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At least 739 records · Page 41

Hydrogen production from switchgrass via a hybrid pyrolysis-microbial electrolysis process

A new approach to hydrogen production using a hybrid pyrolysis-microbial electrolysis process is described. The aqueous stream generated during pyrolysis of switchgrass was used as a substrate for hydrogen production in a microbial electrolysis cell, achieving a maximum hydrogen production rate of 4.3 L H2/L-day at a loading of 10 g COD/L-anode-day. Hydrogen yields ranged from 50 3.2% to76 0.5% while anode coulombic efficiency ranged from 54 6.5% to 96 0.21%, respectively. Significant conversion of furfural, organic acids and phenolic molecules was observed under both batch and continuous conditions. The electrical and overall energy efficiency ranged from 149-175% and 48-63%, respectively. The results demonstrate the potential of the pyrolysis-microbial electrolysis process as a sustainable and efficient route for production of renewable hydrogen with significant implications for hydrocarbon production from biomass.

08 HYDROGEN↗

Characterization of the response of radiochromic film to quasi-monoenergetic x rays through a cross-calibration with image plates

Radiochromic film (RCF) and image plates (IPs) are both commonly used detectors in diagnostics fielded at inertial confinement fusion (ICF) and high-energy-density physics (HEDP) research facilities. Due to the intense x-ray background in all ICF/HEDP experiments, accurately calibrating the optical density of RCF as a function of x-ray dose, and the photostimulated luminescence per photon of IPs as a function of x-ray energy, is necessary for interpreting experimental results. Various measurements of the sensitivity curve of different IPs to x rays have been performed [Izumi et al., Proc. SPIE 8850, 885006 (2013) and Rosenberg et al., Rev. Sci. Instrum. 90(1), 013506 (2019)]; however, calibrating RCF is a tedious process that depends on factors such as the orientation in which the RCF is scanned in the film scanner and the batch of RCF used. These issues can be mitigated by cross-calibrating RCF with IPs to enable the use of IPs for the determination of dose on the RCF without scanning the RCF. Here, the first cross-calibration of RCF with IPs to quasi-monoenergetic titanium, copper, and molybdenum K-line x rays is presented. It is found that the IP-inferred dose rates on the RCF for the Ti and Mo x rays agree well with the measured dose rates, while the IP-inferred dose rate for the Cu x rays is larger than the measured dose rate by ∼2×. Explanations for this discrepancy and plans for future work are discussed.

Instruments & Instrumentation↗

Cesium Ion Exchange with Crystalline Silicotitanate Literature Review

Crystalline silicotinante (CST) is planned for use as the ion exchange media to accomplish the cesium (Cs) decontamination of low-activity waste (LAW) in the current evolution of the Direct Feed Low-Activity Waste flowsheet. CST has yet to be deployed in a production-scale operating waste treatment facility on the Hanford Site. However, CST was used nearly 20 years ago to successfully treat approximately 270,000 gallons of supernatant waste in modular columns at Oak Ridge National Laboratory. As part of the technical maturation of the media for use at Hanford, an assessment of the state-of-the-art was performed by reviewing work in the technical literature. The review considered work from the U.S. Department of Energy (DOE) complex (i.e., national laboratories and government documents), the CST manufacturer, and the open technical literature nationally and internationally. The review focused on information most relevant to the caustic, high-sodium chemical environment typical of Hanford LAW. The topic areas explored in this literature review document include the following: CST structural and physical properties; Isotherm and batch contact data; Mass transport: intraparticle, interparticle, dispersion in the column; Column performance at multiple scales; Hydraulic performance; The effect of process conditions; Gas generation and retention behavior; Post-processing options for spent CST media The reviewed literature demonstrates that CST is well-suited for Cs decontamination of Hanford LAW. However, after consideration of the available literature data in these subject areas, some uncertainties regarding the application of CST for the treatment of Hanford LAW are identified and summarized. These uncertainties are areas where additional information may permit better prediction of CST performance or provide margin to facility operations and safety basis analyses.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Conversion of Uranium Metal to Uranyl Sulfate Solution

Experiments involving conversion of uranium (U) metal to U 3 O 8 , followed by dissolution to form uranyl sulfate solution, were performed with batches of up to 300 g of U metal. The focus was to identify major U species formed during the oxidation process, determine the particle size distribution of the uranium oxide product, and identify the size of the dissolution vessel needed to accommodate the exothermic reaction during the conversion of U 3 O 8 to uranyl sulfate using 30% hydrogen peroxide and H 2 SO 4 . The information obtained in this study will be used for designing full-scale processes to convert kilogram quantities of U metal to uranyl sulfate solution with a concentration of 300 g U/L.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Development of a Novel Bioprocess for Synthesizing and Purifying Adipic Acid

Through DOE’s Bioenergy Technologies Office and the Energy Efficiency and Renewable Energy Small Business Voucher (SBV) Pilot, ZymoChem, Inc received support to work with the ABPDU to accelerate the development of a novel adipic acid (AA) bioprocess by evaluating technologies to demonstrate the following: 1) Process development of AA via ZymoChem’s carbon-conserving (C 2 ) pathway in 2L bioreactors, using industrial feedstocks, and as a salt with hexamethylenediamine (HMDA), i.e., the industrially desired form of AA as AA-HMDA is the precursor for nylon 6,6 synthesis. 2) Pilot scale aerobic fermentation at the 300 L scale (stage 1) followed by a high cell density (HCD) anaerobic resting cell biotransformation (RCB) at the 50 L scale (stage 2). 3) Demonstration of a viable recovery process at the 50 L scale for purifying the product (i.e., AA-HMDA salt) and deliver multiple kg-quantity batches of purified product for further testing.

09 BIOMASS FUELS↗

Water-Quality Issues Related to Uranium In Situ Recovery Sites

Batch tests, column tests, and predictive reactive transport modeling can be done before ISR begins as part of the decision making/permitting process by bracketing possible post-restoration conditions; Help address stakeholder concerns; The best predictions require actual restored groundwater in contact with the downgradient solid phase; Resulting modeling provides a range of natural attenuation rates and assists with designing the best locations and time frames for continued monitoring; Field pilot tests are the best field-scale data and can provide the best model input and calibration data

54 ENVIRONMENTAL SCIENCES↗

Gating System Design Optimization for Investment Casting Process

This article aims to optimize specific castings, characterized as an element of the continuous track for armored vehicle. During the primary melts, defects in the form of oxide films and shrinkage porosity occurred. Steel 20ChGSNM described by the Russian GOST standard was used as a batch material, and the investment casting method was selected for production. To eliminate the above-mentioned defects, only changes in the gating system were allowed, because the interference with an ongoing production regarding technical and technological parameters was unacceptable by the manufacturer. Numerical simulation, x-ray, macro-structural and micro-structural analysis were used during the optimization process. The three variants were analyzed, and the achieved results demonstrated that it is possible to significantly affect the casting internal homogeneity by modifying the gating system individual parts. The final variant ensured a decrease in defects by up to 90% and the production of casting having the quality required by the customer.

36 MATERIALS SCIENCE↗

Scalable, Infiltration-Free Ceramic Matrix Composite (SIF-CMC) manufacturing for Molten Salt Receiver: Investigation of particle-loaded preceramic resin

Due to their unique combination of high temperature, corrosion resistance, and toughness, Ceramic Matrix Composites (CMC) are the optimal materials to be used in the next generation of Concentrated Solar Power (CSP), which will operate at working temperatures up to 800 °C. However, today, CMC is too costly to be used in CSP applications due to its complex manufacturing process based on repeated infiltration-pyrolysis cycles. To solve this issue, PARC is developing a scalable, infiltration-free method (SIF) to manufacture CMC, which can reduce the production cost, increase batch consistency, and leverage all of the intrinsic advantages of current CMCs. The key to the SIF method is using a flowable preceramic resin with high loading of functional components. The formulation impregnates the fiber during curing and leads to high-density, low-shrinkage parts upon pyrolysis. In this paper, we demonstrate a proof-of-concept of the SIF process and report the relationships between key process parameters in the manufacturing process: functional material loading in the resin vs. resin’s flowability and morphology changes upon pyrolysis.

ceramic matrix composite, concentrated solar power↗

Culture-independent detection of 'TM7' bacteria in a streptomycin-resistant acidophilic nitrifying process

Nitrification in biological wastewater treatment processes has been believed for long time to take place under neutral conditions and is inhibited under acidic conditions. However, we previously constructed acidophilic nitrifying sequencing-batch reactors (ANSBRs) being capable of nitrification at < pH 4 and harboring bacteria of the candidate phylum 'TM7' as the major constituents of the microbial community. In light of the fact that the 16S rRNA of TM7 bacteria has a highly atypical base substitution possibly responsible for resistance to streptomycin at the ribosome level, this study was undertaken to construct streptomycin-resistant acidophilic nitrifying (SRAN) reactors and to demonstrate whether TM7 bacteria are abundant in these reactors. The SRAN reactors were constructed by seeding with nitrifying sludge from an ANSBR and cultivating with ammonium-containing mineral medium (pH 4.0), to which streptomycin at a concentration of 10, 30 and 50 mg L{sup −1} was added. In all reactors, the pH varied between 2.7 and 4.0, and ammonium was completely converted to nitrate in every batch cycle. PCR-aided denaturing gradient gel electrophoresis (DGGE) targeting 16S rRNA genes revealed that some major clones assigned to TM7 bacteria and Gammaproteobacteria were constantly present during the overall period of operation. Fluorescence in situ hybridization (FISH) with specific oligonucleotide probes also showed that TM7 bacteria predominated in all SRAN reactors, accounting for 58% of the total bacterial population on average. Although the biological significance of the TM7 bacteria in the SRAN reactors are unknown, our results suggest that these bacteria are possibly streptomycin-resistant and play some important roles in the acidophilic nitrifying process.

60 APPLIED LIFE SCIENCES↗

Efficient screening of rare large pit anomalies on polished surfaces using a minimalist sampling scheme

Lawrence Livermore National Laboratory (LLNL) has made significant strides in generating clean energy through its inertial confinement fusion (ICF) experiments. These experiments rely on high-density carbon (HDC) coated shells to encapsulate the fusion fuel. The success of these experiments is heavily dependent on the surface quality of these shells, as even minor imperfections, such as deep pits, can negatively impact fusion yield. Ensuring the required smoothness involves an extensive surface-finishing process that spans approximately 20 stages, making it both time-intensive and resource-demanding. A critical challenge in this process is the need for high-resolution scans to detect rare deep pits, which can be costly and impractical if performed on every shell. This highlights the necessity of developing more efficient scanning methods to optimize time and cost without compromising accuracy. To address these challenges, we introduce a novel approach that employs the multivariate Dvoretzky–Kiefer–Wolfowitz (DKW) inequality to provide a probabilistic upper bound on the error in estimating pit distribution characteristics via a Kernel Density Estimator (KDE). This error bound enables efficient and reliable estimation of pit distribution characteristics at a specified statistical confidence level using a minimal number of surface scans. The integrated DKW-KDE approach was validated through surface-finishing experiments across two batches of HDC-coated shells, demonstrating consistent and robust performance across multiple stages of the surface-finishing experiments. The validation studies suggest that the integrated DKW-KDE approach achieves comparable accuracy in estimating the risk of deleterious large pits with six scans, thus conserving time and resources. Further evaluations show that performance remains consistent across batches and over multiple polishing stages. In conclusion, based on these findings, one can leverage the minimal-scan insights to strategically improve the bottleneck inspection process, thus enhancing the productivity and quality of shell polishing and similar challenging manufacturing processes.

Inertial confinement fusion↗

Non-biodegradable landfill leachate treatment by combined process of agitation, coagulation, SBR and filtration

Highlights: • A novel method of stripping (agitation) was investigated for NH{sub 3}-N removal. • PFS coagulation followed agitation process enhanced the leachate biodegradation. • Nitrification–denitrification achieved by changing operation process in SBR treatment. • A dual filter of carbon-sand is suitable as a polishing treatment of leachate. • Combined treatment success for the complete treatment of non-biodegradable leachate. - Abstract: This study describes the complete treatment of non-biodegradable landfill leachate by combined treatment processes. The processes consist of agitation as a novel stripping method used to overcome the ammonia toxicity regarding aerobic microorganisms. The NH{sub 3}-N removal ratio was 93.9% obtained at pH 11.5 and a gradient velocity (G) 150 s{sup −1} within a five-hour agitation time. By poly ferric sulphate (PFS) coagulation followed the agitation process; chemical oxygen demand (COD) and biological oxygen demand (BOD{sub 5}) were removed at 70.6% and 49.4%, respectively at an optimum dose of 1200 mg L{sup −1} at pH 5.0. The biodegradable ratio BOD{sub 5}/COD was improved from 0.18 to 0.31 during pretreatment step by agitation and PFS coagulation. Thereafter, the effluent was diluted with sewage at a different ratio before it was subjected to sequencing batch reactor (SBR) treatment. Up to 93.3% BOD{sub 5}, 95.5% COD and 98.1% NH{sub 3}-N removal were achieved by SBR operated under anoxic–aerobic–anoxic conditions. The filtration process was carried out using sand and carbon as a dual filter media as polishing process. The final effluent concentration of COD, BOD{sub 5}, suspended solid (SS), NH{sub 3}-N and total organic carbon (TOC) were 72.4 mg L{sup −1}, 22.8 mg L{sup −1}, 24.2 mg L{sup −1}, 18.4 mg L{sup −1} and 50.8 mg L{sup −1} respectively, which met the discharge standard. The results indicated that a combined process of agitation-coagulation-SBR and filtration effectively eliminated pollutant loading from landfill leachate.

54 ENVIRONMENTAL SCIENCES↗

Chemometrics and visible diffuse reflectance spectroscopy to classify plutonium dioxide

Diffuse reflectance (DR) spectra in the Vis-NIR (∼380–1050 nm) region were acquired for a series of PuO 2 samples with a spot size of about 10 × 10 μm. Two batches of six PuO 2 samples, synthesized approximately 7.5 months apart, were prepared using both Pu(III) and Pu(IV) oxalate precursors at three distinct calcination temperatures (450, 650, and 950 °C). This yielded a total of 12 PuO 2 samples and 433 DR spectra. The DR spectrum of PuO 2 contained numerous peaks in the visible region, and characteristic features were identified with respect to calcination temperature and chemistry. A distinct peak multiplet near 615 nm was observed for samples prepared at low calcination temperatures, and a peak near 660 nm was observed for higher calcination temperatures. A multivariate classification strategy based on principal component analysis (PCA) was developed to distinguish PuO 2 calcination temperatures of 450, 650, and 950 °C with 100 % accuracy. Classification results also indicate the potential to distinguish chemical processing history (i.e., Pu(III) or Pu(IV)) based on the spectra with 72 % accuracy based on k-nearest neighbors applied to the PCA scores. Partial least squares discriminant analysis was used to identify variation among batches with 88 % accuracy and found that peaks near 669, 681, 811, and 970 nm were the most useful for predicting the batch identity. Here, this work demonstrates how micro-diffuse reflectance spectroscopy and chemometrics can be used to classify PuO 2 processing history based on Vis-NIR spectral features. Combining the chemometric approach with mapping sequences could provide a rapid, nondestructive approach to classify Pu oxide materials for environmental, forensics, and nonproliferation applications.

Actinide↗

Process Control Approach to Implement High Waste Loading Glass Formulations for Hanford Low Activity Waste Vitrification - 18435

Acceptable glass formulations for vitrification of Hanford low activity waste (LAW) at The Hanford Tank Waste Treatment and Immobilization Plant (WTP) must meet a variety of product quality, processability, and waste loading requirements. The glass formulation development work underpinning the WTP baseline LAW glasses was captured in a vitrification process control approach developed by the Vitreous State Laboratory (VSL) and Atkins Energy Federal EPC, Inc. that permits the calculation of the glass formulation required for each particular batch of LAW delivered to the LAW vitrification facility. Since that time, we have developed a wide range of glass formulations that achieve considerably higher waste loadings and which therefore are more economically attractive in terms of reduced amounts of glass produced and decreased time for treatment. That work was done in support of the Department of Energy's Office of River Protection program that is examining options to optimize the LAW facility and LAW glass waste form. Implementation of these high waste loading formulations at the WTP requires the development of a new LAW vitrification process control algorithm, which is the subject of this paper. Waste loadings in LAW glasses are typically limited by either the alkali loading for LAW with low sulfate content or the SO{sub 3} loading for LAW with high sulfate content. In the former case, waste loadings are limited by refractory corrosion and glass corrosion on the vapor hydration test (VHT) and product consistency test (PCT), all of which tend to increase with higher alkali concentrations. In the latter case, waste loadings are limited by the formation of a molten sulfate phase in the melter, which has deleterious effects. The LAW vitrification process control strategy must mitigate these effects while optimizing waste loadings. Given the composition of any LAW stream, the new LAW vitrification process control algorithm permits the calculation of a suitable high waste loading glass composition and the required glass forming additives such that all processing, waste loading, and product quality requirements are met. This algorithm was developed from data for a large number of glasses that were formulated, and characterized with respect to a variety of properties affecting processability and product quality; many of these formulations were also subjected to melter testing to verify acceptable processing characteristics, processing rates, and the absence of secondary sulfate phase formation. This paper describes the development of the present algorithm, comparisons to the present lower waste loading baseline WTP process control approach, and plans for further development and testing. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Preliminary analysis of species partitioning in the DWPF melter. Sludge batch 7A

The work described in this report is preliminary in nature since its goal was to demonstrate the feasibility of estimating the off-gas carryover from the Defense Waste Processing Facility (DWPF) melter based on a simple mass balance using measured feed and glass pour stream (PS) compositions and time-averaged melter operating data over the duration of one canister-filling cycle. The DWPF has been in radioactive operation for over 20 years processing a wide range of high-level waste (HLW) feed compositions under varying conditions such as bubbled vs. non-bubbled and feeding vs. idling. So it is desirable to find out how the varying feed compositions and operating parameters would have impacted the off-gas entrainment. However, the DWPF melter is not equipped with off-gas sampling or monitoring capabilities, so it is not feasible to measure off-gas entrainment rates directly. The proposed method provides an indirect way of doing so.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Large-Batch Reduction of Molybdenum Trioxide

Unconverted, isotopically-enriched molybdenum metal must be recovered from the spent radiopharmaceutical solution used in NorthStar’s Technetium-99m generator and reused. The recycle process begins by recovering the metal from the aqueous potassium molybdate (K 2 MoO 4 ) solutions as molybdenum trioxide (MoO 3 ) employing a process developed at Argonne National Laboratory. The MoO 3 powder is subsequently reduced to molybdenum metal powder which can be blended with new powder and further processed into a flowable form to be used to produce target disks for irradiation. The molybdenum oxide reduction process has been examined and scaled to produce kilogram quantities of metal powder suitable for processing into a useable form employing spray drying or similar technique and ultimately used for target fabrication.

36 MATERIALS SCIENCE↗

Centrifugal Contactor Operations for UREX Process Flowsheet

The uranium extraction (UREX) process separates uranium and technetium from the other components of the fuel in nitric acid solution. The time and equipment requirements were evaluated for treatment of 260-L batches of a solution containing 130 gU/L using commercial annular centrifugal contactors from CINC Industries. An earlier evaluation was done assuming 150 L of feed solution per batch. Two different contactor versions from CINC were evaluated, the V-2 and V-5 units. The V-2 has a 2-in. (5-cm) rotor with a reported maximum through of 1.9 L/min. We evaluated this version for a throughput of 1 L/min. The V-5 has a 5-in. (~12.5-cm) rotor with a reported maximum throughput of 19 L/min. We evaluated this unit for throughputs of 10 and 15 L/min. The lower-than-maximum throughputs selected for this evaluation are based on Argonne National Laboratory’s (Argonne’s) ROTOR model, which calculates the operational envelope for a given process O:A ratio based on contactor parameters (weir dimensions, rotor diameter, etc.), the physical properties of the two fluids, and the allowable phase carryover. Because the UREX process designed for this application has O:A ratios ranging from 0.8 to 5.6, adjustments to the weirs in different sections of the contactor bank can broaden the operational envelope for satisfactory separations but throughput will remain short of the equipment maximum.

Pereira, Candido↗

The effect of thermomechanical treatment and tempering on the subsurface microstructure and bendability of direct-quenched low-carbon strip steel

Highlights: • Surface properties mainly determine the bendability of high strength steel. • Tempering improves bendability by softening the microstructure. • Surface texture is affected by thermomechanical treatment but not by tempering. • Strong shear texture component and upper bainite are detrimental to bendability. - Abstract: Recent results in the literature have shown that subsurface properties play a key role during the bending of steel plates. Now, for the first time, surface microstructure, surface texture, subsurface hardness and dislocation density have been studied to reveal the effect of tempering and thermomechanical treatment on the bendability of a direct-quenched strip steel. In the experiments, different thermomechanical treatments as well as non-isothermal tempering treatments were performed with slow heating to 570 °C and slow cooling to simulate the tempering of large steel coils in a batch annealing furnace. The results show that in addition to the improved production efficiency obtained through direct quenching and a single tempering process, tempering improves bendability by reducing subsurface dislocation density and hardness without a significant loss of strip yield strength. The subsurface microstructure and texture of the strip are the result of thermo-mechanical processing and transformation behaviour. Upper bainite containing elongated Martensite-Austenite (MA) islands in addition to an intense shear texture component {112}<111>{sub α} leads to shear band formation, and therefore poorer bendability when the bend axis is perpendicular to the rolling direction. This texture is not affected by tempering. Therefore, tempering does not improve the bendability of steels with an unfavourable texture. When the subsurface layers comprise a softer ferritic microstructure, good bendability is obtained in the untempered direct-quenched condition with a modest improvement caused by tempering.

36 MATERIALS SCIENCE↗

Production of renewable alcohols from maple wood using supercritical methanol hydrodeoxygenation in a semi-continuous flowthrough reactor

Biomass conversion to alcohols using supercritical methanol depolymerization and hydrodeoxygenation (SCM-DHO) with CuMgAl mixed metal oxide is a promising process for biofuel production. Here, we demonstrate how maple wood can be converted at high weight loadings and product concentrations in a batch and a semi-continuous reactor to a mixture of C 2 –C 10 linear and cyclic alcohols. Maple wood was solubilized semi-continuously in supercritical methanol and then converted to a mixture of C 2 –C 9 alcohols and aromatics over a packed bed of CuMgAlO x catalyst. Up to 95 wt% of maple wood can be solubilized in the methanol by using four temperature holds at 190, 230, 300, and 330 °C. Lignin was solubilized at 190 and 230 °C to a mixture of monomers, dimers, and trimers while hemicellulose and cellulose solubilized at 300 and 330 °C to a mixture of oligomeric sugars and liquefaction products. The hemicellulose, cellulose, and lignin were converted to C 2 –C 10 alcohol fuel precursors over a packed bed of CuMgAlO x catalyst with 70–80% carbon yield of the entire maple wood. The methanol reforming activity of the catalyst decreased by 25% over four beds of biomass, which corresponds to 5 turnovers for the catalyst, but was regenerable after calcination and reduction. In batch reactions, maple wood was converted at 10 wt% in methanol with 93% carbon yield to liquid products. The product concentration can be increased to 20 wt% by partially replacing the methanol with liquid products. The yield of alcohols in the semi-continuous reactor was approximately 30% lower than in batch reactions likely due to degradation of lignin and cellulose during solubilization. These results show that solubilization of whole biomass can be separated from catalytic conversion of the intermediates while still achieving a high yield of products. However, close contact of the catalyst and the biomass during solubilization is critical to achieve the highest yields and concentration of products.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗