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At least 505 records · Page 28

Technology Summary DNATRAX

DNATrax (DNA Tagged Reagents for Aerosol eXperiments) was developed to provide a safe simulant for understanding the transport and dispersion of pathogens. Specifically, it was developed as a safe surrogate for the Bacillus anthrasis spore bioagent, since most naturally occurring spores are not safe for public release. As DNA-tagged sugar particles, DNATrax aerosols are safe for public release. Scientists can add unique DNA barcode sequences to the sugar particles to produce a wide variety of test particles that can be easily differentiated, making it possible to release and test them simultaneously. The unique barcodes also eliminate the need to conduct decontamination between tests, dramatically reducing the cost and time to run experiments. Additionally, the surrogate offers a high-sensitivity detection method to understand key public health issues. We conducted both lab-based and largescale field studies using DNATrax to validate its capabilities for use as a pathogen surrogate. We have demonstrated the ability to produce DNATrax in a range of sizes, adjusting the microparticles to simulate different sized pathogens with ability to create unique sequences of DNA bases, enabling them to create a nearly unlimited variety of test particles.

59 BASIC BIOLOGICAL SCIENCES↗

Study of Poly(ether ketone ketone) (PEKK): Outgassing Characteristics and Likely Residual Synthesis Impurities

In May-June, 2020, a study was conducted to characterize the outgassing properties of a series PEKK (Poly(ether ketone ketone)) samples using cryo-GC/MS headspace analysis. Three sets of samples were interrogated: sample group 1 consisted of 2 additively manufactured PEKK samples (PEKK "ole and "New") prepared by KCNSC from powder material from Solvay Specialty Polymers USA, LLC. Sample groups 2 and 3 consist of 5 PEKK powder types (used as feedstock for additive manufacturing processes) and 4 additively-manufactured PEKK material lots, respectively. Contrary to expectations, all samples of PEKK material were observed to outgas sulfur-containing compounds. Other analyses (EDS/EMA, GC-TOF/MS of PEKK sample extractions) confirmed the presence of sulfur in the PEKK bulk material. Specifically, Diphenyl sulfone (used as a reagent or high-temperature solvent in the synthesis of Polyaryletherketone or PAEK polymers) was observed in three of the powders and in both the PEKK "Old" and "New" samples, suggesting that the source of the sulfur can be traced to impurities in the material left over from the synthesis process.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Validation of pooling strategies of clinical COVID-19 samples for more efficient diagnostic testing

Pooling of COVID-19 clinical samples can offer significant reduction in reagents, time, and labor needed to test large numbers of clinical samples. Especially for testing asymptomatic and return-towork/ school cases, where the prevalence of COVID-19 may be relatively low, large groups of clinical samples can be classified as negative with a single test, with no need to test every sample individually. LANL has performed validation for two different pooling strategies to assess diagnostic assay sensitivity in pooled samples compared to the clinical positive sample alone. (1) Pooling study - Determine diagnostic assay sensitivity in pooled samples with ratios of 1:5, 1:10, 1:20, and 1:30 positive to negative clinical samples. (2) Reloading study - Determine diagnostic assay sensitivity in reloading of multiple clinical samples through a Qiagen column in 5x, 10, and 20x sample volumes (1 positive plus 4, 9, and 19 negative samples).

59 BASIC BIOLOGICAL SCIENCES↗

Recovery of Rare Earth Elements from Bioleachates by Precipitation

Rare earth elements are essential components in electronic devices, however because of the limited imports and mining capabilities in the US, recycling these rare earths is crucial. Common practices used to recover REEs including hydrometallurgy and pyrometallurgy are harmful to the environment. Bioleaching, a form of biohydrometallurgy, is an emerging process that uses organic acids synthesized by microorganisms and can leach REEs at comparable efficiencies to less environmentally conscious processes. Once the REEs are leached by the bio-lixiviant produced by microorganisms, the REEs are suspended in the solution and need to precipitate out in order to be harvested for reuse. Common chemicals used for rare earth precipitation in hydrometallurgy processes include sodium sulfate and oxalic acid. These two reagents were tested at varying stoichiometric excess concentrations in bio-leachate derived from smart phone speaker magnets and bio-lixiviant. Following the precipitation reactions, it was observed that the oxalic acid reaction precipitated an abundance of iron (II) oxalate, an REE contaminate. This is most likely due to the bio-leachate having a higher pH compared to the hydrometallurgical leachates. Therefore, it was determined that sodium sulfate is a better candidate for REE precipitation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Handheld Biosensor for COVID-19 Screening

We have made significant progress toward the development of an integrated nucleic acid amplification system for Autonomous Medical Devices Incorporated (AMDIs) Optikus handheld diagnostic device. In this effort, we developed a set of loop-mediated isothermal amplification (LAMP) primers for SARS-CoV-2 and then demonstrate amplification directly on a surface acoustic wave (SAW) sensor. We built associated hardware and developed a C-code to control the amplification process. The goal of this project was to develop a nucleic amplification assay that is compatible with SAW sensors to enable both nucleic and serological testing in a single handheld diagnostic device. Toward this goal, AMDI is collaborating Sandia National Laboratories to develop a rapid, portable diagnostic screening device that utilizes Sandias unique surface acoustic wave biosensor (SAW) for COVID-19 detection. Previously, the SANDIA- AMDI SAW sensor has successfully detected multiple high-profile bacteria viruses, including Ebola, HIV, Sin Nombre, and Anthrax. Over the last two years, AMDI and SANDIA have significantly improved the sensitivity and detection capability of the SAW biosensor and have also developed a modular hand-held, portable platform called the Optikus, which uses CD microfluidics and handheld instrumentation to automate all sample preparation, reagent introduction, sample delivery, and measurement for a number of different assay targets. We propose to use this platform for the development of a rapid (%3C30 minutes), point-of-care diagnostic test for detection of COVID-19 from nasal swab samples.

47 OTHER INSTRUMENTATION↗

AX Farm and A Farm Third Retrieval Technology Chemical Dissolution Options Evaluation

In response to DOE-ORP direction to prepare a Practicability Evaluation for Waste Tank AX-102, and to address the Washington State Department of Ecology recommendation to evaluate the use of acid reagents for chemical dissolution, an Integrated Project Team (IPT) consisting of retrieval, process chemistry, corrosion, closure and laboratory subject matter experts was assembled to evaluate chemical dissolution options. This document provides a summary of these efforts and is intended to aid in the evaluation and third retrieval technology decision process not only for AX-102, but for all the AX and A Farm tanks, since the tanks contain similar waste and are flat-bottomed with uneven bottom plates.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

19-LW-045 Full Length Final Report. Molecular Mechanisms of Bacterial Pathogenesis: Waging the Arms Race with Superbugs

As the current global pandemic makes abundantly clear, we need a better understanding of infectious disease to safeguard human health, the economy and global security. Modern omics techniques hold the promise of providing a comprehensive understanding of the molecular mechanisms of life, including causes of pathogenesis from infectious disease at the molecular level, but we there is a serious gap in annotation of gene function. For as much as half of the genes and gene products encoded in genomes the molecular and/or cellular function is unknown or only partially understood. Recent innovations in fluorescence microscopy for live cell imaging and genetic engineering make it possible to determine the temporal correlation between molecular events, such as a gene being expressed due to host-pathogen interaction, and cellular events, such as bacterial invasion of immune cells. This is turn allows us to gain new insight as to the molecular and cellular role of individual genes and will enable the discovery and validation of new molecular mechanisms essential for infectious disease. Knowing the molecular mechanisms of disease processes will provide new therapeutic targets or novel countermeasure strategies. We aimed to develop a lattice light sheet fluorescence microscope as a unique resource at LLNL for long time course live cell imaging experiments; to develop the reagents and cell lines needed to monitor molecular events during the course pathogenic bacteria infecting mammalian immune cells; and to demonstrate that we could capture molecular events during an infection. We fully commissioned the LLNL lattice light sheet microscope and conducted initial proof of principle imaging experiments on mammalian immune cells and pathogenic bacteria. It is clear from the experience gained that long time course live cell imaging has tremendous potential to help elucidate molecular mechanisms of host-pathogen interactions and to help annotate gene function, which would establish a basis for new countermeasures. It is also clear that if live cell imaging is to realize its full potential new data processing and analysis tools will need to be developed to facilitate analysis of molecular events within cells; new sample chambers and stages could facilitate studies with a wider range of cell and tissue types; and alternative molecular tagging methods need to be explored to enable more facile engineering of cells labeled with molecular specificity.

59 BASIC BIOLOGICAL SCIENCES↗

Imaging APO-BMI with Micro X-ray Computed Tomography (CT)

APO-BMI is a high-strength, high-temperature, and low-density foam comprised of 1,2-bis(2-aminophenylthio) ethane (APO-Link, formerly Apocure-601) and 4,4’-bismaleimidodiphenylmethane (BMI) that is used structural applications within the aerospace and weapons manufacturing sectors. APO-link is the diamine reagent used to synthesize BMI, a thermosetting resin. This resin can remain in a molten, flowing state for an extended period of time before crosslinking, allowing addition of glass or carbon microballoons to form its final structure. A portion of the current project was to observe the thermal effects on the structural integrity of the foam associated with exposure to an ion beam. Features within the foam were imaged using micro X-ray computed tomography (CT). The resulting imaging provided evidence that microballoon structure remained mostly intact at the points of failure, indicating that the failure of the material was occurring in the binder material.

36 MATERIALS SCIENCE↗

Production and Performance of High Sulfur Concentration Waste Glasses (FY21)

In FY21 Savannah River National Laboratory (SRNL) was tasked to investigate the practical aspects of low activity waste (LAW) glass production with high sulfur loading for the Office of River Protection (ORP). Relationships between sulfur solubility, retention, and melter resonance need to be evaluated to refine waste loading limits and the super saturated melting (triple melt, grind, and wash) methodology. The impact of high sulfur concentration on durability and phase stability (crystallization and liquid-liquid immiscibility) during slow cooling also needs to be further evaluated. To accomplish this, SRNL proposed scaled melter testing using simulants with matched physicochemical properties to melter feed, as opposed to laboratory reagents. This type of testing is expected to validate applicability to design parameters and functional criteria expected during unit operations. This work was expected to commence in FY21, with the first melter tests being performed near the end of the FY. However, reduced access to Savannah River Site and personnel availability during the COVID-19 pandemic significantly reduced the amount of time and resources available to perform the task. This report documents the experimental plan and progress towards this task. The following is a summarized list of scheduled testing that will be performed on feed, condensate, cold cap and glass: 1) Melter runs; 2) Product consistency test (PCT); 3) Inductively coupled plasma optical emission spectroscopy (ICP-OES); and 4) Optical (OM) and scanning electron microscopy (SEM).

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Potential for Evaporation and In Situ Reaction of Organic Compounds in Hanford Supplemental LAW

The presence of regulated organic species in Hanford nuclear tank waste is assessed in this report, along with fate of the organics and possible evaporative treatment. A narrowed list of regulated organic species of concern is developed based upon published analyses, chemical properties like aqueous solubility, and chemical reactivity under alkaline conditions. Published analyses include tank headspace and liquid samples, review of chemical reagents formerly used at Hanford, and the Tank Waste Information Network System (TWINS). This work supports possible stabilization of Hanford Supplemental Low Activity Waste (SLAW) by grouting.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Potential for Evaporation and In Situ Reaction of Organic Compounds in Hanford Supplemental LAW

The presence of regulated organic species in Hanford nuclear tank waste is assessed in this report, along with fate of the organics and possible evaporative treatment. A narrowed list of regulated organic species of concern is developed based upon published analyses, chemical properties like aqueous solubility, and chemical reactivity under alkaline conditions. Published analyses include tank headspace and liquid samples, review of chemical reagents formerly used at Hanford, and the Tank Waste Information Network System (TWINS). This work supports possible stabilization of Hanford Supplemental Low Activity Waste (SLAW) by grouting.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

In Situ Thermodynamics and Kinetics of Mixed-Valence Inorganic Crystal Formation

We have found that the established methods to discover and produce earth-abundant iron-containing active layers are very inefficient. The prospective new material iron silicon sulfide, Fe 2 SiS 4 , was previously only synthesized by slow reactions of metallic iron, silicon, and sulfur powders, resulting in poor yield. We found that using an ordered iron-silicon alloy as a feedstock results in a much faster reaction at a lower temperature. We could track this reaction using our unique in-situ X-ray diffractometer, which allows us to heat our encapsulated material up to 1000°C while providing a simultaneous picture of how the atoms in the structure rearrange. We are using this powerful new technique to search for new active layers and optimize their formation by creative use of more complex reagents. Our key accomplishments are mechanisms for improving synthesis, and new materials that result from them. We have demonstrated the utility of high-throughput, DOE-developed infrastructure, such as the Materials Project, to accelerate materials discovery and synthesis. We have pioneered new capabilities of user facilities, such as beamlines 6-BM, 17-BM, and 11-BM at the Advanced Photon Source (APS) and POWGEN and NOMAD at the Spallation Neutron Source.

36 MATERIALS SCIENCE↗

High Yield, Economical and Environmentally Benign Production of Rare Earth Elements from Coal Ash (Phase II Final Summary Report)

Fly ash stored in landfills and ponds across the United States is an attractive, abundant domestic resource for the cost-effective recovery of rare earth elements (REE) and other critical minerals (CM). Physical Sciences Inc. (PSI) and its team members, Winner Water Services (WWS) and University of Kentucky/Center for Applied Energy Research (UK/CAER) successfully executed a multiphase program that developed technologies and their implementation in a pilot plant. We demonstrated plant operations for cost-effective and environmentally-friendly production of rare earth element oxide (REO) concentrates, and the critical minerals scandium and aluminum (in the forms of salts or oxide products), from coal ash. We also constructed and demonstrated a research-scale (0.5 kg/day) micropilot facility to validate the key physical and chemical processing operations, predict yields, and troubleshoot process bottlenecks. The project team then designed, constructed and operated two decoupled pilot plants: (1) an operational pilot plant for physical separation processes with capacity of 0.4 metric tons per day (tpd), where we optimized processes to produce selected ash fractions as the feedstock for chemical processing and as valuable byproducts such as cenospheres, magnetic ash, and secondary fuel carbon, and (2) an operational pilot plant for chemical ash processing with a capacity of 0.5 tpd that developed optimized processes for the production of: (a) REO concentrates, (b) critical minerals (Sc, Al), and (c) beneficiated ash as a valuable byproduct suitable for cement applications. In Phase I, the project team (with Equinox Chemicals in place of WWS) developed and demonstrated the feasibility of the physical and chemical separation processes, developed the design of a pilot plant, and began the development of a preliminary techno-economic model. In the baseline (initial) Phase II program, the project team developed and demonstrated the above pilot scale plant, producing salable REE concentrates, including Y and Sc (REYSc), plus commercially viable byproducts, using environmentally safe and high-yield physical and chemical enrichment processes. The team successfully demonstrated chemical pilot design, construction, shakedown, and operations of the plant. We produced the Phase II deliverable REYSc concentrate ((50 g of >60 wt.% purity REYSc salts on elemental basis), generated the feed for the Phase II follow-on program, identified processing challenges for future optimizations, and refined the techno-economic model. In the Phase II follow-on program, the project team: (1) developed and demonstrated processes to increase the REE amount by 3X (content basis) and convert the Phase II REE salt mixture to an oxide mixture, (2) produced/delivered >38 g of REO mixture with >85 wt.% purity (elemental basis); (3) developed processes to recover critical minerals scandium and aluminum from intermediate streams; (4) produced/delivered > 1 g of scandium salt mixture with >85 wt. % purity (elemental basis); (5) produced/delivered > 100 g of aluminum oxide type material with >70% wt. purity (elemental basis); and (6) updated the techno-economic model from the baseline Phase II program to assess CAPEX and OPEX of a commercial operation. This program has developed extensive databases on process chemistry, unit operations, plant engineering, and techno-economics that will enable further scale-up toward commercial plant design. Specific future developments will be focused on achieving dramatic savings in energy, reagent usage, and operating costs. The combined results will contribute significantly for maturing the technologies of REE recovery from coal byproducts and promote the establishment of domestic REE and CM supply chains.

01 COAL, LIGNITE, AND PEAT↗

ETF Grout Expansion: Effects of Different Slags and Struvite Precipitation Protocols (Stirring Time)

The ETF ammonia tolerant grout waste form was developed by the Vitreous State Laboratory (VSL) to stabilize ammonium and thereby prevent emission of ammonia vapor during solidification of an ammonium-rich, concentrated sodium sulfate aqueous waste stream generated at the Hanford Effluent Treatment Facility (ETF). VSL personnel did not observe expansion in samples prepared during the waste form development work. However, Savannah River National Laboratory (SRNL) personnel detected expansion, in a few ETF grout samples, up to ~ 20 percent vertical expansion, while preforming work scope to evaluate the effect of ETF brine compositional ranges on the precipitation and solidification processes. The initial work requests can be found in Washington River Protection Services (WRPS) Statement of Work (SOW, Requisitions #: 339922 Revisions 0 and 1, March 11, 2021, and November 2021, respectively. As a result of the waste form expansion observed by SRNL, additional evaluation was requested by WRPS SOW Requisitions #: 356730 Revision 0 and Revision 1, February 1, 2022, and July 11, 2022, respectively. The goal of these requests was to determine whether differences in the slags and / or in sample preparation protocols used by VSL and SRNL were the cause of the expansion observed in the SRNL samples. G. Chen, WRPS, arranged a materials exchange between VSL and SRNL and coordinated the VSL protocol(s) for grouting and curing 1L batches of Base Case ETF base case simulant. Materials were exchanged between VSL and SRNL. Both laboratories performed the VSL struvite precipitation-solidification protocol and cured samples for at least 28 days. Differences in VSL and SRNL slag compositions, mineralogy and particle size results in themselves or combined were determined to not be the cause of the expansion because all samples expanded regardless of whether the VSL or SRNL slags were used. The fundamental cause of the observed expansion could not be attributed to minor variations in the following: 1) chemistry of the slag and other reagents, 2) container wall thickness, 3) ambient bench top curing conditions at VSL and SRNL, 4) pH adjustments to 7 ± a few tenths of unit, nor 5) stirring time between the precipitation and solidification process steps. Additional observations include: grout samples prepared with VSL slag expanded less than those prepared with the SRNL slag and, based on a very limited sample set, some samples stirred for longer times expanded less than those stirred for 20 minutes.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

CO2 Electrolyzer to Produce Formic Acid Using Flue Gas at Industry Relevant Current Density

The electrochemical conversion of carbon dioxide (CO2) into valuable fuels and feedstocks has gained great attention recently due to the global urgency to mitigate the rapid climate change. A wide variety of chemicals can be obtained through the electrochemical CO2 reduction reaction (CO2RR). Among all the chemicals generated through CO2RR, formic acid has attracted great interest because of its wide applications in silage preservation in agriculture, as an antibacterial agent in animal food additives, as a chemical additive in leather and tanning processing, as a chemical component in textile dyeing and finishing, as a reagent in pharmaceutical and chemical synthesis, and as deicing agents and a component in drilling fluids. Recently, the use of formic acid as a feedstock for biorefineries has also attracted increasing interest.

Yang, Hongzhou↗

Microfluidic Uranium Microspheres Production for TRISO and Advanced Fuel Concepts

The purpose of this project was to expand existing internal gelation sol-gel capabilities at PNNL to explore producing uranium dioxide spheres for potential use as fuel kernels in next generation Tri-isotropic (TRISO) particle fuel. This project expands on previous sol-gel efforts at PNNL by (1) increasing the size regime of sphere production from the micro-fluidic range to the milli-fluidic range, and (2) producing uranium spheres. The approach involved first scaling up the channel size of the fluidic system to the millimeter range, with radiation safety considerations in mind; testing and demonstration on non-radioactive surrogate material, cerium oxide; then transitioning to uranium production and finally optimizing system parameters. Commercially available fluidic chips in the desired size range were could not be found, therefore the project designed and fabricated a T-junction with 1mm channels for droplet production. Because the production process is temperature sensitive, prior efforts have involved performing droplet production in a lab freezer. To reduce radiological waste and footprint, two alternative chilling methods were explored using aluminum thermal beads as a chill bath and a custom aluminum block fit to reagent reservoir sizes. Both were successful in the cerium tests, however the aluminum block design outperformed the thermal bead bath and was further adapted for the radiological test and production run in the Radiochemical Processing Laboratory (RPL). Gelation trials were performed to determine an acceptable range of feed solution parameters for the uranium dioxide gels, characterized by R-values, which is determined by the ratio of uranium nitrate to Hexamethylenetetramine (HMTA)/urea in the feed solution. R-values ranging from 1.6-2 were examined in the gelation trials, with only the 1.8 condition being tested in production. The project was successful in demonstrating a proof of concept design for producing uranium dioxide spheres, however further optimization is needed to dial in production parameters and improve sphere quality and homogeneity.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

The Recovery of Medical Isotope 188 W from Irradiated W Metal Target - A New Approach

Tungsten-188 is in widespread use in 188 W(t 1/2 = 69 d )/ 188 Re(t 1/2 = 16.9 h ) biomedical generators. Oak Ridge National Laboratory has been providing this product to the world since 1999. At ORNL, 188 W is produced via irradiation in ORNL’s High Flux Isotope Reactor (HFIR). Enriched 186 W targets in the form of sintered metallic pellets or rings achieve a compact loading in the irradiation vessel, providing a high yield per unit target. The enrichment of the target is >90% 186 W, and this isotope undergoes double neutron capture to produce the desired 188 W product. While 188 W is produced by neutron bombardment, 191 Os(t 1/2 = 15.4 d ) is simultaneously produced as a by-product and expected to be separated from 188 W by postirradiation treatment.In the current processing pathway, the irradiated W metal rings are first converted into an oxide form of WO 3 by heating the irradiated W metal target at 750°C in a quartz reaction vessel inside a vertical furnace under a constant flow of air. During heating, W metal reacts with oxygen in the air to produce WO 3 , which is soluble in 6 M NaOH for preparation of 188 W product. This oxidation process also converts 188 Os (the decay daughter of 188 W) and 191 Os (15.4 d , the irradiation produced byproduct) into OsO 4 , a highly volatile and toxic gas. The gaseous effluents driven from the quartz reaction vessel are passed through a scrubbing array to remove OsO 4 before the air is discharged from the process. This heterogeneous oxidation method simultaneously achieves goals of (1) converting metal target to a soluble oxide form and (2) removing volatile OsO 4 away from the solid WO 3 product by air flow and absorbing the harmful Os species by the scrubbing array. But this method has two potential problems as well: (1) O 2 reacts with only W metal at high temperatures, not with W alloyed with other elements. The O 2 –W reaction will be retarded when formation of WRe or WC occurs, or even when a layer of non-W materials on the surface of the irradiated W rings.; (2) 100% absorption of OsO 4 of high yield (>90%) from the reaction of Os + O 2 is a strict requirement to the OsO 4 scrubbing system--so NaOH scrubbers of a redundant size (2x 1.5 L) are in use for safety reasons.To resolve above two potential problems, direct dissolution of the irradiated W metal target by a selected reagent is a preferred pathway to avoid heating step with generation of tremendous amount of volatile OsO 4 . Hydrogen peroxide (H 2 O 2 ) is such a candidate to dissolve W in forms of either metal or alloys, although literature lacks information of solubilities of Re or Os in H 2 O 2 . With experimental results of dissolving non-radioactive W, Re and Os in H 2 O 2 under various conditions, this report illustrates a method of H 2 O 2 dissolution for irradiated W target, with a complete dissolution of W and Re, but ≤10% dissolution of Os (converted into gaseous OsO 4 and carried out into a scrubbing for absorption) during processing irradiated W target. The portion of undissolved Os can be separated from W solution by a follow up filtration step. Solubilities of W, Re and Os in H 2 O 2 at a temperature range from 14° to 50°C are presented. And a dissolution rate of W metal per surface area of W metal in H 2 O 2 is calculated based on results of dissolving a W metal cylinder of known surface area in H 2 O 2 at room temperature without stirring.

07 ISOTOPE AND RADIATION SOURCES↗

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↗