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At least 631 records · Page 35

Influence of the air-cooled supercritical carbon dioxide recompression cycle design-point on molten salt power tower techno-economic performance

Here, this paper investigates the techno-economic performance of a molten salt power tower integrated with an air-cooled supercritical carbon dioxide recompression cycle. Prior research into the cycle design point showed trade-offs between efficiency, cost, and temperature difference across the heat input, resulting in trade-offs between the design-point generation of the molten salt power tower system and the cost of sensible-heat thermal energy storage. Prior research into cycle off-design showed that colder ambient temperature designs have higher efficiencies on cold days but lower efficiency and capacity degradation on hot days. We present a framework to evaluate how cycle design, cost, and corresponding off-design performance affect the techno-economic performance of the molten salt power tower system. We use a steady-state off-design cycle model assuming fixed shaft speeds, inventory control, and air-cooler fan power control and integrate the cycle model with the molten salt power tower model from the National Renewable Energy Laboratory's System Advisor Model. First, we present a surrogate model that uses a heuristic approach to correct the interpolation when the cycle reaches capacity limitations at ambient temperatures hotter than design. Next, we evaluate how the recompression cycle design-point ambient temperature, air-cooler approach temperature, air-cooler fan power, and recuperator conductance influence cycle and system design metrics. Finally, we complete annual simulations using an hourly "duck curve" pricing schedule and present annual performance metrics to evaluate the cumulative effects of the cycle design parameters and corresponding off-design performance on molten salt power tower techno-economics.

14 SOLAR ENERGY↗

Chemical compatibility of hollow ceramic cenospheres as thermal insulation for high-temperature thermal energy storage applications with molten nitrate salt

An effective insulation material that is both thermally and chemically stable in molten salts could transform the design of molten-salt-based thermal energy storage (TES) tanks. Most current molten salt TES tanks hold the metallic tank structure in direct contact with hot salt inventory, a design which leads to thermal expansion of the tank and triggers stresses that can lead to thermomechanical failures. With an internal insulation to lower the temperature at the tank structure, the extent of thermal expansion can be reduced, thereby reducing expansion-induced stresses and allowing for consideration of lower-cost tank structure materials. Conventional insulation materials are either 1) too porous and allow molten salts to permeate into the matrix, which significantly increases the thermal conductivity or 2) too dense and have a thermal conductivity that cannot provide sufficient thermal insulation. This paper presents an alternative thermal insulation concept using cenospheres which have an alumino-silicate structure. The cost analysis suggests that the low-density cenospheres can be one of the cheapest materials to provide cost-effective thermal insulation. The chemical compatibility of cenospheres is investigated in molten 60 wt% NaNO3/40 wt% KNO3 salt which is close to industrial-grade Solar Salt. This paper shows that diffusion of the sodium and potassium cations from the salt into the cenospheres occurs based on weight analysis, energy dispersive spectroscopy (EDS), X-ray diffraction (XRD) and Fourier-transform infrared (FTIR) spectroscopy. The cation diffusion breaks the bridging oxygen bonds and causes volume expansion of the microstructure which is responsible for the failure of the cenosphere particles. The chemical composition of the cenospheres is found to affect their compatibility with molten nitrate salt. A cenosphere product with low iron content showed the best compatibility with an average survival rate of 77.9% +/- 9.8% after 7 days of immersion in the molten nitrate salt. While even the low-iron cenospheres appear to require protection from direct molten salt contact, their slow degradation rate, closed-cell porosity, and low cost hold potential for effective use as internal tank insulation.

14 SOLAR ENERGY↗

Environmental life cycle assessment methods applied to amine-ionic liquid hybrid CO 2 absorbents

A hybrid solvent mixture of triethyl(octyl)phosphonium cyanopyrrolide [P2228][2-CNPyr] and aqueous monoethanolamine (MEA) has the potential for absorbing CO 2 from post combustion flue gas. However, previous studies have found that the production of phosphonium based ionic liquids (IL) had significantly higher potential environmental impacts compared to MEA. Literature attributes these higher environmental impacts to the phosphine and phosgene-based intermediates required to produce the phosphonium ion of the ionic liquid. This study proposes a novel synthesis pathway that eliminates the need for phosphine and phosgene intermediates in the production of [P2228][2-CNPyr]. The environmental impacts of producing 1kg of the ionic liquid through this novel synthesis route was evaluated using the TRACI 2.1 methodology within the life cycle assessment (LCA) framework. Additionally, the environmental impacts for the production of 1kg of a hybrid solvent was also evaluated and compared against MEA. The life cycle inventory for the production of the IL and its hybrid solvent were calculated based on the stoichiometry and then scaled up. This study found that the IL and its hybrid solvents had higher environmental impacts among 9 of the 10 environmental impact categories calculated by the TRACI 2.1 methodology, except for the ecotoxicity potential. A sensitivity analysis indicated that these solvents were more sensitive to the assumptions of the material requirements of the phosphonium cation than the overall energy or transportation requirements. Despite this sensitivity, both the solvents demonstrated a lower Ecotoxicity Potential compared to MEA, the rest of the environmental impacts were still found to be higher than that of MEA, thereby underscoring the need to investigate novel synthesis routes for the production of phosphonium cation. The uncertainty analysis performed confirmed the findings that the IL has a higher environmental impact potentials across all categories except ecotoxicity potential. The uncertainty analysis also confirms that the phosphonium cation is a major hotspot in production route of these solvents and a source of uncertainty in the model compared to the anion. Altogether, this study underscores the need for investigating novel green chemistry pathway for the synthesis of phosphonium based ionic liquids, such as [P2228][2-CNPyr], to ensure that the these ILs can be a truly green alternative to MEA by not only offering superior CO₂ capture capacity compared to MEA but also being sustainably produced.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Resilient NdFeB magnet recycling under the impacts of COVID-19 pandemic: Stochastic programming and Benders decomposition

Neodymium-iron-boron (NdFeB) magnets are the most powerful magnets per unit volume sold in the commercial market. Despite the increasing demand for clean energy applications such as electric vehicles and wind turbines, disruptive events including the COVID-19 pandemic have caused significant uncertainties in the supply and demand for NdFeB magnets. Therefore, this study aims to alleviate the risk of supply shortage for NdFeB magnets and the containing critical materials, rare-earth elements (REEs), through the development of a resilient reverse supply chain and logistics network design. We develop scenarios to model the unique impact of the COVID-19 pandemic on the proposed business, incorporating both disruption intensity and recovery rate. We formulate a chance-constrained two-stage stochastic programming model to maximize the profit while guaranteeing the network resiliency against disruption risks. To solve the problem in large-scale instances, we develop an efficient Benders decomposition algorithm that reduces the computational time by 98.5% on average compared to the default CPLEX algorithm. When applied to the United States, the model suggests the optimal facility locations, processing capacities, inventory levels, and material flows for NdFeB magnet recyclers that could meet 99.7% of the demand. To the best of our knowledge, this study is the first to incorporate the impacts of the COVID-19 pandemic to design a resilient NdFeB magnet recycling supply chain and logistics network, leveraging risk-averse stochastic programming.

42 ENGINEERING↗

Life cycle assessment of utilizing freshly cut urban wood: A case study

Large amounts of urban wood resources are generated through tree removals in urban areas. Therefore, there is a growing interest to improve the environmental performance of the urban wood supply chain by quantifying the environmental impacts of creating high-value products from urban tree removals to enhance its utilization. By surveying existing urban wood utilization operations for primary data in two major cities: Baltimore, Maryland, and Milwaukee, Wisconsin, a new life cycle inventory (LCI) dataset per m 3 of dry urban hardwood lumber and live edge slabs was created. Incorporating the new LCI data into life cycle assessment method, the total global warming (GW) impact of converting urban trees to kiln-dried lumber was estimated to be 122 kg CO 2 eq and 336 kg CO 2 eq per m 3 of lumber produced for Baltimore and Milwaukee, respectively. In both cases, the total environmental impact of the product was dominated by the conversion of urban trees to kiln dried lumber at the sawmill processing stage. Using scenario analysis for the source of heat generation used in kiln (force) drying wood, substituting wood fuel from coproducts for natural gas in a boiler for Milwaukee resulted in a substantial reduction in fossil-derived GW impact. Urban and traditional hardwood lumber production follow similar GW impact trajectories over their life-cycle stages with the lumber processing stage having the highest environmental impacts for both. Finally, increasing the overall lumber yield and decreasing kiln (force) drying would substantially improve the environmental performance of urban hardwood lumber and help make it comparable to traditional lumber.

54 ENVIRONMENTAL SCIENCES↗

Environmental Life Cycle Assessment of small water resource recovery facilities: Comparison of mechanical and lagoon systems

Small water resource recovery facilities (WRRFs) serving communities with populations of less than 10,000 people account for 70% of centralized wastewater treatment systems in the United States. Here, with growing interest globally in improving the sustainability of these systems, this study evaluated the environmental life cycle impact and land use tradeoffs of different lagoon and mechanical WRRFs across the diverse climate of Nebraska. Life cycle inventory including construction and operations was collected for 35 existing systems representing a range of commonly used mechanical WRRFs: oxidation ditch, extended aeration, and sequencing batch reactors, and lagoon treatment systems: complete retention, irrigation, and controlled discharge lagoons.

42 ENGINEERING↗

Quantifying lithium loss in amorphous silicon thin-film anodes via titration-gas chromatography

Silicon with a high theoretical capacity (3,579 mAh/g) is a promising anode candidate for lithium-ion batteries. However, commercialization is still impeded by low Coulombic efficiency, caused by solid electrolyte interphase (SEI) formation and trapped lithium (Li)-silicon (Si) alloy during repeated volume change. Quantifying capacity losses from each factor is crucial to formulate rational design strategies for further improvement. In this work, titration-gas chromatography and cryogenic transmission electron microscopy are applied to characterize the evolution of trapped Li-Si alloy and SEI growth in a silicon thin-film anode. It is found that continuous growth of the SEI is the dominant factor for lithium inventory loss during cycling, with only a marginal increase in trapped Li-Si alloy. This study offers a quantitative approach to differentiate Li in the SEI from trapped Li in Li-Si alloy through a silicon thin-film anode, providing unique insights into identifying critical bottlenecks for developing Si anodes.

25 ENERGY STORAGE↗

Identifying University Chemicals That Pose Security Risks: A Simple Qualitative Approach

Various laboratory-focused tools and methodologies for completing a safety risk assessment have been published, yet few similar resources to address chemical security exist. Herein, we describe a chemical security risk assessment case study at a university in a developing country. In this case study, we demonstrate a chemical security risk assessment for a university chemistry department, using an original inventory of 645 entries which was condensed to 295 chemicals after removing duplicates and erroneous entries. We then prioritized to highlight 83 chemicals of interest based on hazardous or dual-use properties that could lead to unacceptable consequences. We further refined to a list of 34 high-risk chemicals that required action, 48 chemicals that may need further justification and consideration for additional protection, and 1 chemical that did not need further consideration for additional protection.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of Annealing on Direct Recycled NMC Cathodes

A substantial number of electric vehicle batteries are poised to reach end-of-life conditions in the next decade. Direct recycling has advantages over typical recycling processes because it preserves the chemical structure of the material. One key step of direct recycling materials like nickel manganese cobalt oxide (NMC) cathodes is relithiation, which includes replacing the depleted lithium inventory in the cathode and annealing the material to fix crystallographic degradation. This work uses multiple characterization techniques (synchrotron X-ray diffraction, Ni X-ray absorption near edge structure, scanning transmission electron microscopy) to understand the lithiation mechanism of degraded and chemically relithiated NMC 622. Despite the necessary reconstruction after relithiation being limited to the surface of the degraded NMC 622, a high annealing temperature of 720 °C is still necessary to restore the NMC 622 structure back to pristine condition after relithiation. This work also finds that treating degraded NMC 622 with an annealing step is sufficient to restore key electrochemical and structural properties, other essential features of pristine NMC 622 material such as particle porosity and morphology are largely unaffected. Understanding the effect of this annealing step has important implications on defining the degree of success of any given direct recycling strategy.

36 MATERIALS SCIENCE↗

Methane Emissions from Gathering Compressor Stations in the U.S.

Using results from a nationally representative measurement campaign at 180 gathering compressor stations conducted with nine industry partners, this study estimated emissions for the U.S. gathering sector, where sector-specific emission factors have not been previously available. The study drew from a partner station population of 1705 stations—a significantly larger pool than was available for prior studies. Data indicated that whole gas emission rates from components on gathering stations were comparable to or higher than emission factors utilized by the EPA’s greenhouse gas reporting program (GHGRP) but less than emission factors used for similar components on transmission compressor stations. Field data also indicated that the national population of stations likely has a higher fraction of smaller stations, operating at lower throughput per station, than the data used to develop the per-station emission factor used in EPA’s greenhouse gas inventory (GHGI). This was the first national study to incorporate extensive activity data reported to the GHGRP, including 319 basin-level reports, covering 15,895 reported compressors. Further, combining study emission data with 2017 GHGRP activity data, the study indicated statistically lower national emissions of 1290 [1246–1342] Gg methane per year or 66% [64–69%] of current GHGI estimates, despite estimating 17% [12–22%] more stations than the 2017 GHGI (95% confidence interval). Finally, we propose a replicable method that uses GHGRP activity data to annually update GHGI gathering and boost sector emissions.

03 NATURAL GAS↗

Methane Exhaust Measurements at Gathering Compressor Stations in the United States

Unburned methane entrained in exhaust from natural gas-fired compressor engines (“combustion slip”) can account for a substantial portion of station-level methane emissions. A novel in-stack, tracer gas method was coupled with Fourier transform infrared (FTIR) species measurements to quantify combustion slip from natural gas compressor engines at 67 gathering and boosting stations owned or managed by nine “study partner” operators in 11 U.S. states. The mean methane emission rate from 63 four-stroke, lean-burn (4SLB) compressor engines was 5.62 kg/h (95% CI = 5.15–6.17 kg/h) and ranged from 0.3 to 12.6 kg/h. The mean methane emission rate from 39 fourstroke, rich-burn (4SRB) compressor engines was 0.40 kg/h (95% CI = 0.37– 0.42 kg/h) and ranged from 0.01 to 4.5 kg/h. Study results for 4SLB engines were lower than both the U.S. EPA compilation of air pollutant emission factors (AP-42) and Inventory of U.S. Greenhouse Gas Emissions and Sinks (GHGI) by 8 and 9%, respectively. Study results for 4SRB engines were 43% of the AP-42 emission factor and 8% of the GHGI emission factor, the latter of which does not distinguish between engine types. Total annual combustion slip from the U.S. natural gas gathering and boosting sector was modeled using measured emission rates and compressor unit counts from the U.S. EPA Greenhouse Gas Reporting Program. Modeled results [328 Gg/y (95% CI = 235–436 Gg/y) of unburned methane] would account for 24% (95% CI = 17–31%) of the 1391 Gg of methane emissions for “Gathering and Boosting Stations”, or 6% of the net emissions for “Natural Gas Systems” (5598 Gg) as reported in the 2020 U.S. EPA GHGI. In conclusion, gathering and boosting combustion slip emissions reported in the 2020 GHGI (374 Gg) fall within the uncertainty of this model.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Assessing the Relative Climate Impact of Carbon Utilization for Concrete, Chemical, and Mineral Production

Estimates show that 6.2 gigatons of carbon dioxide (CO2) can be captured and utilized across three pathways, concrete, chemical, and minerals, by 2050. However, it is difficult to compare the climate benefit across these three carbon capture and utilization (CCU) pathways to determine the most effective use of captured CO2. The life cycle assessment methods to evaluate the climate benefit of CCU chemicals should additionally account for the change in material properties of concrete due to CO2 utilization. Furthermore, with most CO2 utilization technologies being in the early stages of research and development, the uncertainty and variability in process and inventory data present a significant challenge in evaluating the climate benefit. We present a stochastically determined climate return on investment (ROI) metric to rank and prioritize CO2 utilization across 20 concrete, chemical and mineral pathways based on the realized climate benefit. We show that two concrete pathways, which use CO2 during concrete mixing, and two chemical pathways, which produce formic acid through hydrogenation of CO2 and carbon monoxide through dry reforming of methane, generate the greatest climate ROI and are the only CCU pathways with a higher likelihood of generating a climate benefit than a climate burden.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Greenhouse Gas and Air Pollutant Emissions from Composting

Composting can divert organic waste from landfills, reduce landfill methane emissions, and recycle nutrients back to soils. However, the composting process is also a source of greenhouse gas and air pollutant emissions. Researchers, regulators, and policy decision-makers all rely on emissions estimates to develop local emissions inventories and weigh competing waste diversion options, yet reported emission factors are difficult to interpret and highly variable. This review explores the impacts of waste characteristics, pretreatment processes, and composting conditions on CO 2 , CH 4 , N 2 O, NH 3 , and VOC emissions by critically reviewing and analyzing 388 emission factors from 46 studies. The values reported to date suggest that CH 4 is the single largest contributor to 100-year global warming potential (GWP 100 ) for yard waste composting, comprising approximately 80% of the total GWP 100 . For nitrogen-rich wastes including manure, mixed municipal organic waste, and wastewater treatment sludge, N 2 O is the largest contributor to GWP 100 , accounting for half to as much as 90% of the total GWP 100 . If waste is anaerobically digested prior to composting, N 2 O, NH 3 , and VOC emissions tend to decrease relative to composting the untreated waste. Effective pile management and aeration are key to minimizing CH 4 emissions. However, forced aeration can increase NH 3 emissions in some cases.

54 ENVIRONMENTAL SCIENCES↗

Correction to “Greenhouse Gas and Air Pollutant Emissions from Composting”

Composting can divert organic waste from landfills, reduce landfill methane emissions, and recycle nutrients back to soils. However, the composting process is also a source of greenhouse gas and air pollutant emissions. Researchers, regulators, and policy decision-makers all rely on emissions estimates to develop local emissions inventories and weigh competing waste diversion options, yet reported emission factors are difficult to interpret and highly variable. This review explores the impacts of waste characteristics, pretreatment processes, and composting conditions on CO 2 , CH 4 , N 2 O, NH 3 , and VOC emissions by critically reviewing and analyzing 388 emission factors from 46 studies. The values reported to date suggest that CH 4 is the single largest contributor to 100-year global warming potential (GWP100) for yard waste composting, comprising approximately 80% of the total GWP 100 . For nitrogen-rich wastes including manure, mixed municipal organic waste, and wastewater treatment sludge, N 2 O is the largest contributor to GWP 100 , accounting for half to as much as 90% of the total GWP 100 . If waste is anaerobically digested prior to composting, N 2 O, NH 3 , and VOC emissions tend to decrease relative to composting the untreated waste. Effective pile management and aeration are key to minimizing CH 4 emissions. However, forced aeration can increase NH 3 emissions in some cases.

54 ENVIRONMENTAL SCIENCES↗

A Proxy Method to Bridge LCA Data Gaps Using Automated Material Classification and Probabilistic Under-Specification

Life cycle assessments (LCAs) are essential for understanding the environmental impacts of material production. However, gaps in life cycle inventory (LCI) data for material and chemical inputs present a key challenge for LCA practitioners, especially in the early design stages. Strategies for filling in these gaps require additional time and expertise, which can hinder the LCA’s completion. This study combined automatic material classification and probabilistic under-specification to create a time-efficient method to fill material LCI data gaps. To illustrate the proposed method, proxy environmental impact distributions were generated using publicly available material LCI data classified into the ChemOnt chemical taxonomy using the open-source chemical classification software ClassyFire. Input materials with data gaps were then classified into the same taxonomy, where proxy environmental impact values could be selected from the available distributions to quickly fill in any data gaps. Although these methods were applied to classify material production processes available in the Federal LCA Commons and Ecoinvent databases, they can be applied to any LCA database. This study shows that classifying materials by their chemical structure produces taxonomies with increased granularity relative to industrial classification, improving the ability of under-specified proxy data to be used for differentiating the environmental impacts of competing designs.

biological databases↗

Ten-Fold Solvent Kinetic Isotope Effect for the Nonradiative Relaxation of the Aqueous Ferrate(VI) Ion

Hypervalent iron intermediates have been invoked in the catalytic cycles of many metalloproteins, and thus, it is crucial to understand how the coupling between such species and their environment can impact their chemical and physical properties in such contexts. In this work, we take advantage of the solvent kinetic isotope effect (SKIE) to gain insight into the nonradiative deactivation of electronic excited states of the aqueous ferrate-(VI) ion. Here we observe an exceptionally large SKIE of 9.7 for the nanosecond-scale relaxation of the lowest energy triplet ligand field state to the ground state. Proton inventory studies demonstrate that a single solvent O-H bond is coupled to the ion during deactivation, likely due to the sparse vibrational structure of ferrate-(VI). Such a mechanism is consistent with that reported for the deactivation of f-f excited states of aqueous trivalent lanthanides, which exhibit comparably large SKIE values. This phenomenon is ascribed entirely to dissipation of energy into a higher overtone of a solvent acceptor mode, as any impact on the apparent relaxation rate due to a change in solvent viscosity is negligible.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Unraveling the Early-Stage Ordering of Krypton Solid Bubbles in Molybdenum: A Multimodal Study

Self-organization of defects such as fission gas bubbles in materials can lead to high inventory capacity for fission gas storage and help mitigate swelling caused by fission gases in nuclear fuel materials under radiation in nuclear reactors. Here, we report the physical mechanism of self-organization of krypton (Kr) gas bubbles in molybdenum (Mo) under ion implantation. The ion fluence and temperature-dependent formation of Kr solid bubble superlattice (SBS) in Mo were investigated by using both synchrotron-based small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM). Early stage self-organization of gas bubbles is observed at a fluence of 2.5 × 10 16 ions/cm 2 at temperatures of 300–400 °C. The bubble lattice constant increases with increasing implantation temperature from 300 to 400 °C. Both experiments and atomic kinetic Monte Carlo modeling indicate that the Kr solid bubbles are weakly ordered in comparison to previously studied helium (He) gas bubble superlattice (GBS) while the lattice constant are relatively smaller for Kr SBS compared to that of He GBS. The irradiation conditions suggest that spinodal decomposition, which is a form of phase separation, probably precedes gas bubble ordering in Mo. Altogether, our work sheds light on the formation mechanism of noble gas superlattice toward the development of radiation-tolerant materials which are important for the design of advanced nuclear reactors.

36 MATERIALS SCIENCE↗

Prelithiated SiO x /Graphite-NMC811 Cells: Capacity Loss, Impedance Rise and Hidden Degradation Pathways Revealed Using Three-Electrode Diagnostics

Electrodes containing SiO x /graphite (Gr) materials are attractive as anodes for high-energy lithium-ion batteries. However, their mechanical deformation, electrochemical response, and impedance evolution during long-term cycling are strongly coupled, complicating accurate diagnosis of performance fade mechanisms. In this work, the behavior of electrochemically prelithiated SiO x /Gr anodes paired with NMC811 cathodes is systematically investigated using techniques that include in-situ dilatometry, three-electrode electrochemistry, and multiscale post-cycling microscopy. The SiO x /Gr electrode exhibits a maximum expansion of 49% upon lithiation to 10 mV vs Li + /Li, with 84% of the expansion and 91% of the capacity being reversible. In full cells, relatively stable cycling with only 12% capacity fade over 500 cycles is observed. Three-electrode experiments reveal cell-level impedance growth, which is dominated by the NMC811 cathode: the SiO x /Gr anode exhibits minimal net impedance rise and an initial impedance decrease at low potentials. Despite this apparent electrochemical stability, cross-sectional SEM, PFIB tomography, and cryo-STEM reveal irreversible anode thickening caused by the accumulation of an inorganic-rich solid electrolyte interphase (SEI) permeating the anode bulk. Electrode potential-shift analysis further demonstrates that Li + ions released from lithium reservoirs in the prelithiated anode mask true lithium inventory loss during aging. These results demonstrate that low-expansion SiO x /Gr anodes can simultaneously exhibit favorable cycling and impedance metrics while undergoing substantial, hidden degradation, underscoring the importance of electrode-resolved diagnostics for evaluating prelithiated silicon-based anodes.

25 ENERGY STORAGE↗