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At least 181 records · Page 10

Non-equilibrium plasma co-upcycling of waste plastics and CO 2 for carbon-negative oleochemicals

Mechanical recycling and chemical upcycling by thermochemical reactions have been the major approaches for recycling end-of-life plastics. Herein, we report an electrified approach to upcycle waste plastics into carbon-negative commodity chemicals using greenhouse gas CO 2 as the oxidant and additional carbon source. In this non-equilibrium plasma process, waste polyolefins were oxidatively depolymerized by plasma-activated CO 2 to produce oleochemicals and hydrocarbon chemicals in a single-step process at high reaction rates. In addition, a mixture of CO 2 and a small amount of O 2 was employed as plasma gases to selectively produce fatty alcohols from polyolefins. Based on this atmospheric pressure, non-solvent, and non-catalyst process, up to 97.6% of fatty alcohols could be produced within minutes. In this article, the co-conversion approach was demonstrated using common polyolefins and real-world mixed waste plastics to obtain comparable results. The techno-economic analysis estimates the internal rate of return to be 42.2% and 43.5% for the plasma-based conversion of waste plastics, depending on the plasma gas composition. Lifecycle assessment indicates the global warming potential is between −3.33 and −3.07 kg CO 2e per kg of plastic.

42 ENGINEERING↗

TRA Warm Waste Treatment Facility Process Controller Replacement

This poster details the work I did to replace the TRA Warm Waste Treatment System Process Controller. Additionally, my poster explains what Warm waste is, how the warm waste treatment system functions, and the next steps moving forward in the engineering process.

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Examining Thermolytic Production of Hydrogen from Lubrication Oil

Savannah River National Laboratory (SRNL) was requested by Savannah River Remediation (SRR) to conduct testing via Technical Task Request (HR) to determine the thermolytic HGR of Mobil SHC™ 630, a lubrication oil. Currently, 35 gallons of contaminated Mobil SHC 630 is proposed for release into the recycle stream from the Defense Waste Processing Facility (DWPF) to Tank 22 and then to the 242-16H (2H) Evaporator system. Inhibited recycle waste in the Recycle Collection Tank (RCT) is transferred to Recycle Pump Tank (RPT) in the Low Point Pump Pit (LPPP) and then to the Concentration, Storage and Transfer Facilities (CSTF) H-area. The lubrication oil would be added directly to the RPT, bypassing the RCT. The current DWPF waste compliance plan for liquid transfers from the RCT to the CSTF limits the concentration of Mobil SHC 630 to <1,100 ppm which is equal to <9.3 gallons of Mobil SHC 630 when considering a 7,500 gal RCT batch with an initial Mobil SHC 630 concentration of 42 mg/L. Mobil SHC 630 is expected to be largely immiscible in the caustic aqueous waste stream. It is a blend of base oils including polyalphaolefin (PAO) base oil and additives such as triphenylphosphate and cresyl diphenyl phosphate at various concentrations (<0.25 wt%). While the base oils are expected to be largely unreactive in CSTF waste, the triarylphosphates additives would be expected to hydrolyze in the caustic waste, forming diarylphosphates and phenol. The tests described herein were governed by a single Run Plan and will determine thermolytic HGR from the caustic aqueous solution, as well as from any organic phases present.

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Flue-Gas Desulfurization Effluent Management using an Innovative Low-Energy Biosorpotion Treatment System to Remove Key Contaminants

Among the most critical water contaminants of concern affecting wide geographical regions and a number of industries and natural systems is selenium. Selenium found in surface, ground and wastewater in originates from natural sources, as well as industrial sources such as petroleum refineries, electronics manufacturing, pesticides, and coal power plants and mining also contribute to selenium contamination in water in the US. At high concentrations, selenium is toxic to human and wildlife. There are a number of technologies that have been used to treat selenium and other similar contaminants in water. Biological treatment of selenium has been used in the past to reduce soluble SeVI and/or SeIV to insoluble Se0, which is then filtered in the same vessel. The insoluble selenium (Se0) is then backwashed from the system and solids are separated for subsequent disposal, if they meet the leaching and water content criteria. In order to promote biological reduction to insoluble Se0, heating of bioreactor is needed in some applications, and excess food source (electron donor) is added so that all selenium can be filtered. An additional disadvantage of these systems is the significant amount of water lost due to extensive and frequent backwash and rinse cycles. When comparing the advantages and energy requirements of the various treatment technologies, RO membrane filtration immediately stands out due to the excessive energy expenditure needed to pump water across the membrane although RO is an effective way to remove selenium. In addition, RO requires extensive pretreatment, such as MF membrane, and frequent maintenance, rendering it an expensive option that may be out of reach for certain applications. In fact, although the performance was good during the pilot testing by the NSMP Working Group for treatment naturally occurring selenium in the surface water, the high electricity requirements and significant reject water stream made it an infeasible alternative. While conventional ion exchange maybe an effective treatment option, it requires frequent regeneration of the resin when applied to highly contaminated water, which leads to several tons of contaminant-laden, high-salinity brine that needs to be disposed off-site each day. One of the water systems in the west coast currently uses ion exchange for selenium treatment and has been trucking selenium laden hazardous brine waste weekly in the last several years. Pneumatic pumping and rinse water pumping required for ion exchange also increase the energy usage. In comparison, adsorption process is a passive treatment system where contaminated water comes in contact with an adsorption media in a vessel. Typically, there is no mixing, backwash, or recycle pumping required, thus significantly reducing the energy usage. A passive single-use adsorption system does not require backwash, thereby generating small amount of process waste, and producing the highest water yield among the alternatives. The energy and water efficiencies, and applicability for SeVI and SeIV are summarized in Table 1. Despite these benefits though, adsorption typically does not work for the most oxidized form of selenium (SeVI). The innovative biosorption process integrates both process to increase the treatment efficiency while minimizing energy, chemical, and time required to treat both SeVI and SeIV. Additional advantages include simple partial biological reduction with reduced on-site waste generation, which lead to water and electricity savings, and less operational need compared to biological treatment alone. This makes biosorption especially suitable for remote areas, where liquid backwash and brine disposal may be cost prohibitive or infeasible.

20 FOSSIL-FUELED POWER PLANTS↗

Evaluation of Sludge Solids Returns Impacts on Sludge Batch 10 Flammability, Glass Quality, and Glass Processability

The Savannah River National Laboratory (SRNL) is currently preparing to return ≤ 20 kgs of sludge solids collected over time from Tank Farm characterization activities and demonstrations of the Defense Waste Processing Facility (DWPF) flowsheets (nitric-formic and nitric-glycolic). These sludge solids will be transported and added to Tank 51 which is currently preparing Sludge Batch (SB) 10. DWPF plans to operate the under the nitric-glycolic flowsheet for the processing of SB10. The hydrogen generation rate for the nitric-glycolic flowsheet is 0.024 lb h -1 . The addition of ≤20 kg of sludge solids returns to SB 10 does not have an impact on flammability in the DWPF Chemical Process Cell (CPC) or glass quality and processability. The relatively low mass of the addition (≤20 kg) is insufficient to detect a significant analytical change to the expected SB 10 compositions.

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Analysis of the sludge batch 9 (Macrobatch 10) DWPF pour stream glass sample

A pour stream (PS) sample taken during processing of Sludge Batch 8 (SB8, Macrobatch 10) was analyzed by Savannah River National Laboratory (SRNL) to verify compliance with the Defense Waste Processing Facility (DWPF) Glass Product Control Program. The following conclusions were drawn from these analyses; The sum of oxides for the SB8 PS glass (97.41 wt%) is within the Product Composition Control System (PCCS) limits (100 ± 5 wt%); The average Waste Dilution Factor (WDF) calculated from the Tank 40 dried sludge analysis results for SB8 is 1.9 ± 0.1. In general, the radionuclide concentration of the SB8 PS glass sample calculated using this WDF is in good agreement with the measured radionuclide content; The Product Consistency Test (PCT) results indicate that the SB8 PS glass meets the Waste Acceptance Product Specifications (WAPS) for durability, with normalized release rates for boron, lithium and sodium all at least two standard deviations lower than those of the Environmental Assessment (EA) glass; The average measured density of the SB8 PS glass is 2.72 g/cm 3 , consistent with previous PS samples; and, The average measured Fe 2+ /ΣFe ratio of the SB8 PS glass is 0.15, within the target range of 0.09- 0.33, and closely resembling the predicted REDOX value of 0.15.

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Sludge Batch 10 (SB10) Acceptance Evaluation: Radionuclide Concentrations in Tank 51 Washed Qualification Sample

Savannah River National Laboratory (SRNL) has been tasked with the radionuclide characterization of the washed Sludge Batch 10 (SB10) qualification sample. The washed SB10 qualification sample is based on SRR Engineering guidance and the sample slurry is expected to be similar in composition to Tank 51 slurry after final preparations for transfer to Tank 40. Forty-four radionuclides along with total alpha and beta activity have been reported herein. These radionuclide measurements are required for the Defense Waste Processing Facility (DWPF) Radiological Evaluation Program, DWPF Technical Safety Requirements (TSR)/Waste Acceptance Criteria (WAC) Evaluation, and the DWPF Solid Waste Characterization Program.

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Measurement Acceptance Region (MAR) Assessment Results Based on the October 2019 Sludge Batch 10 Projections

Recent analysis of a Tank 26 sample indicated a higher than anticipated sulfur concentration in the supernatant and a significant amount of insoluble sulfur. The final concentration in the glass product would be well above the sulfate limits of 0.6-0.65 weight percent (wt.%) determined for previous sludge batches. In preparation for Sludge Batch 10 (SB10) processing, washing of Tank 51 will be performed to reduce the sulfate concentration in the glass product to less than 0.65 wt.% at waste loadings (WLs) of interest. To evaluate the feasibility of two Tank 51 Na wash endpoints (0.8 and 1.2M), Savannah River Remediation requested that the Savannah River National Laboratory perform assessments using the Defense Waste Processing Facility Product Composition Control System (PCCS) models and their associated Measurement Acceptance Region (MAR) constraints.

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Studies on the Vitrification Potential of High Risk Spent Nuclear Fuels

This research explored vitrification of U-Zr nuclear fuel that exhibits an explosion hazard when processed by common nitric acid dissolution. Glass frits were chosen based on properties that had been previously measured as well as being demonstrated successfully in production at the Defense Waste Process Facility (DWPF). Zirconium and Aluminum metal powders were chosen to represent the spent fuels after literature demonstrated that the potential phase that causes the issue for explosive reaction in the effluent stream is tied to the Zirconium-III phase field. DSC measurements were carried out on various simulants and waste forms to better understand thermal behavior of these materials. Zirconium (Zr) was tested with both nitric acid and the new effluent flowsheet that is under development by the SRNL Chemical Process Control (CPC) group. The nitric acid test did show the expected exothermic behavior as well as how the behavior is affected by particle size of the powders used. In contrast, the effluent samples did not show an exothermic peak. However, the concentration of metal in the samples was orders of magnitude lower than in the nitric acid testing and further testing of the effect of concentration on the exothermicity that could be measured confirmed a dampened signal. Tests were run that included frit, both DWPF Frit 510 and Iron Phosphate frit, exhibiting complex curves that included multiple endothermic and exothermic peaks during heating and cooling. The final crucible samples appear similarly to the bulk glasses pointing to these peaks being a part of the dissolution of the simulant into the base glasses.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Raman Spectroscopy Based On-Line, Real-Time Monitoring to Reduce Composition Uncertainties: Enhanced sensitivity through optimization of Raman Parameters

Optical spectroscopy-based on-line monitoring of Hanford processing streams can enable real-time characterization of chemical composition of process streams and batches, ultimately enabling and enhancing process control. It can provide immediate feedback on process conditions and has the potential to reduce the needed number of grab sample collections, thereby reducing times and costs associated with laboratory processing. Here we discuss the utilization of Raman spectroscopy to quantify multiple target analytes that are common within Hanford tanks and waste processing streams. Analytes include: nitrate, nitrite, carbonate, chromate, sulfate, phosphate, hydroxide, oxalate, ammonia, and aluminate. Most notably in this work, Raman applications to low-concentration streams are explored and optimized. Raman instrument specifications are compared; specifically, the impact of utilizing three different Raman excitation wavelengths, 405, 532, and 671 nm, is discussed. Also, Raman data collection parameters such as collection time and spectral averaging are measured and discussed. Finally, optical libraries of chemical targets were collected using optimized collection parameters and chemometric models were built to automate quantification of chemical targets. These models were validated through application to simulants and real Hanford process samples. Chemometric models performed well on both training and validation sets, suggesting these approaches can be successfully applied to on-line and real-time monitoring of low concentration Hanford processing streams. The use of the combine Raman wave lengths with the enhanced chemometric models for the low concentration streams significantly improved the chemical detection levels and significantly reduced uncertainties of those measurements.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Evaluations of the Fates of Alkali Metals, Actinides, Mercury, and Iodine During DWPF Recycle Diversion

The fates of alkali metals, actinides, mercury, and iodine in the Defense Waste Processing Facility Recycle Diversion process (as currently conceptualized) have been evaluated through paper studies based on available knowledge of the chemistry, physical properties, solubility, and volatility of the various species involved. The effect of pH in the range from 9 to 13 has been discussed. Recommendations for additional studies to close technology gaps have been provided, many of which are contingent upon the results of pending testing and sample characterization efforts. There is uncertainty in the amounts of soluble actinides passing through the process filter, though the bulk of the actinides should be captured on the filter with the Recycle Collection Tank solids and the total amounts of actinides should be relatively low. The Recycle Collection Tank pH could impact the fraction of actinides reaching the evaporator, but the primary factors determining the actinide fate are expected to be the amount of CO 2 sorption from air sparging or, for certain actinides (such as plutonium), oxidation and/or sorption to MnO 2 solids from permanganate additions to destroy the glycolate anion. Process optimization could minimize the amounts of actinides passing the filter. Depending upon the levels of mercury observed in recycle stream samples and because of the volatility of mercury, the evaporator should be designed with the capability to remove dense mercury phases from the condensate to avoid exceeding ETP WAC limits. The facility design must be adequate to transfer dense mercury phases and testing to confirm mercury transfer is needed. Simulant containing mercury is recommended for both filtration and evaporation testing. OLI Modeling of the various recycle streams is recommended to provide insight on the fate of iodine. Iodine-spiked simulants are recommended for upcoming evaporation tests. The pro) ect should consider the likelihood and impact of NAS scale formation in the evaporators. Process optimization may be needed to minimize the accumulation of NAS scale and possibly the sorption of actinides in the evaporator. Actual waste testing of the Recycle Diversion filtration and evaporation should include the analysis of actinides, mercury, and iodine to determine their partitioning.

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Part IV: Remedial Action

This part of the book focuses on the remedial action where the remedy is selected and approved with associated regulatory documentation, detailed designs are prepared, and construction and/or implementation of the remedy is completed. The application may include remediation of environmental media (e.g., subsurface sediments or surface water sources), waste processing, and/or deactivation and decommissioning of historical facilities. Once a preferred remedy is implemented, the final steps include long-term stewardship and site closure (discussed in Part V). Refer to Section 3.2 of Chapter 1, Remediation Strategy for Complex Waste Sites, for context on how these steps fit into the broader remediation process.

Johnson, Christian D.↗

Baseline Hypothetical Facility for the Production of 131 I and 99 Mo using Activation Targets

This report describes a hypothetical facility for production of medical radioisotopes via activation under the Proliferation Resistance and Optimization (PRO-X) program. The facility uses neutron activation of non-special nuclear material (SNM) to produce the medical isotopes 131 I and 99 Mo at a throughput of 60 Ci/week of 131 I and 5 Ci/week of 99 Mo. The hypothetical design was carried out using a 10 MWt research reactor. The precursors used for the activation process were TeO2 for 131 I and MoO 3 for 99 Mo. The processes are performed in 3 hot cells used for target receipt, extraction, purification low specific activity (LSA) generator introduction, and packaging. A fourth hotcell is used for waste processing. The hot cell processing area takes up a footprint of 15.4 m 2 with the total footprint of the facility, including space for administrative offices, non-rad labs, quality assurance, and radiation buffer areas set at 763 m 2 . Waste is produced at a weekly rate of 257.8 g low activity solid waste and 8032.7 mL of low activity liquid waste, 8032 mL of which is water. This baseline hypothetical facility for production of medical isotopes via activation was then compared and contrasted to the hypothetical facility for production of medical isotopes via fission products to show the differences in approach for the two production modes. The two production modes had several highlighted differences including the overall facility and hot cell layout, the type and amount of waste produced by the respective facilities, and economic factors impacting production mode. Finally, a decision tree for which production mode might be more beneficial for an entrant into medical isotope production was developed based on the differences examined and the desired output of medical isotopes desired by the entrant.

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Corrosion Testing of Refractory in Contact with Molten Glasses Designed for Waste Vitrification

It is known that the predictive life of the refractory ceramic liner of nuclear waste glass melters is conservative, as demonstrated by performance of these materials such as in the Defense Waste Processing Facility (DWPF). The motivation for this task is to maximize the useful life of the melters that will be operated at the Waste Treatment and Immobilization Plant (WTP), which will in turn minimize procurement and disposal costs and melter outage times, as well as to identify maximum loadings in the waste glass of those species that corrode melter components. This task was initiated jointly with Pacific Northwest National Laboratory (PNNL) with the objective to develop a methodology and model to enable more accurate prediction of refractory service life under prototypic conditions from laboratory-scale material corrosion tests.

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Corrosion Testing of Refractory in Contact with Molten Glasses Designed for Waste Vitrification - APPS1 Matrix Glasses

It is known that the predictive life of the refractory ceramic liner of nuclear waste glass melters is conservative, as demonstrated by performance of these materials such as in the Defense Waste Processing Facility (DWPF). The motivation for this task is to maximize the useful life of the melters that will be operated at the Waste Treatment and Immobilization Plant (WTP), which will in turn minimize procurement and disposal costs and melter outage times, as well as to identify maximum loadings in the waste glass of those species that corrode melter components. This task was initiated jointly with Pacific Northwest National Laboratory (PNNL) with the objective to develop a methodology and model to enable more accurate prediction of refractory service life under prototypic conditions from laboratory-scale material corrosion tests.

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Corrosion Testing of Refractory inContact with Molten Glasses Designed for Waste Vitrification - VSL Touchpoint Matrix Glasses

It is known that the predictive life of the refractory ceramic liner of nuclear waste glass melters is conservative, as demonstrated by performance of these materials such as in the Defense Waste Processing Facility (DWPF). The motivation for this task is to maximize the useful life of the melters that will be operated at the Waste Treatment and Immobilization Plant (WTP), which will in turn minimize procurement and disposal costs and melter outage times, as well as to identify maximum loadings in the waste glass of those species that corrode melter components. This task was initiated jointly with Pacific Northwest National Laboratory (PNNL) with the objective to develop a methodology and model to enable more accurate prediction of refractory service life under prototypic conditions from laboratory-scale material corrosion tests. Refractory corrosion is generally reported as physical material loss, measured in units of distance (e.g., inch) or as physical material loss rate, measured in units of distance per time (e.g., inch/day). In post-operational melters, the refractory corrosion is measured directly, sometimes reported as corrosion depth. Crucible tests are used in the laboratory to accelerate the refractory corrosion to facilitate a meaningful measurement in a commensurate amount of time. Crucible tests are particularly useful in understanding refractory corrosion across a large glass composition space, where operational testing would be prohibitive. Some of the critical parameters that are known to influence refractory corrosion by molten glass in a crucible test are temperature, system redox, molten salt phases, glass chemistry, and test duration. The majority of data collected for Monofrax® K-3 (hereafter referred to as K-3) corrosion is from crucible tests, but a small amount comes directly from scaled and production melters. Crucible test data has been collected under varying conditions, whereas data collected from operational melters is relatively fewer and represents conditions specific to the melter campaign. The result is that the published data can be grouped and analyzed in multiple ways, not all of which are readily comparable. The Standard Test Method for Isothermal Corrosion Resistance of Refractories to Molten Glass (ASTM C621) outlines the general guidelines used across industry. That method describes a sealed, static test in which the surface area of the refractory coupon and the volume of glass are fixed. A significant portion of the crucible data pertaining to nuclear waste glasses has been collected in a modified configuration; the most notable differences being the surface area of the refractory coupon to volume of the glass and use of a method for bubbling the melt. To our knowledge, the influence of those parameters on the refractory corrosion has not been quantified. In this work, it was determined that static tests and bubbled tests would be performed. Savannah River National Laboratory (SRNL) was tasked with setting up and performing static testing while PNNL was tasked with setting up and performing bubbled testing. Initial activities were performed to establish laboratory methods that reproduce data comparable to existing data sets of K-3 refractory corrosion by low activity waste (LAW) and high-level waste (HLW) glass compositions. Later activities were focused on refining the test parameters to establish a standard test practice to be used between Laboratories and collecting additional data to be used in the enhanced waste glass model development. This document serves primarily to convey the refractory loss measurement results from corrosion testing of K-3 refractory with waste glass compositions developed for use in the WTP melters. The data will be used in the enhanced property/composition models being developed for waste glass vitrification and melter operations.

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Corrosion Testing of Refractory in Contact with Molten Glasses Designed for Waste Vitrification - HAL24 M1 Matrix Glasses

It is known that the predictive life of the refractory ceramic liner of nuclear waste glass melters is conservative, as demonstrated by performance of these materials such as in the Defense Waste Processing Facility (DWPF). The motivation for this task is to maximize the useful life of the melters that will be operated at the Waste Treatment and Immobilization Plant (WTP), which will in turn minimize procurement and disposal costs and melter outage times, as well as to identify maximum loadings in the waste glass of those species that corrode melter components. This task was initiated jointly with Pacific Northwest National Laboratory (PNNL) with the objective to develop a methodology and model to enable more accurate prediction of refractory service life under prototypic conditions from laboratory-scale material corrosion tests.

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Analysis Of The Sludge Batch 7b (Macrobatch 9) DWPF Pour Stream Glass Sample (Rev. 1)

The Defense Waste Processing Facility (DWPF) began processing Sludge Batch 7b (SB7b), also referred to as Macrobatch 9 (MB9), in January 2012. SB7b is a blend of the heel of Tank 40 from Sludge Batch 7a (SB7a) and the SB7b material that was transferred to Tank 40 from Tank 51. SB7b was processed using Frit 418. During processing of each sludge batch, the DWPF is required to take at least one glass sample to meet the objectives of the Glass Product Control Program (GPCP), which is governed by the DWPF Waste Form Compliance Plan, and to complete the necessary Production Records so that the final glass product may be disposed of at a Federal Repository. Two pour stream glass samples were collected while processing SB7b. The samples were transferred to the Savannah River National Laboratory (SRNL) where one was analyzed and the other was archived. The following conclusions were drawn from the analytical results provided in this report: The sum of oxides for the official SB7b pour stream glass is within the Product Composition Control System (PCCS) limits (95-105 wt%); The average calculated Waste Dilution Factor (WDF) for SB7b is 2.3. In general, the measured radionuclide content of the official SB7b pour stream glass is in good agreement with the calculated values from the Tank 40 dried sludge results from the SB7b Waste Acceptance Program Specification (WAPS) sample; As in previous pour stream samples, ruthenium and rhodium inclusions were detected by Scanning Electron Microscopy-Electron Dispersive Spectroscopy (SEM-EDS) in the SB7b pour stream sample; The Product Consistency Test (PCT) results indicate that the official SB7b pour stream glass meets the waste acceptance criteria for durability with a normalized boron release of 0.8 g/L, which is an order of magnitude less than the Environmental Assessment (EA) glass; The measured density of the SB7b pour stream glass was 2.70 g/cm 3 ; The Fe 2+ /ΣFe ratio of the SB7b pour stream samples was 0.07.

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