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Impacts of Guanidine Degradation Products on Next Generation Solvent (NGS) Caustic Side Solvent Extraction (CSSX) Processing

Savannah River National Laboratory researchers have been requested to perform testing to assess the potential for build-up of guanidine degradation compounds in the Next Generation Solvent Caustic Side Solvent Extraction process. Testing was also requested to determine the impact of guanidine degradation compounds [3,7-dimethyloctylamine (iDA) and Bis-N,N’-(3,7-dimethyloctyl)urea (DiDU)] on cesium behavior in the flowsheet. Twelve partitioning experiments were performed to quantify the partitioning coefficient of identified guanidine degradation compounds in various organic-aqueous mixtures. Six Extraction, Scrub, and Strip (ESS) experiments were performed to quantify the impact of degradation products on cesium behavior.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Literature Review on Next Generation Solvent Isopar ® L Vapor Pressure Curve and the Partitioning of its Modifier and Extractant

The Next Generation Solvent (NGS) is set to replace the Original Caustic Side Solvent Extractant (CSSX) at the Salt Waste Processing Facility (SWPF). The Savannah River National Laboratory (SRNL) was requested by Savannah River Mission Completion (SRMC), formerly Savannah River Remediation (SRR), to perform a literature review on the following topics to address flammability concerns with the current solvent: Isopar ® L vapor pressure curve for NGS, partitioning ratio for the extractant MaxCalix and the modifier Cs-7SB, and high cesium concentration impacts on NGS radiolysis and potential solvent degradation rates in high cesium concentrations. The following conclusions and recommendations are made based on previous experimental work and literature: (1) Current SWPF flammable gas generation calculations use an Isopar ® L vapor pressure curve based on experimental testing with the Original CSSX solvent. No such testing to date has been performed with NGS. It is suggested that the decrease in Cs-7SB concentration for NGS compared to the Original CSSX solvent would lead to a slightly higher vapor pressure at all temperatures in SWPF vessels. A bounding NGS vapor pressure curve has been provided; it is recommended to see if these values would challenge current flammability controls and to perform testing if needed.(2) The partitioning ratio for Cs-7SB is known in the Original CSSX solvent with dilute nitric acid and caustic solutions. No tests could be found for the partitioning of Cs-7SB to dilute boric acid solutions; however, a similar partitioning ratio is expected. Due to the lipophilic alkyl chains on MaxCalix, it is expected to be even less soluble than BOBCalixC6 in the aqueous phase and should not be considered a significant contributor to the f organic term. Additionally, the reaction rate of N,N’,N’’-Tris(3,7-dimethyloctyl)guanidine (TiDG) or its degradation products with a hydrogen radical should be estimated/determined if they are found to be significant contributors to the f organic term. (3) NGS is expected to see much higher Cs concentrations at SWPF in comparison to its use at the Modular CSSX Unit (MCU). These higher Cs concentrations could influence radiolytic degradation rates of the solvent. NGS appears to be fairly stable to radiolytic degradation based on previous testing and its use at MCU. However, there has not been radiolytic flammable gas generation testing with NGS to date. There is a risk that the continued use of G-values obtained for flammable gases produced from the irradiation of the Original CSSX solvent is not bounding for NGS, but this is considered a very low risk due to the similarities in the composition of the solvents, as well as the conservatisms in the experimental design of the Original CSSX testing.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Next Generation Solvent Vapor Pressure Testing

Previous work by Savannah River National Laboratory (SRNL) indicated that the actual Next Generation Solvent vapor pressure would be higher than the Original Caustic Side Solvent Extraction (CSSX) solvent vapor pressure, but below a bounding vapor pressure using Raoult’s Law. Since solvent vapor pressure has a significant impact on Composite Lower Flammability Limits (CLFL) and attendant accident analyses, obtaining an additional margin from the bounding NGS vapor pressure would be valuable. In order to quantify how much margin might be gained from the NGS bounding solvent, SRNL researchers were requested to perform vapor pressure testing with the Next Generation Solvent (NGS) by Savannah River Mission Completion (SRMC). The vapor pressure curve for the NGS formulation set to be deployed at the Salt Waste Processing Facility (SWPF) has been determined by SRNL up to 55°C (131°F) using headspace Gas Chromatography (GC). It was expected that NGS would have a higher vapor pressure than the Original CSSX solvent; however, experimental results indicate a lower vapor pressure. At this time, it is uncertain if this difference is due to the 7x increase in concentration of the large calixarene in the solvent (0.007M BOBCalix in Original CSSX solvent vs. 0.05M MaxCalix in NGS) or to minor batch-to-batch variations in Isopar-L constituents. The NGS and the Original CSSX solvent vapor pressure data were fitted to the Antoine Equation. The Antoine equation gives a more accurate representation of the expected vapor pressure of the solvents outside of the temperature range tested. The Antoine equation fitting for NGS is given below: $P=10^{6.364⁻\frac{1788.4}{T+219.3}}$. Where, p is the vapor pressure (partial pressure) of NGS in mmHg and T is the temperature in °C. It is recommended that SRMC either continue using the more conservative Isopar-L vapor pressure calculations at SWPF with the equation developed for the Original CSSX solvent, or the equation presented above for the NGS solvent. Additionally, it is recommended to study the variability in Isopar-L vapor pressure between lots.

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Analysis of Solids Obtained from 201O, 201P, 202A, and 202B Contactors in the Salt Waste Processing Facility

In December 2022, Savannah River Mission Completion personnel recovered solids samples from four contractors (EXT-001, EXT-007, EXT-031, and EXT-040) employed at the Salt Waste Processing Facility (SWPF). These solids were submitted to Savannah River National Laboratory for analysis and characterization. This Technical Report outlines the analytical findings and observations associated with these samples and explores the potential source of solid generation within the SWPF. The following conclusions are offered as a result of this work: the light color solids recovered from EXT-007 are consistent with crystallized, soluble salt components (such as sodium nitrate, sodium hydroxide, and sodium carbonate), all of which can be easily re-dissolved in process water and do not represent a threat to SWPF CSSX processing. While the light solids from the top of EXT-040 were not analyzed, it is believed that they share similar characteristics to those recovered from EXT-007; The dark color solids recovered from EXT-001, EXT-031, and the inside of EXT-040 appear to be complex, consisting of several different types of solids: High concentrations of mercury (Hg, 40-75% by mass) partially present as elemental Hg are consistent with the precipitation of Hg 0 /Hg 2+ from disproportionation of Hg + species in pH swing conditions; Moderate concentrations of titanium (Ti) (2-7%, by mass) are also present, often co-located with Hg. This is consistent with co-precipitation, entrainment, and/or amalgamation of Ti and Hg; Moderate concentrations of iron (Fe) (1-3%, by mass) are observed in SWPF solids and are likely attributable to erosion of stainless-steel components within the CSSX process; Small concentrations of tungsten (W) and cobalt (Co) (<1%, by mass) are observed in SWPF solids. The presence of these solids is consistent with the erosion of components coated with W and Co (e.g., Stellite); Small concentrations of aluminum (Al) (<1%, by mass) are observed in the form of gibbsite and potentially sodium aluminosilicate. The presence of these compounds is likely attributable to the pH swing observed between the scrub and extraction cycles within the CSSX process. The following recommendations are made as a result of this work: Testing should be performed to determine the chemical drivers, process, and mechanism of Hg precipitation in CSSX processing. Special care should be taken to include titanium in tests to evaluate the potential for co-precipitation, entrainment, and amalgamation; Hg-mitigation options that would minimize or eliminate risks of Hg precipitation and solids accumulation (e.g., Hg-absorption techniques, ion exchange/adsorbents, flowsheet changes, etc.) should be assessed.

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A Review of the Literature on the Radiolytic Stability of the Next-Generation Solvent

The Original Caustic-Side Solvent Extraction (CSSX) solvent (based on the BOBCalixC6 extractant) currently in use at the Salt Waste Processing Facility (SWPF) is set to be replaced by the Next-Generation Solvent (NGS, based on the MaxCalix extractant). Current SWPF flammability safety controls use G-values for volatile gases obtained from radiolysis studies with the Original CSSX solvent. A review of past irradiation tests of both solvent systems was performed to assess the radiolytic stability of NGS with respect to flammable gas generation from radiolysis.

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Literature Review on the Impact of Thermolytic Hydrogen Generation Rate from the Next Generation Solvent

A literature review was undertaken to assess the thermolytic hydrogen generation potential of the Next Generation Solvent (NGS) system, which is planned to replace the Original Caustic-Side Solvent Extraction (CSSX) Solvent at the Salt Waste Processing Facility. NGS uses a new extractant and suppressor and the same modifier and organic carrier solvent as the Original CSSX Solvent at different concentrations.

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Synthesis and Purity Specifications for N,N'-Dicyclohexyl-N"-(10-nonadecyl)guanidinium Chloride for Use in Next Generation Caustic-Side Solvent Extraction

This report describes a synthesis procedure for the alkylguanidine, N,N'-dicyclohexyl-N"-(10-nonadecyl)guanidine (DCNDG), which has been identified as a promising candidate for replacing the less stable N,N',N"-tri(3,7-dimethyloctyl)guanidine (TiDG) suppressor in the Next Generation Caustic-Side Solvent Extraction (NG-CSSX) process. A verified procedure for the preparation of the amine used in this synthesis is also included. In addition, requirements for the purity of DCNDG to be utilized in the NG-CSSX process without adverse effect on the Cs + extraction and stripping are given.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

An Application of Molecular Recognition for the Efficient Removal of Cesium from Hanford Nuclear Waste by Modular Solvent Extraction

In this work, experimental results leading to flowsheet design are presented showing how a calixarene-crown ether based solvent-extraction process can meet the challenge of cesium removal from nuclear tank wastes stored at the US Department of Energy Hanford site. Cleanup of legacy Cold War nuclear waste stored in underground tanks represents one of the greatest environmental challenges facing the US Department of Energy in terms of risk, cost, and effectiveness of applicable science and technology. Planning for the cleanup at the Hanford Site calls for the removal of the radioactive fission product 137Cs from its alkaline salt waste, including the use of modular processes that can be deployed near the tank farms. To meet the resulting need for extremely high selectivity, the Next-Generation Caustic-Side Solvent Extraction (NG-CSSX) process employing a calix[4]arene-crown ether in modified kerosene has been adapted to remove sub-millimolar cesium in competition with molar sodium and potassium in a high-nitrate alkaline matrix. Potassium loading in the solvent was determined in extraction, scrubbing, and stripping, leading to an empirical model closely approximating cesium distribution ratios for a variety of Hanford waste types. Process chemistry has been developed based on this molecular-recognition approach, focusing on the competitive effect of potassium loading and the mitigating process modifications needed, including extending the scrub section. The result is a modular flowsheet design that can achieve cesium decontamination factors well in excess of 15,000 even for the worst-case Hanford waste.

Williams, Neil [ORNL] (ORCID:000000023159226X)↗

The Compatibility of Tefzel™ and Viton™ B with Caustic-Side Solvent Extraction Solvents

The Salt Waste Processing Facility (SWPF) plans to switch from the current Caustic-Side Solvent Extraction (CSSX) solvent to the Next Generation Solvent-Phase II (NGS-Phase II). SRNL was requested to evaluate the compatibility between polymeric materials of construction at SWPF and NGS-Phase II solvent. The work presented here concentrated on two materials of interest: Tefzel™ and Viton™ B.

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Extraction, Scrub, and Strip Test Results for the IBC BOBCalix Solvent Samples

A second vendor for solvent extraction components has been chosen for use at the Salt Waste Processing Facility (SWPF). IBC Advanced Technologies (IBC) has provided samples of their BOBCalix, as well as complete solvent. These samples were tested for quality assurance purposes to ensure their use at SWPF is acceptable. Two Extraction, Scrub, and Strip (ESS) tests were performed on solvent samples from IBC. The purpose of testing these samples was to determine if the solvents are displaying the correct extraction and stripping behavior with cesium.

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