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DOE OSTI2016

Quantification of Cation Sorption to Engineered Barrier Materials Under Extreme Conditions

The objective of this research is to examine mechanisms and thermodynamics of actinide sorption to engineered barrier materials (iron (oxyhydr)oxides and bentonite clay) for nuclear waste repositories under high temperature and high ionic strength conditions using a suite of macroscopic and microscopic techniques which will be coupled with interfacial reaction models. Gaining a mechanistic understanding of interfacial processes governing the sorption/sequestration of actinides at mineral-water interfaces is fundamental for the accurate prediction of actinide behavior in waste repositories. Although macroscale sorption data and various spectroscopic techniques have provided valuable information regarding speciation of actinides at solid-water interfaces, significant knowledge gaps still exist with respect to sorption mechanisms and the ability to quantify sorption, particularly at high temperatures and ionic strengths. This objective is addressed through three major tasks: (1) influence of oxidation state on actinide sorption to iron oxides and clay minerals at elevated temperatures and ionic strengths; (2) calorimetric titrations of actinide-mineral suspensions; (3) evaluation of bentonite performance under repository conditions. The results of the work will include a qualitative conceptual model and a quantitative thermodynamic speciation model describing actinide partitioning to minerals and sediments, which is based upon a mechanistic understanding of specific sorption processes as determined from both micro-scale and macroscale experimental techniques. The speciation model will be a thermodynamic aqueous and surface complexation model of actinide interactions with mineral surfaces that is self-consistent with macroscopic batch sorption data, calorimetric and potentiometric titrations, X-ray absorption Spectroscopy (XAS, mainly Extended X-ray Absorption Fine Structure (EXAFS)), and electron microscopy analyses. The novelty of the proposed work lies largely in the unique system conditions which will be examined (i.e. elevated temperature and ionic strength) and the manner in which the surface complexation model will be developed in terms of specific surface species identified using XAS. These experiments will thus provide a fundamental understanding of the chemical and physical processes occurring at the solid-solution interface under expected repository conditions. Additionally, the focus on thermodynamic treatment of actinide ion interactions with minerals as proposed will provide information on the driving forces involved and contribute to the overall understanding of the high affinity many actinide ions have for oxide surfaces. The utility of this model will be demonstrated in this work through a series of advective and diffusive flow experiments.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2017

Bench Scale Process for Low Cost CO 2 Capture Using a Phase-Changing Absorbent: Final Scientific/Technical Report

The objective of this project is to design and build a bench-scale process for a novel phase-changing aminosilicone-based CO 2 -capture solvent. The project will establish scalability and technical and economic feasibility of using a phase-changing CO 2 -capture absorbent for post-combustion capture of CO 2 from coal-fired power plants. The U.S. Department of Energy’s goal for Transformational Carbon Capture Technologies is the development of technologies available for demonstration by 2025 that can capture 90% of emitted CO 2 with at least 95% CO 2 purity for less than $40/tonne of CO 2 captured. In the first budget period of the project, the bench-scale phase-changing CO2 capture process was designed using data and operating experience generated under a previous project (ARPA-e project DE-AR0000084). Sizing and specification of all major unit operations was completed, including detailed process and instrumentation diagrams. The system was designed to operate over a wide range of operating conditions to allow for exploration of the effect of process variables on CO 2 capture performance. In the second budget period of the project, individual bench-scale unit operations were tested to determine the performance of each of each unit. Solids production was demonstrated in dry simulated flue gas across a wide range of absorber operating conditions, with single stage CO 2 conversion rates up to 75mol%. Desorber operation was demonstrated in batch mode, resulting in desorption performance consistent with the equilibrium isotherms for GAP-0/CO 2 reaction. Important risks associated with gas humidity impact on solids consistency and desorber temperature impact on thermal degradation were explored, and adjustments to the bench-scale process were made to address those effects. Corrosion experiments were conducted to support selection of suitable materials of construction for the major unit operations in the process. The bench scale unit operations were assembled into a continuous system to support steady state system testing. In the third budget period of the project, continuous system testing was conducted, including closed-loop operation of the absorber and desober systems. Slurries of GAP-0/GAP-0 carbamate/water mixtures produced in the absorber were pumped successfully to the desorber unit, and regenerated solvent was returned to the absorber. A techno-economic analysis, EH&S risk assessment, and solvent manufacturability study were completed.

20 FOSSIL-FUELED POWER PLANTS↗

DOE OSTI2026

Simulated moving bed-inspired method for continuous adsorptive denitrogenation of model fuel

Efficient, continuous routes for removing nitrogen-containing compounds from hydrothermal liquefaction-derived synthetic aviation fuel are needed to enable direct blending with conventional jet fuels. Here, we report a simulated moving bed-inspired process for adsorptive denitrogenation of a model fuel. Unlike conventional simulated moving bed systems, which are designed for sharp separations between similar solutes, this approach was run deliberately outside the classical separation region so that both pyridine and indole were removed together from the hydrocarbon stream. Alcohol solvents were used to regenerate the silica adsorbent, maintaining performance over extended operation and avoiding the downtime and energy demand associated with calcination. Under these conditions, the system demonstrates removal of more than 98% of nitrogen while cutting solvent use by 28% compared to batch operation. Classical modeling tools predicted column concentration profiles even in this nontraditional regime, suggesting a straightforward path to scaling. Together, these results motivate solvent-efficient, continuous denitrogenation strategies that could be integrated with biorefinery processes.

Adsorption↗

DOE OSTI2016

Developing a Scalable System for Biorecovery of Critical Materials from Industrial Waste with Gluconobacter Oxydans

Organic acid production by Gluconobacter oxydans has been proposed as part of a potential economical and environmentally friendly heterotrophic bioleaching process for recovery of rare earth elements from industrial waste. To provide organic acids in a quantity and at a rate useful for commercial bioleaching, continuous culture of the acid-producing organism will be necessary. The objective of this research project was to determine optimal conditions for continuous cultivation of G. oxydans for production of organic acids. Cultures were subjected to dilution rates ranging from .05 hr -1 to .38 hr -1 to determine the optimum conditions for production of lixiviant agents. Previous studies have identified methods for maximizing production of gluconic acid and 2,5-diketogluconic acid from G. oxydans , yet the utilization of these and other unidentified G. oxydans metabolites for leaching of rare earth metals is largely unexplored. Continuous cultures exhibited sustained organic acid production for at least 110 hours, while batch fermentations showed slowed growth rates after 16 hours. Several parameters, namely optical density, dissolved oxygen, organic acid concentration and pH, were monitored to characterize the steady state conditions of the fermentation process. The observed trend was increasing acidity with decreasing dilution rates, as the lowest dilution rate of 0.05 hr -1 yielded the highest gluconic acid concentration of 176 mM and lowest pH of 2.20. Trace amounts of 2,5-diketogluconic acid were detected only at the 0.05 hr-1 dilution rate, likely because the pH of the bioreactors was not maintained within the window for gluconate dehydrogenase activity [Silberbach, M., et al., Appl Microbiol Biotechnol, 2003. 62(1): p. 92-8].

60 APPLIED LIFE SCIENCES↗

DOE OSTI2018

Direct Feed Low Activity Waste Test Platform - Pretreatment Unit Operations - 18613

The Low-Activity Waste Pretreatment System (LAWPS) facility is planned to pretreat Hanford tank waste supernate by filtering solids and processing through ion exchange columns to remove cesium. Note that cesium ion exchange is not discussed in this paper. The filtration process is achieved through cross flow filtration using a stainless steel Mott filter with a 0.1-micron grade. The goal of this effort was to assess whether a batch, or dead end, filtration (DEF) device replicating the LAWPS cross flow filter could be employed to qualify each feed campaign prior to delivery to LAWPS. The objective for filtration feed qualification is to determine whether the cross flow filters deployed in LAWPS will remove solids while maintaining a de minimis flow rate of permeate. To that end, the DEF was tested with simulants and the results compared with those obtained from cross flow filtration tests. In addition, actual waste samples were retrieved from Hanford Site Tank AP-105 and were composited for testing. These composited samples were first tested with cross flow filtration to determine the filter flux under typical LAWPS conditions. The same material was subsequently tested with DEF to determine a filter flux. While the DEF correctly predicted the cross flow filter's ability to filter solids from the feed, there was limited correlation between DEF and cross flow filtration flux results. This lack of correlation suggests a fundamental difference between cross flow filtration and DEF as used in these tests. Taken in total, these results indicate that DEF is not a good candidate to provide qualification of feed for LAWPS cross flow filtration. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2020

Scalable Synthesis of Ti 3 C 2 T x MXene

Scaling the production of synthetic 2D materials to industrial quantities has faced significant challenges due to synthesis bottlenecks whereby few have been produced in large volumes. These challenges typically stem from bottom‐up approaches limiting the production to the substrate size or precursor availability for chemical synthesis and/or exfoliation. In contrast, MXenes, a large class of 2D transition metal carbides and/or nitrides, are produced via a top‐down synthesis approach. The selective wet etching process does not have similar synthesis constraints as some other 2D materials. The reaction occurs in the whole volume; therefore, the process can be readily scaled with reactor volume. Herein, the synthesis of 2D titanium carbide MXene (Ti 3 C 2 T x ) is studied in two batch sizes, 1 and 50 g, to determine if large‐volume synthesis affects the resultant structure or composition of MXene flakes. Characterization of the morphology and properties of the produced MXene using scanning electron microscopy, X‐ray diffraction, dynamic light scattering, Raman spectroscopy, X‐ray photoelectron spectroscopy, UV–visible spectroscopy, and conductivity measurements show that the materials produced in both batch sizes are essentially identical. This illustrates that MXenes experience no change in structure or properties when scaling synthesis, making them viable for further scale‐up and commercialization.

Shuck, Christopher E.↗

DOE OSTI2017

Ru-Sn/AC for the Aqueous-Phase Reduction of Succinic Acid to 1,4-Butanediol under Continuous Process Conditions

Succinic acid is a biomass-derived platform chemical that can be catalytically converted in the aqueous phase to 1,4-butanediol (BDO), a prevalent building block used in the polymer and chemical industries. Despite significant interest, limited work has been reported regarding sustained catalyst performance and stability under continuous aqueous-phase process conditions. As such, this work examines Ru-Sn on activated carbon (AC) for the aqueous-phase conversion of succinic acid to BDO under batch and flow reactor conditions. Initially, powder Ru-Sn catalysts were screened to determine the most effective bimetallic ratio and provide a comparison to other monometallic (Pd, Pt, Ru) and bimetallic (Pt-Sn, Pd-Re) catalysts. Batch reactor tests determined that a ~1:1 metal weight ratio of Ru to Sn was effective for producing BDO in high yields, with complete conversion resulting in 82% molar yield. Characterization of the fresh Ru-Sn catalyst suggests that the sequential loading method results in Ru sites that are colocated and surface-enriched with Sn. Postbatch reaction characterization confirmed stable Ru-Sn material properties; however, upon a transition to continuous conditions, significant Ru-Sn/AC deactivation occurred due to stainless steel leaching of Ni that resulted in Ru-Sn metal crystallite restructuring to form discrete Ni-Sn sites. Computational modeling confirmed favorable energetics for Ru-Sn segregation and Ni-Sn formation at submonolayer Sn incorporation. To address stainless steel leaching, reactor walls were treated with an inert silica coating by chemical vapor deposition. With leaching reduced, stable Ru-Sn/AC performance was observed that resulted in a molar yield of 71% BDO and 15% tetrahydrofuran for 96 h of time on stream. Postreaction catalyst characterization confirmed low levels of Ni and Cr deposition, although early-stage islanding of Ni-Sn will likely be problematic for industrially relevant time scales (i.e., thousands of hours). Overall, these results (i) demonstrate the performance of Ru-Sn/AC for aqueous phase succinic acid reduction, (ii) provide insight into the Ru-Sn bimetallic structure and deactivation in the presence of leached Ni, and (iii) underscore the importance of compatible reactor metallurgy and durable catalysts.

09 BIOMASS FUELS↗

DOE OSTI2017

Optical follow-up of gravitational wave triggers with DECam

Gravitational wave (GW) events have several possible progenitors, including black hole mergers, cosmic string cusps, supernovae, neutron star mergers, and black hole{neutron star mergers. A subset of GW events are expected to produce electromagnetic (EM) emission that, once detected, will provide complementary information about their astrophysical context. To that end, the LIGO-Virgo Collaboration has partnered with other teams to send GW candidate alerts so that searches for their EM counterparts can be pursued. One such partner is the Dark Energy Survey (DES) and Dark Energy Camera (DECam) Gravitational Waves Program (DES- GW). Situated on the 4m Blanco Telescope at the Cerro Tololo Inter-American Observatory in Chile, DECam is an ideal instrument for optical followup observations of GW triggers in the southern sky. The DES-GW program performs subtraction of new search images with respect to preexisting overlapping images to select candidate sources. Due to the short decay timescale of the expected EM counterparts and the need to quickly eliminate survey areas with no counterpart candidates, it is critical to complete the initial analysis of each night's images within 24 hours. The computational challenges in achieving this goal include maintaining robust I/O pipelines during the processing, being able to quickly acquire template images of new sky regions outside of the typical DES observing regions, and being able to rapidly provision additional batch computing resources with little advance notice. We will discuss the search area determination, imaging pipeline, general data transfer strategy, and methods to quickly increase the available amount of batch computing. We will present results from the rst season of observations from September 2015 to January 2016 and conclude by presenting improvements planned for the second observing season.

79 ASTRONOMY AND ASTROPHYSICS↗

NASA NTRS1973

Validity test for linear error analysis

To determine whether estimation process simulated by linear error analysis will converge, criterion has been developed based on extension of classical observability. Particular application of technique is with groups of batched navigation data where statistics of estimation errors are derived with classical minimum-variance methods.

Diamant, L. S.↗

NASA NTRS2015

Integration of Nanostructures into Microsensor Devices on Whole Wafers

Chemical sensors are used in a wide variety of applications, such as environmental monitoring, fire detection, emission monitoring, and health monitoring. The fabrication of chemical sensors involving nanostructured materials holds the potential for the development of sensor systems with unique properties and improved performance. However, the fabrication and processing of nanostructures for sensor applications currently are limited in the ability to control their location on the sensor, which in turn hinders the progress for batch fabrication. This report discusses the advantages of using nanomaterials in sensor designs, some of the challenges encountered with the integration of nanostructures into microsensor / devices, and then briefly describes different methods attempted by other groups to address this issue. Finally, this report will describe how our approach for the controlled alignment of nanostructures onto a sensor platform was applied to demonstrate an approach for the mass production of sensors with nanostructures.

Nanostructures (Devices)↗

DOE OSTI2022

Evolution of HEP Processing Frameworks

HEP data-processing software must support the disparate physics needs of many experiments. For both collider and neutrino environments, HEP experiments typically use data-processing frameworks to manage the computational complexities of their large-scale data processing needs. Data-processing frameworks are being faced with new challenges this decade. The computing landscape has changed from the past three decades of homogeneous single-core x86 batch jobs running on grid sites. Frameworks must now work on a heterogeneous mixture of different platforms: multi-core machines, different CPU architectures, and computational accelerators; and different computing sites: grid, cloud, and high-performance computing. We describe these challenges in more detail and how frameworks may confront them. Given their historic success, frameworks will continue to be critical software systems that enable HEP experiments to meet their computing needs. Frameworks have weathered computing revolutions in the past; they will do so again with support from the HEP community

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

DOE OSTI2014

Centrifugal contactor operations for UREX process flowsheet. An update

The uranium extraction (UREX) process separates uranium, technetium, and a fraction of the iodine from the other components of the irradiated fuel in nitric acid solution. In May 2012, the time, material, and footprint requirements for treatment of 260 L batches of a solution containing 130 g-U/L were evaluated for two commercial annular centrifugal contactors from CINC Industries. These calculated values were based on the expected volume and concentration of fuel arising from treatment of a single target solution vessel (TSV). The general conclusions of that report were that a CINC V-2 contactor would occupy a footprint of 3.2 m 2 (0.25 m x 15 m) if each stage required twice the nominal footprint of an individual stage, and approximately 1,131 minutes or nearly 19 hours is required to process all of the feed solution. A CINC V-5 would require approximately 9.9 m 2 (0.4 m x 25 m) of floor space but would require only 182 minutes or ~ 3 hours to process the spent target solution. Subsequent comparison with the Modular Caustic Side Solvent Extraction Unit (MCU) at Savannah River Site (SRS) in October 2013 suggested that a more compact arrangement is feasible, and the linear dimension for the CINC V-5 may be reduced to about 8 m; a comparable reduction for the CINC V-2 yields a length of 5 m. That report also described an intermediate-scale (10 cm) contactor design developed by Argonne in the early 1980s that would better align with the SHINE operations as they stood in May 2012. In this report, we revisit the previous evaluation of contactor operations after discussions with CINC Industries and analysis of the SHINE process flow diagrams for the cleanup of the TSV, which were not available at the time of the first assessment.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2020

High solids loading biorefinery for the production of cellulosic sugars from bioenergy sorghum

A novel process applying high solids loading in chemical-free pretreatment and enzymatic hydrolysis was developed to produce sugars from bioenergy sorghum. Hydrothermal pretreatment with 50% solids loading was performed in a pilot scale continuous reactor followed by disc refining. Sugars were extracted from the enzymatic hydrolysis at 10% to 50% solids content using fed-batch operations. Here, three surfactants (Tween 80, PEG 4000, and PEG 6000) were evaluated to increase sugar yields. Hydrolysis using 2% PEG 4000 had the highest sugar yields. Glucose concentrations of 105, 130, and 147 g/L were obtained from the reaction at 30%, 40%, and 50% solids content, respectively. The maximum sugar concentration of the hydrolysate, including glucose and xylose, obtained was 232 g/L. Additionally, the glucose recovery (73.14%) was increased compared to that of the batch reaction (52.74%) by using two- stage enzymatic hydrolysis combined with fed-batch operation at 50% w/v solids content.

09 BIOMASS FUELS↗

DOE OSTI2015

Technetium Reduction and Permanent Sequestration by Abiotic and Biotic Formation of Low-Solubility Sulfide Mineral Phases

One way to minimize the mobility of the Tc VII oxyanion pertechnetate (TcO 4 - ) is to effect reduction under sulfidogenic conditions (generated abiotically by Fe 0 or biotically) to form TcS x , which is significantly slower to oxidize than Tc IV O 2 . In sediment systems, TcS x and other precipitates may oxidize more slowly due to oxygen diffusion limitations to these low permeability precipitate zones. In addition, the TcO 4 - reduction rate may be more rapid in the presence of sediment because of additional reductive surface phases. This project aims to provide a fundamental understanding of the feasibility of immobilization of TcO 4 - as TcS x in the vadose zone or groundwater by application nano zero-valent iron (nZVI), and sulfide or sulfate. Biotic batch experiments have used the sulfate-reducing bacterium (SRB) Desulfotomaculum reducens . The iron sulfide mineral mackinawite was generated under these conditions, while vivianite was formed in nZVI only controls. The sulfide/bacteria-containing system consistently reduced aqueous pertechnetate rapidly (> 95% in the first hour), a rate similar to that for the sulfide-free, nZVI only system. Reduced Tc (aged for 3 months) generated in both SRB/nZVI systems was highly resistant to reoxidation. In reduced samples, Tc was found associated with solid phases containing Fe and S (D. reducens/nZVI) or Fe (nZVI only). Experiments using D. reducens without nZVI provided some additional insights. Firstly, stationary phase cultures were able to slowly reduce pertechnetate. Secondly, addition of pertechnetate at the beginning of cell growth (lag phase) resulted in a faster rate of Tc reduction, possibly indicating a direct (e.g. enzymatic) role for D. reducens in Tc reduction. Abiotic batch experiments were conducted with Na 2 S as the sulfide source. Pertechnetate reduction was rapid in the presence of sulfide and nZVI, although the rate was suppressed at the higher S/Fe ratios tested. This suppression appeared to be due to the formation of Tc-containing colloids. As with the biotic experiments, pertechnetate reduced under sulfidic conditions was highly resistant to reoxidation. The microscopic morphology of abiotically-transformed nZVI particles varied significantly with those in the biotic experiment, although mackinawite was formed in both systems (as indicated by μXRD and Mössbauer spectroscopy). Preliminary XAS analysis pointed to a mixture of Tc-O and Tc-S binding in the abiotic sulfide/nZVI system, while the major reduced solids under non-sulfidic conditions were TcO 2 •nH 2 O. The presence of sediment and advective flow to the TcO 4 - /nZVI/sulfide system results in additional processes occurring. Although the natural Hanford sediment used has sufficient available ferrous iron to slowly reduce TcO 4 - , under anaerobic conditions, that rate is orders of magnitude slower than reduction by nZVI/sulfide. Batch and 1-D column experiments showed that the TcO 4 - reduction rate increased with the sediment surface area (with the same nZVI mass). As in batch systems, column studies showed that the presence of sulfide with TcO 4 - at low (2-5 mM) concentrations increased the TcO 4 - reduction rate and high (10-30 mM) sulfide decreased the rate. This change is attributed to the formation of sulfide precipitates on the nZVI and sediment surfaces. Injection of low and high sulfide (i.e. pretreatment) prior to TcO 4 - /sulfide injection also greatly decreased the TcO 4 - reduction rate, likely decreasing the generation of ferrous iron from the nZVI. Although the high sulfide systems have slower Tc reduction rates, 190 times more Tc mass precipitated than in the low sulfide systems and the highest fraction of Tc mass remained immobilized.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2015

Thermal degradation of the solvent employed in the next-generation caustic-side solvent extraction process and its effect on the extraction, scrubbing, and stripping of cesium

As part of the ongoing development of the Next-Generation Caustic-Side Solvent Extraction (NGS) process, the thermal stability of the process solvent was investigated and shown to be adequate for industrial application. The solvent was thermally treated at 35 C over a period of 13 months whilst in dynamic contact with each of the aqueous phases of the current NGS process, namely SRS 15 (a highly caustic waste simulant), sodium hydroxide scrub solution (0.025 M), and boric acid strip solution (0.01 M). The effect of thermal treatment was evaluated by assessing batch extract/scrub/strip performance as a function of time, by monitoring the sodium extraction capacity of the solvent, and by analysis of the solvent using electrospray mass spectrometry. Current studies indicate that the NGS solvent should be thermally robust for a period of XXX months at the Modular Caustic-Side Solvent Extraction Unit (MCU) pilot plant located at Savannah River Site. Furthermore, the guanidine suppressor appears to be the solvent component most significantly impacted by thermal treatment of the solvent, showing significant degradation over time.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2016

Development of Treatment Process for Radioactive Wastewater Generated from Molybdenum-99 Study - 16415

Molybdenum-99 (Mo-99) high acidic waste solution was securely stored at INER for numerous years. Until 2004, the procedures of waste solution draw-out and pressure-release were accompanied, along with construction of treatment facilities. In 2009, after simulated solution and small volume Mo-99 waste solution tests, the treatment procedure was determined. Then batch-scale treatment facilities were set up. The waste solution was preserved using the instrument, along with modification of some facilities simultaneously. Ultimately all of 12 tanks of Mo-99 inorganic waste solution stored in Building 014 were finished on July, 2012. And residential 5 tanks of those solution served in Building 015B were also completed on September, 2014. A practicable process has been developed for treating radioactive waste generated from Mo-99 study, and it can effectively remove radionuclides from a nitric acid solution. At first, after the waste was sucked from the bucket, the pH value was adjusted to about 10.0 through acid-alkali neutralization. Then, an adsorbent of natural zeolite powder was added to adsorb nuclides, and two adsorption columns filled with Cs-treat and Sr-treat adsorbents were used for removing nuclear species of Cs-137 and Sr-90. In this step, the nuclear species of Cs-137 and Sr-90 contained in the liquid waste are significantly reduced to a degree for manual operation allowable. Then, nitrate ion and mercury ion were removed through another procedure. As a result, the operations were safer and more efficient than other conventional methods. Additionally, the hazard of accidental leakage caused by corrosion of the bucket after long period of storage can be effectively prevented and potential pollution threats are also eliminated. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

NASA NTRS1981

Synthesis of perfluoroalkylene dianilines

The objective of this contrast was to optimize and scale-up the synthesis of 2,2-bis(4-aminophenyl)-hexafluoropropane and 1,3-bis(4-aminophenyl)hexafluoropropane, as well as to explore avenues to other perfluoroalkyl-bridged dianilines. Routes other than Friedel-Crafts reaction leading to 2,2-bis(4-aminophenyl)hexafluoropropane were investigated. The processes utilizing bisphenol-AF were all unsuccessful; reactions aimed at the production of 4-(hexafluoro-2-halo-isopropyl)aniline from the hydroxyl intermediate failed to yield the desired products. Tailoring the conditions of the Friedel-Crafts reaction of 4-(hexafluoro-2-hydroxyisopropyl)aniline, aniline, and aluminum chloride by using hydrochloride salts and selecting optimum reagent ratios, reaction times, and temperature resulted in approx. 20% yield of pure crystallized 2,2-bis(4-aminophenyl)hexafluoropropane in 0.2 mole reaction batches. Yields up to approx. 40% were realized in small, approx. 0.01 mole, batches. The synthesis of 1,3-bis(4-aminophenyl)hexafluoropropane starting with perfluoroglutarimidine was reinvestigated. The yield of the 4-step reaction sequence giving 1,3-bis(4-acetamidophenyl)hexafluoropropane was raised to 44%. The yield of the subsequent hydrolysis process was improved by a factor of approx. 2. Approaches to prepare other perfluoroalkyl-bridged dianilines were unsuccessful. Reactions reported to proceed readily with trifluoromethyl substituents failed when longer chain perfluoroalkyl groups were employed.

Paciorek, K. L.↗

DOE OSTI2020

Simulation of DWPF Chemical Process Cell Using a Reaction Calorimeter

The Defense Waste Processing Facility (DWPF) converts liquid radioactive waste into glass using a Sludge Receipt Adjustment Tank (SRAT) and Slurry Mix Evaporator (SME) in addition to other processes. The SRAT and SME processes can be simulated on a small-scale using the Mettler-Toledo Reaction Calorimeter (RC1). This equipment is able to automate the execution and monitoring of experiments involving nonradioactive chemical simulants. During the chemical processing of sludge in the SRAT process, foam begins to form and can foam over the reaction vessel. The current antifoam used at DWPF creates a risk of increased flammability and has a limited pH range. Usually, mercury is circulated back into the reaction vessel during the SRAT process, making it difficult to remove. To combat foam over, novel antifoams will be tested during the boil-up process using the RC1. To improve mercury extraction, 3D-printed coalescer columns will be tested within the Mercury Water Wash Tank (MWWT) of the RC1. Testing of Simulant Sludge Batch 6 (SB6) was performed to ensure: the sludge would form a stable foam at boiling during full SRAT/SME runs; the antifoam would reduce the amount of foam within the vessel The sludge and a Precipitate Reactor Feed Tank (PRFT) simulant with monosodium titanate (MST) were mixed separately, combined, and then heated to boiling. As shown below, the antifoam used was able to eliminate the foam within the vessel, as expected. The FormLabs Form2 3D Printer can be used to create roughly 3-inch tall and 1-inch diameter columns from clear and ceramic resins. The columns will utilize chemical and physical forces to draw the mercury out of a condensed offgas stream leaving the RC1 reaction vessel. These columns will be tested during full SRAT/SME runs on the basis of how well they are able to collect elemental mercury. In preparation for full-scale runs, the RC1 equipment was assembled onto a custom table and tested with water runs. The software used to control automation, iControl, has a user-friendly interface that allows the experiment to be altered as needed. An example of the data recorded during an experimental run is represented in Figure 1 below. Water runs were utilized as a way to prove if the RC1 system was functioning in the following areas: Boil-up rates, Chemical additions using pumps, Temperature readings, Balance readings, Probe readings, Offgas system, Agitation. Future Plans: Five novel antifoams will be tested during full SRAT/SME runs. The most effective antifoam will be utilized in DWPF's Chemical Process Cell. The design of the Mercury Extraction Coalescer can be further manipulated to increase the extraction of not only elemental mercury, but other heavy metals in environmental remediation processes as well.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗