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At least 199 records · Page 11

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DOE OSTI2019

Optimization of the IPP-bypass mevalonate pathway and fed-batch fermentation for the production of isoprenol in Escherichia coli

Isoprenol (3-methyl-3-buten-1-ol) is a drop-in biofuel and a precursor for commodity chemicals. Biological production of isoprenol via the mevalonate pathway has been developed and optimized extensively in Escherichia coli, but high ATP requirements and isopentenyl diphosphate (IPP) toxicity have made it difficult to achieve high titer, yield, and large-scale production. To overcome these limitations, an IPP-bypass pathway was previously developed using the promiscuous activity of diphosphomevalonate decarboxylase, and enabled the production of isoprenol at a comparable yield and titer to the original pathway. In this study, we optimized this pathway, substantially improving isoprenol production. A titer of 3.7 g/L (0.14 g isoprenol per g glucose) was achieved in batch conditions using minimal medium by pathway optimization, and a further optimization of the fed-batch fermentation process enabled an isoprenol titer of 10.8 g/L (yield of 0.105 g/g and maximum productivity of 0.157 g L -1 h -1 ), which is the highest reported titer for this compound. The substantial increase in isoprenol titer via the IPP-bypass pathway in this study will facilitate progress toward commercialization.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2022

Assessing the impact of substrate-level enzyme regulations limiting ethanol titer in Clostridium thermocellum using a core kinetic model

Clostridium thermocellum is a promising candidate for consolidated bioprocessing because it can directly ferment cellulose to ethanol. Despite significant efforts, achieved yields and titers fall below industrially relevant targets. This implies that there still exist unknown enzymatic, regulatory, and/or possibly thermodynamic bottlenecks that can throttle back metabolic flow. By (i) elucidating internal metabolic fluxes in wild-type C. thermocellum grown on cellobiose via 13 C-metabolic flux analysis ( 13 C-MFA), (ii) parameterizing a core kinetic model, and (iii) subsequently deploying an ensemble-docking workflow for discovering substrate-level regulations, this paper aims to reveal some of these factors and expand our knowledgebase governing C. thermocellum metabolism. Generated 13 C labeling data were used with 13 C-MFA to generate a wild-type flux distribution for the metabolic network. Notably, flux elucidation through MFA alluded to serine generation via the mercaptopyruvate pathway. Using the elucidated flux distributions in conjunction with batch fermentation process yield data for various mutant strains, we constructed a kinetic model of C. thermocellum core metabolism (i.e. k-ctherm138). Subsequently, we used the parameterized kinetic model to explore the effect of removing substrate-level regulations on ethanol yield and titer. Upon exploring all possible simultaneous (up to four) regulation removals we identified combinations that lead to many-fold model predicted improvement in ethanol titer. In addition, by coupling a systematic method for identifying putative competitive inhibitory mechanisms using K-FIT kinetic parameterization with the ensemble-docking workflow, we flagged 67 putative substrate-level inhibition mechanisms across central carbon metabolism supported by both kinetic formalism and docking analysis.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2014

A resonant sensor composed of quartz double ended tuning fork and silicon substrate for digital acceleration measurement

Presented in this paper is a micro-resonant acceleration sensor based on the frequency shift of quartz double ended tuning fork (DETF). The structure is silicon substrate having a proof mass supported by two parallel flexure hinges as doubly sustained cantilever, with a resonating DETF located between the hinges. The acceleration normal to the chip plane induces an axial stress in the DETF beam and, in turn, a proportional shift in the beam resonant frequency. Substrate is manufactured by single-crystal silicon for stable mechanical properties and batch-fabrication processes. Electrodes on the four surfaces of DETF beam excite anti-phase vibration model, to balance inner stress and torque and imply a high quality factor. The sensor is simply packaged and operates unsealed in atmosphere for measurements. The tested natural frequency is 36.9 kHz and the sensitivity is 21 Hz/g on a nominally ±100 g device, which is in good agreement with analytical calculation and finite element simulation. The output frequency drifting is less than 0.5 Hz (0.0014% of steady output) within 1 h. The nonlinearity is 0.0019%FS and hysteresis is 0.0026%FS. The testing results confirm the feasibility of combining quartz DETF and silicon substrate to achieve a micro-resonant sensor based on simple processing for digital acceleration measurements.

36 MATERIALS SCIENCE↗

DOE OSTI2015

An Elegant Sufficiency: Load-Aware Differentiated Scheduling of Data Transfers

We investigate the file transfer scheduling problem, where transfers among different endpoints must be scheduled to maximize pertinent metrics. We propose two new algorithms that exploit the fact that the aggregate bandwidth obtained over a network or at a storage system tends to increase with the number of concurrent transfers—but only up to a certain limit. The first algorithm, SEAL, uses runtime information and data-driven models to approximate system load and adapt transfer schedules and concurrency so as to maximize performance while avoiding saturation. We implement this algorithm using GridFTP as the transfer protocol and evaluate it using real transfer logs in a production WAN environment. Results show that SEAL can improve average slowdowns and turnaround times by up to 25% and worst-case slowdown and turnaround times by up to 50%, compared with the best-performing baseline scheme. Our second algorithm, STEAL, further leverages user-supplied categorization of transfers as either “interactive” (requiring immediate processing) or “batch” (less time-critical). Results show that STEAL reduces the average slowdown of interactive transfers by 63% compared to the best-performing baseline and by 21% compared to SEAL. For batch transfers, compared to the best-performing baseline, STEAL improves by 18% the utilization of the bandwidth unused by interactive transfers. By elegantly ensuring a sufficient, but not excessive, allocation of concurrency to the right transfers, we significantly improve overall performance despite constraints.

Kettimuthu, Rajkumar↗

DOE OSTI2018

Analytical Results from final Salt Batch 9 Routine DSSHT and SEHT Monthly Samples

Strip Effluent Hold Tank (SEHT) and Decontaminated Salt Solution Hold Tank (DSSHT) samples from several of the “microbatches” of Integrated Salt Disposition Project (ISDP) Salt Batch (“Macrobatch”) 9 have been analyzed for 238 Pu, 90 Sr, 137 Cs, cations (Inductively Coupled Plasma Emission Spectroscopy - ICPES), and in some cases anions (Ion Chromatography Anions - IC-A). These three samples are from Salt Batch 9 material in the Modular Caustic-Side Solvent Extraction Unit (MCU) system, and prior to actual Salt Batch 10 processing. These samples are known to contain contactor cleaning material and should not be considered typical for samples under operating conditions. While the DSSHT sample is typical of this type of sample, the SEHT samples indicate a gross inclusion of nitric acid, likely from contactor cleaning solutions.

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DOE OSTI2020

Preliminary Determination of the Impact of Alkaline Earth Metals on Crystalline Silicotitanate

Savannah River Remediation (SRR) recently deployed the Tank Closure Cesium Removal (TCCR) system which utilizes an ion exchange process to remove 137 Cs from tank waste supernate. In TCCR, salt solution is filtered and then passed through ion exchange columns containing crystalline silicotitanate (CST) media, commercially known as UOP IONSIV™ R9120-B, which is highly selective for removing cesium. The current process focuses on dissolving salt in Savannah River Site (SRS) Tank 10H, followed by processing in the TCCR skid located near the tank. Prior to processing each batch of waste generated in Tank 10H, the projected maximum cesium loading on the CST is determined using an in-tank batch contact equilibrium test. This involves placing a small amount (~0.1 g) of CST in a “teabag” device and submerging it in the tank waste for a period of 10 days. Results from those earlier teabag tests had indicated much lower cesium loading than predicted by the equilibrium sorption model (ZAM). There are numerous possible explanations for this result; however, based on the observed loadings of Ca (and other metals) on the CST from the teabag tests, it was hypothesized that competition from these other ions may be limiting the cesium loadings.

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DOE OSTI2016

Calcium Phosphate Constraints in HLW Glasses: Phosphate Liquidus Model

About 50 million gallons of high-level mixed waste is currently stored in underground tanks at the United States Department of Energy’s (DOE’s) Hanford site in the State of Washington. The Hanford Tank Waste Treatment and Immobilization Plant (WTP) will provide DOE’s Office of River Protection (ORP) with a means of treating this waste by vitrification for subsequent disposal. The tank waste will be separated into low- and high-activity waste fractions, which will then be vitrified respectively into Immobilized Low Activity Waste (ILAW) and Immobilized High Level Waste (IHLW) products. The ILAW product will be disposed in an engineered facility on the Hanford site while the IHLW product is designed for acceptance into a national geological disposal facility for high-level nuclear waste. The ILAW and IHLW products must meet a variety of requirements before they can be accepted for disposal. Glass property-composition models will be used to control the vitrification process at the WTP to ensure that the glass meets product quality and processability requirements. The quality and the validity ranges of the property-composition models and the supporting database will greatly influence waste treatment operations, including the waste loading that is achievable in the glass for each waste composition. The current baseline models for operation of the WTP were developed under the Bechtel National, Inc. (BNI) WTP contract. These models were based on LAW and HLW glass property data over a range of compositions that was guided primarily by the WTP contract and the set of tanks specified therein. The HLW testing was directed towards waste streams from the then-planned early feed tanks for the WTP (i.e., AZ-101, AZ-102, C-106/AY-102, and C-104/AY-101). These wastes are high in iron (AZ-101, AZ-102, and C-106/AY-102) or thorium (C-104/AY-101). While the baseline models may be adequate for commissioning of the facility and processing of the specified tanks, refinements and extensions or augmentations of these models will be required to process the balance of the tank waste inventory. The overall mission of the WTP will require the immobilization of tank waste compositions that are variously dominated by mixtures of aluminum, chromium, bismuth, iron, phosphorous, zirconium, and sulfur compounds as waste-loading-limiting components. Further, the WTP contract includes minimum waste loading requirements that are generally rather modest while loadings significantly higher than those in the current baseline are likely achievable. In order to achieve these higher waste loadings and to expand the applicable composition regions, new models will be needed to support the optimized operation of the WTP. Since the development of the baseline WTP models, ORP directed a program of work at the Vitreous State Laboratory (VSL) to examine various approaches for optimization of the performance of the WTP, including increasing the waste loadings in the LAW and HLW glass products. That work involved HLW rich in Al, Al+Na, Cr, Bi, S, Zr, Sr, P and Fe, in contrast to old baseline models that were based mostly on HLW tanks that were high in Fe, with one other that was also high in Th. Glass property data collected under the ORP program were compiled and combined with data collected to develop the WTP models. The combined databases have been used to update pre-existing HLW composition models or to develop new models for properties such as Product Consistency Test (PCT) responses, spinel crystallization (one-percent crystal fraction temperature, T 1% ), melt viscosity, melt electrical conductivity, nepheline formation upon slow cooling (i.e., Canister Centerline Cooling [CCC]), and Toxicity Characteristic Leach Procedure (TCLP) Cd response. While spinel is typically the most commonly occurring phase in HLW glasses, other phases can be limiting depending on the waste and glass composition. For example, various phosphate phases can become important as the phosphorus content increases. Lithium phosphate crystallization can impact PCT releases of HLW glasses, while calcium phosphate phases forming in the cold-cap can deleteriously impact feed processing in the melter. At present, however, no models exist that relate glass composition and crystallization of phosphate phases in general and calcium phosphate in particular. The present work was therefore directed towards the initial development of such models. Future work may be directed at studying amorphous phase separation in high phosphate HLW glasses. Within the River Protection Project, feed compositions are projected using the Hanford Tank Waste Operations Simulator (HTWOS), a dynamic computer model that tracks the waste through storage, retrieval, feed staging, and treatment processes. A review of the HTWOS data shows that WTP will process 4106 batches of HLW glass for the overall mission (System Plan Rev. 6, ORP-11242), each with its own waste feed and glass composition. Some of the projected HTWOS feed batches are expected to have relatively high concentrations of phosphorous compared to typical HLW streams. In the 4106 batches of HLW for the overall WTP mission P 2 O 5 varies from 0.59 wt% to 13.00 wt%, with 95 batches containing at least 10 wt% P 2 O 5 . Occurrences of phosphate crystals have commonly been noted in glasses with high bismuth and phosphorus contents. In addition, recently collected data from a set of statistically designed HLW matrix glasses prepared and characterized to support enhancement of the HLW glass property-composition models identified apatite in a number of glass samples. However, the current HLW model for crystallization (one-percent crystal fraction temperature) is applicable only to spinel crystallization in glasses. Previous projections of waste loadings and glass volume (such as those in System Plan Rev. 6, ORP-11242) have used preliminary constraints for calcium phosphate crystallization that are based on the limited available data. Additional data and improved constraints or, preferably, models that relate glass composition to crystallization of phosphate-containing phases, are therefore needed to support HLW vitrification at the WTP. The present study focuses on the development of such a model based on data from previously characterized glasses and a set of newly fabricated glasses.

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DOE OSTI2020

Ammonia Fiber Expansion (AFEX) Pretreatment of Lignocellulosic Biomass

Lignocellulosic materials are plant-derived feedstocks, such as crop residues (e.g., corn stover, rice straw, and sugar cane bagasse) and purpose-grown energy crops (e.g., miscanthus, and switchgrass) that are available in large quantities to produce biofuels, biochemicals, and animal feed. Plant polysaccharides (i.e., cellulose, hemicellulose, and pectin) embedded within cell walls are highly recalcitrant towards conversion into useful products. Ammonia fiber expansion (AFEX) is a thermochemical pretreatment that increases accessibility of polysaccharides to enzymes for hydrolysis into fermentable sugars. These released sugars can be converted into fuels and chemicals in a biorefinery. Here, we describe a laboratory-scale batch AFEX process to produce pretreated biomass on the gram-scale without any ammonia recycling. The laboratory-scale process can be used to identify optimal pretreatment conditions (e.g., ammonia loading, water loading, biomass loading, temperature, pressure, residence time, etc.) and generates sufficient quantities of pretreated samples for detailed physicochemical characterization and enzymatic/microbial analysis. The yield of fermentable sugars from enzymatic hydrolysis of corn stover pretreated using the laboratory-scale AFEX process is comparable to pilot-scale AFEX process under similar pretreatment conditions. This paper is intended to provide a detailed standard operating procedure for the safe and consistent operation of laboratory-scale reactors for performing AFEX pretreatment of lignocellulosic biomass.

09 BIOMASS FUELS↗

DOE OSTI2018

Use of High-Throughput Automated Microbioreactor System for Production of Model IgG1 in CHO Cells

Automated microscale bioreactors (15 mL) can be a useful tool for cell culture engineers. They facilitate the simultaneous execution of a wide variety of experimental conditions while minimizing potential process variability. Applications of this approach include: clone screening, temperature and pH shifts, media and supplement optimization. Furthermore, the small reactor volumes are conducive to large Design of Experiments that investigate a wide range of conditions. This allows upstream processes to be significantly optimized before scale-up where experimentation is more limited in scope due to time and economic constraints. Automated microscale bioreactor systems offer various advantages over traditional small scale cell culture units, such as shake flasks or spinner flasks. However, during pilot scale process development significant care must be taken to ensure that these advantages are realized. When run with care, the system can enable high level automation, can be programmed to run DOE's with a higher number of variables and can reduce sampling time when integrated with a nutrient analyzer or cell counter. Integration of the expert-derived heuristics presented here, with current automated microscale bioreactor experiments can minimize common pitfalls that hinder meaningful results. In the extreme, failure to adhere to the principles laid out here can lead to equipment damage that requires expensive repairs. Furthermore, the microbioreactor systems have small culture volumes making characterization of cell culture conditions difficult. The number and amount of samples taken in-process in batch mode culture is limited as operating volumes cannot fall below 10 mL. This method will discuss the benefits and drawbacks of microscale bioreactor systems.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2015

Roll to Roll Manufacturing

ORNL researchers are developing roll to roll technologies for manufacturing, automotive, and clean energy applications in collaboration with industry partners such as Eastman Kodak.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

DOE OSTI2015

Electrodeposition of high magnetostrictive cobalt-iron alloy films for smart tags and sensor applications

Magnetostrictive CoFe films were investigated for use as magnetoelastic tags or sensors. The ability to electrodeposit these films enables batch fabrication processes to pattern a variety of geometries while controlling the film stoichiometry and crystallography. In current research looking at CoFe, improved magnetostriction was achieved using a co-sputtering, annealing, and quenching method1. Other current research has reported electrodeposited CoFe films using a sulfate based chemistry resulting in film compositions that are Fe rich in the range of Co 0.3-0.4 Fe 0.7-0.6 and have problems of codeposition of undesirables that can have a negative impact on magnetic properties. The research presented here focused on maximizing magnetostriction at the optimal stoichiometry range of Co 0.7-0.75 Fe 0.3-0.25 , targeting the (fcc+bcc)/bcc phase boundary, and using a novel chemistry and plating parameters to deposit films without being limited to “line of sight” deposition.

36 MATERIALS SCIENCE↗

DOE OSTI2016

Computational Fluid Dynamics Modeling of Bubbling in a Viscous Fluid for Validation of Waste Glass Melter Modeling

At the Hanford site, radioactive waste stored in underground tanks is slated for vitrification for final disposal. A comprehensive knowledge of the glass batch melting process will be useful in optimizing the process, which could potentially reduce the cost and duration of this multi-billion dollar cleanup effort. We are developing a high-fidelity heat transfer model of a Joule-heated ceramic lined melter to improve the understanding of the complex, inter-related processes occurring with the melter. The glass conversion rates in the cold cap layer are dependent on promoting efficient heat transfer. In practice, heat transfer is augmented by inserting air bubblers into the molten glass. However, the computational simulations must be validated to provide confidence in the solutions. As part of a larger validation procedure, it is beneficial to split the physics of the melter into smaller systems to validate individually. The substitution of molten glass for a simulant liquid with similar density and viscosity at room temperature provides a way to study mixing through bubbling as an isolated effect without considering the heat transfer dynamics. The simulation results are compared to experimental data obtained by the Vitreous State Laboratory at the Catholic University of America using bubblers placed within a large acrylic tank that is similar in scale to a pilot glass waste melter. Comparisons are made for surface area of the rising air bubbles between experiments and CFD simulations for a variety of air flow rates and bubble injection depths. Also, computed bubble rise velocity is compared to a well-accepted expression for bubble terminal velocity.

bubbling↗

DOE OSTI2017

The Innovative Universal Separation Process (USEP) for Disposal of Mixed Liquid Waste Via Unconditional Clearance Approach - 17570

Historically, Mixed Liquid Waste (MLW) drums from Canadian nuclear facilities containing Tritium (H-3) and other radionuclides (alpha as well as beta/gamma emitting) were shipped to a licensed US facility for destruction via incineration. This option is relatively complex considering the logistics associated with cross-border shipments and the destruction costs (e.g. H-3 surcharge). Because of this, Kinectrics has developed a novel and flexible process for disposal of oily as well as other (solvents, aqueous etc.) MLW within Canada. This process avoids the need for cross-border shipments and significantly reduces the complexity as well as cost for waste disposal. An overview of the various approaches and activities undertaken by Kinectrics during the period 2009-2013 for successfully processing and disposing of several MLW drums (oils, solvents, aqueous and solids) was reported at the WM-2013 conference. One of the key approaches for management of both oily Polychlorinated Biphenyls (PCB) as well as non-PCB MLW involves treatment of the mixed waste using various well-known unit operations such as filtration, treatment with commercial sorbents, and various proprietary treatment methods developed at Kinectrics. These approaches result in reduction of radionuclide activity levels to below the unconditional clearance criteria and allows disposal of the waste via incineration at a conventional chemical waste facility. A small amount of radioactive secondary waste (the captured radionuclides) is returned to the customer. This approach was successfully employed for processing several drums of PCB and non-PCB MLW. Kinectrics recently completed two projects involving processing for disposal of legacy oily and solvent MLW inventory for a Canadian nuclear customer. Waste treatment processes used previously for unconditional clearance of oily/solvent MLW were ineffective for treatment of these legacy waste drums. Some drums were particularly challenging to process since H-3 was chemically associated with the oil backbone. To address these challenges, Kinectrics developed the innovative Universal Separation (USEP) process for disposal of problematic MLW. This paper presents an overview of the USEP process, the latest results of drum scale (205 L) process demonstration work, and the design concept of a Mobile Processing Unit (MPU) for large scale batch (1500 L) processing of MLW employing the USEP process. (authors)

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DOE OSTI2016

Computational Fluid Dynamics Modeling of Bubbling in a Viscous Fluid for Validation of Waste Glass Melter Modeling

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DOE OSTI2020

White Paper to Justify the Use of Strip Effluent in the Defense Waste Processing Facility During Slurry Mix Evaporator Processing

At the request of Savannah River Remediation (SRR), a white paper was written to assess whether it would be acceptable to process Strip Effluent (SE) in both the Sludge Receipt and Adjustment Tank (SRAT) and Slurry Mix Evaporator (SME) in the Defense Waste Processing Facility (DWPF) for the nitric-glycolic acid flowsheet. Savannah River National Laboratory (SRNL) experimental data and DWPF Sludge Batch 9 (SB9) process data was reviewed, looking at batches which included Precipitate Reactor Feed Tank (PRFT) and/or Strip Effluent Feed Tank (SEFT) feeds that led to long processing times. These batches were reviewed looking for processing problems such as melter feed trips, foamovers, heating rod or steam coil fouling, missed Reduction/Oxidation (REDOX) targets, and other process anomalies.

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DOE OSTI2022

Summary of Results from November 2021 Qualification Samples for Tank Closure Cesium Removal 1A (TCCR 1A)

Savannah River Remediation (SRR) is currently operating the Tank Closure Cesium Removal 1A (TCCR 1A) process to remove 137 Cs from tank waste supernate using an ion exchange process. As part of that process, Savannah River National Laboratory (SRNL) receives and analyzes samples in support of the qualification of each batch to be processed. SRNL recently received supernate samples retrieved from Tank 10H as well as in-tank batch contact samples for characterization in support of qualifying Batch 1 for processing through the TCCR 1A unit.

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DOE OSTI2022

Radioactive Waste Sludge Washing and Demonstration of the Nitric-Glycolic Acid Flowsheet for Sludge Batch 10 Qualification

For each sludge batch that is processed in the Defense Waste Processing Facility (DWPF), the Savannah River National Laboratory (SRNL) performs qualification testing to demonstrate that the sludge batch (SB) is processible. During processing of SB9, DWPF will be transitioning from the Nitric-Formic Acid (NFA) flowsheet to the Nitric-Glycolic Acid (NGA) flowsheet. Thus, the qualification of SB10 was requested to only be performed using the NGA flowsheet. In order to qualify the batch for the NGA flowsheet, Sludge Receipt and Adjustment Tank (SRAT) and Slurry Mix Evaporator (SME) cycles, designated SC-19, were performed using SB10 Tank 51 sample material. SRNL received Tank 51 material in the midst of Tank Farm washing. SRNL continued the washing in the SRNL Shielded Cells. The SRNL process included the addition of Sodium Reactor Experiment (SRE) material from H Canyon, simulating the transfer of SRE from H Canyon to Tank 51 during Tank Farm washing. The washed SB10 Tank 51 material, with SRE, was characterized prior to flowsheet qualification testing.

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DOE OSTI2023

Summary of Savannah River Site FY22 Salt Waste Qualification Data

The Savannah River National Laboratory analyzed samples from Savannah River Site Waste Tank 41H, 21H and 42H to support qualification of Salt Waste Processing Facility (SWPF) Waste Batches 5, 6, and 7 for processing (the FY22 Salt Batch Qualification samples). None 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 Mission Completion (Liquid Waste Operations subcontractor) as External Sample Results LIMS Reports and the Tank 41H (Salt Batch 5 sample) was also summarized in two separate technical reports. The analytical results (both rapid and long term) are now summarized and discussed in this technical report.

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