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DOE OSTI2020

The rate of development of atomic mixing and temperature equilibration in inertial confinement fusion implosions

The MARBLE project is a novel inertial confinement fusion platform for studying the development of atomic mixing and temperature equilibration in inertial confinement fusion implosions and their impact on thermonuclear burn. Experiments involve the laser-driven implosion of capsules filled with deuterated engineered foams whose pores are filled with a gaseous mixture of hydrogen and tritium. By varying the size of the foam pores, we can study the timescale of the development of atomic mix relative to the development of thermal equilibrium between species. In contrast, previous separated reactant experiments have only provided information on the total amount of mix mass. Additionally, we report on the series of MARBLE experiments [first reported in Haines et al., Nat. Commun. 11, 544 (2020)] performed on the University of Rochester's OMEGA laser facility and detailed and highly resolved three-dimensional radiation-hydrodynamic simulations of the implosions. In both the experimental and simulation results, we observe that the reactants do not achieve thermal equilibrium during the course of the implosion except in atomically mixed regions—i.e., that atomic mixing develops faster than thermal equilibration between species. The results suggest that ion temperature variations in the mixture are at least as important as reactant concentration variations for determining the fusion reaction rates.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

DOE OSTI2021

Unraveling the Ion Adsorption Kinetics in Microporous Carbon Electrodes: A Multiscale Quantum-Continuum Simulation and Experimental Approach

With the understanding that sorption in porous carbon electrodes is crucial to many environmental and energy technologies, such as capacitive deionization (CDI), supercapacitor energy storage, and activated carbon filters. In each of these examples, a practical model that can describe ion electrosorption kinetics is highly desirable for accelerating material design. Here, we proposed a multiscale model to study the ion electrosorption kinetics in porous carbon electrodes by combining quantum mechanical simulations with continuum approaches. Our model integrates the Butler-Volmer (BV) equation for sorption kinetics and a continuously stirred tank reactor (CSTR) formulation with atomistic calculations of ion hydration and ion-pore interactions based on density functional theory (DFT). We validated our model experimentally by using ion mixtures in a flow-through electrode CDI device and developed an in-line UV absorption system to provide unprecedented resolution of individual ions in the separation process. We showed that the multiscale model captures unexpected experimental phenomena that cannot be explained by the traditional ion electrosorption theory. The proposed multiscale framework provides a viable approach for modeling separation processes in systems where pore sizes and ion hydration effects strongly influence the sorption kinetics, which can be leveraged to explore possible strategies for improving carbon-based and, more broadly, pore-based technologies

36 MATERIALS SCIENCE↗

DOE OSTI2022

Hydrogen Blending into Natural Gas Pipeline Infrastructure: Review of the State of Technology

Hydrogen is an energy carrier that could play an important role in reducing emissions associated with difficult-to-decarbonize sectors including peaking and load-following electricity and industrial heating. Blending hydrogen into the natural gas pipelines has been proposed as an approach for achieving near-term emissions reductions and early-market access for hydrogen technologies such as electrolyzers. Numerous challenges and uncertainties complicate this approach to natural gas decarbonization, however, and this review summarizes current research on the material, economic, and operational factors that must be considered for hydrogen blending. First, this review explores previous research regarding the effects of blending hydrogen on gas mixture fluid and thermodynamic properties, pipeline materials and equipment performance within transmission and distribution networks, and supporting facilities such as underground storage and end-use hydrogen separation. We also investigate and summarize studies that developed mathematical models of natural gas pipeline networks with hydrogen blending, and the operational and techno-economic findings of these network studies. Finally, we discuss notable hydrogen blending demonstrations and their key outcomes. Many blending demonstrations internationally have proven that low hydrogen percentage blending is feasible under very specific scenarios with limited end-usage applications on both high-pressure transmission lines and low-pressure distribution lines. This report summarizes findings from literature into key areas of consensus and disagreement. Research gaps and disagreements between the literature are highlighted to provide directions for future hydrogen blending research.

03 NATURAL GAS↗

DOE OSTI2025

Technical Assessment of Off-Gas System Technologies for Potential Use in Molten Salt Reactors

Molten salt reactors (MSRs) are a class of Generation IV advanced reactor technologies aimed to enhance and improve the safety, fuel utilization and cost-effectiveness of nuclear power generation. MSR concepts are based on using a molten salt mixture as a primary nuclear reactor coolant, while the fuel can be either directly dissolved in the coolant (i.e., fluid-fueled) or can be in a separate solid form (i.e., salt-cooled solid-fueled). MSRs can be operated in either thermal or fast neutron spectra, as simple fissile convertors, or breeder reactors (e.g., utilizing both fissile and fertile fuels), as well as accelerator-driven sub-critical reactors or transuranic element burners. Operation of MSRs will necessitate management and treatment of the off-gas streams released to the headspace of the reactor where, in some designs, a cover gas can be circulated to remove certain fission products and maintain an inert atmosphere. An inert MSR cover gas swept over or sparged into the salt will confine radionuclides emerging from the free surface, including radioactive noble and non-noble gases, aerosols, and volatile species. The elements and compounds of these species will have a wide range of thermochemical and physical properties, some of which will decay to different products in the off-gas stream. Therefore, system components used to manage and treat MSR off-gas streams will need to be robust under dynamic reactor and chemistry conditions to support adequate reactor performance by managing the composition and species in the salt coolant and cover gas space. Off-gas system components would perform as a radionuclide boundary to the reactor vessel and a primary means for preventing radionuclide release; therefore, they are of high safety significance for MSR operations. This report reviews various technologies and materials for potential implementation in the design of an MSR off-gas system per a general conceptual framework. The reviewed technologies operate based on scrubbing, capture, delay, or separation of species in the off-gas stream. These include molten hydroxide scrubbers, solid sorbents, delay off-gas systems, particle traps, and cryogenic distillation. Since aspects of an off-gas system will be design-specific, the approach is to provide general discussions on attributes of these technologies and materials, including target off-gas stream species, operational parameters and conditions of importance to decontamination factors, implementation maturity, system component monitoring, potential off-normal conditions and considerations for waste products. The information aims to support the U.S. Nuclear Regulatory Commission in their safety evaluations for MSR designs.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

DOE OSTI2023

Study on Electrostatic Separation of Quinoline Insolubles from Coal Tar Pitch

The feasibility of electrical separation in the removal of quinoline insoluble (QI) particles from coal tar pitch (CTP) was experimentally investigated. QI particle involvement prohibits the effective fabrication of high-quality value-added products, such as carbon fibers, from CTP. A substantial and sustainable CTP market exists around the world; therefore, a strong incentive exists to develop a viable technical approach to effectively and economically remove QI particles from CTP. The electrical separation method shows promise to achieve this technical goal (Cao et al., 2012). Even with the given setup (wire- cylinder adapted), critical issues remain to be addressed for this method to be applicable to the CTP: (1) identifying the wash oil used in the original QI separation, (2) understanding the mechanism of QI separation, (3) characterizing the deposit, and (4) identifying the QI. This study integrated a set of experimental and analysis techniques into the electrical separation tests to address the aforementioned issues. Key findings are as follows: 1. Electric current responses: • The electric current level of the CTP–wash oil solution reported by Cao et al. (2012) can be attained by using a mixture of 25% quinoline and 75% toluene for the CTPs examined in this study under the same electrical load condition. • The electric current tends to decrease during the test period because of the decreasing number of charged particles. • The reversed field corresponded to the configuration of electrostatic precipitation for positive corona discharge. The high electric field can result in dielectric breakdown and lead to an abrupt current surge. 2 Deposit response and solvent candidates: • Deposit of particles in CTP mixture can be effectively implemented in a wire-cylinder configuration as proposed and examined in this study. • Deposit depends on the solvents. Among the solvents tested, two- and three-part solvents that included quinoline and ethanol (i.e., 25% quinoline and 75% toluene; 50% quinoline and 50% toluene; and 33% wash oil, 33% BTX, and 34% ethanol) produced the highest deposit weight. • The deposit process examined in this study is derived from the charged particles. An appreciable relation exists between deposit weight and electric charge. 3. QI removal efficiency (RE): • The RE of the electrostatic separation can reach as high as 76.2% for Carbores, and 61.6% for Koppers. • The RE can be further enhanced if the field level increases from 0.16 kV/mm that was used in the current study to 0.23 kV/mm, according to the relation established between the RE and the electric field. 4. Testing of the modeling system: • The motion of particles is originally driven by the charge-based electric force in the cases tested. The solid particle separation mechanism is similar to that of QI deposition in CTP. • The mechanical movement of solid particles can be strongly affected by the gravitational and viscous forces in the electric field. 5. EDS analysis and chemical compositions: • The main chemical composition of deposit QI matches that of as-prepared CTP QI. The deposit QI is derived from the same group of the CTP QI. • In addition to carbon, the QI contains oxygen, sodium, aluminum, silicon, iron, and sulfur. The work for the near future is also discussed.

01 COAL, LIGNITE, AND PEAT↗

DOE OSTI2024

Ion Mobility Separations Using Cocentric Architecture

Ion mobility separations are usually performed in linear channels, which, when extended, can have a large footprint. In this work, we explored the performance of an ion mobility device with a curved architecture which can have a more compact form. The Co-centric Ion Mobility Spectrometer (CIMS) works by manipulating ions between two co-centric surfaces, each containing a serpentine track. The mobility separation inside CIMS is achieved using traveling waveforms (TWs). We initially evaluated the device using ion trajectory simulations using SIMION, which indicated that when ions traveled circularly inside CIMS, they resulted in similar resolving powers and transmitted m/z range as traveling in a straight path in structures for lossless ion manipulations (SLIM). We then performed experimental validation of CIMS in conjunction with a TOF MS. The CIMS was made of 2 flexible printed circuit board materials folded into concentric cylinders separated by a gap of 2.8 mm. The device was about 50 mm diameter × 152 mm long and provided 1.846 m of serpentine path length. Three sets of mixtures (Agilent tune mixture, tetraalkylammonium salts, and 8 peptide mixture) and four traveling waveform profiles (square, sine, triangle, and sawtooth) were used. The sawtooth TW profile produced a slightly higher resolving power for the Agilent tuning mixture and tetraalkylammonium ions. The average resolving power for Agilent tune mixture ions ranged from 37 (using sawtooth TW) to 27 (using square TW). For tetraalkylammonium ions, the average resolving powers ranged from 45 (sawtooth TW) to 31 (square TW). For the peptide mixture ions, the resolving power was similar among the four TW profiles and ranged from 51 to 56. The average percent error in TW CCS for the peptide mixture ions ranged was about 0.4%. In conclusion, the new device showed promising results for a device made of a flexible printed circuit board material, but improvements are needed to further increase the resolving power.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2023

Selective Electrochemical Capture and Release of Uranyl in Solution (Final Report)

The goal of this project is to investigate the selective, electrochemical capture and release of uranyl ((UO 2 ) 2 +) from biphasic or heterogeneous mixtures using a class of cluster molecules, ortho-carboranes (Cb), containing selective binding groups. Possible applications in PUREX, seawater uranyl extraction, or in actinide/lanthanide (An/Ln) or Ln/Ln separations are envisioned. With this funding, we sought to achieve these goals by harnessing the redox-switchable chelating properties of the “closo” Cb to the reduced “nido” Cb enabling the electrochemical control of the ligand bite angle. Using this premise, specific goals include: 1) integrating new selective coordinating groups (L) onto the carbon positions of Cb for the selective capture and release of uranyl, and; 2) anchoring these selective carboranes onto electrode and/or heterogeneous surfaces for the selective, heterogeneous capture and release of uranyl from aqueous solutions under flow conditions. Overall, this work focuses on advancing our understanding and controlling the properties of this new platform for metal capture and release chemistry which, we believe, has the potential for broader applicability in the separation sciences.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2026

Techno Economic Analysis for Production of Renewable Natural Gas and Value-Added Chemicals from Forest Biomass Residues (CRADA Final Report)

West Biofuels - in collaboration with the University of California San Diego, the University of California Davis, the National Laboratory of the Rockies (NLR), the Colorado School of Mines’ Center for Hydrate Research, Placer County Air Pollution Control District, the Sierra Business Council, and the Southern California Gas Company (SoCalGas)-will demonstrate an innovative pathway to convert forest biomass to renewable gas (RG). The project, Production of Pipeline Grade Renewable Natural Gas and Value-Added Chemicals from Forest Biomass Residues, will utilize an existing pilot-scale gasification system and data and lessons learned from a lab-scale catalytic reactor design, develop, and demonstrate an integrated pilot-scale RG process with a scaled-up catalytic reactor and hydrate-based gas separation process. This robust and simple process uses a commercial proven gasifier, a commercially available catalyst that can tolerate gas contaminants, and a gas separation process that simplifies the downstream processing. Current testing has shown that the process can yield a large amount of methane rich renewable gas in addition to a mixture of propanol, ethanol and other higher alcohols and the relative amounts can be controlled by shifting the process conditions. This process is novel and groundbreaking because the product mixture of RG and valuable alcohols byproducts makes RG production economically feasible at $\$$12 per million British thermal units (MMBtu) or less using forest biomass from high hazard zones.

09 BIOMASS FUELS↗

DOE OSTI2023

A Review of Advanced Test Reactor Fuel and Assessment of Its Compatibility with the ZIRCEX Chlorination Process

Advanced Test Reactor (ATR) fuel has been identified as a resource for high-assay low-enriched uranium (HALEU) production. A survey was performed on the published literature describing ATR fuel. The geometry of the fuel is complex; different parts of the fuel compact experience differing neutron flux and burnup. The literature is sparse, and access is controlled. Therefore, fundamental studies of fuel reprocessing must use a model fuel that represents the main chemical and structural features. Advanced chlorination, or chlorination with sulfur-chlorine bearing reagents is being investigated as way to separate the fuel from metal matrix alloys. A UAl x alloy will be fabricated with x = 3, 4, and 5. The potential chlorination of individual UAl x intermetallics will be assessed in the advanced chlorination process of Al-8001 and Al-6061 as well as a representative mixture. Initial studies will track the alloying elements of the Al, which are Si, Fe, Cu, Mn, Mg, Cr, Zn, and Ti, in addition to the U itself. Further studies will include fission product simulants. Because advanced chlorination solvents include sulfur, the chemistry of sulfur with major and minor constituents will also be investigated. The experimental work accompanied by neutronic calculations will allow the assessment of the feasibility of advanced chlorination to separate aluminum from uranium. If bench-scale testing appears promising, then small-scale tests in shielded facilities with irradiated cladding, lightly irradiated fuel, and spent nuclear fuel are recommended to track the complete inventory of fissile actinides, fission product impurities, and reagent solids and liquids.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2023

Unit-cell-thick zeolitic imidazolate framework films for membrane application

Zeolitic imidazolate frameworks (ZIFs) are a subset of metal–organic frameworks with more than 200 characterized crystalline and amorphous networks made of divalent transition metal centres (for example, Zn 2+ and Co 2+ ) linked by imidazolate linkers. ZIF thin films have been intensively pursued, motivated by the desire to prepare membranes for selective gas and liquid separations. To achieve membranes with high throughput, as in ångström-scale biological channels with nanometre-scale path lengths, ZIF films with the minimum possible thickness—down to just one unit cell—are highly desired. However, the state-of-the-art methods yield membranes where ZIF films have thickness exceeding 50 nm. Here we report a crystallization method from ultradilute precursor mixtures, which exploits registry with the underlying crystalline substrate, yielding (within minutes) crystalline ZIF films with thickness down to that of a single structural building unit (2 nm). The film crystallized on graphene has a rigid aperture made of a six-membered zinc imidazolate coordination ring, enabling high-permselective H 2 separation performance. The method reported here will probably accelerate the development of two-dimensional metal–organic framework films for efficient membrane separation.

36 MATERIALS SCIENCE↗

DOE OSTI2022

Understanding the structure and composition of recalcitrant oligosaccharides in hydrolysate using high-throughput biotin-based glycome profiling and mass spectrometry

Novel Immunological and Mass Spectrometry Methods for Comprehensive Analysis of Recalcitrant Oligosaccharides in AFEX Pretreated Corn Stover. Lignocellulosic biomass is a sustainable alternative to fossil fuel and is extensively used for developing bio-based technologies to produce products such as food, feed, fuel, and chemicals. The key to these technologies is to develop cost competitive processes to convert complex carbohydrates present in plant cell wall to simple sugars such as glucose, xylose, and arabinose. Since lignocellulosic biomass is highly recalcitrant, it must undergo a combination of thermochemical treatment such as Ammonia Fiber Expansion (AFEX), dilute acid (DA), Ionic Liquid (IL) and biological treatment such as enzyme hydrolysis and microbial fermentation to produce desired products. However, when using commercial fungal enzymes during hydrolysis, only 75–85% of the soluble sugars generated are monomeric sugars, while the remaining 15–25% are soluble recalcitrant oligosaccharides that cannot be easily utilized by microorganisms. Previously, we successfully separated and purified the soluble recalcitrant oligosaccharides using a combination of charcoal and celite-based separation followed by size exclusion chromatography and studies their inhibitory properties on enzymes. We discovered that the oligosaccharides with higher degree of polymerization (DP) containing methylated uronic acid substitutions were more recalcitrant towards commercial enzyme mixtures than lower DP and neutral oligosaccharides. Here, we report the use of several complementary techniques that include glycome profiling using plant biomass glycan specific monoclonal antibodies (mAbs) to characterize sugar linkages in plant cell walls and enzymatic hydrolysate, matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS) using structurally-informative diagnostic peaks offered by negative ion post-secondary decay spectra, gas chromatography followed by mass spectrometry (GC–MS) to characterize oligosaccharide sugar linkages with and without derivatization. Since oligosaccharides (DP 4–20) are small, it is challenging to mobilize these molecules for mAbs binding and characterization. To overcome this problem, we have applied a new biotin-coupling based oligosaccharide immobilization method that successfully tagged most of the low DP soluble oligosaccharides on to a micro-plate surface followed by specific linkage analysis using mAbs in a high-throughput system. This new approach will help develop more advanced versions of future high throughput glycome profiling methods that can be used to separate and characterize oligosaccharides present in biomarkers for diagnostic applications.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2025

Exploring nonmultiplicativity in the geometric measure of entanglement

The geometric measure of entanglement (GME) quantifies how close a multipartite quantum state is to the set of separable states under the Hilbert-Schmidt inner product. The GME can be nonmultiplicative, meaning that the closest product state to two states is entangled across subsystems. In this work, we explore the GME in two families of states: those that are invariant under bilateral orthogonal (𝑂⊗𝑂) transformations, and mixtures of singlet states. In both cases, a region of GME nonmultiplicativity is identified around the antisymmetric projector state. We employ state-of-the-art numerical optimization methods and models to quantitatively analyze nonmultiplicativity in these states for 𝑑=3. Here, we also investigate a constrained form of GME that measures closeness to the set of real product states and show that this measure can be nonmultiplicative even for real separable states.

Quantum correlations in quantum information↗

DOE OSTI2020

Determining Activity Coefficients of SOA from Isothermal Evaporation in a Laboratory Chamber

Nonideal molecular interactions in aerosol particles influence the partitioning of semivolatile organic compounds (SVOCs). However, few direct measurements exist that determine activity coefficients (γ), which quantify nonideality, for individual organic compounds in different atmospheric mixtures. By measuring the isothermal evaporation of SOA formed from multifunctional SVOCs in an environmental chamber, this study determines the mole-fraction-based γ of the bulk SOA in a variety of pre-existing chemically complex particles, approximated as if the bulk SOA behaved like a single SVOC. These multicomponent mixtures contain molecular structures commonly found in the atmosphere. When treated as a single liquid phase, γ of the bulk SOA tends to increase from ~1 to ~5 as the organic seeds and the SOA have more differing polarities. A high computed γ value of 74 for a wet ammonium sulfate-SOA system indicates phase separation. The γ for some individual species was also quantified based on gas-phase measurements and AIOMFAC model predictions. However, the bulk SOA γ cannot be explained by the simplified speciated SVOC–seed interactions, suggesting incomplete compositional understanding of the bulk SOA. In this work, these results demonstrate a method to quantify nonideal behavior and show that it can occur in multicomponent mixtures and therefore influence OA formation, evolution, and lifetimes.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2024

Electrically Powered High-Salinity Brine Separation Using Dimethyl Ether

Dewatering highly saline aqueous streams, from mining and geothermal leachates to industrial wastewater, is essential for effective resource recovery and safe disposal. Membraneless water extraction (MWE) uses a low-polarity solvent to separate water from concentrated aqueous solutions. In this study, we design a new MWE that uses dimethyl ether (DME) to selectively extract water from high-salinity brines, leveraging the volatility of DME to achieve rapid solvent recovery. By separating water and dissolved salts at a liquid–liquid interface, MWE minimizes the deleterious effects of scaling on vulnerable membrane and heat exchanger surfaces, reducing the need for extensive pretreatment and expensive materials. We begin by developing a computational framework for a multistage counterflow liquid–liquid contactor, which extracts water into DME, coupled with a multistage solvent regenerator that uses vapor compression to efficiently separate the desalinated water from the DME extractant. Excess Gibbs free energy and equation of state frameworks are used to model fluid phase equilibria in water–DME–sodium chloride (NaCl) mixtures, with interaction parameters estimated from experimental data. Incorporating equilibrium calculations into a system-scale computational model, we examine the performance of MWE using DME for the first time. Our analysis demonstrates that MWE can concentrate seawater desalination brine (>1.0 mol NaCl kg –1 ) to zero-liquid discharge salinities, with an energy consumption of under 50 kW h per m 3 of water extracted with a solvent recovery ratio greater than 99.9%. We highlight the importance of staging the vapor compression process to simultaneously minimize energy consumption while enabling brine concentration and product water solvent contamination. Finally, the thermodynamic framework developed here allows for the robust evaluation of new MWE solvents and systems for critical brine concentration and fractional precipitation applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Host Design for Carbon Capture and Regeneration in Porous Liquids

The demand for efficient gas capture technologies drives the exploration of porous liquids (PLs) as alternatives to traditional amine mixtures, which incur high operational costs due to energy-intensive regeneration processes. This research investigates the use of porous organic cages (POCs) within PLs to enhance gas capture and separation capabilities. We demonstrate that the flexibility of POCs under isostatic pressure facilitates the expulsion of captured gas molecules, enabling low-energy regeneration and the creation of an isostatic pressure testing capability for PLs. Additionally, a new CC3-OH POC derivative with scrambled hydroxides exhibits a twofold increase in CO 2 adsorption capacity, attributed to enhanced interactions between hydroxide linkers and CO 2 . Furthermore, we explore the stability of azobenzene-containing organic cages formed via imine and amine bonds, revealing that the flexible amine bond allows for more efficient E-Z isomerization. Our findings highlight the transformative potential of PLs and azobenzene-derived systems in gas separation technologies, paving the way for innovative low-energy regeneration pathways.

36 MATERIALS SCIENCE↗

DOE OSTI2023

Identification and localization of rotational spectra using recurrent neural networks

A method of identifying molecular parameters in a complex mixture may include receiving a set of combined transition frequencies and analyzing the set of combined transition frequencies using a first trained artificial neural network to generate a plurality of separated transition frequency sets. Each of the plurality of separated frequency sets may be analyzed using a second trained artificial neural network to generate a respective set of estimated spectral parameters. The method may include identifying a set of molecular parameters corresponding to the set of separated transition frequencies.

Prozuments, Kirills↗

DOE OSTI2025

Tuning the Selectivity of Carboxylic Acid–Based Eutectic Solvents for the Dissolution and Electrochemical Separation of Metal Oxides

Extracting metals from natural resources and recovering from waste materials with less-hazardous solvents is essential for sustainable technological advancements. The commonly employed method utilizes harsh chemicals for metal dissolution and the ensuing separation. Here, in this study, we examined the potential of eutectic solvents (types III and IV) as alternative media for the selective dissolution of metals and metal oxides and their subsequent electrochemical separation. Notably, type III eutectics composed of betaine:acetic acid and triazole:lactic acid exhibited excellent solubility for cobalt oxide (24.1 g·L –1 ) and copper oxide (30.5 g·L –1 ), respectively. In comparison, the type IV eutectic mixture of Ca(NO 3 ) 2 ·4H 2 O:acetic acid demonstrated the highest conductivity and lowest viscosity with solubility for both copper oxide (6.1 g·L –1 ) and metallic copper (5.4 g·L –1 from a used electronic circuit). Using a Ca(NO 3 ) 2 ·4H 2 O:acetic acid mixture, copper was selectively dissolved from a waste printed circuit board and subsequently electrodeposited onto a nickel electrode. These findings highlight the tunability of DESs for the selective recovery of metals from electronic waste, offering a promising approach for sustainable metal recycling and resource recovery.

electrodeposition↗

DOE OSTI2024

An experimental and chemical kinetic modeling study of 4-butoxyheptane combustion

Here, the combustion kinetics of a novel oxygenated bioblendstock for diesel, 4-butoxyheptane (4-BH), was investigated experimentally using a flow reactor and a heated, high-pressure shock tube. The flow reactor experiments employed oxygen as the oxidizer and helium as the diluent with oxidation conducted at atmospheric pressure and 10 bar for temperatures from 400 to 1000 K at 20-K intervals. The fuel, oxidizer, and diluent flow rates were varied at different temperatures to maintain a constant initial fuel mole fraction of 1000 ppm, with stoichiometric equivalence ratio, and a residence time of 2.0 s. The reacted gas was fed to two separate GC systems that could qualitatively and quantitatively detect product species. Additionally, real fuel-air ignition delay time (IDT) data were collected using a heated, high-pressure shock-tube facility. Fuel lean (φ = 0.5) and stoichiometric (φ = 1.0) mixtures were investigated at 10 atm as well as at 30 atm for the fuel lean case for temperatures between 847 and 1259 K. A detailed chemical kinetics mechanism was developed to model the product distribution from the flow reactor and IDTs from the shock tube. The proposed model was able to predict the double NTC behavior in flow reactor experiments reasonably well. Model predictions at low temperatures were observed to be highly sensitive to the rate constants of ketohydroperoxide (KHP) decomposition in the case of the OOH group in α position which were modeled based on existing literature studies on ethers. It was noted that in the absence of theoretical or experimental studies, the rate constants for KHP decomposition used in the literature were empirically set. Additional studies are required to address the gap in model prediction obtained in this study and to reduce the uncertainty in kinetics models for ether oxidation. Predicted product concentrations and IDTs showed some quantitative agreement with experimental data, but the overall reactivity of the IDTs is underpredicted. Additionally, significant deviation is observed for the IDT results at 10 atm for the stoichiometric case with minor deviations for the other cases. The reaction pathways to the missing products were then further analyzed theoretically through quantum-mechanical calculations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗