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DOE OSTI2021

The controlling role of atmosphere in dawsonite versus gibbsite precipitation from tetrahedral aluminate species

In highly alkaline solution, aluminum speciates as the tetrahedrally coordinated aluminate monomer, Al(OH)4- and/or dimer Al2O(OH)62-, yet precipitates as octahedrally coordinated gibbsite (Al(OH)3). This tetrahedral to octahedral transformation governs Al precipitation, which is crucial to worldwide Al production, and to the processing of caustic high-level radioactive wastes. Despite its significance, the transformation pathway remains unknown. Here we explore the roles of atmospheric water and carbon dioxide in mediating the transformation of the tetrahedrally coordinated potassium aluminate dimer salt (K2Al2O(OH)6) to gibbsite versus potassium dawsonite (KAl(CO3)(OH)2). A combination of in-situ attenuated total reflection infrared spectroscopy, ex-situ micro X-ray diffraction, and multivariate curve resolution-alternating least squares chemometrics analysis reveals that humidity plays a key role in the transformation by limiting the amount of alkalinity neutralization by dissolved CO2. Lower humidity favors higher alkalinity and incorporation of carbonate species in the final Al product to form KAl(CO3)(OH)2. Higher humidity enables more acid generation that destabilizes dawsonite and favors gibbsite as the solubility limiting phase. Because the transformation was restricted to occur in thin water films, the results suggest that transition from tetra- to octahedrally coordinated Al does not have to occur in bulk solution, as has often been hypothesized, but may instead appear on the source mineral surface.

Dembowski, Mateusz↗

NASA NTRS1984

Design considerations for a 10-kW integrated hydrogen-oxygen regenerative fuel cell system

Integration of an alkaline fuel cell subsystem with an alkaline electrolysis subsystem to form a regenerative fuel cell (RFC) system for low earth orbit (LEO) applications characterized by relatively high overall round trip electrical efficiency, long life, and high reliability is possible with present state of the art technology. A hypothetical 10 kW system computer modeled and studied based on data from ongoing contractual efforts in both the alkaline fuel cell and alkaline water electrolysis areas. The alkaline fuel cell technology is under development utilizing advanced cell components and standard Shuttle Orbiter system hardware. The alkaline electrolysis technology uses a static water vapor feed technique and scaled up cell hardware is developed. The computer aided study of the performance, operating, and design parameters of the hypothetical system is addressed.

Hoberecht, M. A.↗

NASA NTRS1984

Design considerations for a 10-kW integrated hydrogen-oxygen regenerative fuel cell system

Hoberecht, M. A.↗

DOE OSTI2020

Stability of plutonium oxide nanoparticles in the presence of montmorillonite and implications for colloid facilitated transport

The physical and chemical stability of PuO 2 nanoparticles (intrinsic colloids) in groundwater will control their transport and may affect the performance of high-level radioactive waste repositories. In this study, we examined the chemical stability of two types of PuO 2 nanoparticles at both 25 and 80 °C. The “alkaline” PuO 2 nanoparticles were prepared by neutralizing an acidic Pu(IV) solution with dilute NaOH to pH ~9.5. The “acidic” PuO 2 nanoparticles were precipitated from 0.1 M nitric acid by heating a Pu(IV) solution at 60–80 °C for 30 min. The chemical stability of these PuO 2 nanoparticles was tested in the presence of montmorillonite, a common mineral in the environment and potentially relevant backfill material in some nuclear waste repository designs. The “alkaline” PuO 2 nanoparticles were found to be unstable over a timescale of months at both 25 and 80 °C, with elevated temperature enhancing their dissolution rates and sorption to montmorillonite. PuO 2 nanoparticle dissolution rates decreased with increasing Pu concentration, consistent with solution saturation. The “acidic” PuO 2 nanoparticles appeared to remain stable for much longer than the “alkaline” PuO2 nanoparticles. The “alkaline” PuO 2 nanoparticle dissolution rate constants were as high as 10 -11.9±0.4 mol m -2 s -1 and 10 -11.2±0.2 mol m -2 s -1 at 25 and 80 °C, respectively, while the “acidic” PuO 2 nanoparticle dissolution rate at 80 °C was 10 -13.5 mol m -2 s -1 . Based on transmission electron microscopy, the “alkaline” and “acidic” PuO 2 nanoparticles were of similar size (2.5–4.5 and 2–3 nm nanoparticles, respectively). However, the “acidic” PuO 2 nanoparticles formed more ordered nanoparticle aggregates. Our results suggest that the specific conditions experienced during PuO 2 nanoparticle formation could significantly affect the stability of PuO 2 in the presence of competing sorption processes and, in turn, the relative importance of intrinsic versus pseudocolloid transport in the environment.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

DOE OSTI2020

Role of electron pathway in dimensionally increasing water splitting reaction sites in liquid electrolytes

Hydrogen from water splitting is one of the most promising alternatives for fossil fuels in solving the global energy crisis, while its electrochemical reaction mechanism, especially in liquid electrolytes, remains unclear. Herein, how the electrode conductivity affects the reaction sites of oxygen evolution reactions (OERs) in acidic and alkaline solutions was investigated by employing visualization system and electrochemical testing. Inserting Au nanolayers greatly increased electrode conductivities, improved OER kinetics and reduced cell ohmic resistance, leading to excellent water splitting performances in both acidic and alkaline electrolytes. Furthermore, the in-situ visualization results showed more reaction sites and higher catalyst utilizations were achieved by augmenting the electrode conductivity, and reaction sites increased from 1-dimension to 2-dimension. Additionally, it was discovered that electrical conductivities of acidic and alkaline solutions are insufficient to overcome the sharp drop of potential in the electrical double layer for activating OER uniformly on low-conductivity catalysts, indicating the importance of electrical conductivity of the electrode in acidic and alkaline water electrolyzers. This study provided a guidance on how to develop efficient and compact electrodes for acidic and alkaline water electrolyzer stacks and other electrochemical devices, such as fuel cell, N2 reduction, CO 2 conversion, etc.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

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 OSTI2023

Recovery of high-quality calcium phosphate fertilizer products from anaerobic membrane bioreactor treated swine wastewater

The aim of this study is the sustainable recovery of phosphorus as high-quality calcium phosphate from anaerobic membrane bioreactor treated swine permeate for targeted use as fertilizer or raw material for the fertilizer industry. Phosphorus removal efficiencies from treated swine permeate were evaluated by adding various calcium/phosphorus molar ratios ranging from 1/1 to 12/1. Results showed that removal efficiencies were inconsistent in duplicate trials at the same calcium doses (maximum P removal 93% in Trial 1 and <20% removal in Trial 2). The variability in P removal was due to the high bicarbonate alkalinity of the swine permeate, which buffered the system and thereby prevented it from reaching alkaline pH conditions ideal for P removal. Total alkalinity and initial solution pH had the greatest impact on P removal and caused unintended precipitation of non-specific calcium minerals (Calcite). Further, the carbonate alkalinity from the permeate was removed using process modifications that included acid addition and aeration for removal as CO 2 . Carbonate removal resulted in 97% P removal with increased total P content (11.8% P) in the final product and better solubility. Additional COD removal was also observed during the flocculation process.

09 BIOMASS FUELS↗

DOE OSTI2023

Synthesis of PHI-type zeolite harmotome using barium as an inorganic structure-directing agent inspired from natural mineral compositions

Zeolites are nanoporous aluminosilicates widely used as commercial adsorbents, heterogeneous catalysts, and ion-exchange materials due to their unique porosity, acidity, and thermal stability. The vast majority of synthetically-realized zeolite structures are prepared under hydrothermal conditions in alkaline media, and often in the presence of an organic structure-directing agent that facilitates the crystallization of diverse porous networks. Due to economic and environmental disadvantages of organic-based syntheses, it is often desirable to produce zeolites in organic-free media using alkali metal ions as the most commonly employed inorganic structure-directing agents (ISDAs). Here, in this study, we were inspired by the elemental compositions of natural zeolite minerals to examine the use of an alkaline earth metal ion as the ISDA to prepare zeolites with the PHI framework type. Two natural minerals exhibiting this crystal structure are phillipsite and harmotome. Both structures contain sodium and potassium as extra-framework cations, but only harmotome contains barium cations. Here we examined how the combination of alkali and alkaline earth ISDAs promote the formation of PHI-type zeolites. Our findings reveal that each isostructure is prepared under different synthesis conditions where simply adding barium to a growth mixture does not always lead to harmotome formation. Harmotome is formed in more dilute and alkaline growth media; however, time-resolved analyses of zeolite crystallization reveal that harmotome can be synthesized at low temperatures (ca. 65 °C) with rates that are 5-times faster than syntheses of phillipsite. This seemingly indicates that barium reduces the energetic barrier for PHI-type zeolite nucleation in ways that are not fully understood. Moreover, harmotome crystals exhibit an average particle size of ca. 60 nm, which is nearly 40-fold smaller than phillipsite crystals prepared under similar conditions. Collectively, these findings identify routes to control crystallization of PHI-type zeolites and may provide a broader strategy for using the composition of natural zeolite minerals to optimize the preparation of synthetic analogues.

36 MATERIALS SCIENCE↗

DOE OSTI2020

LixNiO/Ni Heterostructure with Strong Basic Lattice Oxygen Enables Electrocatalytic Hydrogen Evolution with Pt-like Activity

The low-cost hydrogen production from water electrolysis is crucial for practical deployment of sustainable hydrogen economy, but is often constrained by the lack of active and robust electrocatalysts from Earth-abundant materials. We describe here an unconventional heterostructure composed of strongly coupled Ni-deficient LixNiO nanoclusters and polycrystalline Ni nanocrystals, and its exceptional activities toward hydrogen evolution reaction (HER) in aqueous electrolytes. The presence of unique lattice oxygen species with strong Brønsted basicity is a significant feature, which spontaneously split water molecules and effectively accelerate the sluggish Volmer H-OH dissociation step in neutral and alkaline HER. In combination with the unpreceded level of intimate LixNiO and Ni interfacial junctions that produces abundant “hotspots” for promoted hydride coupling, the catalyst exhibited kinetic activities almost identical as Pt/C and decent long term stability in universal pH.

Lu, Ke↗

DOE OSTI2024

Optimizing Direct Air Capture Solvents to Minimize Energy Consumption of CO 2 Release in a Carbonate Electrolyzer

Addressing climate change by carbon management is critical to achieving the goal of net zero carbon emissions by 2050. In this work, we examined the electrochemically-driven recovery of CO 2 during alkaline solvent regeneration for solvent-based direct air capture. A mathematical model was developed by incorporating carbonate chemistry with water electrolysis to predict the energy consumption per unit of CO 2 released. The predicted results were consistent with the experimental data, in which the experimental work was achieved by characterizing alkalinity and carbon loading values of solvent collected from a flow carbonate electrolyzer. Through this study, we learned that minimizing the energy expended on CO 2 release can be achieved by using an anolyte with a lower alkalinity, increasing the electric charge input to the electrolyzer, and reducing the ohmic resistance of the electrolyzer. Furthermore, using a supporting electrolyte, e.g., Na 2 SO 4 in the present work, effectively compensates for the higher ohmic resistance from using an anolyte with a lower alkalinity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

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 OSTI2021

Comparing elemental measurements at packaging and after storage for signatures of chloride salt radiolysis

Radiolysis of hydrated alkaline earth chloride salts by alpha radiation from plutonium produces the chloride containing gases HCl and Cl 2 . These gases are known to diffuse out of the plutonium-containing material and contribute to corrosion outside of the convenience container. The alkaline earth elements remain with the plutonium-containing material as oxides or hydroxides. The amount of chlorine within the material after storage will be reduced compared to the amount at packaging. The fraction of the alkaline earth elements that are soluble after storage will be reduced compared to the amount at packaging. These signatures may be observable by comparing the chemical analysis measurements made at packaging and after storage. Comparison of measurements on a single Hanford container shows that the chloride does decrease and the alkaline earth elements have reduced solubility in water. Differences seen with other elements make conclusions difficult.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2021

CO2 Capture Strategies via Mineralization with Industrial Waste Brines

Large coal-fired power plants (>500 MW) account for 30% of global CO2 emissions, and long-term management of this CO2 to is urgently needed mitigate global temperature increases. Sequestration of CO2 within stable mineral carbonates (e.g., CaCO3) represents an attractive emission reduction strategy because it offers a leakage-free alternative to geological storage of CO2 in an environmentally friendly form. We have previously described a mineralization process in which divalent cations are sourced from various waste streams (e.g., produced water and brackish water) and alkalinity is induced via regenerable ion-exchange materials (Bustillos et. al. Frontiers in Energy Research. 2020, 8, 352). In our process, aqueous carbonate-bearing streams with pH > 8 are produced by contacting fresh water and carbon dioxide with various ion-exchange materials (e.g., Na form zeolites or ion exchange resins). These streams are mixed with produced water containing varying concentrations (~0.01 – 1.0 M) of Ca2+ leading to the precipitation of solid calcium carbonate (PCC). This process has the advantages of using regenerable solids in a simple and continuous process to increase the pH of water by ion exchange instead of relying on the consumption of costly and unsustainable sources of alkalinity (e.g., sodium hydroxide). While once-through column experiments showed the above benefits, the same were yet to established in a steady-state process with recycle streams. In this work, we set up a process simulation to quantify the energy requirements and CO2 emissions associated with the process and seek optimal produced water compositions and CO2 concentrations (5 – 20 vol%). The process simulation was set up in ASPEN Plus using eRNTL as the thermodynamic property method and sequential modular strategy. Ion exchange alkaline solution was simulated using sodium hydroxide and validated against the experimental data obtained from once-through kinetic experiments. Nanofiltration and reverse osmosis membrane steps were also implemented for the separation of divalent cations and production of fresh water and a regeneration stream following mineralization. Sensitivity analysis was carried out using a range of produced water compositions (0.01 – 1.0 M Ca2+, 0.001 – 0.15 M Mg2+, 0.5 – 3.5 M Na+ and 0.0004 – 0.002 M Fe2+) according to the United States Geological Survey (USGS) database. Calcium carbonate yields increased with increasing CO2 concentrations and were maximized using produced water compositions with larger Ca2+ concentrations. Maximum calcium carbonate yields produced at 5 vol%, 12 vol% and 20 vol% CO2 were 2.3 mmol/L, 5.5 mmol/L, and 9.3 mmol/L, respectively, with the formation of brucite (a magnesium hydroxide phase, Mg(OH)2) and goethite (an iron hydroxide phase, FeOOH) as the primary contaminant phases (99% calcite, 0.6% brucite, 0.4% goethite), which agree with phases detected by XRD experimentally. These results indicate high purity calcium carbonate can be precipitated using industrial waste streams. Consequentially, energy consumption and net CO2 emissions were minimized where precipitated calcium carbonate was maximized for all produced water compositions and CO2 concentrations. Minimum energy consumptions were 0.21 kWh/ton CO2 processed, with 98% of the energy input required coming from the membrane filtration steps. Produced water compositions with large Na+ concentrations (> 0.5 M) were effective at reducing energy consumptions due to faster regeneration time of ion exchange materials. Additionally, calculated net CO2 emissions were negative for the process and ranged from -0.02 kg/ton CO2 to -0.15 kg/ton CO2 processed, indicating a low emission process. We will also present techno-economic assessment showing the economic benefits of the current process as an alternative to the addition of stoichiometric bases to induce alkalinity for the precipitation of CaCO3.

Simonetti, Dante↗

DOE OSTI2023

Synthetic Calcium Carbonate Production by Carbon Dioxide (CO 2 ) Mineralization of Industrial Waste Brines

The global scale of CO 2 emission has crossed 36 B tons, and the United State represents 14% of the total emissions. In light of the high cost associated with current CO 2 capture processes ($60-to-150 per ton of CO 2 ), carbon capture and utilization (CCU), wherein CO 2 is converted to beneficial products, provides a pragmatic path to overcome the economic barrier for CO 2 emissions control. In particular, CO 2 mineralization offers an attractive route as it produces high-value mineral carbonates that sequester CO 2 in a stable form. For instance, fine precipitated calcium carbonate, a valuable product with unit price in the range of $230-280/t and a global market projected to reach 99 M tons in 2020, can be produced by capturing CO 2 within aqueous Ca 2+ solution. However, two critical challenges need to be overcome—(i) the need for costly processes such as electrolysis or addition of alkali hydroxides to maintain alkalinity during mineralization, and (ii) the geographic availability of Ca-rich solutions (or brines) which often renders efficient integration with power plants impractical. To simultaneously address these challenges, this project developed two novel routes to enable carbonate production based on efficient CO 2 mineralization. In one variation, the project developed a new alkaline carbonation process to capture CO 2 and produce calcite precipitates from coal ashes. Herein, coal ash is carbonated first in a sodium carbonate solution. The carbonation reaction produces sodium hydroxide and raises the solution pH. This high-pH hydroxide solution is then used for CO 2 capture, which converts the sodium hydroxide solution back to sodium carbonate to repeat the carbonation cycle. The carbonated ash residue is refined with a CO 2 pressure swing step to produce high-purity precipitated calcium carbonate. In another variation, Ca-rich produced water brine serves as the Ca-source to mineralize CO 2 . An H + /Na + ion-exchange cycle was designed to provision alkalinity during mineralization and regenerate the ion-exchange reagent in brines with high salinity. Ca-depleted brines can then be treated within a centralized water treatment facility. Both variations beneficially utilize reject streams—such as coal ashes and brines from oil and gas extraction or CO 2 storage operations—that are available at substantial quantities in the vicinity of coal power plants within the U.S. In addition to technology development, this project included techno-economic and life-cycle analysis to identify technically and economically appropriate solutions for power plants in different geographic locations. Taken together, the project provides a unique route to integrate CO 2 emissions control and waste handling/treatment for coal power plants, while producing a high-value product to offset the economic burden associated with waste management. The developed processes utilize post-desulfurization flue gas from coal-fired power plants as is. The CO 2 conversion reactions are performed in alkaline brines at ambient pressure from the flue gas, thereby minimizing the energy burden. By beneficiation of industrial waste streams with low energy input, the processes offers significant technical advantages in energy and CO 2 footprint over the current paradigm of precipitated calcium carbonate production, which involves calcination of limestone at processing temperatures in excess of 800 °C. Overall, this project developed viable CO 2 mineralization processes while strategically maximizing the economic benefit.

01 COAL, LIGNITE, AND PEAT↗

DOE OSTI2020

Implementation of Ion Exchange Processes for Carbon Dioxide Mineralization Using Industrial Waste Streams

Sequestration of CO 2 within stable mineral carbonates (e.g., CaCO 3 ) represents an attractive emission reduction strategy because it offers a leakage-free alternative to geological storage of CO 2 in an environmentally benign form. However, the pH of aqueous streams equilibrated with gaseous streams containing CO 2 (pH < 4) are typically lower than that which is required for carbonate precipitation (pH > 8). Traditionally, alkalinity is provided by a stoichiometric reagent (e.g., NaOH) which renders these processes environmentally hazardous and economically unfeasible. This work investigates the use of regenerable ion-exchange materials to induce alkalinity in CO 2 -saturated aqueous solutions such that the pH shift required for mineralization occurs without the need for stoichiometric reagents. Na + -H + exchange isotherms (at [H + ] = 10 −8 –10 −1 M) and rates were measured for 13X and 4A zeolites and TP-207 and TP-260 organic exchange resins in batch equilibrium and fixed-bed exchange experiments, respectively. At solutions equilibrated with CO 2 at 1.0 atm (pH = 3.9), H + exchange capacities for the materials were similar (1.7–2.4 mmol H + /g material) and resulted in pH increases from 3.9 to greater than 8.0. Multi-component mixtures using Ca 2+ and Mg 2+ cations (at 10 −3 –10 −1 M) in CO 2 -saturated water were used to probe competitive ion exchange. The presence of divalent cations in solution inhibited H + exchange, reducing capacities to as low as 0.2 mmol H + /g for both resins and zeolites. Dynamic H + exchange capacities in fixed-bed ion exchange columns were similar to equilibrium values for resins (∼1.5 mmol/g) and zeolites (∼0.8 mmol/g) using inlet solutions that were equilibrated with gaseous streams of CO 2 at 1.0 atm. However, exchange kinetics were limited by intraparticle diffusion as indicated by the increased rate parameters with increasing inlet flow rates (20–160 cm 3 min −1 ). Experimental calcite precipitation from mixing the alkaline CO 3 2− -rich water solution obtained from the ion-exchange column with a simulated liquid waste stream solution achieved thermodynamic maximum yields. The results from these studies indicate that ion exchange processes can be used as an alternative to the addition of stoichiometric bases to induce alkalinity for the precipitation of CaCO 3 , thereby opening a pathway toward sustainable and economic mineralization processes.

42 ENGINEERING↗

NASA NTRS1981

Advanced technology lightweight fuel cell program

The potential of the alkaline electrolyte fuel cell as the power source in a multi hundred kilowatt orbital energy storage system was studied. The total system weight of an electrolysis cell energy storage system was determined. The tests demonstrated: (1) the performance stability of a platinum on carbon anode catalyst configuration after 5000 hours of testing has no loss in performance; (2) capability of the alkaline fuel cell to operate to a cyclical load profile; (3) suitability of a lightweight graphite electrolyte reservoir plate for use in the alkaline fuel cell; (4) long life potential of a hybrid polysulfone cell edge frame construction; and (5) long term stability of a fiber reinforced potassium titanate matrix structure. The power section tested operates with passive water removal eliminating the requirement for a dynamic hydrogen pump water separator thereby allowing a powerplant design with reduced weight, lower parasite power, and a potential for high reliability and extended endurance. It is concluded that two perovskites are unsuitable for use as a catalyst or as a catalyst support at the cathode of an alkaline fuel cell.

Martin, R. E.↗

NASA NTRS1987

Regenerative fuel cell study for satellites in GEO orbit

Summarized are the results of a 12-month study to identify high performance regenerative hydrogen-oxygen fuel cell concepts for geosynchronous satellite application. Emphasis was placed on concepts with the potential for high energy density (W-hr/lb) and passive means for water and heat management to maximize system reliability. Both polymer membrane and alkaline electrolyte fuel cells were considered, with emphasis on the alkaline cell because of its high performance, advanced state of development, and proven ability to operate in a launch and space environment. Three alkaline system concepts were studied. The first, the integrated design, utilized a configuration in which the fuel cell and electrolysis cells are alternately stacked inside a pressure vessel. Product water is transferred by diffusion during electrolysis and waste heat is conducted through the pressure wall, thus using completely passive means for transfer and control. The second alkaline system, the dedicated design, uses a separate fuel cell and electrolysis stack so that each unit can be optimized in size and weight based on its orbital operating period. The third design was a dual function stack configuration, in which each cell can operate in both fuel cell and electrolysis mode, thus eliminating the need for two separate stacks and associated equipment. Results indicate that using near term technology energy densities between 46 and 52 W-hr/lb can be achieved at efficiencies of 55 percent. System densities of 115 W-hr/lb are contemplated.

Levy, Alexander↗

NASA NTRS1994

Primary battery design and safety guidelines handbook

This handbook provides engineers and safety personnel with guidelines for the safe design or selection and use of primary batteries in spaceflight programs. Types of primary batteries described are silver oxide zinc alkaline, carbon-zinc, zinc-air alkaline, manganese dioxide-zionc alkaline, mercuric oxide-zinc alkaline, and lithium anode cells. Along with typical applications, the discussions of the individual battery types include electrochemistry, construction, capacities and configurations, and appropriate safety measures. A chapter on general battery safety covers hazard sources and controls applicable to all battery types. Guidelines are given for qualification and acceptance testing that should precede space applications. Permissible failure levels for NASA applications are discussed.

Bragg, Bobby J.↗