Tandem Heterogeneous Catalysis for Polyethylene Depolymerization via an Olefin-Intermediate Process
Open accessAbstract
High Resolution Image Download MS PowerPoint Slide The accumulation of plastic waste in the environment has prompted the development of new chemical recycling technologies. A recently reported approach employed homogeneous organometallic catalysts for tandem dehydrogenation and olefin cross metathesis to depolymerize polyethylene (PE) feedstocks to a mixture of alkane products. Here, we build on that prior work by developing a fully heterogeneous catalyst system using a physical mixture of SnPt/γ-Al 2 O 3 and Re 2 O 7 /γ-Al 2 O 3 . This heterogeneous catalyst system produces a distribution of linear alkane products from a model, linear C 20 alkane, n -eicosane, and from a linear PE substrate (which is representative of high-density polyethylene), both in an n -pentane solvent. For the PE substrate, a molecular weight decrease of 73% was observed at 200 °C in 15 h. This type of tandem chemistry is an example of an olefin-intermediate process, in which poorly reactive aliphatic substrates are first activated through dehydrogenation and then functionalized or cleaved by a highly-active olefin catalyst. Olefin-intermediate processes like that examined here offer both a selective and versatile means to depolymerize polyolefins at lower severity than traditional pyrolysis or cracking conditions.
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In polyethylene, C=C bonds in the main chain act as weak sites that can initiate controllable cleavage via oxidation and metathesis reactions, enabling upcycling into liquid fuels, value-added precursors, or propylene monomer.
“Creating unsaturated C=C bonds into PE main chains to break the homogeneous stable C–C bonds, which are “weak” sites to initiate controllable cleavage via oxidation and metathesis reactions to realize upcycling PE into liquid fuels17,18 or value-added precursors19−23 and even propylene monomer24−26 provides a sustainable development route for PE (Scheme 1b).”
From Installing a Trigger to Upcycle High-Density Polyethylene (2024) · cites this paper as [18]
The Introduction (page not supplied) describes forming an olefin in the PE backbone and using tandem dehydrogenation and olefin metathesis to depolymerize PE. The Conclusions report a distribution of alkane products. The paper discusses oxidation as a separate free-radical pathway; it does not show that the backbone C=C sites initiate oxidative cleavage or that this process yields propylene monomer. (LLM, conf=0.86)
Experimental — accuracy not yet measuredDegradation of P7 in the presence of ethylene and stoichiometric HG II yielded telechelic macromonomers capped with vinyl ends.
“Thus, the degradation ability of P7 was examined in the presence of E and stoichiometric HG II following previously reported procedure.24 Telechelic macromonomers capped with vinyl ends were harvested (Table S3, entry 1; Figure S1).18”
From Installing a Trigger to Upcycle High-Density Polyethylene (2024) · cites this paper as [18]
The cited paper’s Results and Discussion describe polyethylene depolymerization in n-pentane and report alkane products, not the vinyl-capped telechelic macromonomers attributed to it here. Searches for P7, stoichiometric HG II, and vinyl-capped macromonomers found no passage addressing that experiment or product; the different products reported for this paper’s own experiments do not establish a contradiction. (LLM, conf=0.76)
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- Authors
- Ellis, L. D., Orski, S. V., Kenlaw, G. A., Norman, A. G., Beers, K. L., Román-Leshkov, Y., & Beckham, G. T.
- Affiliations
- National Laboratory of the Rockies (US)
- National Institute of Standards and Technology (US)
- Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States
- Corresponding author
- Beckham, Gregg T.
- ORCID
- Venue
- ACS Sustainable Chemistry & Engineering
- Publisher
- American Chemical Society (ACS)
- Published
- 2021-01-08
- Volume
- 9
- Issue
- 2
- Pages
- 623-628
- ISSN
- 2168-0485 (ISSN-L)
- PMC
- PMC11066966
- OpenAlex
- W3121051028
- Cited by
- 166
- References
- 39
- Citations by year
- 2026: 23 · 2025: 35 · 2024: 35 · 2023: 34 · 2022: 28 · 2021: 11
- FWCI
- 10.70
- Type
- journal article
- Language
- en
- Open access
- hybrid
- doi.org
- Locations
- ACS Sustainable Chemistry & Engineering (publishedVersion, cc-by)
- PubMed Central (publishedVersion, cc-by)
- PubMed (publishedVersion)
- OSTI OAI (U.S. Department of Energy Office of Scientific and Technical Information) (submittedVersion)
- Funders
- Office of Energy Efficiency and Renewable Energy
- Laboratory Directed Research and Development
- U.S. Department of Energy (DE-AC36-08GO28308)
- Topics
- Physical Sciences › Chemistry › Organic Chemistry › Organometallic Complex Synthesis and Catalysis
- Physical Sciences › Chemical Engineering › Catalysis › Catalysis and Oxidation Reactions
- Physical Sciences › Materials Science › Polymers and Plastics › Polymer crystallization and properties
- Keywords
- heterogeneous catalysis, tandem catalysis, dehydrogenation, olefin cross-metathesis, chemical recycling, plastic waste, high-density polyethylene, n-eicosane
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