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At least 307 records · Page 17
All sourcesNASA NTRSDOE OSTI
DOE OSTI2016

Effect of aqueous‐based cathode slurry pH and immersion time on corrosion of aluminum current collector in lithium‐ion batteries

Corrosion of aluminum can occur during the manufacturing of lithium‐ion batteries when using aqueous‐based cathode slurries. In exposure tests, the alkaline pH value of aqueous‐based cathode slurries and immersing time were revealed as the principle factors that control the corrosion of aluminum during the cathode manufacturing process. The nickel manganese cobalt oxide active material used in the slurry does not have a direct impact on corrosion of the aluminum current collector. The initiation and evolution of localized corrosion on aluminum are closely related to the formation of galvanic cells between aluminum matrix and intermetallic particles. X‐ray photoelectron spectroscopy results confirmed that the pH of cathode slurry was the only factor that alters aluminum surface composition, during which the oxide passive film was gradually degraded into hydroxide. Electrochemical characterizations showed that aluminum electrodes gave remarkably different response to the different pH of test solutions. The time‐pH‐variant electrochemical response was ascribed to the change of passive film and electric double layer properties.

Li, S. Y.↗
NASA NTRS2017

Fe-Containing Allophane and Hisingerite Dissolution and Implications for Gale Crater, Mars

The mass-normalized dissolution rates measured in this study demonstrate that hisingerite and Fe-substituted allophane dissolve rapidly, much faster than crystalline phyllosilicates such as nontronite and kaolinite that have similar compositions. In addition, hisingerite dissolves more rapidly than allophane. Future work will focus on measuring dissolution rates at other pH values, so that dissolution rate laws for allophane and hisingerite can be derived. Results will be used to interpret data from Gale Crater. These initial experiments suggest that, if the liquid water present in Gale Crater was highly acidic, it was likely present for only a short time, allowing some amorphous soil-material similar to allophane to persist. Further experiments will enable us to constrain the timescales over which liquid water was present in Gale Crater and provide insight into its pH. This information is essential to assessing the potential habitability of ancient Mars.

Ralston, S. J.↗
DOE OSTI2020

Enhanced carbon-transfer and -utilization efficiencies achieved using membrane carbonation with gas sources having a range of CO 2 concentrations

The economic viability of microalgal biofuels relies on increasing productivity in a cost-effective manner. As microalgal biomass contains > 50% carbon, a high rate of CO 2 delivery is required for high productivity, and inefficient CO 2 delivery amplifies operating costs. Membrane carbonation using non-porous hollow fiber membranes can ideally deliver CO 2 without bubble formation and high carbon transfer efficiency. Because CO 2 streams from industrial resources are not 100% CO 2 , the buildup of inert gasses can significantly lower the CO 2 delivery rate when the distal end of the membrane is closed. To overcome the buildup of inert gases, we managed the distal end of the membranes with three different approaches: fully open end, restricted bleed valve, and restricted bleed valve with pH-actuated venting. For all approaches, CO 2 was delivered to membranes ondemand based on a pH set point. Evaluating a wide range of CO 2 concentrations (10% to 100%), we found that all approaches eliminated the buildup of inert gases, could maintain target pH values and gave the same biomass productivities and carbon distributions. However, carbon transfer efficiency depended on the operation of the distal end. Fully open-end operation gave a poor carbon transfer efficiency because of excessive loss of CO 2 from the distal end. However, restricting the exit flow rate to ≤4 cm 3 /min mitigated the problems of excessive CO 2 loss, but without incurring a large loss of CO 2 -delivery flux. For the continuous cultivation, combining a restricted bleed valve with pH-actuated venting improved the carbon-transfer efficiency and -utilization efficiencies up to 85% and 67%, respectively, with a sufficient CO 2 delivery flux.

42 ENGINEERING↗
DOE OSTI2013

Perrhenate extraction studies by Cyphos 101-IL; screening for implementation in technetium removal

The solvent extraction of rhenium (VII) from chloride solutions by Cyphos 101-IL in toluene has been studied. Distribution values for the extraction of perrhenate are extremely high leading to almost quantitative extraction. From slope analysis, an anion exchange extraction mechanism is proposed, with formation of a ReO4 association with one Cyphos IL-101 cation. The extraction kinetics are fast, with complete equilibration occurring within 60 s. Under identical conditions, distribution coefficients for Cyphos 101-IL are greater than for Aliquat-336. Extraction of the perrhenate anion does not seem to be negatively impacted by common environmental contaminants including iron, sulphate and nitrate at the pH values tested.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
NASA NTRSDate not supplied

Acid Alteration of Clay Minerals With Implication for Mars’ Surface Processes

The co-occurrence of phyllosilicates (clays) and sulfate stratigraphies at many locations on Mars are associated with a sharp change in surface conditions from neutral/alkaline pH during the Noachian (4.1-3.7 Ga) which favored the formation of clays to acidic conditions during the Hesperian (3.7-2.9 Ga) which favored the formation of sulfates. Yet, if these two contrasting geosystems were temporarily sequential, it is unknown how the Hesperian acidic conditions altered the previously formed clay units. We performed laboratory batch experiments to fingerprint the diagnostic features produced during interactions of Mars-analog clays and acidic solutions. Two clays, and silicon (IV) oxide, were reacted with solution of either sulfuric acid or filtered natural acid rock drainage (ARD) in plastic bottles. The solutions were adjusted at four pH values (1, 3, 5, and 7) and reacted at 4, 30, and 80°C for 3, 7, and 14 days. At the end of the experiments, the filtered supernatants were analyzed by ICP-MS while the solids were characterized by X-Ray Diffraction; Energy-Dispersive X-Ray Fluorescence analyses; Raman and Short-Wave Infrared spectroscopies and Scanning Electron Microscopy. Results show that the solution chemistry played a key role in the evolution of the clay-solution systems. In H2SO4 systems, the solution pH steadily increased due to partial clay dissolution with no secondary phase formation detected. Contrary, in the ARD systems, the pH decreased due to the ample presence of Fe which controlled both the reactivity of clays by the growth of protecting surface coatings and the solution pH by the precipitation of Fe nanophases; secondary phase detected included goethite, jarosite, gypsum, and siderite. These results indicate that, on Mars, the chemical interaction between clays and acidic solutions was complex and dependent on the solution chemistry. Acidic, sulfate-rich solutions have a high dissolution capacity and could have induced widespread clay disintegration. Notably, if Fe-rich ARD was involved, the clays on Mars could have remained stable during acidic Hesperian period due to formation of protective coatings. Comparison of our results with martian observations will be performed to determine how acidic conditions could potentially affect clays in sedimentary settings, including the Gale crater.

L. Lefticariu↗
DOE OSTI2020

Soil chemistry data across a catena in the Luquillo Experimental Forest, Puerto Rico

Landscape topography can influence biogeochemical processes across the wet tropical forest soils. This dataset contains soil chemistry data such as pH and dissolved organic carbon (DOC) from April 1, 2017 to May 1, 2018 across a catena in the Luquillo Experimental Forest, Puerto Rico. The attached CSV file contains information on sampling date, location (El Verde field station) in LEF, topographic positions (ridge, slope, and valley, respectively), field replicate number, laboratory replicate number, water extractable pH, CaCl2 extractable pH, and DOC (unit: mg/g). Overall, soil pH values were highest in the valley, followed by slope, and lowest in the ridge topographic positions. However, DOC values followed the opposite trend: ridge>slope>valley. This dataset can facilitate our understanding of the biogeochemical cycling of carbon and nutrient associated with complex topography in wet tropical forest soils.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Non-Fouling, Low Cost Electrolytic Coagulation & Disinfection for Treating Flowback and Produced Water for Reuse

Executive Summary This Final Report is composed of two major sections. The first section presents experimental results obtained in the laboratory during Budget Period 1. The second section presents results from the field test conducted during Budget Period 2. Laboratory Results This research investigated a novel electrochemical process for producing a ferric iron coagulant for use in treating flowback and produced water from hydraulic fracturing and oil production operations. The treatment system improves the effectiveness and lowers the cost of coagulation processes using Fe3+ as the coagulant. The electrolytic coagulant generation (ECG) system uses an electrochemical cell to produce acid and base from oilfield brine solutions. The acid is used to dissolve scrap iron to provide a Fe3+ coagulating agent. The base is used to neutralize the treated water. Compared to conventional electrocoagulation (EC), the main advantage of the ECG system is an order of magnitude lower cost for the source of iron. The second advantage over conventional EC is that it can deliver Fe3+ doses greater than 1 mM, since it is not limited by the amount of dissolved oxygen in the water required to oxidize ferrous to ferric iron. The capital costs for conventional EC and the ECG system are similar, but the operational costs for the ECG system are an order of magnitude lower than conventional EC. The combined costs for iron and electrical energy for treating 1 m3 of FPW with 1 mM Fe3+ is estimated to be $0.87 for conventional EC, and $0.087 for the ECG system. The estimated all-in cost for treating FPW with a 2 mM Fe3+ dose is $0.73/m3 ($0.12/bbl). Field Test Results The field test was conducted at the Paul Foster Central Tank Battery (CTB) in Lea County, New Mexico from November 10, 2022 through December 15, 2022. The feed water to the system was produced water from the Tatanka 1H formation. After approximately two weeks of testing, the initial batch of produced water had been treated and no untreated produced water was available. Thus, after this time, the feed water to the system consisted of previously treated water (i.e., recycled water). The recycled water had nearly all colloidal particles removed, and had a much lower alkalinity due to precipitation of carbonate minerals during the first pass through the system. Although the recycled water was not an ideal test solution due to its low particulate concentrations, its lower alkalinity did allow us to identify the main problem with the treatment system. The main problem with the treatment system was caused by the high alkalinity of the initial feed water (5.4 meq/L) that consumed a significant fraction of the electrochemically generated acid. This resulted in pH values exiting the iron contact tank that were too high to dissolve enough iron to effectively treat the produced water. Tests performed with recycled water with lower alkalinity did not have this issue, and dissolved iron concentrations greater than 20 mM could be achieved. One consistent observation was that effluent water from the iron contact tank was always free of particulates, even when fed with circumneutral solutions. This suggests that there is no need to dissolve high concentrations of iron if all the water to be treated is passed through the scrap iron canister. In this case, dissolved O2 and hypochlorous acid can promote sufficient iron corrosion to provide an effective coagulating agent – even in neutral pH water. This solves the problem resulting from highly alkaline produced water. Modifications to the design of the treatment system were made based on the field test results. These modifications will add minimal additional cost, and were tested in bench-scale laboratory experiments. In short-term testing, the modified treatment process was able to remove colloidal FeS particulates to levels below detection. Long-term, steady state testing will be required to determine whether the modified process is suitable for commercial treatment systems.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2016

Sustainable Remediation of Radionuclides By a Common Sense Approach to Enhanced Attenuation - 16441

Development of in situ and relatively passive remedies for treatment of groundwater contaminated by metals and radionuclides is becoming more important because of the difficulty and cost - both to the environment and financially -- of removing these types of contaminants from the subsurface by pump-and-treat or excavation. In situ technologies rely on reactions that tend to remove contaminants from groundwater by partitioning them to solid phases in the aquifer. Monitored natural attenuation (MNA) relies solely on natural reactions to achieve remedial goals. Enhanced attenuation (EA) uses engineered approaches to supplement remediation when MNA is not sufficient to meet remedial goals. Both approaches leave contaminants in the subsurface and require a high burden of proof that contaminants will not be mobilized and become a risk in the future. Proof of the sustained effectiveness of an EA remedy is made much easier by strategic design. In multi-contaminant plumes, it is important to prioritize contaminants according to the risk they pose, with the recognition that one remedy rarely treats all contaminants. The goal for the engineered portion of the remedy should be maximum risk reduction with minimal engineering. Natural attenuation or negotiated alternate concentration levels will often allow low risk contaminants to go untreated. Whenever possible, the remedy should be consistent with the geochemical evolution of the waste site, insuring that the treated immobilized contaminants are likely to remain relatively immobile for long time frames. Finally, use what nature provides geologically, hydrologically, geochemically, or microbiologically in the remedy design. One of the impediments faced by waste site managers in implementing EA remedies is paralysis by perceived complexity. There are things that must be known to design an effective EA remedy, but there is always the temptation to know everything to eliminate the possibility of failure. Furthermore, there are plenty of people warning of failure if all is not known and they are usually willing to help the design team know all, for a price. Yet, the price of trying to eliminate all risk is never implementing an innovative remedy. All parties involved -- scientists/engineers, waste site managers, regulators and stakeholders must assume some degree of risk to deploy an EA remedy. If all parties are to assume some risk, then trust built through close communication from the start is required. The U.S. Department of Energy Office of Environmental Management has funded an applied field research initiative for several years focused, in part, on developing EA remedies for metals and radionuclides using these guiding principles. This approach to EA remedies grew out of developing and deploying a remediation strategy to replace a pump-and-treat system at the F-Area Seepage Basins on the Savannah River Site. The pump-and-treat system was energy intensive, produced several thousand cubic feet of solid radioactive waste per year, and cost $ 1 million per month to operate. The EA remedy that replaced the pump-and-treat is energy efficient, produces no waste, and costs approximately $1 million per year to maintain. At the F-Area Seepage Basins approximately 7 billion liters of low level radioactive waste solutions were disposed in three unlined basins resulting in contaminated groundwater containing various radionuclides and other contaminants. The primary contaminants of concern are tritium, strontium-90, uranium, and iodine-129. Other key features of the contaminant plume are its acidic nature with pH values as low as 3.2, its vertical stratification in the water table aquifer, and the tendency of the most contaminated portions to follow troughs in the top of the clay separating the upper aquifer zone from the lower aquifer zone. The geology was exploited by installing a funnel-and-gate system into the clay with the barrier portion blocking contaminant flow paths in the troughs in the clay. This forces the most contaminated water to flow through the gates where it encounters an in situ treatment zone created by periodic injections of alkaline solution. The flux of tritium has been reduced significantly by the barrier walls. Strontium-90 and uranium are treated by enhanced sorption in the circum-neutral pH treatment zone, consistent with natural geochemical evolution of the waste site from acidic to more neutral pH. An additional in situ treatment zone was created up-gradient of the one of the gates to treat iodine-129. Sub-micrometer diameter silver chloride particles were injected into the aquifer by direct push methods to create the treatment zone. In the laboratory and in a field pilot test the poorly soluble silver chloride particles reacted with iodide to form much less soluble silver iodide. Evaluation of the effectiveness of the silver chloride is ongoing. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2014

Evaluation of laboratory-scale in-vessel co-composting of tobacco and apple waste

Highlights: • Apple and tobacco waste mixture was efficiently composted during 22 days. • Physical–chemical and microbiological properties of the mixture were suitable the process. • Evaluation of selected mathematical model showed good prediction of the temperature. • The temperature curve was a “mirror image” of the oxygen concentration curve. • The peak values of the temperature were occurred 9.5 h after the peak oxygen consumption. - Abstract: Efficient composting process requires set of adequate parameters among which physical–chemical properties of the composting substrate play the key-role. Combining different types of biodegradable solid waste it is possible to obtain a substrate eligible to microorganisms in the composting process. In this work the composting of apple and tobacco solid waste mixture (1:7, dry weight) was explored. The aim of the work was to investigate an efficiency of biodegradation of the given mixture and to characterize incurred raw compost. Composting was conducted in 24 L thermally insulated column reactor at airflow rate of 1.1 L min{sup −1}. During 22 days several parameters were closely monitored: temperature and mass of the substrate, volatile solids content, C/N ratio and pH-value of the mixture and oxygen consumption. The composting of the apple and tobacco waste resulted with high degradation of the volatile solids (53.1%). During the experiment 1.76 kg of oxygen was consumed and the C/N ratio of the product was 11.6. The obtained temperature curve was almost a “mirror image” of the oxygen concentration curve while the peak values of the temperature were occurred 9.5 h after the peak oxygen consumption.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2015

Bioinspired design of redox-active ligands for multielectron catalysis: Effects of positioning pyrazine reservoirs on cobalt for electro- and photocatalytic generation of hydrogen from water

Here, mononuclear metalloenzymes in nature can function in cooperation with precisely positioned redox-active organic cofactors in order to carry out multielectron catalysis. Inspired by the finely tuned redox management of these bioinorganic systems, we present the design, synthesis, and experimental and theoretical characterization of a homologous series of cobalt complexes bearing redox-active pyrazines. These donor moieties are locked into key positions within a pentadentate ligand scaffold in order to evaluate the effects of positioning redox non-innocent ligands on hydrogen evolution catalysis. Both metal- and ligand-centered redox features are observed in organic as well as aqueous solutions over a range of pH values, and comparison with analogs bearing redox-inactive zinc(II) allows for assignments of ligand-based redox events. Varying the geometric placement of redox non-innocent pyrazine donors on isostructural pentadentate ligand platforms results in marked effects on observed cobalt-catalyzed proton reduction activity. Electrocatalytic hydrogen evolution from weak acids in acetonitrile solution, under diffusion-limited conditions, reveals that the pyrazine donor of axial isomer 1-Co behaves as an unproductive electron sink, resulting in high overpotentials for proton reduction, whereas the equatorial pyrazine isomer complex 2-Co is significantly more active for hydrogen generation at lower voltages. Addition of a second equatorial pyrazine in complex 3-Co further minimizes overpotentials required for catalysis. The equatorial derivative 2-Co is also superior to its axial 1-Co congener for electrocatalytic and visible-light photocatalytic hydrogen generation in biologically relevant, neutral pH aqueous media. Density functional theory calculations (B3LYP-D2) indicate that the first reduction of catalyst isomers 1-Co, 2-Co, and 3-Co is largely metal-centered while the second reduction occurs at pyrazine. Taken together, the data establish that proper positioning of non-innocent pyrazine ligands on a single cobalt center is indeed critical for promoting efficient hydrogen catalysis in aqueous media, akin to optimally positioned redox-active cofactors in metalloenzymes. In a broader sense, these findings highlight the significance of electronic structure considerations in the design of effective electron–hole reservoirs for multielectron transformations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2011

Catalytic Upgrading of bio-oil using 1-octene and 1-butanol over sulfonic acid resin catalysts

Raw bio-oil from fast pyrolysis of biomass must be refined before it can be used as a transporation fuel, a petroleum refinery feed or for many other fuel uses. Raw bio-oil was upgraded with the neat model olefin, 1-octene, and with 1-octene/1-butanol mixtures over sulfonic acid resin catalysts frin 80 to 150 degrees celisus in order to simultaneously lower water content and acidity and to increase hydrophobicity and heating value. Phase separation and coke formation were key factors limiting the reaction rate during upgrading with neat 1-octene although octanols were formed by 1-octene hydration along with small amounts of octyl acetates and ethers. GC-MS analysis confirmed that olefin hydration, carboxylic acid esterification, acetal formation from aldehydes and ketones and O- and C-alkylations of phenolic compounds occurred simultaneously during upgrading with 1-octene/1-butanol mixtures. Addition of 1-butanol increased olefin conversion dramatically be reducing mass transfer restraints and serving as a cosolvent or emulsifying agent. It also reacted with carboxylic acids and aldehydes/ketones to form esters, and acetals, respectively, while also serving to stabilize bio-oil during heating. 1-Butanol addition also protected the catalysts, increasing catalyst lifetime and reducing or eliminationg coking. Upgrading sharply increased ester content and decreased the amounts of levoglucosan, polyhydric alcohols and organic acids. Upgrading lowered acidity (pH value rise from 2.5 to >3.0), removed the uppleasant ordor and increased hydrocarbon solubility. Water content decreased from 37.2% to < 7.5% dramatically and calorific value increased from 12.6 MJ kg to about 30.0 MJ kg.

Zhang, Zhijun↗
DOE OSTI2017

Mechanisms and Rates of U(VI) Reduction by Fe(II) in Homogeneous Aqueous Solution and the Role of U(V) Disproportionation

Molecular-level pathways in the aqueous redox transformation of uranium by iron remain unclear, despite the importance of this knowledge for predicting uranium transport and distribution in natural and engineered environments. As the relative importance of homogeneous versus heterogeneous pathways is difficult to probe experimentally, here we apply computational molecular simulation to isolate rates of key one electron transfer reactions in the homogeneous pathway. By comparison to experimental observations the role of the heterogeneous pathway also becomes clear. Density functional theory (DFT) and Marcus theory calculations for all primary monomeric species at pH values ≤7 show for UO22+ and its hydrolysis species UO2OH+ and UO2(OH)20 that reduction by Fe2+ is thermodynamically favorable, though kinetically limited for UO22+. An inner-sphere encounter complex between UO2OH+ and Fe2+ was the most stable for the first hydrolysis species and displayed an electron transfer rate constant ket = 4.3 × 103 s-1. Three stable inner- and outer-sphere encounter complexes between UO2(OH)20 and Fe2+ were found, with electron transfer rate constants ranging from ket = 7.6 × 102 to 7.2 × 104 s-1. Homogeneous reduction of these U(VI) hydrolysis species to U(V) is, therefore, predicted to be facile. In contrast, homogeneous reduction of UO2+ by Fe2+ was found to be thermodynamically unfavorable, suggesting the possible importance of U(V)-U(V) disproportionation as a route to U(IV). Calculations on homogeneous disproportionation, however, while yielding a stable outer-sphere U(V)-U(V) encounter complex, indicate that this electron transfer reaction is not feasible at circumneutral pH. Protonation of both axial O atoms of acceptor U(V) (i.e., by H3O+) was found to be a prerequisite to stabilize U(IV), consistent with the experimental observation that the rate of this reaction is inversely correlated with pH. Thus, despite prevailing notions that U(V) is rapidly eliminated by homogeneous disproportionation, this pathway is irrelevant at environmental conditions.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2017

Ceramic Proppant Design for In-situ Microbially Enhanced Methane Recovery

This project designed a new type of multi-functional lightweight proppant. The proppant is utilized as the conventional lightweight proppant but also transports microorganisms to coalbed reservoirs. The proppant is coated with a polymer which protects the methanogenic microorganisms and serves as a time-release delivery for methane generation. To produce the multifunctional proppant, we assigned five tasks: 1) culturing methanogenic microbes from natural carbon sources; 2) identifying optimized growth and methanogenesis conditions for the microbial consortia; 3) synthesizing the lightweight ceramic proppant; 4) encapsulating the consortia and proppant; and 5) demonstrating lab scale simulated performance by monitoring in-situ methane generation and hydraulic conductivity. Task 1) To evaluate the feasibility of ex-situ cultivation, natural microbial populations were collected from various hydrocarbon-rich environments and locations characterized by natural methanogenesis. Different rank coals, complex hydrocarbon sources, hydrocarbon seeps, and natural biogenic environments were incorporated in the sampling. Three levels of screening allowed selection of microbial populations, favorable nutrient amendments, sources of the microbial community, and quantification of methane produced from various coal types. Incubation periods of up to 24 weeks were evaluated at 23°C. Headspace concentrations of CH 4 and CO 2 were analyzed by gas chromatography. After a two-week incubation period of the most promising microbes, generated headspace gas concentrations reached 873,400 ppm for methane and 176,370 ppm for carbon dioxide. Task 2) A central composite design (CCD) was used to explore a broad range of operational conditions, examine the effects of the important environmental factors, such as temperature, pH and salt concentration, and query a feasible region of operation to maximize methane production from coal. Coal biogasification was optimal for this consortium at an initial pH value of 5.5, at 30 °C, and at a NaCl concentration 3.7 mg/cm 3 (i.e., 145,165 ppm). Task 3) To create the lightweight ceramic proppant, the kaolinite and iron oxide (Fe 2 O 3 ) mixture were sintered under reducing atmosphere varying partial pressures of oxygen from 1.7×10 -13 atm to 1.8×10-11 atm. The Fe 2 O 3 reduces to FeO and reacts with kaolinite decomposed to mullite to form Fe 2 SiO 4 , FeSiO 3 , and FeAl 2 O 4 . As a result the proppant develops large pores (~100 µm), giving it a low bulk density (1.43 g/cm 3 ), and high porosity (45.2 vol%) at P_(O_2 )of 1.8×10 -11 atm. The proppant sintered at P_(O_2 )of 1.7×10 -13 atm is characterized by smaller pores (26 µm), higher density (1.72 g/cm3) and lower porosity (37.5 vol%). Crush resistance testing at 9,000 psi yields 6.8 wt% fine particles increasing to 17.7 wt% in porous samples. Acid solubility varies from 5.5 wt% loss increasing to 12.9 wt% in porous samples. Task 4 and 5) The microbial consortia obtained from the optimized condition and lightweight proppant were encapsulated by calcium-alginate polymer. The encapsulation system, including microbes and a proppant, was stored at 20°C and 36°C. The sample stored at 36°C generated 7.1×[10] 3 ppm of methane at 670 h, whereas the sample incubated at 20°C generated 1.1×[10] 3 ppm of methane. Benchtop lab-scale bioreactors were constructed and showed with real-time measurements that, as the microbes produced methane, the pH decreased, and hydrogen and carbon dioxide gases were consumed. A calcium ion-selective sensor revealed the release mechanism of the microbes from encapsulation. The calcium ions interconnecting the alginate monomers were disassociated by counter cations such as protons and potassium ions. The counter cations bound to the carboxyl group on the alginate monomer, which thus lost its ionic interactions with the calcium ions, resulting in decomposition of the hydrogel structure. Furthermore, the conductivity was increased to ~700 mD-ft from ~530 mD-ft once the encapsulated sample was applied to the coal pack. The particle size of coal was reduced when the encapsulated sample was added to the coal. The reduced coal size implied that the microbes would consume the hydrocarbon in coal.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2020

At-source Recovery of Rare Earth Elements from Coal Mine Drainage

Conventional acid mine drainage (AMD) treatment consists of pH adjustment, oxidation, and separation of solid precipitates from discharge quality water. Alkaline addition increases the pH to the range 7 to 9 to precipitate the regulated metals Al and Mn ions as hydroxides. Mechanical or chemical oxidation then converts the reduced iron species Fe 2+ to Fe 3+ which precipitates at a low pH value as ferric hydroxide (Fe(OH) 3 ). Co-precipitation of Rare Earth Elements (REEs) with hydroxides creates a gangue-rich matrix from which REEs must be separated. Fe(OH)3 is generally the most abundant gangue-forming metal. Current research by the project team has shown raw, untreated AMD has an average total rare earth element content (TREE) of about 287 μg/L (0.287 ppm). Operators of AMD-producing facilities are obliged to treat it to neutralize acidity and remove regulated metals (e.g., iron (Fe), aluminum (Al), and manganese (Mn)) prior to discharge. Ongoing research indicates conventional AMD treatment concentrates TREE in resulting precipitates (AMD sludge) by an average factor of 2,635x to an average dry weight, elemental concentration of 708 g/t (ppm). While the economics of recovering REEs from AMD sludge are appealing, much of the cost of REE recovery would be incurred during separation of REEs from the gangue metals: Fe, Al, and Mn. Significant gains can be made by precipitating REEs when most of these gangue metals are still in solution. Significant improvements in REE extraction efficiency can be obtained through separation of REEs from the aqueous phase AMD, upstream of conventional AMD treatment by: 1) creating an enriched REE feedstock, 2) producing a more consistent feedstock, 3) reducing transportation costs to an REE refinery, 4) reducing acid consumption in the acid leaching step, and 5) reducing the volume of waste produced at the ALSX plant. This project is exploring two novel approaches for extracting REEs upstream of the conventional AMD treatment plants to create a purified REE feedstock while leaving the bulk of the Fe, Al, and Mn in solution for subsequent treatment. While the average TREE concentration of raw AMD is low and individual sites range between 10 and 2,200 μg/L, successful at-source REE separation will generate a superior feedstock to a conventional ALSX process and significantly improve the economics and environmental performance of REE extraction from AMD. AMD can be classified into two types: type A is net acid and iron is partly oxidized while type B is net alkaline, and iron occurs in the reduced, ferrous state. In Case A, the pH is raised slightly, which will precipitate Fe 3+ and Al 3+ but not REEs. The other important type of AMD is net alkaline water found in flooded, anoxic deep mines. These generally have a pH > 6.0 and are net alkaline. REE concentrations are also much lower than those found in acidic AMD while the volumes and flux are much higher. Most of these are pumped discharges with almost no Al. Case B AMD is strongly reduced and, like Case A water, Fe and Mn ions are similarly reduced and therefore soluble at pH <9.0. REEs and an array of transition ions will be the only trivalent cations in this type of AMD. In Case B, both upward pH adjustment under reducing conditions and application of an electrochemically stimulated supported liquid membrane strategy to separate REEs from ferrous ion will be explored.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2025

Ion Transport in Carbon Nanotube Porins with a pH-Switchable Entrance Gate

Molecular transport in nanofluidic channels often differs drastically from conventional bulk transport. Strong confinement in those channels amplifies the roles of surface transport, surface defects, and molecular gates. Here, in this study, we introduce a chemical functionality at the nanotube rim that acts as a pH-triggered molecular gate by forming a movable lid that blocks the pore entrance. We use ion and proton transport measurements to show that these sub-1 nm diameter fluorescent ultrashort carbon nanotube porins (FUNPs) modulate ion transport by switching between the “open” and “closed” conformations of this gate. Specifically, at neutral pH the channel lid is open, allowing unimpeded ion transport through the gate, whereas at acidic pH values the lid forms a “closed” conformation that blocks transport through the nanotube. We also report first-principles MD simulations that confirm this gating mechanism and reveal molecular details of the ion and proton transport processes in these functional nanopores.

Carbon nanotubes↗
DOE OSTI2016

Spinel LiNi 0.5 Mn 1.5 O 4 Cathode for High-Energy Aqueous Lithium-Ion Batteries

A 2.9 V intrinsic safe aqueous LiNi 0.5 Mn 1.5 O 4 /Mo 6 S 8 full cell delivers 80 W h kg -1 energy density with capacity decay of 0.075% per cycle (5 C). After the electrolyte pH value adjustment, almost full capacity of LiNi 0.5 Mn 1.5 O 4 (125 mA h kg -1 ) is achieved, and 126 W h kg -1 energy density is provided for LiNi 0.5 Mn 1.5 O 4 /Mo 6 S 8 cell, representing one of the highest voltage and energy density among all the aqueous batteries.

25 ENERGY STORAGE↗
DOE OSTI2019

Analysis of equilibrium CO 2 solubility and thermodynamic models for aqueous 1‐(2‐hydoxyethyl)‐piperidine solution

Abstract 1‐(2‐Hydoxyethyl)‐piperidine (1‐(2HE)‐PP) is a new tertiary amine with desirable properties and can be potentially used to formulate superior absorbents for CO 2 capture. The equilibrium CO 2 solubility of 1‐(2HE)‐PP solution is measured over temperatures from 298 to 333 K, CO 2 partial pressures from 8.1 to 101.3 kPa and initial amine concentrations from 1 to 5 M. Two thermodynamic models, namely semiempirical model and activity coefficient model are developed for the system. The activity coefficient model shows better estimation solubility with an absolute average relative deviation (AARD) of 7.6%. In the comparison between the two models, a comprehensive analysis is presented. Some suggestions are provided for the similar model development. In addition, the speciation plot of CO 2 loaded 1‐(2HE)‐PP solution is predicted based on the activity coefficient model. The predictive pH values agree well with experimental data with AARD of 1.0%. Finally, the potential of 1‐(2‐HE)PP to be an alternative amine in CO 2 capture is evaluated.

Xiao, Min↗