to controllably dechlorinate PVC at mild temperatures to generate narrowly distributed carbon materials. We present a catalytic route to dechlorinate PVC (~90% reduction of Cl content) at mild temperature (200°C) to produce gas H₂ (with negligible coproduction of corrosive gas HCl) and carbon materials using Ga as a liquid metal (LM) catalyst. A LM was used to promote intimate contact between PVC and the catalytic sites. During dechlorination of PVC, Cl is sequestrated in the carbonaceous solid product. Later, chlorine is easily removed with an acetone wash at room temperature. The Ga LM catalyst is reusable, outperforms a traditional supported metal catalyst, and successfully converts (untreated) discarded PVC pipe.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC05-00OR22725; SC0012704

OSTI ID:: 2426028

Journal Information:: Science Advances, Journal Name: Science Advances Journal Issue: 30 Vol. 10; ISSN 2375-2548

Publisher:: AAASCopyright Statement

Country of Publication:: United States

Language:: English

References (67)

Highly Reliable Liquid Metal–Solid Metal Contacts with a Corrugated Single‐Walled Carbon Nanotube Diffusion Barrier for Stretchable Electronics Oh, Eunho; Kim, Taehoon; Yoon, Jaeyoung Advanced Functional Materials, Vol. 28, Issue 51 https://doi.org/10.1002/adfm.201806014	journal	October 2018
Stimuli‐Driven Insulator–Conductor Transition in a Flexible Polymer Composite Enabled by Biphasic Liquid Metal Liu, Huaizhi; Xin, Yumeng; Bisoyi, Hari Krishna Advanced Materials, Vol. 33, Issue 43 https://doi.org/10.1002/adma.202104634	journal	September 2021
Liquid‐Metal‐Enabled Mechanical‐Energy‐Induced CO₂ Conversion Tang, Junma; Tang, Jianbo; Mayyas, Mohannad Advanced Materials, Vol. 34, Issue 1 https://doi.org/10.1002/adma.202105789	journal	October 2021
Thermal decomposition study of polyvinyl chloride in the presence of commercially available oxides catalysts Nisar, Jan; Khan, Muhammad Sufaid; Iqbal, Munawar Advances in Polymer Technology, Vol. 37, Issue 6 https://doi.org/10.1002/adv.21909	journal	October 2017
Coke Formation during Propane Dehydrogenation over Ga−Rh Supported Catalytically Active Liquid Metal Solutions Wolf, Moritz; Raman, Narayanan; Taccardi, Nicola ChemCatChem, Vol. 12, Issue 4 https://doi.org/10.1002/cctc.201901922	journal	December 2019
Solid Base Assisted Dual‐Promoted Heterogeneous Conversion of PVC to Metal‐Free Porous Carbon Catalyst Wang, Haobo; Xu, Shumao; Dong, Wujie Chemistry – A European Journal, Vol. 28, Issue 23 https://doi.org/10.1002/chem.202200124	journal	March 2022
Catalytic conversion of waste plastics: focus on waste PVC Keane, Mark A. Journal of Chemical Technology & Biotechnology, Vol. 82, Issue 9 https://doi.org/10.1002/jctb.1757	journal	July 2007
Multifunctional liquid metal polymer composites Guymon, Gregory G.; Malakooti, Mohammad H. Journal of Polymer Science, Vol. 60, Issue 8 https://doi.org/10.1002/pol.20210867	journal	January 2022
Resonance Raman spectroscopy of graphite and graphene: Resonance Raman spectroscopy of graphite and graphene Zólyomi, V.; Koltai, J.; Kürti, J. physica status solidi (b), Vol. 248, Issue 11 https://doi.org/10.1002/pssb.201100295	journal	September 2011
Reversible crosslinking during thermal degradation of PVC Kelen, Tibor; Iván, Béla; Nagy, Tamás Tibor Polymer Bulletin, Vol. 1, Issue 2 https://doi.org/10.1007/BF00255718	journal	September 1978
Kinetics and reaction scheme of coal liquefaction over molten tin catalyst Ozawa, Sentaro; Matsuura, Masafumi; Matsunaga, Shin-ichi Fuel, Vol. 63, Issue 5 https://doi.org/10.1016/0016-2361(84)90175-3	journal	May 1984
Characterisation of PVC/NBR and PVC/ENR50 binary blends and PVC/ENR50/NBR ternary blends by DMA and solid state NMR Senake Perera, M. C.; Ishiaku, U. S.; Mohd. Ishak, Z. A. European Polymer Journal, Vol. 37, Issue 1 https://doi.org/10.1016/S0014-3057(00)00085-9	journal	January 2001
Fourier Transform Infrared Spectroscopy Applied to the Study of pvc Decomposition BeltrÁN, M.; Marcilla, A. European Polymer Journal, Vol. 33, Issue 7 https://doi.org/10.1016/S0014-3057(97)00001-3	journal	July 1997
Thermal degradation of PVC/NBR and PVC/ENR50 binary blends and PVC/ENR50/NBR ternary blends studied by DMA and solid state NMR Perera, M. C. S.; Ishiaku, U. S.; Ishak, Z. A. M. Polymer Degradation and Stability, Vol. 68, Issue 3 https://doi.org/10.1016/S0141-3910(00)00024-0	journal	May 2000
Waste PVC upcycling: Transferring unmanageable Cl species into value-added Cl-containing chemicals Feng, Bo; Jing, Yaxuan; Liu, Xiaohui Applied Catalysis B: Environmental, Vol. 331 https://doi.org/10.1016/j.apcatb.2023.122671	journal	August 2023
Upcycling of polyvinyl chloride to hydrocarbon waxes via dechlorination and catalytic hydrogenation Svadlenak, Scott; Wojcik, Sophie; Ogunlalu, Oluwafemi Applied Catalysis B: Environmental, Vol. 338 https://doi.org/10.1016/j.apcatb.2023.123065	journal	December 2023
ZSM-5 zeolites performance assessment in catalytic pyrolysis of PVC-containing real WEEE plastic wastes Marino, Alessia; Aloise, Alfredo; Hernando, Hector Catalysis Today, Vol. 390-391 https://doi.org/10.1016/j.cattod.2021.11.033	journal	May 2022
Hydrogen production via methane pyrolysis in a liquid metal bubble column reactor with a packed bed Geißler, T.; Abánades, A.; Heinzel, A. Chemical Engineering Journal, Vol. 299 https://doi.org/10.1016/j.cej.2016.04.066	journal	September 2016
Hydrothermal treatment of polyvinyl chloride: Reactors, dechlorination chemistry, application, and challenges Ling, Mengxue; Ma, Dachao; Hu, Xuan Chemosphere, Vol. 316 https://doi.org/10.1016/j.chemosphere.2022.137718	journal	March 2023
A comparison between TGA, SEM-EDX and Raman spectroscopy to assess PVC plasticizer loss Apchain, Emilande; Royaux, Adeline; Fichet, Odile Journal of Cultural Heritage, Vol. 57 https://doi.org/10.1016/j.culher.2022.07.008	journal	September 2022
Thermal cracking of methane in a liquid metal bubble column reactor: Experiments and kinetic analysis Plevan, M.; Geißler, T.; Abánades, A. International Journal of Hydrogen Energy, Vol. 40, Issue 25 https://doi.org/10.1016/j.ijhydene.2015.04.062	journal	July 2015
Experimental investigation and thermo-chemical modeling of methane pyrolysis in a liquid metal bubble column reactor with a packed bed Geißler, T.; Plevan, M.; Abánades, A. International Journal of Hydrogen Energy, Vol. 40, Issue 41 https://doi.org/10.1016/j.ijhydene.2015.08.102	journal	November 2015
Upcycling waste polyvinyl chloride: One-pot synthesis of valuable carbon materials and pipeline-quality syngas via pyrolysis in a closed reactor Zhou, Xiao-Li; He, Pin-Jing; Peng, Wei Journal of Hazardous Materials, Vol. 427 https://doi.org/10.1016/j.jhazmat.2021.128210	journal	April 2022
Liquid Metals in Catalysis for Energy Applications Zuraiqi, Karma; Zavabeti, Ali; Allioux, Francois-Marie Joule, Vol. 4, Issue 11 https://doi.org/10.1016/j.joule.2020.10.012	journal	November 2020
Liquid Metal Composites Chen, Sen; Wang, Hong-Zhang; Zhao, Rui-Qi Matter, Vol. 2, Issue 6 https://doi.org/10.1016/j.matt.2020.03.016	journal	June 2020
Performance evaluation of new plasticizers for stretch PVC films Coltro, Leda; Pitta, Joyce B.; Madaleno, Emerson Polymer Testing, Vol. 32, Issue 2 https://doi.org/10.1016/j.polymertesting.2012.11.009	journal	April 2013
Synthesis of Carbon Materials by the Short-term Mechanochemical Activation of Polyvinyl Chloride Solodovnichenko, V. S.; Polyboyarov, V. A.; Zhdanok, A. A. Procedia Engineering, Vol. 152 https://doi.org/10.1016/j.proeng.2016.07.684	journal	January 2016
First principles phonon calculations in materials science Togo, Atsushi; Tanaka, Isao Scripta Materialia, Vol. 108 https://doi.org/10.1016/j.scriptamat.2015.07.021	journal	November 2015
Upcycling and catalytic degradation of plastic wastes Hou, Qidong; Zhen, Meinan; Qian, Hengli Cell Reports Physical Science, Vol. 2, Issue 8 https://doi.org/10.1016/j.xcrp.2021.100514	journal	August 2021
Simulation of Inelastic Neutron Scattering Spectra Using OCLIMAX Cheng, Y. Q.; Daemen, L. L.; Kolesnikov, A. I. Journal of Chemical Theory and Computation, Vol. 15, Issue 3 https://doi.org/10.1021/acs.jctc.8b01250	journal	January 2019
Three-Dimensional, High-Resolution Printing of Carbon Nanotube/Liquid Metal Composites with Mechanical and Electrical Reinforcement Park, Young-Geun; Min, Hyegi; Kim, Hyobeom Nano Letters, Vol. 19, Issue 8 https://doi.org/10.1021/acs.nanolett.9b00150	journal	April 2019
Methane Pyrolysis with a Molten Cu–Bi Alloy Catalyst Palmer, Clarke; Tarazkar, Maryam; Kristoffersen, Henrik H. ACS Catalysis, Vol. 9, Issue 9 https://doi.org/10.1021/acscatal.9b01833	journal	August 2019
Highly Effective Propane Dehydrogenation Using Ga–Rh Supported Catalytically Active Liquid Metal Solutions Raman, Narayanan; Maisel, Sven; Grabau, Mathias ACS Catalysis, Vol. 9, Issue 10 https://doi.org/10.1021/acscatal.9b02459	journal	September 2019
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
Patterned Liquid Metal Contacts for Printed Carbon Nanotube Transistors Andrews, Joseph B.; Mondal, Kunal; Neumann, Taylor V. ACS Nano, Vol. 12, Issue 6 https://doi.org/10.1021/acsnano.8b00909	journal	May 2018
Chlor-alkali technology Venkatesh, S.; Tilak, B. V. Journal of Chemical Education, Vol. 60, Issue 4 https://doi.org/10.1021/ed060p276	journal	April 1983
Poly(vinyl chloride)/Kaolinite Nanocomposites: Characterization and Thermal and Optical Properties Turhan, Yasemin; Doǧan, Mehmet; Alkan, Mahir Industrial & Engineering Chemistry Research, Vol. 49, Issue 4 https://doi.org/10.1021/ie901384x	journal	January 2010
A Joined Theoretical−Experimental Investigation on the ¹ H and ¹³ C NMR Signatures of Defects in Poly(vinyl chloride) d’Antuono, Philippe; Botek, Edith; Champagne, Benoît The Journal of Physical Chemistry B, Vol. 112, Issue 47 https://doi.org/10.1021/jp805676q	journal	November 2008
Probing Defect Sites on CeO ₂ Nanocrystals with Well-Defined Surface Planes by Raman Spectroscopy and O ₂ Adsorption ^† Wu, Zili; Li, Meijun; Howe, Jane Langmuir, Vol. 26, Issue 21 https://doi.org/10.1021/la101723w	journal	November 2010
Compositional Assignments for Chemically Modified PVC by Two-Dimensional NMR Spectroscopy Mijangos, Carmen; Lopez, Daniel Macromolecules, Vol. 28, Issue 5 https://doi.org/10.1021/ma00109a006	journal	February 1995
Crystal Structure of Poly(vinyl chloride) Single Crystals Wilkes, Charles E.; Folt, Vernon L.; Krimm, S. Macromolecules, Vol. 6, Issue 2 https://doi.org/10.1021/ma60032a017	journal	March 1973
Gallium-rich Pd–Ga phases as supported liquid metal catalysts Taccardi, N.; Grabau, M.; Debuschewitz, J. Nature Chemistry, Vol. 9, Issue 9 https://doi.org/10.1038/nchem.2822	journal	July 2017
Dynamic configurations of metallic atoms in the liquid state for selective propylene synthesis Tang, Junma; Christofferson, Andrew J.; Sun, Jing Nature Nanotechnology, Vol. 19, Issue 3 https://doi.org/10.1038/s41565-023-01540-x	journal	November 2023
Chemical recycling of waste plastics for new materials production Rahimi, AliReza; García, Jeannette M. Nature Reviews Chemistry, Vol. 1, Issue 6 https://doi.org/10.1038/s41570-017-0046	journal	June 2017
A two-stage strategy for upcycling chlorine-contaminated plastic waste Kots, Pavel A.; Vance, Brandon C.; Quinn, Caitlin M. Nature Sustainability, Vol. 6, Issue 10 https://doi.org/10.1038/s41893-023-01147-z	journal	June 2023
Co-upcycling of polyvinyl chloride and polyesters Cao, Ruochen; Zhang, Mei-Qi; Jiao, Yuchen Nature Sustainability, Vol. 6, Issue 12 https://doi.org/10.1038/s41893-023-01234-1	journal	October 2023
Dry reforming of methane catalysed by molten metal alloys Palmer, Clarke; Upham, D. Chester; Smart, Simon Nature Catalysis, Vol. 3, Issue 1 https://doi.org/10.1038/s41929-019-0416-2	journal	January 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
Photoluminescence of monovalent indium centres in phosphate glass Masai, Hirokazu; Yamada, Yasuhiro; Okumura, Shun Scientific Reports, Vol. 5, Issue 1 https://doi.org/10.1038/srep13646	journal	September 2015
Selective CO ₂ electroreduction over an oxide-derived gallium catalyst Yan, Chengcheng; Lin, Long; Gao, Dunfeng Journal of Materials Chemistry A, Vol. 6, Issue 40 https://doi.org/10.1039/C8TA08613C	journal	January 2018
Experimental and theoretical study of multinuclear indium–oxo clusters in CHA zeolite for CH 4 activation at room temperature Maeno, Zen; Yasumura, Shunsaku; Liu, Chong Physical Chemistry Chemical Physics, Vol. 21, Issue 25 https://doi.org/10.1039/C9CP01873E	journal	January 2019
Direct conversion of CO₂ to solid carbon by Ga-based liquid metals Zuraiqi, Karma; Zavabeti, Ali; Clarke-Hannaford, Jonathan Energy & Environmental Science, Vol. 15, Issue 2 https://doi.org/10.1039/D1EE03283F	journal	January 2022
Transforming PVC plastic waste to benzene via hydrothermal treatment in a multi-phase system Feng, Bo; Guo, Yong; Liu, Xiaohui Green Chemistry, Vol. 25, Issue 21 https://doi.org/10.1039/D3GC03063F	journal	January 2023
The chlor-alkali process: A review of history and pollution Crook, Jedidiah; Mousavi, Aliyar Environmental Forensics, Vol. 17, Issue 3 https://doi.org/10.1080/15275922.2016.1177755	journal	June 2016
Chemical accuracy for the van der Waals density functional Klimeš, Jiří; Bowler, David R.; Michaelides, Angelos Journal of Physics: Condensed Matter, Vol. 22, Issue 2 https://doi.org/10.1088/0953-8984/22/2/022201	journal	December 2009
Raman Spectroscopy Evaluation of Polyvinylchloride Structure Prokhorov, K. A.; Aleksandrova, D. A.; Sagitova, E. A. Journal of Physics: Conference Series, Vol. 691 https://doi.org/10.1088/1742-6596/691/1/012001	journal	February 2016
Liquid metal polymer composites: from printed stretchable circuits to soft actuators Majidi, Carmel; Alizadeh, Kaveh; Ohm, Yunsik Flexible and Printed Electronics, Vol. 7, Issue 1 https://doi.org/10.1088/2058-8585/ac515a	journal	February 2022
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Failure investigation of an underground low voltage XLPE insulated cable Ul-Hamid, Anwar; Soufi, Khaled Y.; Al-Hadhrami, Luai M. Anti-Corrosion Methods and Materials, Vol. 62, Issue 5 https://doi.org/10.1108/ACMM-02-2014-1352	journal	September 2015
Catalytic molten metals for the direct conversion of methane to hydrogen and separable carbon Upham, D. Chester; Agarwal, Vishal; Khechfe, Alexander Science, Vol. 358, Issue 6365 https://doi.org/10.1126/science.aao5023	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
Ternary NiMo-Bi liquid alloy catalyst for efficient hydrogen production from methane pyrolysis Chen, Luning; Song, Zhigang; Zhang, Shuchen Science, Vol. 381, Issue 6660 https://doi.org/10.1126/science.adh8872	journal	August 2023
Lipase degradation of plasticized polyvinyl chloride endotracheal tube surfaces to create nanoscale features Machado, Mary; Webster, Thomas International Journal of Nanomedicine, Vol. Volume 12 https://doi.org/10.2147/IJN.S130608	journal	March 2017
Poly(Vinyl Chloride) Spheres Coated with Graphene Oxide Sheets: From Synthesis to Optical Properties and Their Applications as Flame-Retardant Agents Baibarac, Mihaela; Stingescu, Luiza; Stroe, Malvina Polymers, Vol. 13, Issue 4 https://doi.org/10.3390/polym13040565	journal	February 2021