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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Compositional analysis of multilayered plastic constituents and constituent mixtures using benchtop 1 H NMR spectroscopy
Multilayered plastics are widely used in food packaging and other commercial applications due to their tailored functional properties. By layering different polymers, the multilayered composite material can have enhanced mechanical, thermal, and barrier properties compared to a single plastic. However, there is a significant need to recycle these multilayer plastics, but their complex structure offers significant challenges to their successful recycling. Ultimately, the use and recycling of these complex materials requires the ability to characterize the composition and purity as a means of quality control for both production and recycling processes. New advances and availability of low‐field benchtop1H NMR spectrometers have led to increasing interest in its use for characterization of multicomponent polymers and polymer mixtures. Here, we demonstrate the capability of low‐field benchtop1H NMR spectroscopy for characterization of three common polymers associated with multilayered packaging systems (low‐density polyethylene [LDPE], ethylene vinyl alcohol [EVOH], and Nylon) as well as their blends. Calibration curves are obtained for determining the unknown composition of EVOH and Nylon in multilayered packaging plastics using both the EVOH hydroxyl peak area and an observed peak shift, both yielding results in good agreement with the prepared sample compositions. Additionally, comparison of results extracted for the same samples characterized by our benchtop spectrometer and a 500‐MHz spectrometer found results to be consistent and within 2 wt% on average. Overall, low‐field benchtop1H NMR spectroscopy is a reliable and accessible tool for characterization of these polymer systems.
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- Award ID(s):
- 2132093
- PAR ID:
- 10562251
- Publisher / Repository:
- Wiley
- Date Published:
- Journal Name:
- Magnetic Resonance in Chemistry
- Volume:
- 62
- Issue:
- 8
- ISSN:
- 0749-1581
- Page Range / eLocation ID:
- 619 to 628
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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