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At least 541 records · Page 30

Structural Origins of High MoO 3 Solubility in Peraluminous Borosilicate Glasses

Molybdenum (Mo) imposes strict loading limits in conventional borosilicate nuclear waste glasses due to the tendency of tetrahedral molybdate [MoO 4 ] 2− species to phase-separate and crystallize as alkali molybdates. Here, we demonstrate an unprecedented 13.96 wt % (7.51 mol %) MoO 3 solubility in peraluminous sodium aluminoborosilicate glasses a ∼15× increase over their peralkaline counterparts. Using Raman spectroscopy, multinuclear and dipolarcorrelation magic angle spinning nuclear magnetic resonance (MAS NMR), electron paramagnetic resonance (EPR), and scanning transmission electron microscopy (STEM)-energy dispersive spectroscopy (EDS), we reveal that Nadeficient, low optical basicity conditions stabilize octahedral MoO 6 units, which polymerize into molybdite-like Mo−O clusters dispersed within the glass matrix. These Mo-rich clusters suppress the formation of depolymerized [MoO 4 ] 2− environments typically responsible for Na 2 MoO 4 precipitation and instead promote the formation of Na 2 Mo 2 O 7 as the saturation phase. Concurrently, Mo solubility drives the conversion of AlO 4 − to higher-coordination AlO 5 species, liberating Na + that is subsequently sequestered in molybdate-rich domains. The combined evolution of Mo coordination, modifier redistribution, and network depolymerization provides a mechanistic basis for the markedly enhanced Mo solubility in peraluminous compositions. These findings establish new structural guidelines for designing aluminoborosilicate waste forms with substantially greater capacity to incorporate Mo-rich nuclear waste streams.

Amorphous materials↗

Hydrogenolysis of Polypropylene and Mixed Polyolefin Plastic Waste over Ru/C to Produce Liquid Alkanes

Catalytic depolymerization of polyolefins is a promising chemical recycling strategy to create value-added products from waste plastics, which are accumulating in landfills and the natural environment at unsustainable rates. The cleavage of strong C–C bonds in polyolefins can be performed using a noble metal and hydrogen via a hydrogenolysis mechanism. Previously, we identified ruthenium nanoparticles supported on carbon (Ru/C) as a highly active heterogeneous catalyst for the conversion of polyethylene into liquid and gaseous n-alkanes under mild conditions. In the present study, we investigated the catalytic depolymerization of polypropylene (PP) under mild conditions (200–250 °C, 20–50 bar H 2 ). We demonstrate that Ru/C produces C 5 –C 32 iso-alkane yields above 68% in the absence of solvent and identify trade-offs between product yield and temperature, hydrogen pressure, and reaction time. We apply a rigorous analytical method to quantify all liquid and gaseous alkane products. The characterized catalyst was found to be recyclable after the complete depolymerization of high molecular weight PP (M w ~ 340,000 Da) to liquid and gaseous hydrocarbons and after depolymerization of a postconsumer PP centrifuge tube. Finally, the catalyst was shown to be effective in depolymerizing a mixture of high-density polyethylene and PP to produce a mixture of linear and branched liquid alkanes, demonstrating feasibility for the depolymerization of streams of mixed polyolefin waste.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Western Combined Heat and Power Technical Assistance Partnership (Final Technical Report)

Since 2018, the Western Combined Heat and Power Technical Assistance Partnership (CHP TAP) has been dedicated to advancing the adoption and implementation of Combined Heat and Power. The CHP TAP has diligently worked towards its mission of fostering end-user engagement, promoting technical solutions, and enhancing energy security within the region. As we reflect on our journey, we are proud to announce the completion of the required metrics set forth at the beginning of our endeavor. From the outset, our aim has been clear: to leverage CHP technology as a catalyst for bolstering American competitiveness, utilizing local fuels, and fortifying energy resilience. Through collaborative efforts with a diverse array of stakeholders, including manufacturing, commercial, institutional, and federal facilities, and campuses, we have strived to realize this vision. In this report, we outline the achievements, activities, and impact of the Western CHP TAP, highlighting the transformative journey undertaken since 2018. From providing technical assistance and guidance to conducting educational workshops and advocating for supportive policies, our initiatives have been guided by a commitment to excellence and innovation. As we celebrate the completion of our required metrics, we reaffirm our dedication to continuing our mission, building upon our accomplishments, and shaping a sustainable energy future for the Western region. Through ongoing collaboration and engagement, we are confident that the Western CHP TAP will continue to serve as a beacon of progress and a catalyst for positive change in the years to come.

03 NATURAL GAS↗

Investigation of Reaction Pathways and Temperature Inhibition in Methane DBD Plasmas at the Princeton Collaborative Research Facility (PCRF)

The overarching goal of this research is to advance the fundamental understanding of plasma-driven chemical conversion of light hydrocarbons using dielectric barrier discharges (DBDs). Using methane (CH 4 ) as a model system, the primary focus is to elucidate the influence of DBD plasma properties and environmental temperature on CH 4 plasma chemistry by studying decomposition products of the gas effluent across a broad range of conditions using experimental instrumentation at the Princeton Collaborative Research Facility (PCRF) located at the Princeton Plasma Physics Laboratory (PPPL). The insights obtained from this study are expected to form the mechanistic foundation for the design and optimization of plasma-catalytic reactions of light hydrocarbons for practical applications such as the recycling of production flare gas by transforming the uncaptured waste into value-added resources at the source of extraction, presenting a sustainable solution to a longstanding environmental challenge.

03 NATURAL GAS↗

Technoeconomic Analysis of a Microwave-Assisted Novel Process That Converts Polypropylene Plastic Waste to Propylene

Propylene is an important petrochemical that is used in various industries, including the automobile and polymer sectors. Conventionally, propylene has been produced through fluid catalytic cracking, steam cracking, and propane dehydrogenation. In this project, a novel process to produce propylene from polypropylene plastic waste using a microwave reactor is introduced. Propylene production is simulated in Aspen Plus for both the conventional propane dehydrogenation process and the novel design, with heat integration applied to minimize utility demands and the conventional process serving as the base case for comparison. Finally, a tailored technoeconomic analysis is carried out for both simulated cases to estimate important economic indicators. Analysis of the results shows that the novel microwave-assisted process outperforms the conventional route for propylene production, achieving a single-pass conversion of almost 100%, compared with only 33.8% in the conventional plant. The Net Present Value of the novel plant is $\$1720.3$ MM, which is 3.5 times higher than the conventional process, while the Levelized Cost of Propylene is reduced by 40%. Capital and operating expenditure are also improved in the proposed scheme, with reductions of approximately $\$29$ MM and $\$222$ MM/yr, respectively. In addition to cost savings, this novel process also provides a convenient means to recycle waste polypropylene.

42 ENGINEERING↗

Unconventional Thermoelectric Materials for Energy Harvesting and Sensing Applications

Heat is an abundant but often wasted source of energy. Thus, harvesting just a portion of this tremendous amount of energy holds significant promise for a more sustainable society. While traditional solid-state inorganic semiconductors have dominated the research stage on thermal-to-electrical energy conversion, carbon-based semiconductors have recently attracted a great deal of attention as potential thermoelectric materials for low-temperature energy harvesting, primarily driven by the high abundance of their atomic elements, ease of processing/manufacturing, and intrinsically low thermal conductivity. This quest for new materials has resulted in the discovery of several new kinds of thermoelectric materials and concepts capable of converting a heat flux into an electrical current by means of various types of particles transporting the electric charge: (i) electrons, (ii) ions, and (iii) redox molecules. This has contributed to expanding the applications envisaged for thermoelectric materials far beyond simple conversion of heat into electricity. This is the motivation behind this review. This work is divided in three sections. In the first section, we present the basic principle of the thermoelectric effects when the particles transporting the electric charge are electrons, ions, and redox molecules and describe the conceptual differences between the three thermodiffusion phenomena. In the second section, we review the efforts made on developing devices exploiting these three effects and give a thorough understanding of what limits their performance. In the third section, we review the state-of-the-art thermoelectric materials investigated so far and provide a comprehensive understanding of what limits charge and energy transport in each of these classes of materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Adaptive Laboratory Evolution for Enhanced Performance of Cupriavidus Necator on Formic Acid

The threat of global warming, driven by rising carbon emissions, highlights the need to decarbonize our economy. This requires innovative solutions for managing carbon waste and its effective utilization. One promising method for CO2 capture and sequestration is the electrochemical reduction of CO2 to formic acid, a soluble C1 molecule that can be used to store carbon and energy, and as a feedstock for biological conversion. Cupriavidus necator H16, a soil bacterium capable of consuming and growing on formic acid as its sole carbon and energy source, is well positioned to upgrade CO2-derived formic acid into platform chemicals and fuel precursors. To improve the performance of C. necator on formic acid, adaptive laboratory evolution (ALE), a proven tool for improving microbial fitness, has been conducted using continuous pH-stat bioreactors. The system works on the basis that consumption of formic acid raises the pH and triggers the addition of more formic acid to maintain the pH (in this case 6.7), such that formic acid is provided at the same rate as it is consumed. This system has been coupled with level control to achieve continuous fermentation where cells acquiring mutations that improve growth on formic acid become more abundant in the population, from which they can be isolated and characterized. During developmental experiments it was discovered that formic acid accumulated to inhibitory levels. It was determined that the nitrogen source, ammonium hydroxide, must be tailored to the carbon consumption to avoid formic acid accumulation. The ALE ran in three lineages for approximately 3000 hours and more than 500 generations. Evolved isolates obtained from each lineage demonstrated an increase in growth rate in conjunction with improve formate utilization compared to the parental strain when evaluated in pH-stat bioreactors. The isolates with improved performance were then subjected to whole genome sequencing to identify potentially causative mutations. Mutations in several key genes across different lineages have been found and will be evaluated individually and in combination to identify those that improve growth on formic acid. Incorporating these mutations into production strains has the potential to greatly improve formic acid conversion and further industrial decarbonization.

adaptive laboratory evolution↗

Energy Conversion Alternatives Study (ECAS), Westinghouse phase 1. Volume 12: Fuel cells

A parametric assessment of four fuel cell power systems -- based on phosphoric acid, potassium hydroxide, molten carbonate, and stabilized zirconia -- has shown that the most important parameters for electricity-cost reduction and/or efficiency improvement standpoints are fuel cell useful life and power density, use of a waste-heat recovery system, and fuel type. Typical capital costs, overall energy efficiencies (based on the heating value of the coal used to produce the power plant fuel), and electricity costs are: phosphoric acid $350-450/kWe, 24-29%, and 11.7 to 13.9 mills/MJ (42 to 50 mills/kWh); alkaline $450-700/kWe, 26-31%, and 12.8 to 16.9 mills/MJ (46 to 61 mills/kWh); molten carbonate $480-650/kWe, 32-46%, and 10.6 to 19.4 mills/MJ (38 to 70 mills/kWh), stabilized zirconia $420-950/kWe, 26-53%, and 9.7 to 16.9 mills/MJ (35 to 61 mills/kWh). Three types of fuel cell power plants -- solid electrolytic with steam bottoming, molten carbonate with steam bottoming, and solid electrolyte with an integrated coal gasifier -- are recommended for further study.

Warde, C. J.↗

Advances and Challenges in Low‐Temperature Upcycling of Waste Polyolefins via Tandem Catalysis

Abstract Polyolefin waste is the largest polymer waste stream that could potentially serve as an advantageous hydrocarbon feedstock. Upcycling polyolefins poses significant challenges due to their inherent kinetic and thermodynamic stability. Traditional methods, such as thermal and catalytic cracking, are straightforward but require temperatures exceeding 400 °C for complete conversion because of thermodynamic constraints. We summarize and critically compare recent advances in upgrading spent polyolefins and model reactants via kinetic (and thermodynamic) coupling of the endothermic C─C bond cleavage of polyolefins with exothermic reactions including hydrogenation, hydrogenolysis, metathesis, cyclization, oxidation, and alkylation. These approaches enable complete conversion to desired products at low temperatures (<300 °C). The goal is to identify challenges and possible pathways for catalytic conversions that minimize energy and carbon footprints.

Zhang, Wei [State Key Laboratory of Petroleum Mole↗

Advances and Challenges in Low‐Temperature Upcycling of Waste Polyolefins via Tandem Catalysis

Abstract Polyolefin waste is the largest polymer waste stream that could potentially serve as an advantageous hydrocarbon feedstock. Upcycling polyolefins poses significant challenges due to their inherent kinetic and thermodynamic stability. Traditional methods, such as thermal and catalytic cracking, are straightforward but require temperatures exceeding 400 °C for complete conversion because of thermodynamic constraints. We summarize and critically compare recent advances in upgrading spent polyolefins and model reactants via kinetic (and thermodynamic) coupling of the endothermic C─C bond cleavage of polyolefins with exothermic reactions including hydrogenation, hydrogenolysis, metathesis, cyclization, oxidation, and alkylation. These approaches enable complete conversion to desired products at low temperatures (<300 °C). The goal is to identify challenges and possible pathways for catalytic conversions that minimize energy and carbon footprints.

C-C cleavage↗

HOW MUCH FUTURE FOR ELECTRIC PROPULSION

Low powerplant weight and elimination of waste heat in order to provide adequate endurance are the primary aims of electric propulsion system design

ROCKET ENGINE↗

Thermoradiative Conversion for Space Power Systems

The thermoradiative cell is a new method for converting heat energy to electrical power, first detailed by Strandberg in 2015. The cell is structurally similar to a photovoltaic cell, in that it is a p-n junction semiconductor device, but thermodynamically operates in the reverse direction, converting the thermal dark current into electrical power by utilizing the recombination radiation from thermally-generated electron hole pairs to radiate waste heat to space. This technology may have application for space missions in converting thermal energy produced by a radioisotope source or from a nuclear reactor into power. The power and efficiency can be calculated as a function of bandgap in the detailed-balance case (the Shockley-Queisser limit), in which all of the thermal emissivity of the cell is due to the recombination of thermally generated electron-hole pairs, and all other recombination losses are ignored. The current produced is directly proportional to the recombination radiation, and thus the more thermally generated pairs, the higher the current. The voltage is proportional to the external bias. These two constraints allow optimization of the optimum bias point for maximum power, and allow calculation of the efficiency at maximum power point. Unlike photovoltaic cells, the maximum power operating point is not the same as the maximum efficiency point, and higher efficiency can be achieved at a higher (negative) bias in the ideal case. Incorporating non-ideal losses, however, shifts the maximum efficiency point toward lower bias. Since a thermoradiative cell operates by radiating directly to space, the current produced by a themoradiative cells will increase with the Stefan-Boltzman radiative efficiency; roughly the fourth power of the temperature. Thus, in contrast to a photovoltaic converter, the power produced is highest at high operating temperatures. Likewise, in contrast to conventional thermal conversion, high radiator temperature increases, rather than decreases the efficiency. Thus, the thermoradiative conversion may fill a mission niche in which small radiator size is required. The basic operation will be summarized, applications to space power discussed, and the requirements for further research outlined.

Photovoltaic Cell↗

Heat transfer from glass melt to cold cap: Computational fluid dynamics study of cavities beneath cold cap

Efficient glass production depends on the continuous supply of heat from the glass melt to the floating layer of batch, or cold cap. Computational fluid dynamics (CFD) are employed to investigate the formation and behavior of gas cavities that form beneath the batch by gases released from the collapsing primary foam bubbles, ascending secondary bubbles, and in the case of forced bubbling, from the rising bubbling gas. The gas phase fraction, temperature, and velocity distributions below the cold cap are used to calculate local and average heat transfer rates as a function of the bubbling rate. It is shown that the thickness of the cavities is nearly independent of the cold cap shape and the amount of foam evolved during batch conversion. Furthermore, it is ~7 mm and up to ~15 mm for the cases without and with forced bubbling used to promote circulation within the melt, respectively. Using computed velocity and temperature profiles, the melting rate of the simulated high-level nuclear waste glass batch was estimated to increase with the bubbling rate to the power of ~0.3 to 0.9, depending on the flow pattern. The simulation results are in good agreement with experimental data from laboratory- and pilot-scale melter tests.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Gasification of Coal/Plastic Mixtures: Fundamental Studies in a Laminar Entrained Flow Reactor

There is interest in leveraging entrained-flow coal gasification for co-processing plastic waste. However interactions between plastic and coal, particularly possible competition between coal volatiles and plastic vapors for oxygen, are not well understood. This study explores co-gasification of pulverized coal and plastic granules in a lab-scale entrained-flow reactor. Conversion and CO/CO2 ratio are given special attention.

Kareem, Afeez↗

Trash-to-Gas: Using Waste Products to Minimize Logistical Mass During Long Duration Space Missions

Just as waste-to-energy processes utilizing municipal landftll and biomass wastes are finding increased terrestrial uses, the Trash-to-Gas (TtG) project seeks to convert waste generated during spaceflight into high value commodities. These include methane for propulsion and water for life support in addition to a variety of other gasses. TtG is part of the Logistic Reduction and Repurposing (LRR) project under the NASA Advanced Exploration Systems Program. The LRR project will enable a largely mission-independent approach to minimize logistics contributions to total mission architecture mass. LRR includes technologies that reduce the amount of consumables that need to be sent to space, repurpose items sent to space, or convert wastes to commodities. Currently, waste generated on the International Space Station is stored inside a logistic module which is de-orbited into Earth's atmosphere for destruction. The waste consists of food packaging, food, clothing and other items. This paper will discuss current results on incineration as a waste processing method. Incineration is part of a two step process to produce methane from waste: first the waste is converted to carbon oxides; second, the carbon oxides are fed to a Sabatier reactor where they are converted to methane. The quantities of carbon dioxide, carbon monoxide, methane and water were measured under the different thermal degradation conditions. The overall carbon conversion efficiency and water recovery are discussed.

Hintze, Paul. E.↗

Trash-to-Gas: Using Waste Products to Minimize Logistical Mass During Long Duration Space Missions

Just as waste-to-energy processes utilizing municipal landftll and biomass wastes are finding increased terrestrial uses, the Trash-to-Gas (TtG) project seeks to convert waste generated during spaceflight into high value commodities. These include methane for propulsion and water for life support in addition to a variety of other gasses. TtG is part of the Logistic Reduction and Repurposing (LRR) project under the NASA Advanced Exploration Systems Program. The LRR project will enable a largely mission-independent approach to minimize logistics contributions to total mission architecture mass. LRR includes technologies that reduce the amount of consumables that need to be sent to space, repurpose items sent to space, or convert wastes to commodities. Currently, waste generated on the International Space Station is stored inside a logistic module which is de-orbited into Earth's atmosphere for destruction. The waste consists of food packaging, food, clothing and other items. This paper will discuss current results on incineration as a waste processing method. Incineration is part of a two step process to produce methane from waste: first the waste is converted to carbon oxides; second, the carbon oxides are fed to a Sabatier reactor where they are converted to methane. The quantities of carbon dioxide, carbon monoxide, methane and water were measured under the different thermal degradation conditions. The overall carbon conversion efficiency and water recovery are discussed

Hintze, Paul E.↗

Techno-Economic Analysis and Global Warming Potential of a Novel Offshore Macroalgae Biorefinery

The success of a large scale macroalgae-based biorefinery is dependent on the demonstration of favorable system economics and environmental sustainability. This study uses detailed process modeling to quantify the mass and energy flows through the various unit operations required for a novel free-floating macroalgae biorefinery concept. The modular process model served as the foundation for the techno-economic and global warming potential analyses used to quantify the sustainability of the proposed concept. This work includes detailed techno-economic results for a complete macroalgae cultivation and conversion system with multiple hatchery configurations and several emerging technologies. System optimization was achieved through the evaluation of various technology options for each unit operation. Technologies considered include traditional twine and textile substrate hatchery configurations, drone assisted seeding and biomass transport, mechanized line seeding and harvesting, adhesive spore mixtures that simplify seeding operations and improve hatchery energetics, and hydrothermal liquefaction to produce upgradable biocrude. Outputs from the system include renewable diesel (R100), naphtha, biochar, nitrogen and phosphorus fertilizers, and aqueous/solid waste streams. Three different system pathways were explored, yielding a biomass production cost ranging from $210 to $565 per dry metric ton and a minimum fuel selling price from $1.35 to $2.91 per liter of gasoline equivalent. Stochastic manipulation of the process model and sensitivity analyses support these results. The global warming potential analysis shows net greenhouse gas emissions ranging from 14 to 29 gCO2-eq MJ-1, supported by stochastic and sensitivity analyses. The recommendations from this work highlight critical areas for research and development investment such that a sustainable macroalgae cultivation and conversion system can be realized.

NOMAD seaweed cultivation, techno-economic analysi↗

Flexible polyurethanes, renewable fuels, and flavorings from a microalgae oil waste stream

Renewable polymers have become an important focus in next-generation materials, and algae biomass offers an environmentally low-impact feedstock that can serve multiple uses. This study aims to develop a scalable methodology for production of microalgae-based polyols for polyurethane synthesis from waste oils derived from algae biomass. Following separation of omega-3 fatty acids from algae oil, residual oils can offer valuable building blocks for petrochemical replacements. However, unlike vegetable oils, algae oils contain organic contaminants, including photosynthetic pigments and hydrophobic cofactors that can complicate preparative methodologies. Here we convert and purify waste streams from omega-3 depleted Nannochloropsis salina algae oil, with major components consisting of palmitic and palmitoleic acid, into azelaic acid (AA) as a building block for flexible polyurethanes, with a simultaneous production of heptanoic acid (HA) as a flavor and fragrance precursor. Conversion of free fatty acid mixtures into a soft soap allows extraction of organic contaminants, and urea complexation provides isolated palmitoleic acid, which is subsequently ozonolyzed to produce AA and HA. Bio-based polyester diols are prepared from AA via esterification to provide a polyol monomer for flexible polyurethane foam preparation. The HA co-product is modified to produce the flavoring agent methyl heptanoate and also decarboxylated to produce hexane as a renewable solvent. This scalable process can be performed on oils from multiple algal species, offering valuable monomers from a highly sustainable source.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗