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Catalytic conversion of polyolefins to value-added products offers an alternative route to capture value from plastic waste. Here we initially examine reactions of a polyethylene model (hexatriacontane, C36H74) on a Pt/SiO2 catalyst under typical hydrogenolysis and hydrocracking temperatures, which leads to irreversibly adsorbed surface hydrocarbons identified after extraction of hexatriacontane with excess hot toluene. The IR spectra of these catalysts after extraction reveal only aliphatic C–H stretches. SiO2 alone leads similar hydrocarbon adsorption on the surface where extended extraction fails to fully remove the adsorbed hydrocarbons from neat silica. The amount of hydrocarbon irreversibly adsorbed increases nearly 10-fold when the reactant is changed from hexatriacontane to polyethylene (Mn = 4000 Da), but the adsorbed quantity is insensitive to reaction temperature (200–300 °C). These results demonstrate significant, nonextractable hydrocarbon deposition on catalyst support surfaces without dehydrogenation catalyst present at temperatures typical of catalytic deconstruction of polyolefin waste, which may limit catalyst turnover and impact the product distribution.
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Hydrogenolysis of Poly(Ethylene‐co‐Vinyl Alcohol) and Related Polymer Blends over Ruthenium Heterogeneous Catalysts
Abstract The hydrogenolysis of polymers is emerging as a promising approach to deconstruct plastic waste into valuable chemicals. Yet, the complexity of plastic waste, including multilayer packaging, is a significant barrier to handling realistic waste streams. Herein, we reveal fundamental insights into a new chemical route for transforming a previously unaddressed fraction of plastic waste – poly(ethylene‐co‐vinyl alcohol) (EVOH) and related polymer blends – into alkane products. We report that Ru/ZrO2is active for the concurrent hydrogenolysis, hydrogenation, and hydrodeoxygenation of EVOH and its thermal degradation products into alkanes (C1−C35) and water. Detailed reaction data, product analysis, and catalyst characterization reveal that the in‐situ thermal degradation of EVOH forms aromatic intermediates that are detrimental to catalytic activity. Increased hydrogen pressure promotes hydrogenation of these aromatics, preventing catalyst deactivation and improving alkane product yields. Calculated apparent rates of C−C scission reveal that the hydrogenolysis of EVOH is slower than low‐density polyethylene. We apply these findings to achieve hydrogenolysis of EVOH/polyethylene blends and elucidate the sensitivity of hydrogenolysis catalysts to such blends. Overall, we demonstrate progress towards efficient catalytic processes for the hydroconversion of waste multilayer film plastic packaging into valuable products.
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- Award ID(s):
- 1934887
- PAR ID:
- 10507053
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- ChemSusChem
- Volume:
- 17
- Issue:
- 18
- ISSN:
- 1864-5631
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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