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At least 19 records

Summary of Savannah River Site FY21 Salt Waste Qualification Data and Characterization Data from Salt Waste Batches Processed Since 2008

The Savannah River National Laboratory analyzed samples from Savannah River Site Waste Tank 41H and 21H to support qualification of Salt Waste Processing Facility Waste Batches 3 and 4 (the FY21 Salt Batch Qualification samples) for processing. Neither of the samples displayed any unusual or unexpected characteristics such as large amounts of solids, floating solids, or unusual color. Characterization of these samples confirmed similar chemical composition and characteristics to previous salt waste batches. These results were initially provided to Savannah River Remediation (Liquid Waste Operations Sub-contractor) as External Sample Results LIMS Reports. The analytical results (both expedited and routine) are now summarized and discussed in this technical report.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Real-Time Automated pH Control within Batch Processes Relying on Raman pH Measurement

Nuclear fission is an energy source that can provide consistent power with very low associated carbon emissions. However, management of the used nuclear fuel is an important aspect of the application of nuclear power. Recycling of useful components from used fuel is an attractive option, but this involves chemical processing of the fuel. Possible chemical separation technologies that might be used in this regard are sensitive to solution pH. Raman spectroscopy is a promising technique for monitoring the pH of solutions in real time. Classical pH probes are too fragile to be used in the harsh environments encountered in nuclear fuel processing. Raman probes are robust and can withstand these harsh environments to track pH. Coupled with chemometric analysis, the demonstration of the use of Raman spectroscopy to track and predict the pH in carboxylate-buffered systems is made possible. Utilizing this spectroscopy in conjunction with Programmable Logic Controllers mimics industrial control systems used in many modern industrial settings. This showcases a pragmatic approach toward leveraging Raman spectroscopy and chemometric model outputs as inputs for a real-time control system. The model to predict pH created by chemometrics proved to be successful in tracking pH. The optimal pH for TALSPEAK extraction of lanthanides and actinides from aqueous solution is known to proceed in a narrow pH range of around pH = 2.8 ± 0.1. This study uses Raman optical monitoring and automated control to return and maintain solution pH within this range after acid or base perturbations move the solution pH well outside this region. Root-mean-square errors show that pH changes measured using Raman spectroscopy on the batch process solution are reliably measured and used to automatically correct and maintain solution pH. Measurement of solution pH tracks favorably with electrochemical pH probe comparison measurements. As a result, the ability to showcase Raman spectroscopy paired with chemometrics analysis acts as a durable, better alternative data source compared to traditional pH probes to optimize the separation efficiency in the used nuclear fuel processing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Qualification of Processing Batches for Tank Closure Cesium Removal Through In-Tank Batch Contact Testing - 20470

The Tank Closure Cesium Removal (TCCR) process at the Savannah River Site (SRS) is currently processing waste from Tank 10H, generating decontaminated salt solution that is sent to Tank 11H. Transfers out of Tank 11H are then disposed of on site as a grout wasteform in the SRS Saltstone Processing Facility. This is a full-scale demonstration of the use of Crystalline Silicotitanate (CST) for the decontamination of aqueous nuclear waste supernate. CST primarily removes cesium from the high sodium alkaline feed, but also adsorbs strontium, actinides, and some other trace metals. The TCCR unit is an at-tank set of four ion exchange columns, with two typically being operated in series during waste processing. Tank 10H is serving a dual function as both the salt dissolution tank as well as the feed tank for the TCCR system. Prior to operation of TCCR, Tank 10H must undergo dissolution campaigns, dissolving the salt cake to form an aqueous salt solution (supernate). After each dissolution campaign, the supernate created must be qualified prior to processing through the TCCR system. Qualification includes detailed characterization of the supernate as well as in-tank batch contact tests to determine the equilibrium loading of Cs-137 on the CST ion exchange media (IONSIV{sup TM} R9120-Ba). In support of the in-tank batch contact testing, Savannah River National Laboratory (SRNL) developed a CST sample holder, also referred to as a 'tea-bag', to hold a measured amount (∼0.1 grams) of pretreated CST between stainless steel screens. The tea-bag fits within a standard stainless steel sample vial that has been modified to allow the flow of supernate to the CST. This sample holder is then immersed in the waste tank allowing free contact between the CST beads and the surrounding liquid, at an effectively infinite liquid-to-solid phase ratio. A pair of tea-bags are deployed in the tank for a period of 10 days for each batch, after which the CST is recovered, digested, and analyzed to determine the loading of cesium isotopes on the CST. This result then supports the TCCR column thermal loading limits for processing as part of the TCCR safety basis. This paper will discuss the design and testing of the CST sample holder, as well as results from the first few batches of waste qualified and subsequently processed through the TCCR system. In addition, results from analyses of Tank 11H samples, showing decontamination of the product will be included. (authors)

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Investigation on hemolytic effect of poly(lactic co-glycolic) acid nanoparticles synthesized using continuous flow and batch processes

Abstract With the increasing interest in polymeric nanoparticles for biomedical applications, there is a need for continuous flow methodologies that allow for the precise control of nanoparticle synthesis. Poly(lactide-co-glycolic) acid (PLGA) nanoparticles with diameters of 220–250 nm were synthesized using a lab-on-a-chip, exploiting the precise flow control offered by a millifluidic platform. The association and the effect of PLGA nanoparticles on red blood cells (RBCs) were compared for fluorescent PLGA nanoparticles made by this novel continuous flow process using a millifluidic chip and smaller PLGA nanoparticles made by a batch method. Results indicated that all PLGA nanoparticles studied, independent of the synthesis method and size, adhered to the surface of RBCs but had no significant hemolytic effect at concentrations lower than 10 mg/ml.

Libi, Sumit↗

Kinetic Investigation by Batch Processing of Film Growth during the Electrodeposition of Titanium from Ethaline

Titanium electrodeposition as a technological advance has been out of reach due to the poor film quality obtained when using previously developed methods. This study shows that the electrodeposition of Ti is possible and feasible from the deep eutectic solvent ethaline. Moreover, this study shows through batch analysis that this deposition has temperature-dependent aspects that alter the film deposition kinetics upon modest heating. This ultraviolet–visible spectroscopic study is highlighting the more facile reduction of Ti 4+ to Ti 3+ and then to Ti 2+ at elevated temperatures. Understanding the underlying kinetics of electrodeposition opens up new venues for the application of this important metal.

36 MATERIALS SCIENCE↗

An anaerobic-aerobic sequential batch process with simultaneous methanogenesis and short-cut denitrification for the treatment of marine biofoulings

Highlights: • Combined denitritation–methanogenesis was examined to treat intermittent wastes. • Achieved high NO{sub 2}{sup −} accumulation of 96.4% on average in nitritation. • Achieved high substrate COD removal of 96% in denitritation–methanogenesis. • Intensive effluent exchange enhanced nitrogen removal and decreased CH{sub 4} content. • Daily effluent exchange of 80% could maintain both effluent and biogas qualities. - Abstract: Although combination of denitritation and methanogenesis for wastewater treatment has been widely investigated, an application of this technology to solid waste treatment has been rarely studied. This study investigated an anaerobic-aerobic batch system with simultaneous denitritation-methanogenesis as an effective treatment for marine biofoulings, which is a major source of intermittently discharged organic solid wastes. Preliminary NO{sub 2}{sup −}-exposed sludge was inoculated to achieve stable methanogenesis process without NO{sub 2}{sup −} inhibition. Both high NH{sub 4}{sup +}-N removal of 99.5% and high NO{sub 2}{sup −}-N accumulation of 96.4% were achieved on average during the nitritation step. Sufficient CH{sub 4} recovery of 101 L-CH{sub 4} kg-COD{sup −1} was achieved, indicating that the use of NO{sub 2}{sup −}-exposed sludge is effective to avoid NO{sub 2}{sup −} inhibition on methanogenesis. Methanogenesis was the main COD utilization pathway when the substrate solubilization occurred actively, while denitritation was the main when solubilization was limited because of substrate shortage. The results showed a high COD removal efficiency of 96.0% and a relatively low nitrogen removal efficiency of 64.4%. Fitting equations were developed to optimize the effluent exchange ratio. The estimated results showed that the increase of effluent exchange ratio during the active solubilization period increased the nitrogen removal efficiency but decreased CH{sub 4} content in biogas. An appropriate effluent exchange ratio with high anaerobic effluent quality below approximately 120 mg-N L{sup −1} as well as sufficient CH{sub 4} gas quality which can be used as fuel for gas engine generator was achieved by daily effluent exchange of 80% during the first week and 5% during the subsequent 8 days.

09 BIOMASS FUELS↗

Modifications to LEU-Modified Cintichem Process to Allow Processing of Fission-Produced 99 Mo from Up to 750 g of Irradiated Uranium Targets

Eden Radioisotopes, LLC is developing a TRIGA* -sized, 2 MW all-target reactor system licensed from Sandia National Laboratories. This all-target reactor uses up to 60 Argonne-designed annular LEU-foil targets to produce fission-produced 99 Mo. The Eden low-enriched uranium (LEU) target contains ~137 g of uranium and will be irradiated at up to 30 kW, with a target burnup determined by the number of targets processed each week. The annular target utilizes metallic uranium foils 400 mm long by 72 mm wide by 250±25 -µm-thick covered by a thin (10 µm on each face) nickel fission barrier. The foil is placed between two 35 mil aluminum tubes that form the outer and inner walls of the cladding cylinder, which is hydroformed to provide high thermal conductivity within the target. Eden expects to process between three and five targets per process batch, to maintain the process batch 99 Mo inventory at or below 5000 curies to maintain high 99 Mo recovery, within a few hours of discharge from the reactor. Eden expects to meet full U.S. demand by processing 30 targets per week, with each target operated for two weeks at 30 kW. To meet less than full U.S. demand, both the target power and the number of targets processed weekly will be adjusted. With increased 99 Mo production and given the size of U targets processed in a single batch (up to ~750g-U), it is important to identify whether any modifications are needed to the LEU-modified Cintichem process.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Big Data Framework with Machine Learning for D and D Applications - 19108

The nuclear industry is experiencing a steady increase in maintenance costs even though plants are maintained under high levels of safety, capability and reliability. Nuclear power plants are expected to run every unit at maximum capacity at all times, efficiently utilizing assets with minimal downtime. Surveillance and maintenance of nuclear decommissioning infrastructure provides lot challenges with respect to maintenance or decommissioning of the buildings. There is a need for a framework to analyze the huge amount of data generated by the sensors on the nuclear reactor components as well as structures, to monitor the conditions of these building over a period of time. Emerging technologies such as big data analytics have become a requirement in the nuclear industry to improve structural health monitoring and diagnostics. FIU will make use of existing mature technologies in the areas of imaging, robotics, big data, and machine learning/deep learning to assess the structural integrity of aging facilities at DOE sites. As these facilities await decommissioning, there is a need to understand the structural health of these structures. Many of these facilities were built over 50 years ago and in some cases these facilities have gone beyond the operational life expectancy. In other cases, the facilities have been placed in a state of 'cold and dark' and they are sitting unused, awaiting decommissioning. Finally, some older facilities are one-of-a-kind operational/production facilities supporting critical DOE missions and cannot be shut down. In any of these scenarios, the structural integrity of these facilities may be compromised, so it is imperative that adequate inspections and data collection/analysis be performed on a continuous and ongoing basis. The primary goals of the research include collecting various formats of data such as structured, unstructured and streaming data from the various sensors deployed in buildings, collect videos/pictures from various imaging sources, ingest them using a Hadoop distributed file system and process the data using Spark to perform batch processing and real time analytics. Research and development on various machine learning/deep learning algorithms will also be performed to analyze the heterogeneous data collected from nuclear decommission infrastructure. FIU will design the big data framework to ingest, store and process huge amounts of heterogeneous data collected from many sources and optimize the algorithms to provide insights into the data and predict anomalies observed when compared against baseline conditions. Various modules of this framework will include heterogeneous data sources, message broker, Hadoop distributed file system, Spark for stream and batch processing, machine learning/ deep learning, Cassandra - persistent data store and visualization. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Development of a Solvent-Free Process to Prepare DNAN

Objectives: Additive-free, solvent-free chemical reactions are generally more environmentally benign than alternative processes that involve these reaction components. 2,4-Dinitroanisole (DNAN) is of interest to the military and to industry as a replacement for trinitrotoluene (TNT) in melt-cast explosives. As anisole is a widely used feedstock chemical, the development of an efficient, additive-free, solvent-free method for its dinitration could lead to adoption of a new “green” synthetic route for DNAN manufacture. Technical Approach: Our goal is the scale-up (from the previously demonstrated one gram scale to a 500 gram scale) of the additive-free, solvent-free dinitration of anisole using the equipment and facilities available at the Los Alamos National Laboratory. Results: Through a series of simple optimization process, we have been successful at scaling demonstrating the development of a solvent-free process for the synthesis of 2,4-dinitroanisole using a batch process. The overall method involves the use of a mixture of propionic anhydride and 98% nitric acid to form the reactive nitrating species, proprionyl nitrate. This nitrating reagent is then added to a highly concentrated solution mixture of anisole and proprionic anhydride slowly over time to produce the desired 2,4-dinitroanisole product. This batch process could be scaled-up to the 270g scale. Flow-reaction methods should allow for larger scale production of DNAN. Benefits: This work has addressed the SERDP SEED Statement Of Need regarding environmentally benign methods for the synthesis of DNAN. Having achieved our goal, the next step will be to partner with a commercial manufacturer of explosive materials to scale the synthesis up to production levels.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Analysis of Operating Strategies Using Different Target Designs For 238Pu Production

An engineering effort is underway to re-establish capability to produce 238Pu oxide at the kilogram scale in the United States. A multi-step batch process is being developed to produce this important material. Recently, a portion of this process was studied using discrete-event simulation tools to determine whether the conceptual process might achieve its yearly production goal. The study showed the conceptual process can meet the yearly production goal under some circumstances, but process improvements would be needed to ensure greater likelihood of success. This study extends the work performed previously by examining the effects of changing the reactor target design on the yearly process output. Two new reactor target configurations are considered an aluminum-clad reactor target containing 50% greater 237Np oxide content than the original target, and a zirconium alloy-clad target using no aluminum. The results indicate that use of the new aluminum-clad target configuration may allow the process to achieve the same yearly production goal in less time using fewer targets. If the zirconium alloy-clad target is used, then even fewer targets would be needed to reach the production goal, but some process changes would be required to handle the zirconium cladding. The number of days needed to process a target batch to completion, and the steady state 238Pu oxide production rate, for each configuration are compared to the results from the initial simulation study.

campaign↗

B827 Chemical Synthhesis Project - Industrial Control System Integration - Statement of Work & Specification with Attachments 1-14

The Chemical Synthesis Pilot Process at the Lawrence Livermore National Laboratory (LLNL) Site 300 827 Complex will be used to synthesize small quantities of material to support research and development. The project will modernize and increase current capabilities for chemical synthesis at LLNL. The primary objective of this project is the conversion of a non-automated hands-on process to a remoteoperation process, while providing enhanced batch process step control, stored recipe-specific parameter sets, process variable visibility, monitoring, alarm and warning handling, and comprehensive batch record data logging. This Statement of Work and Specification provides the industrial-grade process control requirements for the chemical synthesis batching control system, hereafter referred to as the “Control System” to be delivered by the System Integrator.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A novel defoamer for processing nuclear waste: Testing and performance

Abstract Legacy radioactive waste from nuclear weapons material processing is the biggest environmental challenge in the state of South Carolina, and one of the biggest in the United States. Although substantial progress has been made in processing and vitrifying high‐level radioactive waste at the Savannah River site, approximately 35 million gallons remains to be treated and dispositioned. In this article, we show the development of a new defoamer for use in the processing of high‐level radioactive waste. The application of the new defoamer is not only more effective at controlling foam but will shorten the batch processing time leading to safer and more efficient processing. This has the potential to help shorten the overall site mission lifetime, saving the federal government hundreds of millions of dollars. The novel aspect of the new defoamer is its effectiveness and stability in the harsh conditions needed for processing high‐level radioactive waste: high temperatures, pH 4–13, strong oxidizing and reducing agents, and numerous metal catalysts. The defoamer will replace an existing antifoam agent that decomposes to form multiple flammable gases. Because the existing antifoam agent decomposes quickly, processing changes increased processing time. Statement of novelty We demonstrate that a new defoamer has been developed for use in processing high‐level radioactive waste. This novel defoamer is effective and stable in the harsh processing conditions with no detectable flammable by‐products. Because the existing antifoam agent decomposes quickly, processing changes, including lowering acid addition rates and evaporation rates, increased processing time. The new defoamer is not only more effective at controlling foam but will shorten the batch processing time and lead to safer and more efficient processing by eliminating the production of flammable gases. Statement of industrial relevance Foaming is of great concern in many industrial processes involving three‐phase gas/liquid/fine‐solids systems, like in water evaporation, mineral floatation, air sparging in situ remediation techniques, and in those found in the paper industry.

Lambert, Dan P.↗

Stochastic growth logistic model with aftereffect for batch fermentation process

In this paper, the stochastic growth logistic model with aftereffect for the cell growth of C. acetobutylicum P262 and Luedeking-Piret equations for solvent production in batch fermentation system is introduced. The parameters values of the mathematical models are estimated via Levenberg-Marquardt optimization method of non-linear least squares. We apply Milstein scheme for solving the stochastic models numerically. The effciency of mathematical models is measured by comparing the simulated result and the experimental data of the microbial growth and solvent production in batch system. Low values of Root Mean-Square Error (RMSE) of stochastic models with aftereffect indicate good fits.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Evaluation of no-MST operations in the SRS ARP for Hanford LAWPS

The Savannah River Site (SRS) Actinide Removal Process has been processing salt waste since 2008. This process includes a filtration step in the 512-S facility. Initial operations included the addition, or strike, of monosodium titanate (MST) to remove soluble actinides and strontium. The added MST and any entrained sludge solids were then separated from the supernate by cross flow filtration. During this time, the filter operations have, on many occasions, been the bottleneck process limiting the rate of salt processing. Recently, 512-S- has started operations utilizing “No-MST” where the MST actinide removal strike was not performed and the supernate was simply pre-filtered prior to Cs removal processing. Direct filtration of decanted tank supernate, as demonstrated in 512-S, is the proposed method of operation for the Hanford Low Activity Waste Pretreatment System (LAWPS) facility. Processing decanted supernate without MST solids has been demonstrated for cross flow filtration to provide a significant improvement in production with the SRS Salt Batches 8 and 9 feed chemistries. The average filtration rate for the first 512-S batch processing cycle using No-MST has increased filtrate production by over 35% of the historical average. The increase was sustained for more than double the amount of filtrate batches processed before cleaning of the filter was necessary. While there are differences in the design of the 512-S and Hanford filter systems, the 512-S system should provide a reasonable indication of LAWPS filter performance with similar feed properties. Based on the data from the 512-S facility and with favorable feed properties, the LAWPS filter, as currently sized at over twice the size of the 512-S filter (532 square feet filtration area versus 235 square feet), has the potential to provide sustained filtrate production at the upper range of the planned LAWPS production rate of 17 gpm.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Characterization of tank 51 sludge samples (HTF-51-17-44/ HTF-51-17-48) in support of sludge batch 10 processing

The Savannah River National Laboratory (SRNL) was requested by Savannah River Remediation (SRR) Engineering (SRR-E) to provide sample characterization and analyses of Tank 51 sludge samples in support of Sludge Batch (SB) 10. The two Tank 51 sludge samples were sampled and delivered to SRNL in May of 2017. These two tank 51 sludge samples were combined into one composite sample and analyzed for corrosion controls analytes, select radionuclides, chemical elements, density and weight percent total solids and aluminum hydroxides (gibbsite and boehmite) by x-ray diffraction.

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