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At least 757 records · Page 42

Amphiphilic Block Copolymers for Flocculation and Hydrophobization of Legacy Waste Suspensions in Flotation Driven Dewatering Operations - 20162

Flotation has been effectively demonstrated as a low footprint, high efficiency separation process when utilising simple anionic surface modifying agents such as sodium dodecyl sulphate (SDS). These agents increase hydrophobicity to remove suspended cationic surface charged particulates such as Mg(OH){sub 2} from waste suspensions similar to those at British nuclear fuel management sites- where corrosion processes have degraded fuel cladding. The technology is advantageous as it could effectively be retrofitted into existing waste management facilities at nuclear waste management sites such Sellafield and Hanford as the simplicity (no moving parts) and size of this technology coupled with low cost of construction could be rapidly deployed to aid in risk and hazard reduction decommissioning operations with minimum impact to secondary waste generation. Previously, sodium dodecyl sulphate has been deployed as a collector agent to increase the hydrophobicity of Mg(OH){sub 2} suspended particles, achieving a maximum particulate extraction percentage of 93%. To achieve further particulate extraction, flotation performance has been determined to be a function of the hydrodynamic limitations extracting fine material (>20 μm). Fine particulates have been shown in the minerals industry to have an inability to overcome slipstreams created from rising bubbles in flotation cells, likely due to the low mass and thus momentum of the colloidal material, preventing interaction between the hydrophobized particles and air-water interfaces (bubbles). To combat this mass transfer resistance poly(acrylic acid)-block-poly(n-butyl acrylate) amphiphilic diblock copolymers were synthesised via reversible addition-fragmentation chain-transfer (RAFT) polymerisation. The anticipated mode of action of these polymers involves the hydrophilic poly(acrylic acid) block polymer acting as a flocculation agent to increase the mass of the aggregates, and the hydrophobic poly(n-butyl acrylate) modifies the hydrophobicity of the resulting flocs. The concentration of this polymer (termed a macro-collector) was varied and the change in particle size distribution of the particulate suspension was analysed using static light scattering. The flotation performance was then characterised by several methods including percentage particulate recovery, volume reduction factor and residual bulk particulate concentration. This was then benchmarked against the traditional surfactant collector agent SDS. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

History of Ultrasonic Inspection of High-Level Waste Tanks at SRS - 20220

The Liquid Waste Disposition Projects (LWDP) Structural Authority and Inspection Engineering Support Group has teamed with the Materials Science and Technology Non-destructive Evaluation Group of Savannah River National Laboratory (SRNL) to implement a comprehensive In-Service Inspection (ISI) program for the High-Level Waste (HLW) tanks in the sites tank farms. The purpose of this program is to demonstrate the structural and leak integrity of the tanks to maintain the function of waste containment throughout the desired service life. Four types of waste tanks were constructed at Savannah River Site (SRS) from 1951 thru 1981 to store radioactive nuclear waste from the separations process. The Type I, II and III are carbon steel cylindrical tanks with varying degrees of access to the side walls and very limited access to the tank bottom. The tanks contain 750,000 to 1.3 million gallons of waste and are buried or backfilled with soil. The tanks are 75'-85' in diameter and 24'-33' from tank bottom to the tank roof. Inspection of the HLW tanks is made difficult by radiation, contamination, and small access openings. Through the years these challenges have been overcome by progressive improvements to programs and equipment resulting in the sophisticated wall crawler Ultrasonic Testing (UT) technology of today. A formal inspection program was developed and put in service in 1972. UT thickness measurements were first made in 1967 and 1969 of selected waste tanks using an analog-type instrument to measure the thickness of the carbon steel walls. Routine inspections for thinning were performed from 1972-1985 and then discontinued because no thinning had been observed and this technique could not detect pitting or cracking. UT inspections resumed in 1994 using a sophisticated robotic wall crawler with UT technology capable of detecting thinning, cracking and pitting. The current program focuses on the newer Type III tanks that are used primarily for storage. The program was upgraded in 2003 to include selected regions of the tank wall, secondary wall and annulus floor on a 7 to 10-year frequency. The facility is currently in its third cycle of tank inspections. Thus far, there have been no reportable indications of service induced degradation. This result provides assurance that the chemistry control program has been effective at mitigating corrosion and that the tanks remain structurally sound even after more than 40 years of service. This paper will present the UT technology first used at SRS and the evolution to the current systems and their capabilities. Additionally, plans for equipment upgrades that will improve the extent of inspection will be discussed. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Improvements to neutron detection of Pu in solvent for an aqueous buffer tank, magnox reprocessing plant, Sellafield - 14216

The PP Active Feed Tank (PPAFT) is a buffer tank that is not safe by geometry and which is located between the Medium Active (MA) and Plutonium Purification (PP) cycles of the chemical separation process in the Magnox Reprocessing Plant. The PPAFT receives Pu nitrate in acid which has been conditioned ready for the extraction of Pu with TBP/OK (tri-butyl phosphate in kerosene) solvent in the PP Cycle. The criticality safety case for the PPAFT recognises that during both normal operations and potential maloperations solvent which is dissolved (TBP which is present in solution but can be released upon a change in acidity) and entrained (TBP/OK physically carried over but not in solution) will accumulate in the PPAFT. The only practicable route out for Pu in solvent in the PPAFT is the normal process route out from the base of the PPAFT to the PP cycle through intermediate vacuum lift and feed vessels. However, the dished end base of the PPAFT and the intermediate vacuum lift and feed vessels are of particularly challenging geometry. There are five neutron monitors placed around the PPAFT for the detection of Pu in solvent. The original design intent of the neutron detection system was that any single monitor should be able to reveal an accumulation of Pu in solvent before it would potentially be unsafe if fed downstream. However, over time there have been changes to the fuel feed and chemical process of the plant which have had the potential to affect the performance of the neutron monitoring system. The ability of the neutron monitoring system to function to its original intent was questioned. Work has recently been carried out to investigate the capabilities of the PPAFT neutron monitoring system for current plant conditions and to identify potential improvements while making best use of the existing neutron monitors. It was found that moving a neutron monitor from the side to the top of the PPAFT and adding alarms based on the ratio of signals from multiple neutron detectors would be effective in improving detection of Pu in solvent. This paper describes the challenges involved in detecting thin layers of Pu in solvent using neutron monitors, discusses the improvements made to the PPAFT neutron monitors and details the combination of real plant data and modelling with the shielding code MCBEND used to provide confidence in the enhanced neutron monitoring system. (author)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Impacts of Neodymium Complexation on Radiolysis of Tetramethyl Diglycolamide (TMDGA) in Aqueous Solutions

Hydrophilic diglycolamides (DGA) ligands have been explored for use as stripping agents in various lanthanide and actinide partitioning processes.1 The separation of lanthanide fission products and transplutonic actinides can serve multifaceted advantages, in that the separation of neutron poisoning rare earth element (REE) fission products from the minor actinides in used nuclear fuel (UNF) can be mutually beneficial to the fundamental research behind REE separations and UNF separations. Considerable efforts have been devoted to understanding the radiation chemistry of hydrophilic DGAs. However, recent studies with lipophilic DGAs have shown that metal ion complexation can promote significant changes in their radiolytic susceptibility.2,3 These effects have been attributed to various parameters, including delocalization of electron density, the presence of radiolytically more susceptible counter ions, and steric hindrance. As such, it is pivotal for these complexation effects to be more thoroughly probed to establish mechanistic knowledge for their effects on hydrophilic DGA molecules. Here we present a time-resolved electron pulse and accumulated gamma dose irradiation study on neodymium ion complexes of tetramethyl diglycolamide (TMDGA) under aqueous solution conditions. References (1) Rostaing, C.; Poinssot, C.; Warin, D.; Baron, P.; Lorrain, B. Development and Validation of the EXAm Separation Process for Single Am Recycling. Procedia Chem. 2012, 7, 367–373. https://doi.org/doi: 10.1016/j.proche.2012.10.057. (2) Horne, G. P.; Conrad, J. K.; McLachlan, J. R.; Rotermund, B. M.; Cook, A. R.; Celis-Barros, C.; Mezyk, S. P. Impact of Lanthanide Complexation and Temperature on the Chemical Reactivity of N,N,N’,N’-Tetraoctyl Diglycolamide (TODGA) with the Dodecane Radical Cation. Phys. Chem. Chem. Phys. 2023, Under Review. (3) Kimberlin, A.; Saint-Louis, G.; Guillaumont, D.; Camès, B.; Guilbaud, P.; Berthon, L. Effect of Metal Complexation on Diglycolamide Radiolysis: A Comparison between Ex Situ Gamma and in Situ Alpha Irradiation. Phys. Chem. Chem. Phys. PCCP 2022, 24 (16), 9213–9228. https://doi.org/10.1039/d1cp05731f.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Air Classification of Forestry Residues for Fast Pyrolysis

Understanding critical biomass attributes through efficient fractionation is crucial for advancing sustainable pyrolysis for renewable energy and chemical production. This study investigates the intricate relationship between biomass preprocessing and pyrolysis product yields, employing the air classification technique for the treatment of loblolly pine residues with varying moisture content. A comprehensive exploration of the physicochemical properties of air-classified loblolly pine informs a sophisticated pyrolysis simulation model. Given the complex and multifaceted nature of biomass pyrolysis, operating across diverse temporal and spatial scales, a pyrolysis kinetics-based CFD–DEM simulation method is employed to predict product yields. Results showed that the elevated moisture content amplifies particle adhesiveness, necessitating augmented air velocities for effective separation, thereby influencing the efficiency of the separation process. While carbon and hydrogen contents exhibit relative stability across diverse moisture contents and blower frequencies, the oxygen content undergoes noticeable changes. For example, the oxygen contents were measured as 29.2 and 38.6 wt% in the light fraction of 30% moisture content sample at blower frequencies of 10 and 20 Hz, respectively. An intriguing finding emerges from pyrolysis simulation, indicating that a lower blower frequency in air classification moderately enhances bio-oil yield and significantly improves its quality, particularly in terms of water content. For instance, the water content in the bio-oil was about 1.5% and 10% in the heavy and light fractions, respectively from 10% moisture sample under 15 Hz blower frequency.

09 - BIOMASS FUELS↗

RAPID SEPARATION METHOD FOR 237NP AND PU ISOTOPES IN LARGE SOIL SAMPLES

A new rapid method for the determination of {sup 237}Np and Pu isotopes in soil and sediment samples has been developed at the Savannah River Site Environmental Lab (Aiken, SC, USA) that can be used for large soil samples. The new soil method utilizes an acid leaching method, iron/titanium hydroxide precipitation, a lanthanum fluoride soil matrix removal step, and a rapid column separation process with TEVA Resin. The large soil matrix is removed easily and rapidly using this two simple precipitations with high chemical recoveries and effective removal of interferences. Vacuum box technology and rapid flow rates are used to reduce analytical time.

54 ENVIRONMENTAL SCIENCES↗

Membrane Separations in Biomass Processing

The development of integrated biorefineries and the greater utilization of biomass resources to reduce dependence on fossil fuel-derived products require research emphasis not just on conversion strategies but also on improving separations associated with biorefining. A significant roadblock towards developing biorefineries is the lack of effective separation techniques evidenced by the relative deficiency of literature in this area. Additionally, high conversion yields may only be realized if effective separations generate feedstock of sufficient purity – this makes research into biomass conversion strategies all the more critical. In this review, the challenges associated with biomass separations are discussed, followed by an overview of the most appropriate separation strategies for processing biomass. One of the unit operations most appealing for biorefining, membrane separations (MS), is then considered along with a review of the recent literature utilizing this technique in biomass processing.

09 BIOMASS FUELS↗

A NEW PROCESS DEVELOPED FOR SEPARATION OF LIGNIN FROM AMMONIUM HYDROXIDE PRETREATMENT SOLUTIONS

A method is described for separating lignin from liquid solutions resulting from the pretreatment of lignocellulosic materials such as switchgrass with ammonium hydroxide. The method involves a sequence of steps including acidification, evaporation, and precipitation or centrifugation that are performed under defined conditions, and results in a relatively pure, solid lignin product. The method is tested on ammonium hydroxide solutions containing lignin extracted from switchgrass. Experimental results show that the method is capable of recovering between 66-95% of dissolved lignin as a precipitated solid. Cost estimates of pilot-scale and industrial-scale expressions of the process indicate that breakeven lignin prices of $2.36/kg and $0.78/kg, respectively, may be obtainable with this recovery method.

09 BIOMASS FUELS↗

Recent advances in SRS on hydrogen isotope separation using thermal cycling absorption process

TCAP (Thermal Cycling Absorption Process) is a gas chromatograph in principle using palladium in the column packing, but it is unique in the fact that the carrier gas, hydrogen, is being isotopically separated and the system is operated in a semi-continuous manner. TCAP units are used to purify tritium. The recent TCAP advances at Savannah River Site (SRS) include compressor-free concept for heating/cooling, push and pull separation using an active inverse column, and compact column design. The new developments allow significantly higher throughput and better reliability from 1/10 of the current production system's footprint while consuming 60% less energy. Various versions are derived in the meantime for external customers to be used in fusion energy projects.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Helium Degassing Filter for Mercury Process Gas Liquid Separator

Testing was conducted to find a suitable filter to help separate helium gas from the Spallation Neutron Source’s mercury process loop. This filter is proposed for installation on the gas-liquid separator (GLS) vent line to prevent a column of liquid mercury from flowing outside of the process loop shielding in the service bay. The filter’s desired properties are to prevent the passage of liquid mercury, provide minimal resistance to helium flow, resist radiation, operate for the lifetime of the target, be replaceable, and have a reliable construction. Testing concluded that the Mott Corporation POU-10-S series of filters provided the best performance available. The filters could stop most liquid mercury passage while allowing helium passage at nominal pressures above the GLS in standard conditions. This result has several implications for the design of the GLS vent system.

Weinmeister, Justin↗

In-situ anodic precipitation process for highly efficient separation of aluminum alloys

Electrorefining process has been widely used to separate and purify metals, but it is limited by deposition potential of the metal itself. Here we report in-situ anodic precipitation (IAP), a modified electrorefining process, to purify aluminium from contaminants that are more reactive. During IAP, the target metals that are more cathodic than aluminium are oxidized at the anode and forced to precipitate out in a low oxidation state. This strategy is fundamentally based on different solubilities of target metal chlorides in the NaAlCl4 molten salt rather than deposition potential of metals. The results suggest that IAP is able to efficiently and simply separate components of aluminum alloys with fast kinetics and high recovery yields, and it is also a valuable synthetic approach for metal chlorides in low oxidation states.

36 MATERIALS SCIENCE↗

Thin-film composite membrane and processes for the separation of alkenes from a gaseous feed mixture

This invention discloses an improved thin-film composite membrane and processes that use the membrane for the separation of gaseous mixtures that include an alkene. The membrane is particularly useful for separation of alkenes from alkanes or the separation of alkenes from other non-hydrocarbon gases. The membrane has a more mechanically durable and defect-free gas-separation layer that is fabricated from an ionomer solution that is substantially free of dissolved ionic species not associated with the ionomer and the mean helium permeability of the thin-film composite membrane is less than two times greater than the intrinsic helium permeability of the gas-separation layer.

36 MATERIALS SCIENCE↗

A new approach for drying moist air: The ideal Claridge-Culp-Liu dehumidification process with membrane separation, vacuum compression and sub-atmospheric condensation; Une nouvelle approche pour assécher l’air humide: Le procédé idéal de déshumidification Claridge-Culp-Liu avec séparation membranaire, compression sous vide et condensation sous-atmosphérique

The Claridge-Culp-Liu Dehumidification Process is a novel and efficient approach to removing water vapor from air using a combination of membrane separation, vacuum compression and sub-atmospheric condensation. The basic theory of this process is to separate water vapor from moist air flowing across one side of a membrane by applying a partial vacuum to the opposite side of the membrane and then compressing the water vapor to its saturation pressure at the wet-bulb temperature of the ambient air so as to facilitate condensation. We report this process has a fundamental efficiency limit that approximates the Carnot limit, but for eight different ideal dehumidification-only cases examined herein, the process requires only 26–56% the energy required by a Carnot vapor-compression system. Furthermore, the limiting energy required by an ideal 5-stage membrane system is 16–31% that of a Carnot system for the same cases. Of special importance, the ideal Claridge-Culp-Liu Dehumidification Process requires less than 5% of the energy required by an ideal desiccant process for all cases treated. The Claridge-Culp-Liu Dehumidification Process can also be combined with evaporative cooling to provide dehumidification and sensible cooling with the temperature and humidity controlled independently. Of special importance, this system uses no HFC refrigerants, and it generates pure water as a by-product.

42 ENGINEERING↗

Emerging Rare Earth Element Separation Technologies

Rare earth elements are essential for numerous clean energy applications, yet their mining, separation, and processing pose significant environmental challenges. Traditional separation processes often result in ecological damage, highlighting the critical need for innovative techniques that reduce environmental impacts. This article reviews recent advancements in rare earth separation technologies, with a particular focus on the role of neutral organic compounds. It explores how these compounds change selectivity across the rare earth series, offering promising strategies for designing more effective rare earth element separation systems. Furthermore, the article points out research areas requiring additional investigation to improve the sustainability of these critical processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Apparatus and process for the separation of gases using supersonic expansion and oblique wave compression

The disclosure provides an apparatus and method for gas separation through the supersonic expansion and subsequent deceleration of a gaseous stream. The gaseous constituent changes phase from the gaseous state by desublimation or condensation during the acceleration producing a collectible constituent, and an oblique shock diffuser decelerates the gaseous stream to a subsonic velocity while maintain the collectible constituent in the non-gaseous state. Following deceleration, the carrier gas and the collectible constituent at the subsonic velocity are separated by a separation means, such as a centrifugal, electrostatic, or impingement separator. In an embodiment, the gaseous stream issues from a combustion process and is comprised of N.sub.2 and CO.sub.2.

42 ENGINEERING↗

Minor actinide separation: simplification of the DIAMEX-SANEX strategy by means of novel SANEX processes

The separation of An(III) from PUREX raffinate has previously been demonstrated by applying a DIAMEX process (i.e., co-extraction of An(III) and Ln(III) from HAR) followed by a SANEX process (i.e., selective extraction of An(III) from the DIAMEX product containing An(III) + Ln(III)). In line with process intensification issues, more compact processes have been developed: Recently, a 1c-SANEX process test was successfully performed, directly extracting An(III) from PUREX HAR. More recently, a new i-SANEX process was successfully tested. This process is based on the co-extraction of An(III) + Ln(III) into a TODGA solvent, followed by a selective back-extraction of An(III) by a water soluble complexing agent, in this case SO{sub 3}-Ph-BTP. In both cases, good recoveries were achieved, and very pure product solutions were obtained. However, both 1c-SANEX and i-SANEX used non-CHON chemicals. Nevertheless, these processes are a simplification to the DIAMEX + SANEX process as only one solvent is used. Finally, the new i-SANEX process is the most compact process. (authors)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

A separations and purification process for improving yields and meeting fuel contaminant specifications for high-octane gasoline produced from dimethyl-ether over a Cu/BEA catalyst

In this work, we have been developing a three-step conversion of biomass-derived syngas to methanol to dimethyl-ether (DME) to non-aromatic hydrocarbons for use as high-octane gasoline and sustainable aviation fuel. This process produces branched alkanes from DME using a Cu/BEA catalyst and is a promising alternative to other syngas conversion processes such as Fischer-Tropsch to linear alkanes and traditional ZSM-5 catalyzed methanol to aromatic gasoline. In this short article we describe some advances in our understanding related to separations and purification via the use of more detailed experimental speciation in an updated process model involving multiple phase equilibrium-based separation steps. Primary modeled reactor outlet constituents (and weight %) are: C3 and lighter hydrocarbon gases (11.1%), C4s (54.5%), H 2 (1.2%), CO 2 (2.9%), water (5.0%), unreacted DME (16.5%), methanol (2.3%), and C5+ hydrocarbons (6.4%). DME (the primary reactant) and H 2 recycle and reuse are important for the overall process efficiency, and the recycle of C4s is important to increase the C5+ yield via reactivation and homologation. Thus H 2 , C4s, and DME are targeted for recycle, while methanol and water need to be removed from the product to conform with fuel specifications. Model predictions from Aspen Plus using the NRTL-RK property method indicate a fuel composition with C5+ content of 97.1 wt%, with minor constituents: 2.4 wt% C4s, 0.3 wt% methanol, 0.1 wt% DME, 0.03 wt% water, and 0.01 wt% C3s. These ranges of minor components conform with fuel quality requirements, and the modeled product is amenable for unconstrained blending to boost gasoline octane ratings.

09 BIOMASS FUELS↗