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At least 271 records · Page 15

Large-Scale Compatibilization of Postconsumer Polyolefins in the Presence of Paraffin Wax as a Rheology Modifier

Postconsumer polyolefins (r-POs) are leading plastic waste contributors today. This study reports, for the first time, the compatibilization of r-POs at a 50 kilogram (kg) scale with a styrene block copolymer compatibilizer in the presence of paraffin waxes as rheology modifiers (RMs). The addition of the rheological modifier (RM) and compatibilizer enhances the melt flow indices (MFIs) and mechanical properties, respectively. One aspect of this study is to compare the effectiveness of low-cost paraffin wax to that of specialized and expensive RMs in r-POs. The mechanical and rheological properties such as the melt flow index (MFI) of r-POs were compared in the presence of two types of RMs. Next, the study explores the challenges encountered when scaling the compatibilization of r-POs in the presence of paraffin wax from a 10-g to a 50-kg scale. The mechanical properties were determined and compared for samples at different scales. The study further investigated the effect of the method used for blending paraffin wax with r-PO and its impact on the value of their MFI and mechanical properties. This at-scale validation could pave the way for the commercialization of r-POs.

crystallinity↗

Demystifying group-4 polyolefin hydrogenolysis catalysis: Gaseous propane hydrogenolysis mechanism over the same catalysts

A kinetic/mechanistic investigation of gaseous propane hydrogenolysis over the single-site heterogeneous polyolefin depolymerization catalysts AlS/ZrNp 2 and AlS/HfNp 2 (AlS = sulfated alumina, Np = neopentyl), is use to probe intrinsic catalyst properties without the complexities introduced by time- and viscosity-dependent polymer medium effects. In a polymer-free automated plug-flow catalytic reactor, propane hydrogenolysis turnover frequencies approach 3,000 h −1 at 150 °C. Both catalysts exhibit approximately linear relationships between rate and [H 2 ] at substoichiometric [H 2 ] with rate law orders of 0.66 ± 0.09 and 0.48 ± 0.07 for Hf and Zr, respectively; at higher [H 2 ], the rates approach zero-order in [H 2 ]. Reaction orders in [C 3 H 8 ] and [catalyst] are essentially zero-order under all conditions, with the former implying rapid, irreversible alkane binding/activation. This rate law, activation parameter, and DFT energy span analysis support a scenario in which [H 2 ] is pivotal in one of two plausible and competing rate-determining transition states—bimolecular metal-alkyl bond hydrogenolysis vs. unimolecular β-alkyl elimination. The Zr and Hf catalyst activation parameters, ΔH ‡ = 16.8 ± 0.2 kcal mol −1 and 18.2 ± 0.6 kcal mol −1 , respectively, track the relative turnover frequencies, while ΔS ‡ = −19.1 ± 0.8 and −16.7 ± 1.4 cal mol −1 K −1 , respectively, imply highly organized transition states. These catalysts maintain activity up to 200 °C, while time-on-stream data indicate multiday activities with an extrapolated turnover number ~92,000 at 150 °C for the Zr catalyst. This methodology is attractive for depolymerization catalyst discovery and process optimization.

03 NATURAL GAS↗

Plastics for a Circular Economy Workshop: Summary Report

This report summarizes the results of a public workshop sponsored by the Bioenergy Technologies Office, the Advanced Manufacturing Office, and Mars held on December 11–12, 2019 in Golden, Colorado. The Plastics for a Circular Economy Workshop brought together experts from industry, academia, and national laboratories to discuss opportunities and challenges facing the development of new technologies to address plastic waste.

36 MATERIALS SCIENCE↗

Oxidative Funneling of PVDC (CRADA Final Report)

Poly(vinylidene chloride) (PVDC) is a major polymer product from the Participant. PVDC-containing plastics are not commonly recycled. To overcome the challenges associated with recycling PVDC and multi-layer materials, we propose a tandem catalytic-biological process to convert PVDC containing waste to upcycled, tunable products such as polyhydroxyalkanoates (PHAs). PHAs are commercially relevant, biodegradable polymers that are useful in packaging, biomedical, and personal care applications. This technology, which the Contractor has named oxidative funneling (OxFun), uses a metal-promoted autoxidation step to depolymerize co-mingled polymers to a mixture of oxygenated compounds, which an engineered bacterium can funnel to a single bioproduct: here, medium chain length polyhydroxyalkanoates (mcl-PHAs). The proposed oxidation chemistry is amenable to inclusion of additional polymers, and the biocatalyst can be engineered to convert the deconstruction products to a variety of valuable chemicals, thus presenting a tunable system for both feedstock variability and target product. Pseudomonas putida KT2440 – a metabolically robust microbe that has been engineered and proven viable for upcycling deconstructed polystyrene (PS), high density polyethlene (HDPE), and polyethylene terephthalate (PET) – can be engineered with enzymes capable of de-chlorinating PVDC deconstruction products (e.g., 2,2-dichloroacetate) in addition to PE-derived substrates into mcl-PHAs.

36 MATERIALS SCIENCE↗

Bio-Optimized Technologies to Keep Thermoplastics out of Landfills and the Environment (BOTTLE)

Plastics have revolutionized modern life, but reliance on these fossil-based materials that persist for centuries is causing a pollution crisis and contributing to greenhouse gas (GHG) emissions. To develop new technologies to address this problem, the Bio-Optimized Technologies to keep Thermoplastics out of Landfills and the Environment (BOTTLE) Consortium will deliver selective, scalable technologies to enable cost-effective recycling, upcycling, and increased energy efficiency. BOTTLE is an interdisciplinary team of experts that aim to develop selective, scalable processes to deconstruct and upcycle today's plastics and thermosets, redesign tomorrow's plastics to be recyclable-by-design (RBD) and derived from both bio-based and plastic waste-based feedstocks, work with industrial partners across the value chain to catalyze the circular economy for plastics, and leverage AMO and BETO investments in analysis-guided R&D, integrated process development, chemical and biological catalysis, materials characterization, modeling, and data science. BOTTLE is guided by techno-economic analysis (TEA) and supply chain-based life-cycle assessment (LCA). BOTTLE comprises members from ten partner institutions. Primary outcomes to date include establishment of a full consortium, impactful, benchmarking analyses that will be important for the plastics recycling and upcycling community, and multiple impactful, high-impact publications across the breadth of our research portfolio.

bio-optimized↗

Investigation of pressure-controlled injection molding on the mechanical properties and embodied energy of recycled high-density polyethylene

Manufacturing with secondary feedstock has been identified as an effective strategy to improve plastic circularity. However, product quality inconsistencies arise due to variations in molecular weight, rheology, and mechanical properties. This work evaluates the processing of recycled high-density polyethylene using pressure-controlled injection molding with a focus on processing behavior and energy consumption. Further, the effects of injection velocity, packing pressure, and transfer position are benchmarked against a conventional velocity-controlled process. The experimental results show that the novel process control strategy significantly affects the mechanical properties, in-mold rheology, and energy consumption. Parts fabricated using pressure-controlled injection molding showed higher tensile properties due to increased macromolecular orientation. Additionally, reduced energy was used due to lower melt pressures required to completely replicate the cavity geometry. The results demonstrate the potential of the technology to support increased utilization of secondary feedstock and reduced carbon footprint.

36 MATERIALS SCIENCE↗

Building a Plastics Fabrication Laboratory on the ISS: FabLab, MANTIS, Refabricator, CRISSP, ERASMUS, and MAMBA

The objective of NASA's In Space Manufacturing program is to develop manufacturing technologies and processes necessary to provide "on-demand, sustainable operations for exploration missions." Using the ISS as a test bed, in 2014, NASA installed and successfully tested a 3D printer for in-space operations, demonstrating the 3D printing process as well as sending digital files for printing from earth to the printer. The success of this technology demonstration has shown that on-orbit manufacturing technologies can be used to limit the earth reliance for cis-lunar missions. Because of this success, numerous opportunities have been provided by NASA to further in-space manufacturing by focusing on the development of highly autonomous manufacturing systems, recycling technologies, and robotics with the ultimate goal of building a fabrication laboratory now within reach. From technologies developed for ISS activities and demonstration missions, Tethers Unlimited, Inc. (TUI) is building a Plastics Manufacturing Laboratory capable of fabricating parts on-demand and as-needed while recycling waste plastics with minimal human interaction required. Parts will be manufactured through additive manufacturing. Precision machining will ensure manufactured parts are in tolerance with the end-use requirements. Recycling waste plastics will enable both waste from the crew and waste from processing to be re-processed into something new. In addition, these manufacturing and recycling technologies are supported by part verification/validation technique and robotic servicing, minimizing human interaction with the system and eventually enabling unmanned off-world manufacturing.

Muhlbauer, Rachel↗

Fully Recyclable Polycarbonates from Simple, Bio-Derived Building Blocks

Plastic buildup and accumulation in the environment are an increasingly large problem facing civilization. Petroleum-based plastics can exist for hundreds to thousands of years in the environment, destroying habitats and polluting water. Environmentally conscious replacements for plastics are urgently needed. In this publication, we present a biobased alternative to petroleum-based polycarbonates. Using a diol monomer derived from glycerol and glycerol products, we have synthesized aliphatic polycarbonates with comparable physical properties to petroleum-based incumbents. The polymer can be quantitatively depolymerized using warm methanol to recover the monomer which can be repolymerized multiple times, or alternatively, the monomer, which is inherently nontoxic, can slowly break apart to the original components. This provides two end-of-life options for this material recycle or decomposition under environmental conditions to benign building blocks, thus providing a potential pathway to avoid environmental and bioaccumulation of plastics. We also demonstrate the ability to selectively recover the monomer from a simulated mixed-plastic waste environment; the monomer recovered this way functions identically to the virgin monomer after purification. This work represents an important step in the progress toward environmentally conscious polymer design with multiple end-of-life options.

36 MATERIALS SCIENCE↗

Characterization of Polyhydroxybutyrate-Based Composites Prepared by Injection Molding

The waste generated by single-use plastics is often non-recyclable and non-biodegradable, inevitably ending up in our landfills, ecosystems, and food chain. Through the introduction of biodegradable polymers as substitutes for common plastics, we can decrease our impact on the planet. In this study, we evaluate the changes in mechanical and thermal properties of polyhydroxybutyrate-based composites with various additives: Microspheres, carbon fibers or polyethylene glycol (2000, 10,000, and 20,000 MW). The mixtures were injection molded using an in-house mold attached to a commercial extruder. The resulting samples were characterized using microscopy and a series of spectroscopic, thermal, and mechanical techniques. We have shown that the addition of carbon fibers and microspheres had minimal impact on thermal stability, whereas polyethylene glycol showed slight improvements at higher molecular weights. All of the composite samples showed a decrease in hardness and compressibility. The findings described in this study will improve our understanding of polyhydroxybutyrate-based composites prepared by injection molding, enabling advancements in integrating biodegradable plastics into everyday products.

36 MATERIALS SCIENCE↗

Techno-economic analysis and life cycle assessment for the catalytic hydrogenolysis and hydrocracking of polyethylene

Catalytic hydrogenolysis and hydrocracking are promising technologies for the conversion of polyolefin waste into hydrocarbons. Here, to explore the economic and environmental viability of these approaches, we conducted techno-economic analysis and life cycle assessment of polyethylene hydrogenolysis and hydrocracking processes that produce fuel-range products or olefins, respectively. Relative to primary production, the minimum selling price (MSP) of alkanes for linear-chain naphtha was estimated to be 1.8-fold higher, whereas branched-chain naphtha and propylene were shown to be cost competitive. Environmental impacts showed similar trends across scenarios, with propylene production by hydrocracking exhibiting greenhouse gas emissions comparable with conventional propylene due to relatively low hydrogen demand and high yield. Together, these results suggest that innovations in catalysis and reaction engineering will be required to make viable products that are scale matched with today's plastics, such as light olefins for closed-loop recycling.

09 BIOMASS FUELS↗

Liquid Fed Pyrolysis of Polyethylene Films: Environmental and Economic Assessments of Co-located and Remotely-Located U.S. Facilities

Polyethylene (PE) films are one of the highest production volume plastic products, but they have very low recycling rates. A novel liquid fed pyrolysis process (LFP) is an advanced recycling technology that can be applied to waste PE films. In this work, two environmental and six economic metrics were evaluated for the LFP process under different scenarios with a baseline production capacity of 8,400 Metric Tons (MT) of pyrolysis products/year. The studied scenarios considered process improvement such as heat integration, changing the final product yields, and location of the LFP process facility (i.e., co-located at a petrochemical facility or located remotely). Results show that producing refined pyrolysis wax in remote areas is the most environmentally favorable and profitable scenario. The LFP process co-located at a petrochemical facility and selling only liquid and gaseous pyrolysis products to the facility would require a capacity of >18,000 MT/year to be economically feasible. Heat integration led to greenhouse gas emission savings of at least 14%, 19%, and 32% for the pyrolysis oil, gas, and wax products, respectively. Fianlly, the LFP process in remote and less populated locations producing a high yield of refined wax may be a feasible solution for increasing recycling rates of PE films.

Advanced recycling↗

Treasuring trash: Pt/SrTiO 3 catalysts process plastic waste into high-value materials

Single-use plastics are ubiquitous throughout modern society because they have properties that make them desirable in a wide variety of applications, including low cost of production, high thermal and chemical stability, and tunable mechanical properties. Several of the recycling methods currently used to process single-use plastic waste, such as mechanical recycling and pyrolysis, do not selectively process plastic materials into uniform products, as would be advantageous for repurposing these materials in pursuit of a circular economy. Catalytic hydrogenolysis, whereby C–C bonds in polymers are broken over a supported catalyst in the presence of H 2 , is a promising approach to converting plastics into value-added products that can be sold commercially without further purification. Here, in this account, we present some recent advances in polyolefin hydrogenolysis, with a focus on Pt nanoparticles on SrTiO 3 nanocuboid supports (Pt/STO). Current developments in this field, general challenges, and future directions are discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Green Aerospace Fuels from Nonpetroleum Sources

Efforts to produce green aerospace propellants from nonpetroleum sources are outlined. The paper begins with an overview of feedstock processing and relevant small molecule or C1 chemistry. Gas-to-liquid technologies, notably Fischer-Tropsch (FT) processing of synthesis gas (CO and H2), are being optimized to enhance the fraction of product stream relevant to aviation (and other transportation) fuels at the NASA Glenn Research Center (GRC). Efforts to produce optimized catalysts are described. Given the high cost of space launch, the recycling of human metabolic and plastic wastes to reduce the need to transport consumables to orbit to support the crew of a space station has long been recognized as a high priority. If the much larger costs of transporting consumables to the Moon or beyond are taken into account, the importance of developing waste recycling systems becomes still more imperative. One promising way to transform organic waste products into useful gases is steam reformation; this well-known technology is currently being optimized by a Colorado company for exploration and planetary surface operations. Reduction of terrestrial waste streams while producing energy and/or valuable raw materials is an opportunity being realized by a new generation of visionary entrepreneurs. A technology that has successfully demonstrated production of fuels and related chemicals from waste plastics developed in Northeast Ohio is described. Technologies being developed by a Massachusetts company to remove sulfur impurities are highlighted. Common issues and concerns for nonpetroleum fuel production are emphasized. Energy utilization is a concern for production of fuels whether a terrestrial operation or on the lunar (or Martian) surface; the term green relates to not only mitigating excess carbon release but also to the efficiency of grid-energy usage. For space exploration, energy efficiency can be an essential concern. Other issues of great concern include minimizing impurities in the product stream(s), especially those that potential health risks and/or could degrade operations through catalyst poisoning or equipment damage. The potential impacts on future missions by such concerns are addressed in closing.

Hepp, Aloysius F.↗

Thiol- and Disulfide-Functionalized Polycyclooctene: Metathesis Polymerization, Degradation, and Reformation

The enormous global production and use of polymers and plastics, combined with slower and less efficient disposal and recycling methods, have led to a worldwide growth in plastic waste. Here, we describe an approach that builds degradability into macromolecular polyolefins through the design of telechelic oligomers with reactive functional groups that enables control over polymer deconstruction and reconstruction. Our work exploits disulfide-containing polymers that have emerged as promising cyclable materials due to their dynamic reversibility (bond formation and cleavage) driven by redox chemistry under mild conditions. Specifically, we describe the synthesis of a telechelic α,ω-dithiopolycyclooctene (PCOE) by ring-opening metathesis polymerization using a dithioacetate chain transfer agent, followed by deprotection to convert the chain-end thioacetates to thiols. This process was studied towards control over the degree of oxidation to yield disulfide-containing PCOE, followed by an evaluation of reductive degradation and oxidative repolymerization. Overall, this approach facilitates the production of disulfide-containing unsaturated polyolefins and the integration of degradable and reformable moieties into soluble, processable, metathesis-derived polymers.

Lee, Kyoungwon↗

A hybrid chemical-biological approach can upcycle mixed plastic waste with reduced cost and carbon footprint

Derived from renewable feedstocks, such as biomass, polylactic acid (PLA) is considered a more environmentally friendly plastic than conventional petroleum-based polyethylene terephthalate (PET). However, PLA must still be recycled, and its growing popularity and mixture with PET plastics at the disposal stage poses a cross-contamination threat in existing recycling facilities and results in low-value and low-quality recycled products. Hybrid upcycling has been proposed as a promising sustainable solution for mixed plastic waste, but its techno-economic and life cycle environmental performance remain understudied. We propose a hybrid upcycling approach using a biocompatible ionic liquid (IL) to first chemically depolymerize plastics and then convert the depolymerized stream via biological upgrading with no extra separation. Here we show that over 95% of mixed PET/PLA was depolymerized into the respective monomers, which then served as the sole carbon source for the growth of Pseudomonas putida, enabling the conversion of the depolymerized plastics into biodegradable polyhydroxyalkanoates (PHAs). In comparison to conventional commercial PHAs, the estimated optimal production cost and carbon footprint are reduced by 62% and 29%, respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Minimum GHG emissions and energy consumption of U.S. PET and polyolefin packaging supply chains in a circular economy

There is a wide agreement on the urgency of transforming linear management of plastics towards a circular economy model. However, no clear pathways exist as to required recycling technologies involved and system-wide environmental impacts. This study explores such pathways in the U.S. for the most commonly used packaging plastics through a combination of mechanical and emerging advanced recycling technologies. A system optimization model aimed at minimizing environmental impacts was developed to determine optimal end-of-life (EOL) management and locations of existing and emerging U.S. recycling infrastructures. Our study includes material flows from virgin resin production through semi-manufacturing processes to existing EOL disposal and recycling processes. An optimized circular plastics packaging system achieved greenhouse gas (GHG) emission savings of up to 28% and cumulative energy demand (CED) savings of up to 46%, compared to the linear economy. Moreover, these savings of GHG emissions and CED impacts represent a reduction of 0.16% and 0.49% compared to annual U.S. GHG emissions and energy consumption in 2022, respectively. The optimal recycling rates and systems-level circularity ranged from 78–99% and 57–75%, respectively. Increased energy savings led to increased GHG emissions showing a potential trade-off between GHG emissions and energy. Analysis of 40 scenarios showed the importance of material collection distances, blend limit of mechanically recycled resins, process yields, and mandated recycling rates for achieving a sustainable circular economy of plastics.

09 - BIOMASS FUELS↗

Catalytic closed-loop recycling of polyethylene-like materials produced by acceptorless dehydrogenative polymerization of bio-derived diols

Petroleum-derived polyolefins exhibit diverse properties and are the most important and largest volume class of plastics. However, polyolefins are difficult to efficiently recycle or break down and are now a persistent global contaminant. Broadly replacing polyolefins with bio-derived and degradable polyethylene-like materials is an important yet challenging endeavour towards sustainable plastics. Here, in this study, we report a solution for circular bio-based polyethylene-like materials synthesized by acceptorless dehydrogenative polymerization from linear and branched diols and their catalytic closed-loop recycling. The polymerization and depolymerization processes utilize earth-abundant manganese complexes as catalysts. These materials exhibit a wide range of mechanical properties, encompassing thermoplastics to plastomers to elastomers. The branched diols, produced through a thiol-ene click reaction, can be polymerized to plastics with significantly enhanced tensile properties, toughness and adhesive properties. These materials could be depolymerized back to monomers through hydrogenation and were separatable with a monomer recovery of up to 99%, unaffected by the presence of dyes and additives. Overall, this system establishes a route to more sustainable plastics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗