Catalytic Hydrogenolysis of Polyethylene Under Reactive Separation

Wang, Yi-Yu; Tennakoon, Akalanka; Wu, Xun; Sahasrabudhe, Chinmay; Qi, Long; Peters, Baron G.; Sadow, Aaron D.; Huang, Wenyu

doi:10.1021/acscatal.3c04987

Catalytic Hydrogenolysis of Polyethylene Under Reactive Separation

Journal Article · Wed Jan 24 00:00:00 EST 2024 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.3c04987· OSTI ID:2283201

Wang, Yi-Yu ^[1]; Tennakoon, Akalanka ^[1]; Wu, Xun ^[1]; Sahasrabudhe, Chinmay ^[2]; Qi, Long ^[3]; ^[2]; ^[1]; ^[1]

Ames Lab., and Iowa State Univ., Ames, IA (United States)
Univ. of Illinois at Urbana-Champaign, IL (United States)
Ames Laboratory (AMES), Ames, IA (United States)

Deconstruction of polyolefins by catalytic hydrogenolysis is typically accompanied by the generation of undesired light gases. At reaction temperatures, the desired liquid products also tend to be volatile. Secondary cleavage of these liquid products contributes to light gas formation. The latter process was mitigated by reactive separation, continuously separating the liquid products from the catalyst throughout the experiment. At equivalent conversion, the yield and selectivity for oligomeric liquid species are increased under reactive separation, even though the carbon–carbon bond cleavage rate is slower than that in sealed experiments. More light gas is formed in the sealed reactor. Under 1 atm H₂ partial pressure, alkenes accompany the typical alkane hydrogenolysis products. Further, the alkene yield is higher, with greater selectivity for valuable α-olefins under reactive separation. These results provide the mechanistic insight that terminal alkenes are primary products of carbon–carbon bond cleavage during hydrogenolysis under experimental conditions, and secondary deconstruction of these species produces light gases.

View Accepted Manuscript (DOE)

Research Organization:: Ames Laboratory (AMES), Ames, IA (United States); Energy Frontier Research Centers (EFRC) (United States). Institute for Cooperative Upcycling of Plastics (iCOUP)

Sponsoring Organization:: USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-07CH11358

OSTI ID:: 2283201

Report Number(s):: IS-J--11,251

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Vol. 14; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (40)

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
Composition of Liquid Fuels Derived from the Pyrolysis of Plastics Blazso, Marianne Feedstock Recycling and Pyrolysis of Waste Plastics: Converting Waste Plastics into Diesel and Other Fuels https://doi.org/10.1002/0470021543.ch12	book	March 2006
Biodegradable Polymers in the Circular Plastics Economy Dusselier, Michiel; Lange, Jean‐Paul https://doi.org/10.1002/9783527827589	book	May 2022
Towards Truly Sustainable Polymers: A Metal-Free Recyclable Polyester from Biorenewable Non-Strained γ-Butyrolactone Hong, Miao; Chen, Eugene Y. -X. Angewandte Chemie International Edition, Vol. 55, Issue 13 https://doi.org/10.1002/anie.201601092	journal	March 2016
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
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
Direct Conversion of Polypropylene into Liquid Hydrocarbons on Carbon‐Supported Platinum Catalysts Jaydev, Shibashish D.; Martín, Antonio J.; Pérez‐Ramírez, Javier ChemSusChem, Vol. 14, Issue 23 https://doi.org/10.1002/cssc.202101999	journal	October 2021
Catalytic Activity of Bulk Tungsten Carbides for Alkane Reforming. III. Reaction Mechanisms and the Kinetic Model Garin, F.; Keller, V.; Ducros, R. Journal of Catalysis, Vol. 166, Issue 2 https://doi.org/10.1006/jcat.1997.1517	journal	March 1997
Conversion of natural gas to transportation fuels via the shell middle distillate synthesis process (SMDS) Sie, S. T.; Senden, M. M. G.; Van Wechem, H. M. H. Catalysis Today, Vol. 8, Issue 3 https://doi.org/10.1016/0920-5861(91)80058-H	journal	January 1991
Reactive distillation — industrial applications, process design & scale-up Tuchlenski, A.; Beckmann, A.; Reusch, D. Chemical Engineering Science, Vol. 56, Issue 2 https://doi.org/10.1016/S0009-2509(00)00240-2	journal	January 2001
The stability of a reactive flash Rodrı́guez, Iván E.; Zheng, Alex; Malone, Michael F. Chemical Engineering Science, Vol. 56, Issue 16 https://doi.org/10.1016/S0009-2509(01)00126-9	journal	August 2001
Ni/SiO2 catalysts for polyolefin deconstruction via the divergent hydrogenolysis mechanism Vance, Brandon C.; Kots, Pavel A.; Wang, Cong Applied Catalysis B: Environmental, Vol. 322 https://doi.org/10.1016/j.apcatb.2022.122138	journal	March 2023
Kinetic modeling of hydrocracking of heavy oil fractions: A review Ancheyta, Jorge; Sánchez, Sergio; Rodríguez, Miguel A. Catalysis Today, Vol. 109, Issue 1-4 https://doi.org/10.1016/j.cattod.2005.08.015	journal	November 2005
Bifunctional tandem catalytic upcycling of polyethylene to surfactant-range alkylaromatics Sun, Jiakai; Lee, Yu-Hsuan; Yappert, Ryan D. Chem, Vol. 9, Issue 8 https://doi.org/10.1016/j.chempr.2023.05.017	journal	August 2023
Catalytic hydrogenolysis of plastic to liquid hydrocarbons over a nickel-based catalyst Zhao, Zhigang; Li, Zheng; Zhang, Xiangkun Environmental Pollution, Vol. 313 https://doi.org/10.1016/j.envpol.2022.120154	journal	November 2022
Kinetics of thermal hydrocracking of heavy oils under moderate hydroprocessing reaction conditions Ramírez, Sergio; Martínez, Jeremías; Ancheyta, Jorge Fuel, Vol. 110 https://doi.org/10.1016/j.fuel.2012.03.051	journal	August 2013
Effect of Macro- and Microstructures on Catalytic Hydrogenolysis of Polyolefins Hackler, Ryan A.; Lamb, Jessica V.; Peczak, Ian L. Macromolecules, Vol. 55, Issue 15 https://doi.org/10.1021/acs.macromol.2c00805	journal	July 2022
Polypropylene Plastic Waste Conversion to Lubricants over Ru/TiO ₂ Catalysts Kots, Pavel A.; Liu, Sibao; Vance, Brandon C. ACS Catalysis, Vol. 11, Issue 13 https://doi.org/10.1021/acscatal.1c00874	journal	June 2021
Disordered, Sub-Nanometer Ru Structures on CeO₂ are Highly Efficient and Selective Catalysts in Polymer Upcycling by Hydrogenolysis Chen, Linxiao; Meyer, Laura C.; Kovarik, Libor ACS Catalysis, Vol. 12, Issue 8 https://doi.org/10.1021/acscatal.2c00684	journal	April 2022
Processive Depolymerization Catalysts: A Population Balance Model for Chemistry’s “While” Loop Yappert, Ryan; Peters, Baron ACS Catalysis, Vol. 12, Issue 16 https://doi.org/10.1021/acscatal.2c01195	journal	August 2022
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
A Review of Slurry-Phase Hydrocracking Heavy Oil Technology Zhang, Shuyi; Liu, Dong; Deng, Wenan Energy & Fuels, Vol. 21, Issue 6 https://doi.org/10.1021/ef700253f	journal	November 2007
A Two-Phase Reactor Model for the Hydrocracking of Fischer−Tropsch-Derived Wax Möller, Klaus; le Grange, Philip; Accolla, Carlo Industrial & Engineering Chemistry Research, Vol. 48, Issue 8 https://doi.org/10.1021/ie801350p	journal	March 2009
Transition-State Enthalpy and Entropy Effects on Reactivity and Selectivity in Hydrogenolysis of n -Alkanes Flaherty, David W.; Iglesia, Enrique Journal of the American Chemical Society, Vol. 135, Issue 49 https://doi.org/10.1021/ja4093743	journal	November 2013
Size-Controlled Nanoparticles Embedded in a Mesoporous Architecture Leading to Efficient and Selective Hydrogenolysis of Polyolefins Wu, Xun; Tennakoon, Akalanka; Yappert, Ryan Journal of the American Chemical Society, Vol. 144, Issue 12 https://doi.org/10.1021/jacs.1c11694	journal	February 2022
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
Hydrogenolysis of Polyethylene and Polypropylene into Propane over Cobalt-Based Catalysts Zichittella, Guido; Ebrahim, Amani M.; Zhu, Jie JACS Au, Vol. 2, Issue 10 https://doi.org/10.1021/jacsau.2c00402	journal	October 2022
Electronic modulation of metal-support interactions improves polypropylene hydrogenolysis over ruthenium catalysts Kots, Pavel A.; Xie, Tianjun; Vance, Brandon C. Nature Communications, Vol. 13, Issue 1 https://doi.org/10.1038/s41467-022-32934-5	journal	September 2022
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
Closed-loop recycling of polyethylene-like materials Häußler, Manuel; Eck, Marcel; Rothauer, Dario Nature, Vol. 590, Issue 7846 https://doi.org/10.1038/s41586-020-03149-9	journal	February 2021
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
Ultrasmall amorphous zirconia nanoparticles catalyse polyolefin hydrogenolysis Chen, Shaojiang; Tennakoon, Akalanka; You, Kyung-Eun Nature Catalysis, Vol. 6, Issue 2 https://doi.org/10.1038/s41929-023-00910-x	journal	February 2023
Effect of reaction conditions on the hydrogenolysis of polypropylene and polyethylene into gas and liquid alkanes Chen, Linxiao; Zhu, Yifeng; Meyer, Laura C. Reaction Chemistry & Engineering, Vol. 7, Issue 4 https://doi.org/10.1039/D1RE00431J	journal	January 2022
Catalytic hydroconversion processes for upcycling plastic waste to fuels and chemicals Wei, Junde; Liu, Jieyi; Zeng, Weihao Catalysis Science & Technology, Vol. 13, Issue 5 https://doi.org/10.1039/D2CY01886A	journal	January 2023
Population balance models for polymer upcycling: signatures of the mechanism in the molecular weight evolution Yappert, Ryan; Peters, Baron Journal of Materials Chemistry A, Vol. 10, Issue 45 https://doi.org/10.1039/D2TA04628H	journal	January 2022
Synthesis of platinum nanoparticles on strontium titanate nanocuboids via surface organometallic grafting for the catalytic hydrogenolysis of plastic waste McCullough, Katherine E.; Peczak, Ian L.; Kennedy, Robert M. Journal of Materials Chemistry A, Vol. 11, Issue 3 https://doi.org/10.1039/D2TA08133D	journal	January 2023
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
Chemically recyclable thermoplastics from reversible-deactivation polymerization of cyclic acetals Abel, Brooks A.; Snyder, Rachel L.; Coates, Geoffrey W. Science, Vol. 373, Issue 6556 https://doi.org/10.1126/science.abh0626	journal	August 2021
Low-temperature upcycling of polyolefins into liquid alkanes via tandem cracking-alkylation Zhang, Wei; Kim, Sungmin; Wahl, Lennart Science, Vol. 379, Issue 6634 https://doi.org/10.1126/science.ade7485	journal	February 2023
CRC Handbook of Chemistry and Physics Haynes, William M. CRC Press https://doi.org/10.1201/b17118	book	June 2014

Similar Records

Ni/SiO₂ catalysts for polyolefin deconstruction via the divergent hydrogenolysis mechanism

Journal Article · Tue Nov 01 20:00:00 EDT 2022 · Applied Catalysis. B, Environmental · OSTI ID:2421774

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
hydrogenolysis
plastic waste
polyolefins
reactive separations
upcycling

Catalytic Hydrogenolysis of Polyethylene Under Reactive Separation

Citation Formats

References (40)

Similar Records

Related Subjects