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At least 235 records · Page 13

Bacterial Degradation of Plastics

Plastics are not only a major component of societies on Earth but also those in Space. After use, plastics can accumulate and become difficult to recycle or reuse. Finding ways to degrade and recycle synthetic plastics would provide a way to reduce the upmass of Space Travel, create a closed-loop system of resources and even benefit life on Earth. The purpose of this project is to identify and characterize bacterial species that can degrade and recycle plastics. It has been suggested that bacteria can use plastics, like polyethylene and polystyrene, as a carbon source. These plastics are broken down into intermediary molecules which can then be used in the bacterium's metabolism. Environmental samples were collected from various locations rich in plastic waste. These samples are currently being used to culture bacteria in M9 minimal media containing polyethylene and polystyrene beads as the sole carbon source. High Performance Liquid Chromatography (HPLC), Scanning Electron Microscopy (SEM), and DNA sequencing are among the various methods that will be used identify and characterize bacteria that can degrade plastics. The results from these experiments will provide methods to reduce waste of plastics and ultimately improve sustainability for long-term space exploration.

plastic conversion↗

Increasing pyrolysis oil yields and decreasing energy consumption via thermal oxo-degradation of polyolefins

Commercialization of pyrolysis of plastics in an inert atmosphere is challenging due to large thermal requirements. This study employs thermal oxo-degradation and demonstrates how oxygen supplied at modest equivalence ratios can both accelerate depolymerization and provide the enthalpy for pyrolysis without dramatically impacting desired product yields. The enthalpies for pyrolysis of high-density polyethylene (HDPE) and polypropylene (PP) are measured to be 2,300 ± 90 J g – -1 and 2,800 ± 60 J g –1 , respectively. Using air as an oxygen source in a fluidized bed reactor, HDPE and PP are rapidly deconstructed while using up to 84% less energy through the energy released by partial oxidation. Characterization of the thermal oxo-degradation product oil shows comparable composition to conventional pyrolysis oil. Thermal oxo-degradation proves to be a promising technology for upcycling of plastics by improving thermal depolymerization of waste plastics and reducing energy requirements while maintaining desirable yields.

42 ENGINEERING↗

Large Scale Granulator Development Designed to Process Reclaimed Feedstock for Sustainable Additive Manufacturing Applications

This CRADA between UT-Battelle, LLC (Contractor) and re:3D Inc. (Participant) aims to develop an affordable large-scale granulator system designed to process reclaimed plastic feedstock suitable for additive manufacturing applications. The 24-month project will focus on testing, prototyping, and optimizing a shredder/granulator system. This project also focuses on the processing steps (e.g. washing and sorting) that can convert waste plastics, like discarded water bottles, into flake/granules which can be 3D printed using re:3D’s Fused Granular Fabrication (FGF) 3D printers. If successful, this could enable more localized 3D printing using recycled plastics, reducing waste and feedstock costs.

Wang, Peter [Oak Ridge National Laboratory (ORNL),↗

Pyrolysis in Molten Salts Converts Plastics into a Mesoporous Electrocatalyst with a High Density of Atomic Fe–N–C Active Site

Upcycling plastic waste into value-added products is a promising strategy for both economic and environmental sustainability. However, achieving control over structure–property correlations during the upcycling process remains challenging. Here, in this study, we investigate the modulation of active site formation during pyrolytic conversion of plastics to carbon by composition-controlled molten salts. Using melamine formaldehyde (MF) foams as a precursor, we demonstrate that their pyrolysis in eutectic chloride molten salts with Fe 2+ , Na + , and K + ions directs the carbonization process toward the formation of mesoporous functional carbon enriched with atomically dispersed Fe–N–C sites, which are well-known for their catalytic activity in oxygen reduction reaction (ORR). Compared to pyrolysis in the FeCl 2 -only salt, the incorporation of alkali metal ions (Na + , K + ) in the eutectic mixture facilitates nitrogen retention in the carbon matrix and modulates iron speciation. This synergistic environment promotes a higher density and more uniform dispersion of Fe–N–C moieties within the carbon matrix. Consequently, the resulting catalyst exhibits a high surface area, hierarchical porosity, and improved electrochemical properties. When tested as an ORR catalyst, the Fe–N–C-enriched catalyst delivers a high half-wave potential (E 1/2 = 0.875 V vs RHE) with nearly exclusive 4e – pathway. These properties are comparable to those of commercial Pt/C catalysts, along with improved stability.

Fe−N−C active sites↗

Ni/SiO 2 catalysts for polyolefin deconstruction via the divergent hydrogenolysis mechanism

Noble metal-based hydrogenolysis is emerging as a key chemical deconstruction technology of polyolefins into valuable products. Still, the catalyst cost and availability are significant barriers to handling the large volume of plastics. Cheap earth-abundant metals have been deemed inactive for polyolefin hydrogenolysis. Herein, we report that Ni/SiO 2 is active in deconstructing low-density polyethylene to n-alkanes (C 6 -C 35 ) at mild conditions (300 °C, 30barH 2 ) with maximum liquid yields of 65 wt%. In this study, we expose a new mechanism of long-alkane hydrogenolysis that encompasses chain location-dependent single and multiple C-C bond cracking events and rationalizes product selectivity and molecular weight dependence. Ni/SiO 2 catalysts are reusable and can handle multiple plastics producing feedstock-dependent products (i.e., n-alkanes, iso-alkanes, cyclics, aromatics, etc.). The findings broaden the scope of viable catalysts polyolefin hydrogenolysis and unleash the potential to manage the volume of plastic waste.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Size and Structure Effects of Carbon-Supported Ruthenium Nanoparticles on Waste Polypropylene Hydrogenolysis Activity, Selectivity, and Product Microstructure

Hydrogenolysis of plastic waste using Ru-based catalysts is promising for deconstructing polyolefins into lower molecular weight products. Yet, the effect of catalyst atomic structure and size on activity and product selectivity is poorly understood. Herein, we expose the effect of metal particle size and atomic structure on isotactic-polypropylene (i-PP) hydrogenolysis over Ru supported on carbon. Despite similar molecular weight distributions of solid and liquid products, their physical properties are distinct due to different chain regio-irregular CH3 sequences of steric pentads containing racemo configurations. We propose that i-PP hydrogenolysis entails an interplay of C–C bond scission and stereoisomerization. The active site’s local electronic environment and structure dictate the former, whereas polymer–catalyst surface interactions creating suitable polymer conformations control the latter. C–C scission and stereoisomerization are structure-sensitive. Small, disordered nanoclusters are effective in C–C bond scission, whereas larger metal nanoparticles promote stereoisomerization. Finally, we hypothesize that a heterogeneous distribution of metal active sites is essential for deconstruction and product (lubricant base oil) quality control.

36 MATERIALS SCIENCE↗

Photooxidation of Polyolefins to Produce Materials with In-Chain Ketones and Improved Materials Properties

Herein, we report a selective photooxidation of commodity postconsumer polyolefins to produce polymers with in-chain ketones. The reaction does not involve the use of catalyst, metals, or expensive oxidants, and selectively introduces ketone functional groups. Under mild and operationally simple conditions, yields up to 1.23 mol % of in-chain ketones were achieved. Installation of in-chain ketones resulted in materials with improved adhesion of the materials and miscibility of mixed plastics relative to the unfunctionalized plastics. The introduction of ketone groups into the polymer backbone allows these materials to react with diamines, forming dynamic covalent polyolefin networks. This strategy allows for the upcycling of mixed plastic waste into reprocessable materials with enhanced performance properties compared to polyolefin blends. Mechanistic studies support the involvement of photoexcited nitroaromatics in consecutive hydrogen and oxygen atom transfer reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Catalytic degradation of waste rubbers and plastics over zeolites to produce aromatic hydrocarbons

Catalytic conversion of waste rubbers and plastics into aromatic hydrocarbons is a promising approach to waste management and energy recovery. In the present study, acidic HY zeolites were supported by cobalt, iron, and zirconium, and the catalysts were characterized by powder X-ray diffraction, nitrogen adsorption-desorption, ammonia temperature programmed desorption, X-ray photoelectron spectroscopy, and pyridine-Fourier transform infrared spectroscopy. Here, the catalytic degradation of waste polybutadiene rubbers (BR) was conducted to investigate the degradation mechanism and evaluate the catalytic activity of supported zeolites. Experimental results indicated that HY loaded by zirconium and iron led to a higher content of Lewis acid sites as opposed to cobalt supported one. Compared with the non-catalytic pyrolysis of BR, the zirconium supported HY (Zr/HY) led to a 10-fold increase in aromatic hydrocarbons production with a distinctively high selectivity of 97.9%. A series of waste polymers including waste tires (WT), polyethylene (PE), polycarbonate (PC), and BR, were subjected to catalytic pyrolysis to explore the effects of polymer type on aromatic hydrocarbons generation, and BR was the most effective substrate, with yield enhancement reaching 2.4 over Zr/HY. Catalytic co-pyrolysis of waste rubbers and plastics was conducted to probe the effect of polymer structure on aromatic hydrocarbons formation, where a significant synergistic effect was observed in the PE co-fed with PC run.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Paths to circularity for plastics in the United States

In 2019, the United States consumed over 57 million metric tons (MMT) of plastic with less than 7% recovered for reuse. This study provides an updated material flow analysis at national and regional scales for all durable and single-use plastics in the United States. From this material flow analysis, we develop a series of alternative future national plastic flow scenarios that envision a scale-up of recycling technologies, incorporating technical limitations and sorting infrastructure constraints. The results suggest that a maximum of 68% (24 MMT) of plastic waste could be diverted from landfills by scaling up existing commercial recycling technologies. Based on the current technological landscape, reaching near-zero waste is only possible if processes that are operating at pilot and laboratory scales can be effectively scaled and coupled with improved sorting infrastructure. Through these scenarios with increased recycling, the availability of postconsumer resin stocks could increase by 22–43 MMT.

36 MATERIALS SCIENCE↗

Effect of polymer structure and material properties on mechanochemical reaction environments for polymer recycling

Plastic waste accumulation necessitates innovative recycling approaches to achieve sustainability goals. Mechanochemical depolymerization offers a solvent-free, energy-efficient route to convert polymers into valuable monomers. In addition to their chemical properties, the way that polymers absorb kinetic energy is a key parameter of any mechanochemical process. This perspective explores the principles underpinning mechanochemical recycling, emphasizing how deformation and localized transient heating mediate energy transfer between impacts and localized excitations. Key factors such as polymer crystallinity, molecular weight, viscoelasticity, and thermal effects are analyzed to elucidate their role in energy transfer mechanisms during ball milling. This work establishes a foundational framework for the design and optimization of mechanochemical recycling by connecting polymer response to mechanical energy with the intention to improve depolymerization efficiency. Future research opportunities are outlined to advance the integration of polymer science and mechanochemistry for scalable, sustainable plastic upcycling.

ball mill↗

Selective depolymerization of polyolefin copolymer via high-entropy alloy catalyzed pyrolysis in a double-layered ultrafast heating reactor

Chemical recycling of polyolefin copolymers (PCPs) is essential for mitigating plastic pollution, yet achieving selective depolymerization into C 2 –C 3 monomers at high productivity remains challenging. Here, we introduce a double-layered ultrafast heating reactor (DUHR) that integrates Joule heating with a high-entropy alloy (HEA) catalyst composed of near-equimolar Co, Cu, Fe, Mn, and Ni. We achieve highly selective depolymerization of PCP into ethylene and propylene, yielding a 70% non-condensable fraction. Significant aromatic fractions form via radical-driven pathways—a behavior distinct from conventional externally heated pyrolyzers—highlighting DUHR's ability to generate reactive species and modulate reaction pathways. Furthermore, these findings demonstrate an effective strategy for chemical recycling of real-world plastic waste for polyolefin circularity and sustainable resource recovery.

Chemical recycling↗

Microbial production of fuels, commodity chemicals, and materials from sustainable sources of carbon and energy

Anthropogenic carbon emissions are driving rapid changes to the earth's climate, disrupting whole ecosystems and endangering the stability of human society. Innovations in engineered microbial fermentation enable the fossil resource-free production of fuels, commodity chemicals, and materials, thereby reducing the carbon emissions associated with these products. Microorganisms have been engineered to catabolize sustainable sources of carbon and energy (i.e., plant biomass, plastic waste, and one-carbon feedstocks) and biosynthesize carbon-neutral or carbon-negative products. These engineering efforts exploit and optimize natural biological pathways or generate unnatural pathways which can biosynthesize chemicals that have not yet been accessed using synthetic chemistry. Further, recent advances in microbial fermentation seek not only to maximize the titer, rate, and yield of desired products, but also to tailor microbial catabolism to utilize inexpensive feedstocks. Ultimately, these advances aim to lower the cost of bioproduction so that microorganism-derived chemicals can be economically competitive with fossil-derived chemicals.

09 BIOMASS FUELS↗

A general strategy and a consolidated mechanism for low-methane hydrogenolysis of polyethylene over ruthenium

Polyethylene (PE) is one of the most environment-threatening plastic waste. Its Ru-catalyzed hydrogenolysis is rapid but produces too much methane. Here, in this study, low-density PE hydrogenolysis is performed at mild conditions and short times over Ru-doped zirconia catalysts (Ru-XZr, X = Ti, Nb, Ce, W, V, Mo, Fe) to determine low-methane catalysts. Methane is produced via direct terminal C-C scission and surface cascade of consecutive C-C scissions, with the latter sensitive to hydrogen availability and dominant in hydrogen-lean conditions. Reactivity studies, characterization and theory reveal that the most effective dopant oxides (W, V, and Mo) are intermediately reducible, as they store and supply extra hydrogen to Ru via reverse hydrogen spillover. This hydrogen readily hydrogenates and desorbs long alkyl surface intermediates that would otherwise produce cascade methane. Our proposed mechanism reconciles the low methane production achieved by increasing the hydrogen pressure or reducing the particle size and exposes the key selectivity descriptors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Influence of Pore Length on Hydrogenolysis of Polyethylene within a Mesoporous Support Architecture

Due to the plastic waste crisis, selective chemical upcycling of polyolefins into value-added products is a topic of intense interest, demanding polymer deconstruction processes that afford control over the product chain lengths. Recently, a catalytic architecture was synthesized in which a polyolefin melt infiltrates a porous support, and its chains are cleaved by a metal nanoparticle catalyst at the bottom of the pores, yielding a narrow distribution of alkane products. Although the influence of various parameters of these catalytic materials, including the effects of the nanoparticle size and pore diameter on product chain length, has been examined before, here, we investigate the role of the pore length in the cleavage process through the first study that combines catalytic hydrogenolysis and coarse-grained modeling to gain insights not available by experiment alone. We show that the pore length can permit control over the average product length with qualitative agreement between experiment and simulation. In conclusion, we go beyond this observation to uncover the dynamic phenomenon responsible for the pore-length dependence of the cleavage products.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Reduced-order condensed-phase kinetic models for polyethylene, polypropylene and polystyrene thermochemical recycling

Thermochemical recycling of plastic waste (PW) into chemicals and energy vectors requires coupling particle and reactor-scale simulations to accurate condensed phase pyrolysis mechanisms for each constituent. This work proposes a methodology to derive reduced-order condensed-phase kinetic models from validated semi-detailed kinetic mechanisms. Two types of kinetic models are obtained for polyethylene (PE), polypropylene (PP) and polystyrene (PS): reduced semi-detailed models and multi-step fully lumped ones. These families offer different compromises between accuracy and computational cost. The former employ 50–100 gas + liquid species and describe both the radical degradation and the detailed carbon distribution of the products. Conversely, the latter involves 5–10 species per polymer tracking only the main petroleum cuts. The kinetic mechanisms are complemented by the definition of thermochemical properties of gas, liquid, and solid-phase species, accounting for phase-transitions through pseudo-chemical reactions. Model validations are performed by comparison with experimental data and the original semi-detailed mechanisms in terms of mass loss, heat fluxes and product distribution profiles. The resulting CHEMKIN-like condensed-phase models are attached as Supplementary Material and as a GitHub repository. Extending the proposed approach to other polymers and coupling it with existing subsets in the CRECK kinetic framework (e.g., biomass, PVC, PET) offers a powerful tool to model thermochemical recycling of PW and biomass/PW mixtures.

kinetics↗

Gasification of Coal and Biomass: The Route to Net-Negative-Carbon Power and Hydrogen

One promising process that is a candidate for meeting the goals of the US Department of Energy’s 21st Century Power Plant initiative is to gasify a mixture of coal and biomass to yield a syngas, which can have CO2 removed and then be used to produce hydrogen as well as an off-gas that can be used to flexibly produce power. This concept would overall be carbon net-negative and readily meet the 21st Century Power Plant initiative targets of smaller scale MW generation, high ramp rates and turndown, feedstock flexibility, and high efficiency—at a reasonable cost. Moreover, adding the large-scale production of “ultra-green” hydrogen yields a system tailored for the coming hydrogen economy, providing long-term energy storage and an attractive co-product for sale. The objective of the work being led by the Electric Power Research Institute, Inc. (EPRI), with support by Bechtel Corporation (Bechtel), Gas Technology Institute (GTI), Hamilton Mauer International, Inc. (HMI), Nebraska Public Power District (NPPD), NexantECA, Inc. (Nexant), and Wärtsilä, is to perform a front-end design and engineering (FEED) study on an oxygen-blown gasification system coupled with water-gas shift, pre-combustion CO2 capture, and pressure-swing adsorption working off a coal/biomass mix to yield high-purity hydrogen and a fuel off-gas that can generate power. Several designs are being considered that will be capable of producing 50 MW net from a flexible generator, over 8500 kg/hr of hydrogen, and net-negative CO2 emissions, at an efficiency of 50% net HHV. The plant would be hosted at an NPPD site, where opportunities for enhanced oil recovery and sequestration have been investigated and the need for low-carbon power and hydrogen is imminent. The principal biomass to be used is corn stover—prevalent in Nebraska where the plant will be located—mixed with Powder River Basin (PRB) coal, necessitating a gasifier that can use this feedstock and be flexible to allow other types. Waste plastics will also be reviewed for use. Two oxygen-blown gasifiers have been identified as candidates that have done testing with biomass including corn stover: the GTI gasifier—a high-pressure, fluidized-bed type—and HMI’s, a lower pressure moving-bed type. Both have relative advantages that are being investigated in the Phase I design study, with a resultant down select of one system for which the FEED will be performed in Phase II. The technical tasks for the proposed project are: • Design Development: Completion of design activities necessary to provide inputs for the FEED study. Multiple design cases will be assessed with the selection of the optimal one for the FEED. • Investment Case Preparation: Development of the draft investment case for the proposed process with business cases performed for the proposed host site and two other locations. • Host Site Selection: Evaluation of the two potential host sites within NPPD’s portfolio to select the preferred candidate based on technical, economic, and environmental considerations. • Environmental Information Volume (EIV) Development: Completion of the EIV for the host site. • FEED Study: Completion of a FEED study based on the design selected in Phase I. A Greenhouse Gas Life Cycle Analysis will also be performed for the process. • Update Investment Case: Finalization of the investment case based on findings from the FEED. The advantages of the proposed project are significant. Having an engaged U.S. power utility willing to provide a host site that will produce energy from coal plus a deep and experienced team is critical; the process meets all the goals of DOE’s 21st Century Power Plant initiative at an estimated total plant cost of ~$880M and a production cost of hydrogen of ~$2/kg-H2 while producing net-negative carbon power. If developed, this process has real commercial potential in the United States—supported by EPRI’s initial review of the considerable interest from selected U.S. utilities—and elsewhere around the globe. The process has fewer environmental hurdles compared to other concepts, lowering regulatory and protest risks—providing a pathway to preserving the viability of a critical indigenous energy source by transforming its use to match a changing world. This presentation will outline the motivation for the effort, summarize project plans, work completed to date, results of the Design Development task, and detailed work scope for the remainder of the project.

01 COAL, LIGNITE, AND PEAT↗

Design of solvent-assisted plastics recycling: Integrated economics and environmental impacts analysis

In 2018, the United States generated over 35. 7 million tons of plastic waste, with only 8.4% being recycled and the other 91.6% incinerated or disposed of in a landfill. The continued growth of the polymer market has raised concerns over the end of life of plastics. Currently, the waste management system is faced with issues of inefficient sorting methods and low-efficiency recycling methods when it comes to plastics recycling. Mechanical recycling is the commonest recycling method but presents a lower-valued recycled material due to the material incompatibilities introduced via the inefficient sorting methods. Chemical recycling offers a promising alternative as it potentially allows for plastics to maintain their original properties. To that end, there is the need to investigate feasible chemical recycling methods to help mitigate the challenging problem posed by plastics at the end-of-life stage. This work proposes a conceptual solvent-assisted plastics recycling framework based on a superstructure optimization approach. This framework is evaluated using a representative case study to recover Polyethylene Terephthalate (PET). In this case study, it is found that polymer recovery is both economically and environmentally favorable when compared to traditional methods of disposal such as incineration.

Lehr, Austin L.↗

Systems Analysis and Optimization of Circular PET Packaging Supply Chains in the United States: Environmental and Socioeconomic Impacts

Many actions are underway at global, national, and local levels to address the plastic waste problem and transition toward a circular economy of plastics. Studies evaluating environmental and socioeconomic impacts of such a transition are lacking. Here, the purpose of this study is to conduct a national systems analysis of polyethylene terephthalate (PET) packaging supply chains in the United States. Material flow data was combined with environmental and socioeconomic indicators to evaluate and compare the sustainability of the linear PET packaging supply chain, current (2019) supply chain, and possible future circular supply chain options in the United States. Environmentally optimal circular US PET packaging material flows showed 31% and 38% savings of GHG emissions and energy demand, respectively, with a circularity of 77% when compared with a linear supply chain. Additionally, the environmentally optimal system showed higher employment (29%) and wages (31%) than a linear system, but with a 5% decrease in revenue generation. A socioeconomically optimal circular PET supply chain showed increased employment (by 52%), wages (by 67%), and revenues (by 1%), with a circularity of 59% when compared with the linear system. However, it showed 14% higher GHG emissions than a linear system, indicating a trade-off between environmentally and socioeconomically optimal circular PET packaging systems. Overall, linear-to-circular material flow transition may not necessarily lead to increased revenues and decreased environmental impacts of the entire system, but it does benefit society due to increased employment and wages. Future systems analysis work should focus on improving data quality for environmental and socioeconomic dimensions.

PET↗