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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 253 records · Page 14
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

An Evaluation of the Impact of Glycolate and Glycolate Mitigation on the Defense Waste Processing Facility Recycle Diversion Project Flowsheet

The Savannah River Site (SRS) Defense Waste Processing Facility (DWPF) processes radioactive High Level Waste (HLW) sludge solids from the Concentration, Storage, and Transfer Facilities (CSTF); which includes the SRS Tank Farm and Evaporator facilities, and a concentrated Cs-137 laden stream and a Monosodium Titanate (MST) and sludge solids stream from the SRS Salt Waste Processing Facility (SWPF). The waste is chemically adjusted with acids and reductant (currently with 50 wt.% nitric acid and ~90 wt.% formic acid, but eventually formic acid will be substituted with ~70 wt.% glycolic acid), and frit is added so that a durable, borosilicate glass waste form can be produced when the material is vitrified in the melter. As a result of the evaporation of water during both the melter feed preparation and the melter feed vitrification steps in DWPF, a recycle waste stream is generated, neutralized, and sent back to the CSTF. The recycle waste is a dilute aqueous stream originating from the collection of condensate liquids containing some minor sludge, MST, and frit solids and other waste components resulting from melter feed entrainment during foamover events and transfer of volatile species into the condensate. The recycle stream volume is significant and is expected to approach 3 million gallons per year once SWPF reaches full operation, requiring the use of multiple large CSTF tanks for storage. The recycle waste is currently collected in the SRS Tank Farm and periodically evaporated in the 242-16H (2H) Evaporator to conserve storage space.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2022

Formation of Organic Acids and Carbonyl Compounds in $\textit{n}$-Butane Oxidation via γ-Ketohydroperoxide Decomposition

A crucial chain-branching step in autoignition is the decomposition of ketohydroperoxides (KHP) to form an oxy radical and OH. Other pathways compete with chain-branching, such as “Korcek” dissociation of γ-KHP to a carbonyl and an acid. Here we characterize the formation of a γ-KHP and its decomposition to formic acid+acetone products from observations of $\textit{n}$-butane oxidation in two complementary experiments. In jet-stirred reactor measurements, KHP is observed above 590 K. The KHP concentration decreases with increasing temperature, whereas formic acid and acetone products increase. Observation of characteristic isotopologs acetone-$d_3$ and formic acid-$d_0$ in the oxidation of CH 3 CD 2 CD 2 CH 3 is consistent with a Korcek mechanism. In laser-initiated oxidation experiments of $\textit{n}$-butane, formic acid and acetone are produced on the timescale of KHP removal. Further, modelling the time-resolved production of formic acid provides an estimated upper limit of 2 s –1 for the rate coefficient of KHP decomposition to formic acid+acetone.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

Glycolic-Nitric Acid Flowsheet Demonstration of the DWPF Chemical Processing Cell with Matrix Simulants and Supernate

Savannah River Remediation (SRR) is evaluating changes to its current DWPF flowsheet to improve processing cycle times. This will enable the facility to support higher canister production while maximizing waste loading. Higher throughput is needed in the CPC since the installation of the bubblers into the melter has increased melt rate. Due to the significant maintenance required for the DWPF gas chromatographs (GC) and the potential for production of flammable quantities of hydrogen, reducing or eliminating the amount of formic acid used in the CPC is being developed. Earlier work at Savannah River National Laboratory has shown that replacing formic acid with an 80:20 molar blend of glycolic and formic acids has the potential to remove mercury in the SRAT without any significant catalytic hydrogen generation. This report summarizes the research completed to determine the feasibility of processing without formic acid. In earlier development of the glycolic-formic acid flowsheet, one run (GF8) was completed without formic acid. It is of particular interest that mercury was successfully removed in GF8, no formic acid at 125% stoichiometry. Glycolic acid did not show the ability to reduce mercury to elemental mercury in initial screening studies, which is why previous testing focused on using the formic/glycolic blend. The objective of the testing detailed in this document is to determine the viability of the nitric-glycolic acid flowsheet in processing sludge over a wide compositional range as requested by DWPF. This work was performed under the guidance of Task Technical and Quality Assurance Plan (TT and QAP). The details regarding the simulant preparation and analysis have been documented previously.

08 HYDROGEN↗
DOE OSTI2010

Two-dimensional infrared study of 3-azidopyridine as a potential spectroscopic reporter of protonation state

The lack of general spectroscopic probes that can be used in a range of systems to probe kinetics and dynamics is a major obstacle to the widespread application of two-dimensional infrared (2D IR) spectroscopy. We have studied 3-azidopyridine to characterize its potential as a probe of the protonation state of the pyridine ring. We find that the azido-stretching vibration is split by accidental Fermi resonance interactions with one or more overtones and combination states. Using 2D IR spectroscopy, we determine the state structure of the resulting eigenstates for complexes of 3-azidopyridine with formic acid and trifluoroacetic acid in which the pyridine ring is unprotonated and protonated, respectively. Based on the measurements, we develop a two-oscillator depurturbation model to determine the energies and couplings of the zeroth-order azido-stretching state and the perturbing dark state that couples to it. Based on these results, we conclude that the azido-stretching vibration is, in fact, sensitive to the protonation state of the pyridine shifting up in frequency by 8 cm{sup -1} in the complex with trifluoroacetic acid relative to the formic acid complex. These results suggest that, although 3-azidopyridine is not suitable as a spectroscopic probe, the approach of employing an organic azide as a remote probe of protonation state holds significant promise.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

Glycolic-Nitric Acid Flowsheet Demonstration of the DWPF Chemical Process Cell with Sludge and Supernate Simulants

Savannah River Remediation (SRR) is evaluating changes to its current Defense Waste Processing Facility (DWPF) flowsheet to improve processing cycle times. This will enable the facility to support higher canister production while maximizing waste loading. Higher throughput is needed in the Chemical Process Cell (CPC) since the installation of the bubblers into the melter has increased melt rate. Due to the significant maintenance required for the DWPF gas chromatographs (GC) and the potential for production of flammable quantities of hydrogen, reducing or eliminating the amount of formic acid used in the CPC is being developed. Earlier work at Savannah River National Laboratory has shown that replacing formic acid with an 80:20 molar blend of glycolic and formic acids has the potential to remove mercury in the SRAT without any significant catalytic hydrogen generation. This report summarizes the research completed to determine the feasibility of processing without formic acid. In earlier development of the glycolic-formic acid flowsheet, one run (GF8) was completed without formic acid. It is of particular interest that mercury was successfully removed in GF8, no formic acid at 125% stoichiometry. Glycolic acid did not show the ability to reduce mercury to elemental mercury in initial screening studies, which is why previous testing focused on using the formic/glycolic blend. The objective of the testing detailed in this document is to determine the viability of the nitric-glycolic acid flowsheet in processing sludge over a wide compositional range as requested by DWPF. This work was performed under the guidance of Task Technical and Quality Assurance Plan (TT&QAP). The details regarding the simulant preparation and analysis have been documented previously.

08 HYDROGEN↗
DOE OSTI2020

Antifoam Development for Eliminating Flammability Hazards and Decreasing Cycle Time in the Defense Waste Processing Facility

The Savannah River National Laboratory (SRNL) was requested to develop a new antifoam control method for the Defense Waste Processing Facility’s (DWPF) Chemical Process Cell (CPC). SRNL completed testing of both chemical and nonchemical foam controls. The nonchemical foam controls were either ineffective (or worse, created more foam) or impractical (a water spray can control foam, but excessive water is needed). As a result, the focus of this study was on finding a superwetter or commercial antifoam for controlling foam. Thirty potential antifoams were tested as part of this study. A series of tests were developed to help screen out ineffective alternatives including: 1. Spreading testing of superspreaders, 2. Foam column testing with physical simulants, 3. Boiling testing with physical and chemical simulants, 4. Days-only Sludge Receipt and Adjustment Tank (SRAT) process simulations with sludge (containing noble metals and mercury), Precipitate Reactor Feed Tank (PRFT), and Slurry Mix Evaporator Feed Tank (SEFT) simulants in the RC1 Reaction Calorimeter (purchased for antifoam testing), and 5. Around-the-clock SRAT and Slurry Mix Evaporator (SME) process simulations with sludge(containing noble metals and mercury), PRFT, and SEFT simulants in the RC1 Reaction Calorimeter. Evonik Surfynol® MD20, a commercially available defoamer, was relatively effective in controlling foam, while remaining chemically stable in SRAT and SME processing across the pH range of 4 to 13. No degradation products were detected in the offgas, in the condensate or in the SRAT and SME products. In nitric-glycolic acid flowsheet testing, 250 mg/kg Evonik Surfynol® MD20 was needed for foam control compared to 1,625 mg/kg for Antifoam 747, DWPF’s current antifoam. In nitric-formic acid flowsheet testing, 1,125 mg/kg of Evonik Surfynol® MD20 was needed to control foam throughout the SRAT and SME cycles. The commercially available superspreader Momentive™ Y-17112 was even more effective than Evonik Surfynol® MD20 as both a defoamer and an antifoam. Not only was the foam destroyed upon addition but also was less persistent between additions. It was the most effective antifoam in testing using both the nitric-glycolic acid flowsheet and the nitric-formic acid flowsheet. In nitric-glycolic acid flowsheet testing, only 100 mg/kg Momentive™ Y-17112 was needed to control foam throughout the SRAT and SME cycles. In nitric-formic acid flowsheet testing, 300 mg/kg Momentive™ Y-17112 was needed to control foam throughout the SRAT and SME cycles. Momentive™ Y-17112 is also resistant to hydrolysis as demonstrated by its chemical stability in SRAT and SME processing across the pH range of 4 to 13 and lack of degradation products in offgas or condensate. Both candidates were effective as potential replacements for Antifoam 747, with Y-17112 demonstrating superior foam control. During nitric-glycolic flowsheet testing 50% less antifoam was needed when using Momentive™ Y-17112 compared to MD20. During nitric-formic flowsheet testing 75% less antifoam was needed when using Momentive™ Y-17112 compared to MD20. Foam remediated with Momentive™ Y-17112 was less persistent throughout testing. In addition, no degradation products were detected in the offgas, in the condensate or in the SRAT and SME products. Based on this testing, Momentive™ Y-17112 is clearly superior to Evonik Surfynol® MD20 and Antifoam 747, especially for the nitric-formic acid flowsheet processing; it is recommended that Momentive™ Y-17112 replace Antifoam 747 in DWPF. An antifoam addition strategy is recommended for both the nitric-glycolic acid flowsheet and the nitric-formic acid flowsheet. Implementation of Momentive™ Y-17112 is expected to decrease SRAT and SME boiling times by up to 50%, eliminate the issues resulting from Antifoam 747 degradation products, and minimize foamovers. To validate the effectiveness of these defoaming agents, SRNL recommends irradiation of a SRAT or SME product simulant containing fresh antifoam. The goal of this testing is to determine whether the irradiation causes decomposition of the antifoam that would make it less effective or produce new species in the offgas or slurry. This testing began in April 2020. An evaluation should be completed to determine the thermolytic hydrogen and methane generation rate in downstream equipment, including the High-Level Waste evaporators.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2011

DWPF SIMULANT CPC STUDIES FOR SB7B

Lab-scale DWPF simulations of Sludge Batch 7b (SB7b) processing were performed. Testing was performed at the Savannah River National Laboratory - Aiken County Technology Laboratory (SRNL-ACTL). The primary goal of the simulations was to define a likely operating window for acid stoichiometry for the DWPF Sludge Receipt and Adjustment Tank (SRAT). In addition, the testing established conditions for the SRNL Shielded Cells qualification simulation of SB7b-Tank 40 blend, supported validation of the current glass redox model, and validated the coupled process flowsheet at the nominal acid stoichiometry. An acid window of 105-140% by the Koopman minimum acid (KMA) equation (107-142% DWPF Hsu equation) worked for the sludge-only flowsheet. Nitrite was present in the SRAT product for the 105% KMA run at 366 mg/kg, while SME cycle hydrogen reached 94% of the DWPF Slurry Mix Evaporator (SME) cycle limit in the 140% KMA run. The window was determined for sludge with added caustic (0.28M additional base, or roughly 12,000 gallons 50% NaOH to 820,000 gallons waste slurry). A suitable processing window appears to be 107-130% DWPF acid equation for sludge-only processing allowing some conservatism for the mapping of lab-scale simulant data to full-scale real waste processing including potentially non-conservative noble metal and mercury concentrations. This window should be usable with or without the addition of up to 7,000 gallons of caustic to the batch. The window could potentially be wider if caustic is not added to SB7b. It is recommended that DWPF begin processing SB7b at 115% stoichiometry using the current DWPF equation. The factor could be increased if necessary, but changes should be made with caution and in small increments. DWPF should not concentrate past 48 wt.% total solids in the SME cycle if moderate hydrogen generation is occurring simultaneously. The coupled flowsheet simulation made more hydrogen in the SRAT and SME cycles than the sludge-only run with the same acid stoichiometric factor. The slow acid addition in MCU seemed to alter the reactions that consumed the small excess acid present such that hydrogen generation was promoted relative to sludge-only processing. The coupled test reached higher wt.% total solids, and this likely contributed to the SME cycle hydrogen limit being exceeded at 110% KMA. It is clear from the trends in the SME processing GC data, however, that the frit slurry formic acid contributed to driving the hydrogen generation rate above the SME cycle limit. Hydrogen generation rates after the second frit addition generally exceeded those after the first frit addition. SRAT formate loss increased with increasing acid stoichiometry (15% to 35%). A substantial nitrate gain which was observed to have occurred after acid addition (and nitrite destruction) was reversed to a net nitrate loss in runs with higher acid stoichiometry (nitrate in SRAT product less than sum of sludge nitrate and added nitric acid). Increased ammonium ion formation was also indicated in the runs with nitrate loss. Oxalate loss on the order 20% was indicated in three of the four acid stoichiometry runs and in the coupled flowsheet run. The minimum acid stoichiometry run had no indicated loss. The losses were of the same order as the official analytical uncertainty of the oxalate concentration measurement, but were not randomly distributed about zero loss, so some actual loss was likely occurring. Based on the entire set of SB7b test data, it is recommended that DWPF avoid concentrating additional sludge solids in single SRAT batches to limit the concentrations of noble metals to SB7a processing levels (on a grams noble metal per SRAT batch basis). It is also recommended that DWPF drop the formic acid addition that accompanies the process frit 418 additions, since SME cycle data showed considerable catalytic activity for hydrogen generation from this additional acid (about 5% increase in stoichiometry occurred from the frit formic acid). Frit 418 also does not appear to need formic acid addition to prevent gel formation in the frit slurry. Simulant processing was successful using 100 ppm of 747 antifoam added prior to nitric acid instead of 200 ppm. This is a potential area for DWPF to cut antifoam usage in any future test program. An additional 100 ppm was added before formic acid addition. Foaming during formic acid addition was not observed. No build-up of oily or waxy material was observed in the off-gas equipment. Lab-scale mercury stripping behavior was similar to SB6 and SB7a. More mercury was unaccounted for as the acid stoichiometry increased.

08 HYDROGEN↗
DOE OSTI2010

SLUDGE BATCH SUPPLEMENTAL SRAT RUNS EFFECTS OF YIELD STRESS AND CYCLE TIME INCREASE

The Defense Waste Processing Facility (DWPF) has transitioned from Sludge Batch 5 (SB5) processing to Sludge Batch 6 (SB6) processing. Phase III-Tank 40 Chemical Process Cell (CPC) flowsheet simulations have been completed to determine the initial processing conditions for the DWPF transition. The impact of higher yield stress (SB-25) and cycle time extension (SB6-26) on the physical and chemical effects of SB6 processing during the SRAT (Sludge Receipt and Adjustment Tank) cycle were evaluated. No significant impacts on the SRAT chemistry were noted during the higher yield stress run. In particular, no impact on mercury stripping was noted, indicating that settling of elemental mercury was not the primary factor in the low mercury recovery noted in the flowsheet testing. The SRAT product from this run retained the higher yield stress of the starting sludge. The run indicated that ultrasonication is an effective tool to increase the yield stress of simulants to targeted values and the chemistry of downstream processing is not impacted. Significant differences were noted in the cycle time extension test compared to the Phase III flowsheet baseline runs. Large decreases in the ammonia and hydrogen generation rates were noted along with reduced mercury stripping efficiency. The latter effect is similar to that of operating under a high acid stoichiometry. It is conceivable that, under the distinctly different conditions of high formic acid concentration (high acid run) or slow formic acid addition (extended run), that mercury could form amalgams with noble metals, possibly rendering both inert. Thus, the removal of free mercury and noble metals could decrease the rate of catalytic formic acid reactions which would decrease generation of ammonium and hydrogen. The potential underlying reasons for the behavior noted during this run would require additional testing.

08 HYDROGEN↗
DOE OSTI2023

Intensified Catalytic Conversion of CO2 into High Value Chemicals

The utilization of CO2 produced from power generation plants as a feedstock for creating new valuable products offers a strategy to reduce GHG emissions, offset carbon capture costs, and facilitate the rebalancing of the carbon cycle. After considering the thermodynamic requirement of potential products from CO2 utilization and their market size, formic acid is a desirable target that offers widespread utility in industrial chemical production and chemical energy storage as a liquid fuel. To effectively utilize CO2 from power generation plants, UK proposes an enhanced bimetallic oxide carbon utilization process (EBOCU) that enables electrochemical CO2 conversion to formic acid. The UK intensified electrocatalytic process combines three main components: 1) a novel bimetallic oxide electrocatalyst; 2) a stable electrochemical reactor using robust electrodes; and 3) a pressurized electrochemical reactor. The output from this project showed the economic viability of producing high-value formic acid from CO2 to both offset the cost associated with post-combustion CCS and reduce GHG emissions. This project developed and screened a series engineered catalysts to selectively reduce CO2 directly to formic acid. The best performing catalyst based on formic acid production, stability, and Faradaic efficiency, was immobilized on carbon electrodes, and tested inside a flow through reactor. After lab-scale testing was completed, the experimental data was used to perform a Life-Cycle Analysis (LCA) and conduct an Initial Technical and Economic Feasibility Study. The LCA showed a pathway to a net negative CO2 utilization process with the incorporation of renewable energy, while the TEA showed the potential to produce formic acid below the current commercial price. The UK EBOCU process was successfully demonstrated at the TRL3 level and has a clear pathway to further development and contribution to the nation’s ambitious decarbonization goals.

20 FOSSIL-FUELED POWER PLANTS↗
DOE OSTI2017

Implementation of Glycolic Acid Flowsheet in the Defense Waste Processing Facility (DWPF) - 17348

The disposition of high level waste (HLW) into canistered waste forms began at Savannah River Site (SRS) in 1996. For its entire processing history, DWPF has added formic acid as a pretreatment step in producing acceptable melter feed from incoming waste sludges sent from the HLW Tank Farms. While this process has been used to successfully produce more than 4,000 radioactive canisters, the addition of formic acid and its tendency to catalytically decompose in the presence of trace quantities of noble metals adds substantial process complexity in order to safely accommodate hydrogen generation and pH shifting during batch operations. Research efforts have been in progress for several years to identify a chemical surrogate for formic acid which performs the essential process functions without the associated negative consequences. The final analytical work to demonstrate the effectiveness of glycolic acid in the DWPF is nearly complete and a project team has been created to safely integrate the new acid into the chemical process. The project team is currently executing an implementation schedule which addresses safety basis development, revision to operations procedures and training, facility modifications, chemical procurement, and updated process monitoring. Introduction of glycolic acid into DWPF is currently scheduled to take place in early 2017, beginning with a blended flowsheet of glycolic and formic acid and ultimately transitioning to glycolic-only processing. This paper provides an overview of planned glycolic acid flowsheet implementation in the DWPF. This paper discusses several issues related to implementing such a significant change to the chemical process including: 1) Process chemistry differences between the two flowsheets with quantitative comparison for several properties of interest; 2) Technical approach to hazards analysis and safety basis development strategy; 3) Status of project execution for major deliverables; and 4) Path forward for facility modifications related to legacy formic acid support equipment. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2023

Conformer-Dependent Chemistry: Experimental Product Branching of the Vinyl Alcohol + OH + O 2 Reaction

The concentration of formic acid in Earth's tropo-sphere is underestimated by detailed chemical models compared to field observations. Phototautomerization of acetaldehyde to its less stable tautomer vinyl alcohol, followed by the OH-initiated oxidation of vinyl alcohol, has been proposed as a missing source of formic acid that improves the agreement between models and field measurements. Theoretical investigations of the OH + vinyl alcohol reaction in excess O 2 conclude that OH addition to the alpha carbon of vinyl alcohol produces formaldehyde + formic acid + OH, whereas OH addition to the β site leads to glycoaldehyde + HO 2 . Furthermore, these studies predict that the conformeric structure of vinyl alcohol controls the reaction pathway, with the anti-conformer of vinyl alcohol promoting α OH addition, whereas the syn-conformer promotes β addition. However, the two theoretical studies reach different conclusions regarding which set of products dominate. We studied this reaction using time-resolved multiplexed photoionization mass spectrometry to quantify the product branching fractions. Our results, supported by a detailed kinetic model, conclude that the glycoaldehyde product channel (arising mostly from syn-vinyl alcohol) dominates over formic acid production with a 3.6:1.0 branching ratio. Additionally, this result supports the conclusion of Lei et al. that conformer-dependent hydrogen bonding at the transition state for OH-addition controls the reaction outcome. As a result, tropospheric oxidation of vinyl alcohol creates less formic acid than recently thought, increasing again the discrepancy between models and field observations of Earth's formic acid budget.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Photocatalytic Nitrate Destruction Studies in Complex Environments

One method for denitration of nitric acid used in nuclear facilities is to use formic acid as a reductant. The major problem with formic acid denitration is an induction period of varying duration that may result in excessive accumulation of formic acid at the reaction onset. This accumulation poses an off-gas process control issue. In this talk, we will describe the use of titaniabased photocatalysts for the treatment of nitric acid and nitrate wastes. We find that the photocatalytic process is a simple and straightforward method to completely destroy nitrate ions at room temperature without any initiation period.

nanomaterials↗
DOE OSTI2019

Oxidation of Organics in the Defense Waste Processing Facility Condensate

Defense Waste Processing Facility (DWPF): The state of South Carolina currently holds 35 million gallons of radioactive waste in 51 underground tanks. DWPF was built in an effort to convert the waste into a more stable form. It turns the sludge waste from the tanks into glass, which will keep the waste stable for 10,000 years. Currently, DWPF uses formic acid in its flowsheet and there is one major problem associated with its use: it decomposes into hydrogen, a flammable gas. Glycolic acid, however, has been found as a possible alternative that performs similarly to formic acid but does not directly form hydrogen. One of the main issues with the glycolic acid flowsheet is the potential for there to be glycolate and other organics in DWPF's Recycle Collection Tank (RCT). These organics could lead to hydrogen generation later in the downstream evaporators and must be destroyed in the RCT in order for glycolic acid to be a suitable replacement for formic acid. Oxidants can be added to the RCT to destroy the organics. Two oxidizers, permanganate and Fenton's reagent (iron catalyzed hydrogen peroxide), are possible candidates. Find optimum processing conditions for the oxidation of organic species in a typical RCT simulant. A reactor served as a small-scale version of the RCT. During each run, an RCT simulant with 8 added organics, including glycolate, was created in the reactor. Either permanganate or peroxide was slowly added for each run through a syringe pump. Each experiment lasts 6 hours and a total of 23 runs are scheduled. Variables of Interest: Oxidizer (Permanganate or Peroxide); Temperature (15 deg. C to 50 deg. C); Oxidant addition time (10 mins to 2 hours); Amount of oxidant (1 x to 1.5 x stoichiometric requirements); Solution pH (3 to 13); Glycolate concentration (125 to 250 mg/kg). Offgas Analyzers: Mass spectrometer and FTIR spectrometer. Samples: pulled at 7 different times throughout the run to determine the amount of organic and inorganic carbon and concentrations of various organics through ion chromatography (IC). Only 3 of the runs have been completed at this point, all with permanganate. Based on the first 3 runs, permanganate seems to oxide the majority of the organics and the run at pH 8 and 32.5 deg. C had the most effective oxidation. The rest of the runs will need to be performed to determine the best oxidant and optimum values of the other variables of interest. Once the experiment is completed, DWPF will select one of the oxidants. Testing will continue to determine its performance during foam-over and other non-ideal conditions. Finally, the oxidant will be tested with actual radioactive waste to confirm its effectiveness.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2026

Understanding and Mitigating Stickiness in Biochar Produced through Acid Hydrolysis and Dehydration

Levulinic acid is a platform chemical with significant potential for conversion into a wide range of biobased chemicals and fuels. A common process for producing levulinic acid from lignocellulosic feedstocks involves acid hydrolysis and dehydration (AHDH), where hexose polymers are hydrolyzed into monomeric sugars and subsequently dehydrated to levulinic acid and formic acid in the presence of dilute sulfuric acid. However, scaling the AHDH process is challenging because of the formation of byproducts such as sticky biochar, which accumulates in continuous-flow reactors, reducing effective reaction volume and increasing process downtime. This study investigates the effect of a chemical preconditioning step on mitigating sticky biochar formation. Woody biomass was preconditioned at 170 °C with 0.26 wt % sulfuric acid for 30 min, resulting in substantial removal of hemicellulose and acid-soluble lignin. AHDH of these preconditioned solids produced biochar that did not adhere to reactor surfaces. TGA analysis confirmed that the chemical preconditioning step minimized interactions between hemicellulose-derived degradation products and lignin side chains, reducing sticky char formation. Additionally, the study observed a 6% higher yield of organic acids from softwood species compared to hardwoods, with bark content shown to negatively impact yield. These findings suggest that targeted preconditioning of lignocellulosic biomass can enhance reactor operability and improve organic acid production efficiency in AHDH processes.

biopolymers↗
DOE OSTI2018

Influence of humidity and iron(iii) on photodegradation of atmospheric secondary organic aerosol particles

The absorption of solar actinic radiation by atmospheric secondary organic aerosol (SOA) particles drives condensed-phase photochemical processes, which lead to particle mass loss by the production of CO, CO 2 , hydrocarbons, and various oxygenated volatile organic compounds (OVOCs). We examined the influence of relative humidity (RH) and Fe(III) content on the OVOC release and subsequent mass loss from secondary organic aerosol material (SOM) during UV irradiation. The samples were generated in a flow tube reactor from the oxidation of D-limonene by ozone. The SOM was collected with a Micro Orifice Uniform Deposit Impactor (MOUDI) on CaF 2 windows. To selected samples, a variable amount of FeCl 3 was added before irradiation. The resulting SOM samples, with or without added FeCl3, were irradiated with a 305 nm light-emitting diode and the release of several OVOCs, including acetic acid, acetone, formic acid and acetaldehyde, was measured with a Proton Transfer Reaction Time-of-Flight Mass Spectrometer (PTR-ToF-MS). The release of OVOCs from photodegradation of SOM at typical ambient mid-values of RH (30–70%) was 2–4 times higher than under dry conditions. The release of OVOCs was slightly enhanced in the presence of low concentrations of iron (0.04 Fe molar ratio) but it was suppressed at higher concentrations (0.50 Fe molar ratio) of iron indicating the existence of a complicated radical chemistry driving the photodegradation of SOM. Our findings suggest that the presence of iron in atmospheric aerosol particles will either increase or decrease release of OVOCs due to the photodegradation of SOM depending on whether the relative iron concentration is low or high, respectively. At atmospherically relevant RH conditions, the expected fractional mass loss induced by these photochemical processes from limonene SOA particles would be between 2 and 4% of particle mass per hour. Therefore, photodegradation is an important aging mechanism for this type of SOA.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Emerging concepts in intermediate carbon dioxide emplacement to support carbon dioxide removal

Substantial upscaling of carbon dioxide capture is possible in the coming decades but existing solutions for storage are projected to be limited in annual capacity by as much as 2–10 GtCO 2 per year until mid-century. Temporary storage of CO 2 in a solid or liquid state could prove useful for filling this gap in capacity, until more permanent and ideally lucrative CO 2 sequestration options come online. There are several concepts for reversible solid-state and chemical CO 2 storage, but their advantages and limitations have yet to be reviewed in this context. This article focuses on the physical and chemical aspects of CO 2 storage via liquid and solid chemical carriers and sorbents, and gives an overview of the energetics around their use, as well as prospects for their future development. Exciting opportunities for coupling capture and medium to high maturity multi-year storage technologies could support carbon removal in the coming decades. Highlights of the analysis are the remarkable storage capacity of oxalic acid and formic acid (CO 2 -density of 1857 kg m –3 and 1152 kg m –3 , compared with condensed liquid CO 2 at 993–1096 kg m –3 , respectively), the relative scalability and compatibility of carbonate salts for stationary storage with direct air capture, and the potential promise of multiple carriers for CO 2 transportation. Solid sorbents do not achieve such ultra-high storage capacities, but could improve storage over compressed gas tanks on a capacity and energetics basis.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Non-thermal atmospheric pressure plasma–liquid synthesis of organic acids in aqueous solution from carbon monoxide

This work aims at understanding the conversion of CO to organic acids, namely oxalic acid and formic acid, using non-thermal atmospheric pressure plasma over aqueous solutions. CO exhibited significantly higher conversion to organic acids (more than 15×) compared to CO 2 under the same reaction conditions. The result bolsters a proposed two-step process for CO 2 fixation, whereby CO 2 is first converted to CO, and then CO is converted to organic acids. The organic acids produced from CO are intermediates in the water–gas shift (WGS) reaction of CO in the presence of an aqueous solution to dissolved CO 2 and hydrogen gas. Based on a simple thermodynamic analysis, the organic acid yield was increased by lowering the plasma–liquid reaction temperature using an ice bath to cool the reaction flask. The composition of the organic acids could be varied by changing the pH of the solution. Oxalate was formed in higher concentrations with increasing solution pH above the pK a of the radical species (CO 2 )˙ − . Below the pK a value, formate was the exclusive organic acid formed. The production of formate has a rather weak pH dependence but is enhanced slightly at a basic pH above 10. Furthermore, at basic pH, the effect of electrolyte concentration comes into play. Higher electrolyte concentrations, leading to shorter electrolyte Debye lengths, resulted in lowered organic acid yields. The highest yields of organic acids obtained in our system were 122 mg L −1 for oxalate and 77 mg L −1 for formate at an optimum 1 mM NaOH concentration in the starting solution. This work is a successful pioneering example of CO to organic acids conversion using non-thermal plasmas, which opens the pathway for a promising two-step conversion process of CO 2 to organic acids.

Sudagar, Alcina Johnson [Washington University in ↗
DOE OSTI2014

Structure of the 2, 4′-dihydroxyacetophenone dioxygenase from Alcaligenes sp. 4HAP

The first X-ray structure of a 2, 4′-dihydroxyacetophenone dioxygenase from Alcaligenes sp. 4HAP at a resolution of 2.2 Å is reported. This structure establishes that the enzyme adopts the cupin-fold, forming compact dimers with a pronounced hydrophobic interface between the monomers. Each monomer possesses a catalytic ferrous iron that is coordinated by three histidines (76, 78 and 114) and an additional ligand which has been putatively assigned as a carbonate, although formate and acetate are possibilities. The enzyme 2, 4′-dihydroxyacetophenone dioxygenase (DAD) catalyses the conversion of 2, 4′-dihydroxyacetophenone to 4-hydroxybenzoic acid and formic acid with the incorporation of molecular oxygen. Whilst the vast majority of dioxygenases cleave within the aromatic ring of the substrate, DAD is very unusual in that it is involved in C—C bond cleavage in a substituent of the aromatic ring. There is evidence that the enzyme is a homotetramer of 20.3 kDa subunits, each containing nonhaem iron, and its sequence suggests that it belongs to the cupin family of dioxygenases. In this paper, the first X-ray structure of a DAD enzyme from the Gram-negative bacterium Alcaligenes sp. 4HAP is reported, at a resolution of 2.2 Å. The structure establishes that the enzyme adopts a cupin fold, forming dimers with a pronounced hydrophobic interface between the monomers. The catalytic iron is coordinated by three histidine residues (76, 78 and 114) within a buried active-site cavity. The iron also appears to be tightly coordinated by an additional ligand which was putatively assigned as a carbonate dianion since this fits the electron density optimally, although it might also be the product formate. The modelled carbonate is located in a position which is highly likely to be occupied by the α-hydroxyketone group of the bound substrate during catalysis. Modelling of a substrate molecule in this position indicates that it will interact with many conserved amino acids in the predominantly hydrophobic active-site pocket where it undergoes peroxide radical-mediated heterolysis.

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