Search NASA⌕ Search

SEARCH · Search NASA

Results for “Solvent Extraction”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 379 records · Page 21
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

NH 4 OH Looping with Membrane CO 2 Absorber and Distributed Stripper for Enhanced Algae Growth

The University of Kentucky Center for Applied Energy (UK CAER) has devised a unique, integrated CO2 capture and utilization technology. CO2 from coal-fired power generation flue gas is first captured at half the operating cost of a typical aqueous CO2 capture system (CCS), distributed in an aqueous stream and then fixed by algae in bioreactors where the algae production is increased by 50% over that with a typical intermittent nutrient feeding system. Lower CCS operating cost is achieved by eliminating the flue gas pretreatment step for cooling and SO2 removal, eliminating steam extraction from the power generation steam cycle for solvent regeneration, and eliminating CO2 compression. Higher algae production is achieved by continuous, just-in-time nutrient feed to the bioreactors directly from a distributed solvent regenerator, which maintains the bioreactor pH for optimum growth. The process starts with a uniquely configured membrane absorber, where the flue gas is indirectly contacted with an ammonium hydroxide (NH4OH) solvent. Dissolved NH3 is attractive for both CO2 capture and as an algae nutrient. For CO2 capture it is inexpensive, has a low regeneration energy, is thermally- and oxidatively-stable and has a viscosity near that of water, which makes is easy to transport. Numerous studies have shown that the scrubbing capacity of NH3 is approximately 0.9-1.2 kg of CO2/kg of NH3, with a CO2 removal efficiency of ~99% and half the solvent regeneration energy than that of 30 wt% MEA[1, 2, 3]. NH3 is attractive as an algae nutrient due to its low cost. The rich NH4OH solvent is pumped to a set of distributed regenerators which are co-located with the algae bioreactors. Solvent pumping, transport and distribution reduces the balance of plant (BOP) cost compared to a typical aqueous CCS related to the flue gas duct and boost fan required to transport the flue gas. The energy required for the distributed solvent regeneration is supplied by solar-thermal panels eliminating the need for steam extraction from the power generation steam cycle. After solvent regeneration, the product stream contains both the CO2 captured from the flue gas and volatized NH3 from the solvent. This product stream is fed directly to the bioreactors, eliminating the need for compression of the CO2 stream. The relative amounts of CO2 and NH3 in the product stream are adjusted and controlled by a controlling the regeneration conditions (pressure and temperature). The continuous feed of the right ratio of nutrients overcomes the typical inhibition of algae growth resulting from frequent pH swings in the bioreactor due to unbalanced (intermittent) feeding systems for CO2 and N. Also, because the regenerators will operate at pressure and be located in close proximity to the bioreactors, there is no worry about pressure drop when sparging the gas into the algae. Sparging produces small bubbles which is beneficial for mass transfer efficiency. One known challenge when using an NH4OH solvent is high NH3 emission. Hydrophobic membranes are used for CO2 capture using an aqueous NH3 solution[4, 5] without the direct contact between flue gas and aqueous solution. Additionally, UK CAER CO2 capture and utilization process manages NH3 slip in three extra measures. First, NH3 slip is minimized by working with minimal species partial pressure, which is proportional to the concentration in the liquid. Hence, lowering the capture solvent concentration will lower the NH3 partial pressure. Second, UK CAER’s previous work has demonstrated that the addition of Zn2+ into NH3 solutions to chelate the NH3 can reduce NH3 volatility. Third, the configuration of the membrane CO2 absorber utilizes condensed water from the flue gas to continually wash the gas-side of the membrane to reduce fouling and recapture NH3 slip. Additional details about the UK CAER unique, integrated CO2 capture and utilization technology will be presented along with technology development plans. Diao, N., Q. Li, and Z. Fang. 2004. Heat transfer in ground heat exchangers with groundwater advection. International Journal of Thermal Sciences. 43: 1203-1211, He, Q., M. Chen, L. Meng, K. Liu, and W. Pan. 2004. Study on Carbon Dioxide Removal from Flue Gas by Absorption of Aqueous Ammonia. Western Kentucky University. Yeh, A.C., and H. Bai. 1999. Comparison of ammonia and monoethanolamine solvents to reduce CO2 greenhouse gas emissions. The Science of the Total Environment. 228: 121-133, Villeneuve, K., D. Roizard, J.C. Remigy, M. Iacono, and S. Rode. 2018. CO2 capture by aqueous ammonia with hollow fiber membrane contactors: Gas phase reactions and performance stability. Separation and Purification Technology, 199: 189-197, Toro Molina, C., and C. Bouallou. 2016. Carbon dioxide absorption by ammonia intensified with membrane contactors. Clean Techn Environ Policy 18, 2133–2146 (2016)

20 FOSSIL-FUELED POWER PLANTS↗
DOE OSTI2021

Extraction of Furfural and Furfural/5-Hydroxymethylfurfural from Mixed Lignocellulosic Biomass-Derived Feedstocks

We present a combined in silico and experimental study on the extraction of furfural and 5-hydroxymethylfurfural (HMF) in aqueous–organic biphasic systems. We predict the liquid–liquid equilibria and furfural/HMF partition coefficients of over 2200 water-organic biphasic systems using the multiscale COSMO-RS model and measure experimentally single-component (furfural) and mixture (furfural and HMF) partition coefficients at room and dehydration reaction-relevant temperatures in 28 solvents. We find the experimental data to be within a factor of 2 from the COSMO-RS predictions. Even though furfural and HMF have chemical similarity, the slight differences in molecular structure render the separation of furfural easier by the supply of more solvents of higher partition coefficient for extraction. We leverage this molecular difference and experimentally demonstrate that with an additional extraction step, using dichloromethane or toluene, we can selectively extract furfural from furfural-HMF mixtures, which can coexist in lignocellulosic biomass dehydration products, despite their partition coefficients being generally correlated. We complement solvent selection criteria for biphasic lignocellulosic biomass processes with a simple mass balance extraction model for determining volume ratios in multistage extraction. Lastly, the molecular nature of the preferential furfural extraction is rationalized using COSMO-RS σ-profile analysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Complexation of Astatine(III) with Ketones: Roles of NO 3 – Counterion and Exploration of Possible Binding Modes

Ketones have been proven effective in extracting astatine(III) from aqueous solvents. Previous theoretical studies suggested a mechanism where the “sp 2 ” lone pair on the carbonyl oxygen donates electron density into the π system of the AtO + molecular cation to form a dative-type bond. In this study, co-extraction of NO 3 – as AtO(NO 3 )·(O=CR 1 R 2 ) species into the organic phase appears to be a key factor. Adjusting the electronic properties of the ketone, by having an aryl group instead of an alkyl group in the alpha position of the ketone, increased the electron density on C=O, increased the bond strength between the ketone and AtO + , and in turn increased the extraction of 211 At into the organic phase. Extraction with diketones shows dependence on the bridging distance between the two carbonyl moieties, where a C 3 or longer bridge results in a 10-fold increase in extraction into the organic phase. Furthermore, DFT calculations show the longer bridge allows for the chelation of AtO(NO 3 ) by either the second carbonyl or the phenyl ring.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
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

Identifying Green Solvent Mixtures for Bioproduct Separation Using Bayesian Experimental Design

Liquid–liquid extraction (LLE) is a widely used technique for the separation and purification of liquid-phase products with applications in various industries, including pharmaceuticals, petrochemicals, and renewable chemistry. A critical step in the design of an LLE process is the selection of appropriate solvents. This study presents a new methodology for identifying solvent mixtures for bioproduct separation using Bayesian experimental design (BED). Motivated by the need for environmentally friendly and effective separation methods, we address the challenge of selecting solvent systems that balance separation efficiency, selectivity, and environmental impact while also tackling the difficulty of separating multiple bioproducts using complex solvent systems. Our approach specifically seeks to predict product partition coefficients (log10 Kp values) as thermodynamic parameters underlying solvent selection. The iterative approach integrates Bayesian optimization with experimental measurements to guide solvent selection and leverages COSMO-RS simulations to enhance high-throughput experimentation. Using the design of solvent systems for the separation of lignin-derived aromatic products via centrifugal partition chromatography (CPC) as a case study, we show that within seven iterations/cycles of the methodology, we can identify new mixtures of green solvents that align with CPC design principles. Furthermore, these results demonstrate the efficacy of the BED framework in optimizing green solvent systems for complex separations, highlighting the potential of this method to advance the field of green chemistry and contribute to the development of sustainable industrial processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Direct Extraction of Sodium Hydroxide by Calix[4]pyrrole-Based Ion-Pair Receptors

Here, described in this work, are calix[4]pyrrole-based ion-pair receptors, cis/trans-1 and cis/trans-2, designed for the extraction of sodium hydroxide. An X-ray diffraction analysis of a single crystal of the cis-1·NaOH isomer isolated from a mixture of cis/trans-1 revealed a unique dimeric supramolecular structure. An average dimer in toluene-d 8 solution was inferred on the basis of diffusion-ordered spectroscopy (DOSY). Support for the proposed stoichiometry came from density functional theory (DFT) calculations. The structural stability of the dimeric cis-1·NaOH complex in toluene solution was further confirmed by ab initio molecular dynamics (AIMD) simulation with explicit representation of solvent. Under conditions of liquid–liquid extraction (LLE), purified receptors cis- and trans-2 were both found to remove NaOH from a pH 11.01 aqueous source phase into toluene with extraction efficiencies (E%) of 50–60% when used equimolar to NaOH. However, in all cases, precipitation was observed. Complexities associated with precipitation could be avoided by immobilization of the receptors onto a chemically inert poly(styrene) resin by means of solvent impregnation. The use of solvent-impregnated resins (SIRs) eliminated precipitation in solution while retaining the extraction efficiency toward NaOH. This allowed both the pH and salinity of the alkaline source phase to be lowered.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Lipophilic guanidinium compounds for removal of oxyanions from aqueous solutions

Methods for removing an oxyanion from an aqueous source containing said oxyanion, comprising contacting said aqueous source with an aqueous-insoluble hydrophobic solution containing an oxyanion extractant compound dissolved in an aqueous-insoluble hydrophobic solvent to result in formation of an oxyanion salt of said extractant compound and extraction of said oxyanion salt into said aqueous-insoluble hydrophobic solution, wherein said extraction results in an extraction affinity (D) of said oxyanion of at least 1, wherein D is the concentration ratio of said oxyanion in the organic phase divided by the concentration of said oxyanion in the aqueous phase; wherein said extractant compound has the following composition: wherein at least one of R1-R10 is or contains a hydrocarbon (R) group containing at least 4, 5, 6, 7, 8, 9, 10, 11, or 12 carbon atoms.

Williams, Neil John↗
DOE OSTI2021

CO 2 utilization in built environment via the P CO 2 swing carbonation of alkaline solid wastes with different mineralogy

Carbon mineralization to solid carbonates is one of the reaction pathways that can not only utilize captured CO 2 but also potentially store it in the long term. In this study, the dissolution and carbonation behaviors of alkaline solid wastes (i.e., waste concrete) was investigated. Concrete is one of the main contributors to a large carbon emission in the built environment. Thus, the upcycling of waste concrete via CO 2 utilization has multifaceted environmental benefits including CO 2 emission reduction, waste management and reduced mining. Unlike natural silicate minerals such as olivine and serpentine, alkaline solid wastes including waste concrete are highly reactive, and thus, their dissolution and carbonation behaviors vary significantly. Here, both conventional acid (e.g., hydrochloric acid) and less studied carbonic acid (i.e., CO 2 saturated water) solvent systems were explored to extract Ca from concrete. Non-stoichiometric dissolution behaviors between Ca and Si were confirmed under far-from-equilibrium conditions (0.1 wt% slurry density), and the re-precipitation of the extracted Si was observed at near-equilibrium conditions (5 wt% slurry density), when the Ca extraction was performed at a controlled pH of 3. These experiments, with a wide range of slurry densities, provided valuable insight into Si re-precipitation phenomena and its effect on the mass transfer limitation during concrete dissolution. Next, the use of the partial pressure of CO 2 for the pH swing carbon mineralization process was investigated for concrete, and the results were compared to those of Mg-bearing silicate minerals. In the P CO 2 swing process, the extraction of Ca was significantly limited by the precipitation of the carbonate phase (i.e., calcite), since CO 2 bubbling could not provide a low enough pH condition for concrete–water–CO 2 systems. Furthermore, this study showed that the two-step carbon mineralization via P CO 2 swing, that has been developed for Mg-bearing silicate minerals, may not be viable for highly reactive Ca-bearing silicate materials (e.g., concrete). The precipitated calcium carbonate (PCC) derived from waste concrete via a pH swing process showed very promising results with a high CO 2 utilization potential as an upcycled construction material.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Guest-dependent bond flexibility in UiO-66, a “stable” MOF

We report “flexibility constants”—a conceptual analog to metal–ligand stability constants—of UiO-66, the prototypical “stable” MOF, across a wide temperature range in both vacuum and in the presence of typical guest solvents. With these data, we extract key thermodynamic parameters governing the reversible bond equilibrium and demonstrate that guest molecules strongly favor the reversible dissociation of MOF metal–linker bonds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

An effective QWBA/UHPLC-MS/tissue punch approach: solving a pharmacokinetic issue via quantitative Met-ID

Methods to provide absolute quantitation of the administered drug and corresponding metabolites in tissue in a spatially resolved manner is a challenging but much needed necessity in pharmaceutical research. Quantitative whole-body autoradiography (QWBA) after a single-dose intravenous (3 mg/kg) and extravascular (30 mg/kg) administrations of an in vitro metabolically stable test compound (structure not reported here) indicated quick tissue distribution and excretion. Good bioavailability and short in vivo half-lives were determined formerly for the same test compound. For closing gaps in the understanding of pharmacokinetic data and in vitro results, radioactive hot spots on whole-body tissue sections had been profiled. Punches from selected tissue regions containing high radioactivity in the tissue sections previously analyzed by QWBA were extracted by a highly organic solvent and analyzed without any consecutive sample preparation step, applying ultra high performance liquid chromatography-mass spectrometry (UHPLC-MS) and off-line radioanalysis to maximize signal levels for metabolite identification and profiling. The analysis revealed that the test compound was metabolized intensively by phase I reactions in vivo and the metabolites formed were excreted in bile and in urine. The predominant metabolites showed abundant signal intensities both by MS and by radioanalysis but the MS signal intensities generally underestimated the real abundances of metabolites relative to the unchanged drug. In this work we illustrate that maximizing the sensitivity of tissue punch radioanalysis and the combination with UHPLC-MS leads to a better insight of pharmacokinetic processes by providing quantitative data with high molecular selectivity.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2024

Harnessing dimethyl ether with ultra-low-grade heat for scaling-resistant brine concentration and fractional crystallization

Solvent-driven separations may enable scalable concentration of hypersaline brines, supporting a circular resource economy from the extraction of lithium and rare earth elements from spent battery and magnet leachates. This work analyses a novel solvent-driven water extraction (SDWE) system employing dimethyl ether (DME) and ultra-low-grade heat for brine concentration and fractional crystallization. SDWE exploits DME’s unique properties: (1) a low dielectric constant that promotes water solubility over charged solutes by a factor of 10 3 , and (2) a high volatility that facilitate efficient DME reconcentration with ultra-low-grade heat. The techno-economic viability of SDWE is assessed with a computational framework that encompasses a liquid–liquid separator and a solvent concentrator. We integrate the extended universal quasichemical model with the virial equation of state to predict the compositions of the complex three-phase DME-water mixture at vapor–liquid and liquid–liquid equilibrium. Subsequently, we optimize the thermodynamic and economic performance of SDWE, by controlling the interstage flash pressure, heat source temperature, and the number of concentrating stages. DME-based SDWE concentrates an input saline feed to 5.5 M and regenerates over 99 % of the DME using ultra-low-grade heat below 50 °C, with a DME/water selectivity ratio of 125. Here our calculations reveal that optimal performance is achieved at interstage flash pressures of 0.4 – 0.5 bar for heat source temperatures between 323–373 K, with improved exergetic efficiencies at lower temperatures. At a heat source temperature of 323 K and an interstage pressure of 0.489 bar, DME-driven SDWE achieves an optimal thermodynamic efficiency of 20.5 % and a projected specific cost of US$ 1.93 m -3 . These specific costs suggest that SDWE is competitive with commercialized thermal distillation technologies, while mitigating the traditional risks associated with scaling in heat and mass exchangers with hypersaline brines.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Separation, speciation, and mechanism of astatine and bismuth extraction from nitric acid into 1-octanol and methyl anthranilate

We report a detailed study of At and Bi extraction from nitric acid media into conventional solvents, namely 1-octanol and methyl anthranilate, has been performed. The analysis includes a mathematical modeling which allows the fitting of experimental data and determination of extraction constants of the two above mentioned elements. Also, this approach helped to estimate a stability constant of a weak AtO(NO3) complex along with thermodynamic constants describing the redox process of At species in the acidic solution and formation of an adduct of Bi in the presence of methyl anthranilate. The results of the fitting have been used to calculate corresponding separation factors of Bi and At as well. Moreover, a computational study has been performed to evaluate At interaction with the above mentioned solvents.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Extraction of Oil From Camelina Seeds Using Liquefied Dimethyl Ether

With a changing climate and a push for net-zero carbon emissions, sustainable aviation fuel (SAF) is gaining interest worldwide. Due to its compatibility with current infrastructure and potential to reduce emissions by up to 94%, SAF has been identified as the best near-term opportunity to decrease carbon emissions in the aviation industry. SAF can be produced from various renewable feedstocks, with Camelina sativa (L.) seeds standing out due to their high oil content. Conventionally, the oil is extracted using hydrothermal liquefaction (HTL), which involves the pressurized heating of water and biomass up to 400°C, making it incredibly energy-intensive. Conversely, liquefied dimethyl ether (DME) extraction operates at room temperature and is capable of near 100% solvent recycling. In this work, we propose the use of DME extraction as a substitute for HTL, hypothesizing that it can overcome the challenges of current oil extraction methods while maintaining the same oil yields.

09 - BIOMASS FUELS↗
DOE OSTI2023

Interinstitutional Study of the New EURO-GANEX Process Resistance by Gamma Irradiation Test Loops

As part of the homogeneous actinides recycling strategy, the EURO-GANEX process is one of the most promising options to achieve the goal of minor actinides recovery. However, EURO-GANEX also has various drawbacks that are being addressed. Improvements made to EURO-GANEX system have resulted in the emergence of the so-called New EURO-GANEX process, where the composition of the solvent has been modified by replacing TODGA and DMDOHEMA with cis-mTDDGA in the organic phase and SO3-Ph-BTP with PyTri-Diol in the aqueous phase in order to resolve important issues. The objective of this work is twofold: evaluate the gamma radiolysis resistance of the new EURO-GANEX process by dynamic irradiation conditions simulating the three main steps of the process and validate the design of CIEMAT Náyade, CEA Marcel and INL irradiation loop devices since each of them mimics different aspects of the real process. Náyade and the INL loops could irradiate together the organic and aqueous phases, whereas in the CEA loop, the irradiated solvent is recycled continuously inside a platform with several stages of mixer-settlers containing aqueous flows simulating the three main steps of the process. The extraction performances and changes in the composition of the solvent have been analysed during the irradiation experiment by different techniques: gamma spectrometry and ICP-MS/OES for cations or tracers extraction, and HPLC-MS to quantify the degradation and evaluate the degradation compounds. Additionally, in spite of some differences between the three-irradiation facilities, this inter-institutional study shows that they are three comparative tools, which provide results on the stability towards radiolysis of a liquid-liquid extraction system. Favourable extraction results for the different steps are obtained according to the static irradiation studies found in literature. However, the degradation of cis-mTDDGA is appreciable leading to degradation compounds, some of which form precipitates and produce important changes in viscosity, important aspects that must be addressed prior to the successful industrial application of the new EURO-GANEX process.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2020

Extraction chromatography of 225 Ac and lanthanides on N,N-dioctyldiglycolamic acid /1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide solvent impregnated resin

The alpha-emitter 225 Ac (t 1/2 = 9.92 d) is currently under development for targeted alpha-particle therapy of cancer, and accelerator production of 225 Ac via proton irradiation of thorium targets requires robust separations of 225 Ac from chemically similar fission product lanthanides. Additionally, the lanthanide elements represent critical components in modern technologies, and radiolanthanides such as 140 Nd (t 1/2 = 3.37 d) also have potential application in the field of nuclear medicine. The ionic liquid, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([Bmim][NTf 2 ]), combined with the diglycolamide extractant, N,N-dioctyldiglycolamic acid (DODGAA), was adsorbed on macroporous resin support to produce a solvent impregnated resin (SIR) that was investigated for separations of 225 Ac and lanthanides. The equilibrium distribution coefficients (Kd) of the rare earth elements (Sc(III), Y(III), Ln(III)), 225 Ac(III), Th(IV), and U(VI) on the prepared DODGAA/[Bmim][NTf 2 ]-SIR were determined from batch adsorption experiments in HCl and HNO 3 media. The DODGAA/[Bmim][NTf2]-SIR exhibited preferential uptake of the heavier lanthanide elements while allowing for the separation of the lighter lanthanides. Column separations utilizing the DODGAA/[Bmim][NTf 2 ]-SIR were effective at separating the lighter lanthanides from each other, and separating 225 Ac from a mixture of lanthanides, 213 Bi, and 225 Ra without the need for additional complexing agents.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Deep Eutectic Solvents as Candidates for Lithium Isotope Enrichment

Nuclear fusion is a phenomenon that is well known within the nuclear physics community as a viable option for alternative energy as many natural gases and fossil fuels are phased out of commercial use. Deuterium and tritium fusion reactions are currently the leading candidates for nuclear fusion, with a major limiting factor being a means to produce tritium on an industrial scale. Lithium-6 is a well-known isotope that can produce tritium and helium following a fission reaction with a neutron. Unfortunately, the lithium-6 enrichment methods are limited to the COLEX process, which leaves behind an alarming amount of mercury waste as a potential environmental contaminant. Deep eutectic solvents are believed to be a potential alternative to lithium isotope separations due to the ease of generation, in addition to the minimum environmental waste generated when these solvents are employed. Previous studies have suggested that deep eutectic solvents are capable of separating lithium isotopes by utilizing a 2-thenoyltrifluoroacetone and trioctylphosphine oxide system that can biphasically react with a buffered solution containing lithium chloride. This system displays a separation factor of 1.068, which when compared to the 1.054 separation within the COLEX process, makes it a potential candidate for lithium-6/7 separation. Within this study, we investigate this system in comparison to two newly synthesized deep eutectic solvents and find that within these acetylacetone-based systems, little isotopic separation is observed. We investigate these systems both experimentally and computationally, showing the different lithium cation affinities, in addition to proposing how the electron-donating or -withdrawing nature can influence these systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Use of high throughput screening methods to study dual-functional crosslinkable latexes

Herein, structure-formulation-property relationships for crosslinkable core-shell latexes were studied initially using high throughput screening methods and then using conventional experimental methods to determine optimum coating formulations. Two approaches that are used within coatings technology to improve sustainability are reduction in volatile organic compounds (VOC) and reduction in energy needed to cure coatings. Hybrid crosslinkable core-shell latexes have shown potential in meeting these challenges where film properties provided by particle coalescence are not sufficient and chemical crosslinking is needed. However, with numerous parameters involved such as latex particle architecture, nature and amount of crosslinker, and curing conditions, the screening of formulations via conventional coating testing methods becomes laborious and time-consuming. The results from high-throughput dye extraction and puncture testing were compared to data from conventional testing methods such as chemical resistance (MEK double rubs), pendulum hardness, and tensile testing to identify correlations. The dye extraction results have shown a strong correlation to solvent resistance and pendulum hardness data whereas toughness from puncture testing data correlated to tensile testing. Both high throughput dye extraction and puncture testing methods can be used for the accelerated screening of crosslinkable coating formulations to optimize curing parameters to achieve the best coating performance.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Elucidating the Role of Hydrogen Bond Donor and Acceptor on Solvation in Deep Eutectic Solvents Formed by Ammonium/Phosphonium Salts and Carboxylic Acids

Deep eutectic solvents (DESs) constitute a rapidly emerging class of sustainable liquids that have been widely studied and employed in chemical separations, catalysis, and electrochemistry. The unique physicochemical and solvation properties of DESs can be highly tailored by choosing the appropriate hydrogen bond acceptor (HBA) and hydrogen bond donor (HBD). Understanding the role of the HBA and HBD on the multiple solvation interactions in DESs is important to enable their judicious selection for particular applications. As such, this work constitutes the first study to exploit chromatography to measure solute–solvent interactions of DESs using a wide array of known probe molecules. The constituent components of 20 DESs, formed by ammonium and phosphonium-based salts and carboxylic acids, are systematically modulated to delineate the contribution of the HBA and HBD toward individual solvation properties. Solute–solvent interactions measured in this study are used to interpret and explain the performance of DESs in desulfurization of fuels and extraction of natural products. The results from this study can be used to predict and understand the performance of DESs in various chemical processes where solvation interactions heavily influence outcomes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗