Novel Compatibilizer for Plastic Waste Reduction
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In view of their excellent thermal and chemical resistance, favorable adhesion properties, high tensile strength, and other advantages, epoxy thermosets have numerous industrial applications such as coating, adhesive, and composite material production. However, bisphenol A (BPA)-based resins, which account for a significant fraction of the above thermosets, adversely affect human health by interfering with the normal functioning of the endocrine system and cannot be easily decomposed and recycled. Herein, degradable and sustainable bio-based epoxy thermosets with crosslinked network structures are prepared by the epoxidation of isosorbide with epichlorohydrin and the curing of the produced isosorbide diglycidyl ether (ISDGE) with cyclic lactones through a cationic ring-opening reaction. The ISDGE thermosets fully decompose into soluble and recyclable products under mildly basic conditions within three days, which is ascribed to the presence of ester moieties within the polymer network structure. Compared to a representative BPA-based epoxy, ISDGE-based thermosets exhibit lower dielectric constants and are more flexible. Moreover, the glass fibers in ISDGE-based prepregs can be fully recovered after on-demand degradation. Furthermore, our work provides promising eco-friendly alternatives to conventional epoxy thermosets and paves the way for the reduction of plastic waste generation and the development of recyclable green electronics.
Pyrolysis of waste plastics can produce a product mixture with a high concentration of olefins (>50 wt%). The olefins, as building blocks in the petroleum industry, are potential precursors for valuable commodity chemicals with higher values (>$2000 per ton). In this work, we produce aldehydes by hydroformylation of the olefins present in pyrolysis oil from colored post-consumer recycled high-density polyethylene (PCR-HDPE). The obtained aldehydes in the oil are then converted into aliphatic amines via reductive amination with a Ru/C catalyst. The aminated oil was characterized by multiple analytical chemistry techniques including elemental analysis, nuclear magnetic resonance spectroscopy, high-resolution liquid chromatography-mass spectrometry, and gas chromatography-mass spectrometry with a Polyarc flame ionization detector. The concentration of metals in the PCR-HDPE and oil changes during the tandem processes, showing limited effects of these elements (e.g., Al, Ca, Fe, Mg, Ti, Zn) on hydroformylation and reductive amination. Additionally, we demonstrated that reductive amination of aldehydes with varied carbon numbers and branching properties can be achieved in the presence of a complex mixture, including paraffins and aromatics. The results indicate that waste plastics have the potential to serve as a renewable source for mono and di aliphatic amines, thereby diminishing reliance on fossil feedstocks as the current primary amine source.
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.
The U.S. generates 42 million metric tons of plastic waste each year - the most of any country - of which less than 9% is recycled. This represents an estimated loss of $2.3 billion and 3.4 EJ embodied energy per year. Plastic use reduction, reuse and recycling are thus increasingly important, but making informed policy and research decisions within this space can be challenging given the diverse range of available solutions. Various recycling and waste management options are available for plastics, such as conversion into energy (incineration, pyrolysis, gasification), conversion to lower- or higher-grade plastics (mechanical recycling, chemical or enzymatic depolymerization processes, dissolution) or up-cycling to feedstock chemicals (photo/electro/catalytic methods, pyrolysis, gasification). While many previous publications have investigated a subset of these options, there is currently no modelling platform that can quantitatively assess and compare the economic and environmental impacts of all these different plastic management pathways and their respective products simultaneously. To directly compare the benefits and disadvantages of plastic-to-x technologies, we propose a novel analysis framework: the Plastic Parallel Pathways Platform (4P). 4P will model a systems analysis framework for capturing plastic material flows processed via different waste management scenarios. The total economic cost and greenhouse gas emissions (as well as additional economic, energetic, and environmental metrics indicators) of a given scenario will be calculated enabling comparison to other scenarios, thereby informing decisions on plastic recycling pathways.
Electrochemical methods for the direct reduction of alkyl esters have been understudied but provide a potential advantage for addressing specific waste streams given that such strategies often require only a minimal chemical profile. One such waste stream that could benefit from electrochemical remediation is poly(vinyl chloride) (PVC) plastics. PVC recycling often faces challenges due to the complexity of such waste. Solvent-based recycling methods pose several advantages for addressing post-use PVC; however, such methods are complicated by the high amounts of toxic legacy plasticizers (ortho-phthalates) present in PVC. A potential solution to addressing such phthalates is to address them electrochemically, coupled with recovery of the resulting valuable products. Presented herein is an optimized electrochemical method for ester activation that is leveraged to separate and recover the aromatic and alkyl components of ortho-phthalate plasticizers. The resulting aliphatic alcohols may be reused to prepare other non-toxic plasticizers. This electro-degradation method is demonstrated on six phthalates that have been identified to pose health concerns in addition to plasticizers recovered from commercial samples of PVC.
Human space missions generate trash with a substantial amount of plastic (20% or greater by mass). The trash also contains water trapped in food residue and paper products and other trash items. The Heat Melt Compactor (HMC) under development by NASA Ames Research Center (ARC) compresses the waste, dries it to recover water and melts the plastic to encapsulate the compressed trash. The resulting waste disk or puck represents an approximately ten-fold reduction in the volume of the initial trash loaded into the HMC. In the current design concept being pursued, the trash is compressed by a piston after it is loaded into the trash chamber. The piston face, the side walls of the waste processing chamber and the end surface in contact with the waste can be heated to evaporate the water and to melt the plastic. Water is recovered by the HMC in two phases. The first is a pre-process compaction without heat or with the heaters initially turned on but before the waste heats up. Tests have shown that during this step some liquid water may be expelled from the chamber. This water is believed to be free water (i.e., not bound with or absorbed in other waste constituents) that is present in the trash. This phase is herein termed Phase A of the water recovery process. During HMC operations, it is desired that liquid water recovery in Phase A be eliminated or minimized so that water-vapor processing equipment (e.g., condensers) downstream of the HMC are not fouled by liquid water and its constituents (i.e., suspended or dissolved matter) exiting the HMC. The primary water recovery process takes place next where the trash is further compacted while the heated surfaces reach their set temperatures for this step. This step will be referred to herein as Phase B of the water recovery process. During this step the waste chamber may be exposed to different selected pressures such as ambient, low pressure (e.g., 0.2 atm), or vacuum. The objective for this step is to remove both bound and any remaining free water in the trash by evaporation. The temperature settings of the heated surfaces are usually kept above the saturation temperature of water but below the melting temperature of the plastic in the waste during this step to avoid any encapsulation of wet trash which would reduce the amount of recovered water by blocking the vapor escape. In this paper, we analyze the water recovery rate during Phase B where the trash is heated and water leaves the waste chamber as vapor, for operation of the HMC in reduced gravity. We pursue a quasi-one-dimensional model with and without sidewall heating to determine the water recovery rate and the trash drying time. The influences of the trash thermal properties, the amount of water loading, and the distribution of the water in the trash on the water recovery rates are determined.
This paper describes development at NASA Ames Research Center of a heat melt compactor that can be used on both near term and far term missions. Experiments have been performed to characterize the behavior of composite wastes that are representative of the types of wastes produced on current and previous space missions such as International Space Station, Space Shuttle, MIR and Skylab. Experiments were conducted to characterize the volume reduction, bonding, encapsulation and biological stability of the waste composite and also to investigate other key design issues such as plastic extrusion, noxious off-gassing and removal of the of the plastic waste product from the processor. The experiments provided the data needed to design a prototype plastic melt waste processor, a description of which is included in the paper.
The Logistics Reduction and Repurposing project includes the heat melt compactor (HMC), a device that compacts waste containing plastic into a tile that will minimize volume, and may be used as materials for radiation shielding. During the process, a small purge gas stream is directed through the HMC chamber to transport out gasses and humidity released from the process. NASA Marshall Space Flight Center is tasked with developing and delivering a contamination control system to clean the purge gas prior to exhausting it back into the cabin for crew inhalation.
The Institute for Catalysis in Energy Processes (ICEP) was a multi-PI program located at the Northwestern University Center for Catalysis and Surface Science from 2006-2024. Over several renewal cycles and several organizing themes, ICEP addressed fundamental questions in catalysis science. In turn, the scientific questions addressed were directly relevant to the efficient use of the nation’s resources to produce fuels and commodity chemicals, harness alternate energy sources for chemical reactions such as light or electricity, reduce emissions and waste, and minimize the impact of our use of plastics. Selective oxidation, (oxidative) dehydrogenation, deNOx, CO 2 reduction, hydrogen release, polymer decomposition / depolymerization, and many other reactions of intense interest to the US Department of Energy were studied in the center. Major ICEP strengths were in catalyst synthesis, in measurements that elucidated catalyst properties, in reaction mechanisms and kinetics, and in predictive theory and modeling. ICEP researchers were often the inventors or developers of materials and methods that were brought to bear on the Institute’s catalytic systems. Key characterization tools advanced through this project included resonance Raman and related techniques, sum frequency generation, and X-ray standing wave spectroscopy. Center members relied extensively on computational tools such as density functional theory and microkinetic modeling to fully investigate catalyst structures and catalytic mechanisms. ICEP researchers were early developers of atomic layer deposition (ALD) for catalyst synthesis and were early pioneers of metal organic frameworks for catalysis. ICEP innovations are found in areas of intense research such as single-atom catalysts, catalytic deconstruction of plastics, and catalytic MOFs, to name a few. Research areas initiated by ICEP indirectly led to DOE EFRCs, startup companies, and other achievements. Over its 18 years of existence, ICEP involved two different PIs (Stair and Notestein) and 24 senior investigators across several academic disciplines at Northwestern University. There were tight collaborations with Argonne National Laboratory, including specialized equipment and experiments permanently located there. The center supported ~400 person-years of effort by graduate students and postdocs, either directly through DOE support or indirectly by leveraging independent support provided to the trainees, e.g. through the NSF GRFP or internal fellowships. The project resulted in 328 manuscripts and numerous conference presentations.
A device known as the Trash Compaction Processing System or TCPS has been under development at NASA as part of the Advanced Life Support and Logistics Reduction Program Waste Management element. The TCPS processes trash that includes a variety of components such as plastic pouches that contain wet food and drinks, used cloth towels and t-shirts, adhesive tapes, deodorant, and many other items. The TCPS uses heat and pressure to compact the waste composite into a sturdy and well-defined shape designed to fit in a storage area on a spacecraft. The TCPS removes water from the trash and renders it safe against microbial activity. The focus of this paper is on methods for reducing the Equivalent System Mass of a TCPS with an emphasis on increasing the thermal efficiency of the system.
Reduction and stabilization of solid wastes generated during space missions is a major concern for the Advanced Life Support - Resource Recovery program at the NASA, Kennedy Space Center. Solid wastes provide substrates for pathogen proliferation, produce strong odor, and increase storage requirements during space missions. A five periods experiment was conducted to evaluate the Space Operation Bioconverter (SOB), an in vessel composting system, as a biological processing technology to reduce and stabilize simulated long-term missions space related solid-wastes (SRSW). For all periods, SRSW were sorted into components with fast (FBD) and slow (SBD) biodegradability. Uneaten food and plastic were used as a major FBD and SBD components, respectively. Compost temperature (C), CO2 production (%), mass reduction (%), and final pH were utilized as criteria to determine compost quality. In period 1, SOB was loaded with a 55% FBD: 45% SBD mixture and was allowed to compost for 7 days. An eleven day second composting period was conducted loading the SOB with 45% pre-composted SRSW and 55% FBD. Period 3 and 4 evaluated the use of styrofoam as a bulking agent and the substitution of regular by degradable plastic on the composting characteristics of SRSW, respectively. The use of ceramic as a bulking agent and the relationship between initial FBD mass and heat production was investigated in period 5. Composting SRSW resulted in an acidic fermentation with a minor increase in compost temperature, low CO2 production, and slightly mass reduction. Addition of styrofoam as a bulking agent and substitution of regular by biodegradable plastic improved the composting characteristics of SRSW, as evidenced by higher pH, CO2 production, compost temperature and mass reduction. Ceramic as a bulking agent and increase the initial FBD mass (4.4 kg) did not improve the composting process. In summary, the SOB is a potential biological technology for reduction and stabilization of mission space-related solid wastes. However, the success of the composting process may depend of the physical characteristics (particle size, porosity, structure, texture) of the SBD components which would require pre-processing of solid wastes before placing them in the SOB.
The Heat Melt Compactor (HMC) system has been developed to manage the waste generated on board spacecraft during long-duration missions. The quantity and composition of spacecraft trash depends upon the mission and can have a very high daily variability. This requires a flexible system able to manage extreme waste scenarios. Most missions will generate on average about one kilograms of trash per astronaut per day, derived mainly from the spacecraft logistics supplies and consisting of clothing, food & beverage residues, packaging, paper, plastic, hygiene wipes, and many other personal or scientific items used and discarded by the crew. Uncontained and unprocessed waste is a health hazard and a habitat storage problem. However, trash also contains valuable resources such as water. HMC is designed to provide volume reduction, microbial safening and stabilization, water recovery, and radiation shielding material. The final byproduct generated by HMC is a sterilized tile with the consistency of hard plastic that can be safely handled, easily stored, and used for radiation protection. This paper provides the summary of an extensive campaign of testing performed using the HMC system to simulate different nominal and extreme operational scenarios and to generate the data necessary to finalize requirements for proto-flight hardware to be deployed to an International Space Station (ISS) EXPRESS Rack.
This work outlines a process for producing high‐purity (>95%) carboxylate surfactants from post‐consumer recycled high‐density polyethylene (PCR‐HDPE). The approach involves the thermal depolymerization of PCR‐HDPE via pyrolysis, followed by fractional distillation to isolate C9–C14 olefins. These olefins undergo hydroformylation using cobalt carbonyl catalysts to generate aldehydes, which are subsequently oxidized to carboxylic acids using Pinnick oxidation under mild aqueous‐phase conditions. Neutralization of the resulting carboxylic acids with sodium hydroxide produces plastic‐derived carboxylate surfactants (PDCs) in the form of sodium carboxylates. Subsequent purification steps ensure surfactant‐grade purity and enable accurate assessment of physicochemical properties. The resulting PDCs are evaluated for critical micelle concentration (CMC), foamability, surface tension reduction, and calcium ion tolerance, demonstrating competitive behavior with conventional anionic carboxylate surfactants. This route provides a sustainable alternative for surfactant production, reducing reliance on fossil‐derived feedstocks and valorizing plastic waste streams through chemical upcycling.
Coal is one of the most abundant fossil energy resources in the United States and in the world. The recoverable reserves in the United States are estimated to be about 252 billion tons – more than 350 years of supply at current rates of usage. However, the share of coal in total primary energy consumption in the US has been declining over the years. The decline of coal is mainly attributed to cheap natural gas and precipitous declines in the cost of electricity production from renewable technologies such as wind and solar. Coal can potentially be used if it is coupled with carbon-neutral feedstock such as biomass-agricultural residues, forest biomass, and forest residues. Co-gasification of coal and biomass can become a negative carbon emission technology if the carbon dioxide (CO 2 ) is captured and sequestered. Although the biomass gasification process has a lot of similarities to coal gasification, the large-scale adaptation of power production sourced from biomass has not come to fruition. The main reason is that the power production from biomass is still expensive when compared with natural gas or coal power technologies. To address the feedstock cost, one approach is to use low-cost feedstocks, such as municipal solid wastes (MSW) or plastics, for gasification. Gasification involves the partial oxidation of coal and/or biomass feedstocks to produce a combustible fuel called synthesis gas (syngas) which is composed of carbon monoxide (CO), hydrogen (H 2 ), CO 2 , methane (CH 4 ), nitrogen (N 2 ), water (H 2 O), and other compounds that might be considered as contaminants. Raw syngas from gasification must go through multiple steps to produce high-purity hydrogen. The specific steps depend upon the quality (gas composition, contaminants, and their concentration) and condition (pressure and temperature) of syngas. The long-term goal of the project was to utilize coal and plastics together with biomass to produce energy and fuels using a gasification platform while reducing greenhouse gas emissions. The main objective of this research was to examine gasification performance in a laboratory-scale fluidized-bed gasifier for hydrogen production. The specific objectives of the research were to: (i) study coal-plastic-biomass mixture flowability for consistent feeding in the gasifier; (ii) understand the gasification behavior of the mixture in steam and oxygen environments; (iii) perform thermal property characterization of ash and slag from the mixture feedstock and refractory-ash interface of the mixture under gasification conditions; and (iv) develop process models to determine the technology needed for syngas cleanup and contaminants. The study found that there was no apparent segregation when biomass, coal, and waste plastics were mixed together during feeding. Although there were differences in hydrogen production when individual feedstock were fed, the hydrogen concentration remained almost constant with various blends. Therefore, blending waste plastics with biomass and coal, which are all abundant, is a better approach for energy production. Results of the techno-economic analysis suggested that integration of advanced gasification (GTI’s R-GAS™) and syngas cleanup and conditioning technologies (RTI’s WDP and AFWGS) for clean hydrogen production resulted in substantial benefits, including significant capital cost and operating cost reductions. Advanced technologies resulted in 16% reduction in the hydrogen production cost (COH) from 2.94 $\$$/kg to 2.47 $\$$/g, with further scope for optimization and cost reduction. These advanced technologies also result in lower emissions, and improved energy efficiency.
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.
ABSTRACT Polyolefins derived from plastic wastes are recalcitrant for biological upcycling. However, chemical depolymerization of polyolefins can generate depolymerized plastic (DP) oil, comprising of a complex mixture of saturated, unsaturated, even, and odd hydrocarbons suitable for biological conversion. While DP oil contains a rich carbon and energy source, it is inhibitory to cells. Understanding and harnessing robust metabolic capabilities of microorganisms to upcycle the hydrocarbons in DP oil, both naturally and unnaturally occurring, into high-value chemicals are limited. Here, we discovered that an oleaginous yeast, Yarrowia lipolytica, undergoing short-term adaptation to DP oil robustly utilized a wide range of hydrocarbons for cell growth and production of citric acid and neutral lipids. When growing on hydrocarbons, Y. lipolytica partitioned into planktonic and oil-bound cells with each exhibiting distinct proteomes and amino acid distributions invested in establishing these proteomes. Significant proteome reallocation toward energy and lipid metabolism, belonging to 2 of the 23 Eukaryotic Orthologous Groups classes C and I, enabled robust growth of Y. lipolytica on hydrocarbons, with n-hexadecane as the preferential substrate. This investment was even higher for growth on DP oil where classes C and I were ranked one and two, respectively, and many associated proteins and pathways were expressed and upregulated including the hydrocarbon degradation pathway, Krebs cycle, glyoxylate shunt and, unexpectedly, propionate metabolism. However, a reduction in proteome allocation for protein biosynthesis, at the expense of the observed increase toward energy and lipid metabolisms, might have caused the inhibitory effect of DP oil on cell growth. IMPORTANCE Sustainable processes for biological upcycling of plastic wastes in a circular bioeconomy are needed to promote decarbonization and reduce environmental pollution due to increased plastic consumption, incineration, and landfill storage. Strain characterization and proteomic analysis revealed the robust metabolic capabilities of Yarrowia lipolytica to upcycle polyethylene into high-value chemicals. Significant proteome reallocation toward energy and lipid metabolisms was required for robust growth on hydrocarbons with n-hexadecane as the preferential substrate. However, an apparent over-investment in these same categories to utilize complex depolymerized plastic (DP) oil came at the expense of protein biosynthesis, limiting cell growth. Taken together, this study elucidates how Y. lipolytica activates its metabolism to utilize DP oil and establishes Y. lipolytica as a promising host for the upcycling of plastic wastes.
A spacecraft life support system has been under development at NASA called the Trash Compaction Processing System that manages trash generated on human spaceflight missions. The trash composite typically includes components such as plastic pouches that contain wet food and drinks, used cotton clothing such as underwear and T-shirts, exercise clothing, used washcloths, expended deodorant containers, adhesive tapes, plastic bubble wrap, and other sundry items. The system uses compaction in combination with heat to turn the waste composite into a sturdy and well-defined shape, typically called a tile, which maintains structural integrity and makes the most efficient use of storage space. In addition to reducing the volume of the trash, the Trash Compaction Processing System removes water from the trash. The heating and removal of water from the trash renders it safe against microbial activity. This paper primarily focuses on work aimed at reducing the Equivalent System Mass of a Trash Compaction Processing System via a focus on improving the system’s thermal efficiency.