Selective Separation of Cs and Sr from LiCl-Based Salt for Electrochemical Processing of Oxide Spent Nuclear Fuel

Abstract

Electrochemical processing technology is currently being used for the treatment of metallic spent fuel from the Experimental Breeder Reactor-II at Idaho National Laboratory. The treatment of oxide-based spent nuclear fuel via electrochemical processing is possible provided there is a front-end oxide reduction step. During this reduction process, certain fission products, including Cs and Sr, partition into the salt phase and form chlorides. Both solid state and molten LiCl-zeolite-A ion exchange tests were conducted for selectively removing Cs and Sr from LiCl-based salt. The solid-state tests produced in excess of 99% removal of Cs and Sr. The molten state tests failed due to phase transformation of the zeolite structure when in contact with the molten LiCl salt.     

The Possibility of Reprocessing of Spent Nuclear Fuel Using Supercritical Fluids

For the first time, the possibility of dissolution of spent nuclear fuel from a nuclear power plant in liquid and supercritical carbon dioxide was demonstrated. As shown by the example of spent nuclear fuel, the dissolution and the extraction of actinides and fission products by solutions of tributyl phosphate and nitric acid adducts TBP(HNO₃)_1.8 in carbon dioxide can be used as one of the stages of spent nuclear fuel reprocessing.     

Electrochemical reduction behavior of U3O8 powder in a LiCl molten salt

The reduction path of the U₃O₈ powder vol-oxidized at 1200 °C has been determined by a series of electrochemical experiments in a 1 wt.% Li₂O/LiCl molten salt. Various reaction intermediates are observed by during electrolysis of U₃O₈. The formation of the metallic uranium is caused from two different reduction paths, a direct reduction of uranium oxide and an electro-lithiothermic reduction. As the uranium oxide is converted to the metallic uranium, the lithium metal is more actively formed in the cathode basket. The reducibility of the rare earth oxides with the U₃O₈ powder has been tested by constant voltage electrolysis. The results suggest the advanced vol-oxidation could lead to the enhancement in the reducibility of the rare earth fission products.     

Catalytic Conversion of N2O to N2 over Metal-Based Catalysts in the Presence of Hydrocarbons and Oxygen

The catalytic conversion of N₂O to N₂ in the presence or the absence of propene and oxygen was studied. The catalysts examined in this work were synthesized impregnating metals (Rh, Ru, Pd, Co, Cu, Fe, In) on different supports (Al₂O₃, SiO₂, TiO₂, ZrO₂ and calcined hydrotalcite MgAl₂(OH)₈·H₂O). The experimental results varied both with the type of the active site and with the type of the support. Rh and Ru impregnated on -alumina exhibited the highest activity. The performance of the above most promising catalysts was studied using various hydrocarbons (CH₄, C₃H₆, C₃H₈) as reducing agents. These experimental results showed that the type of reducing agent does not affect the reaction yield. The temperature where complete conversion of N₂O to N₂ was measured was independent of the reductant type. The activity of the most active catalysts was also measured in the presence of SO₂ and H₂O in the feed. A shift of the N₂O conversion versus temperature curve to higher temperatures was observed when SO₂ and H₂O were added, separately or simultaneously, to the feed. The inhibition caused by SO₂ was attributed to the formation of sulfates and that caused by water to the competitive chemisorption of H₂O and N₂O on the same active sites.     

In situ high temperature and high pressure exafs studie of Pt/Al2O3 catalysts. Part I: Reduction and deactivation

EXAFS has been used to follow in situ the structural evolution of a chlorinated and non-chlorinated Pt/Al₂O₃ catalyst during reduction in the temperature range of 300–500 °C. Smaller metal clusters are formed from the hydrogen reduction of the chlorinated catalyst, in contrast to the larger cluster formed from the non-chlorinated one. At 460 °C, the total hydrogen pressure was raised to 5 atm. and n-heptane was injected over the samples. EXAFS measurements at the Pt edge were carried out while hydrocarbon conversion was monitored with a gas Chromatograph. We observe the rapid formation of a carbon-platinum bond. This is unmodified while turnover rates and selectivities indicate evidence for deactivation. From this structural information supplied by EXAFS, correlated with the data obtained from gas chromatography, we find that our results are consistent with a model proposed by others where deactivation is due to the build-up of a multilayer of carbon.     

Catalytic reduction of N2O by ethylbenzene over novel hydrotalcite-derived Mg–Cr–Fe–O as an alternative route for simultaneous N2O abatement and styrene production

New hydrotalcite-like materials containing magnesium, chromium, and/or iron were synthesized by the coprecipitation method and then thermally transformed into mixed metal oxides. The obtained catalysts were characterized with respect to chemical composition (XRF), structural (XRD, Mössbauer spectroscopy) and textural (BET) properties. The catalytic performance of the hydrotalcite-derived oxides was tested in the N₂O decomposition and the N₂O reduction by ethylbenzene. An influence of N₂O/ethylbenzene molar ratio on the process selectivity was studied. The relationship between catalytic performance and structure of catalysts was discussed.     

Application of a Supercritical CO2 Extraction Procedure to Recover Volatile Compounds and Polyphenols from Rosa damascena

Abstract

A supercritical CO₂ (Sc-CO₂) extraction procedure to recover volatile compounds and polyphenols from Rosa damascena is investigated. It consists of two steps: the first by Sc-CO₂ at 16 MPa and 313.15 K and on-line fractionation using two separators (S1: 7 MPa/ 298.15 K; S2: 5 MPa/ 288.15 K) for volatile compounds, the second by Sc-CO₂ added with 10% ethanol-water mixture (57% v/v) at 8 MPa and 313.15 K for polyphenols. Sc-CO₂ extract obtained in S2 resulted of high quality compared with essential oil. Polyphenol yield by SC-CO₂ added with co-solvent resulted about 80 % of methanol extraction (3250 mg GAE/100 g dw).     

Direct Selective Extraction of Actinides (III) from PUREX Raffinate using a Mixture of CyMe4BTBP and TODGA as 1-cycle SANEX Solvent Part III: Demonstration of a Laboratory-Scale Counter-Current Centrifugal Contactor Process

The direct selective separation of the trivalent actinides americium and curium from a simulated Plutonium Uranium Refining by EXtraction (PUREX) raffinate solution by a continuous counter-current solvent extraction process using miniature annular centrifugal contactors was demonstrated on a laboratory scale. In a 32-stage spiked test (12 stages for extraction, 16 stages for scrubbing, and 4 stages for Am/Cm stripping), an extractant mixture of CyMe₄BTBP and TODGA in a TPH/1-octanol mixture was used. The co-extraction of some fission and corrosion product elements, such as zirconium and molybdenum, was prevented by using oxalic acid. Co-extracted palladium was selectively stripped using an L-cysteine scrubbing solution and the trivalent actinides were selectively stripped using a glycolic acid-based stripping solution. It was demonstrated that a selective extraction and high recovery of > 99.4% of the trivalent minor actinides was achieved with low contamination by fission and corrosion products. The product contained 99.8% of the initial americium and 99.4% of the initial curium content. The spent solvent still contained high concentrations of Cu, Cd, and Ni. The experimental steady-state concentration profiles of important solutes were determined and compared with those from computer-code calculations.     

Effects of Addition of Na and S to Alumina Catalyst for the Selective Reduction of Nitrogen Monoxide with Ethene in Excess Oxygen

The addition of Na and S into alumina catalysts brought about a decrease in the catalytic activity for the reduction of NO with ethane in excess oxygen. Aluminas containing Na or S in different amounts were subjected to activity tests for the related reactions to elucidate the causes of the suppressive effects of the addition of Na and S on the reduction of NO. The reactions taken as test reactions were the oxidation of NO with oxygen, the reaction of NO₂ with ethene in the absence of oxygen, and the reaction of ethene with oxygen. The addition of Na suppressed the oxidation of NO, and the reaction of NO₂ with ethene to form N₂, but promoted the reaction of ethene with oxygen to a great extent. The addition of Na also caused the formation of NO in the reaction of NO₂ with ethene. The changes which the addition of Na brought about are all unfavorable directions for the reduction of NO. The most important effect of the addition of Na on the decrease in the reduction of NO is suggested to be due to the enhancement of the reaction of ethene with oxygen. The addition of S suppressed the oxidation of NO to a great extent, but did not affect much the reaction of ethene with oxygen. Like the case of the Na addition, the addition of S caused the formation of NO in the reaction of NO₂ with ethene.     

Competitiveness of CO2 capture from an industrial solid oxide fuel cell combined heat and power system in the early stage of market introduction

In this article, it was investigated whether potentially low-cost CO₂ capture from SOFC systems could enhance the penetration of SOFC in the energy market in a highly carbon-constrained society in the mid-term future (up to year 2025). The application of 5 MWe SOFC systems for industrial combined heat and power (CHP) generation was considered. For CO₂ capture, oxyfuel combustion of anode off-gas using commercially available technologies was selected. Gas turbine (GT-) CHP plant was considered to be the reference case.Technical results showed that despite the energy penalties due to CO₂ capture and compression, net electrical and heat efficiencies were nearly identical with or without CO₂ capture. This was due to higher heat recovery efficiency by separating SOFC off-gas streams for CO₂ capture. However, CO₂ capture significantly increased the required SOFC and heat exchanger areas.Economic results showed that for above 40-50 $ t⁻¹ CO₂ price, SOFC-CHP systems were more economical when equipped with CO₂ capture. CO₂ capture also enabled SOFC-CHP to compete with GT-CHP at higher cell stack production costs. At zero CO₂ price, cell stack production cost had to be as low as 140 kW⁻¹ for SOFC-CHP to outperform GT-CHP. At 100 $ t⁻¹ CO₂ price, the cell stack production cost requirement raised to 350 $ kW⁻¹. With CO₂ capture, SOFC-CHP still outperformed GT-CHP at a significantly higher cell stack production cost above 900 $ kW⁻¹.     

Fluxes of NO and N2O from temperate forest soils: impact of forest type, N deposition and of liming on the NO and N2O emissions

Annual cycles of NO, NO₂ and N₂O emission rates from soil were determined with high temporal resolution at a spruce (control and limed plot) and beech forest site (Höglwald) in Southern Germany (Bavaria) by use of fully automated measuring systems. The fully automated measuring system used for the determination of NO and NO₂ flux rates is described in detail. In addition, NO, NO₂ and N₂O emission rates from soils of different pine forest ecosystems of Northeastern Germany (Brandenburg) were determined during 2 measuring campaigns in 1995. Mean monthly NO and N₂O emission rates (July 1994–June 1995) of the untreated spruce plot at the Höglwald site were in the range of 20–130 µg NO-N m^-2 h^-1 and 3.5–16.4 µg N₂O-N m^-2 h^-1, respectively. Generally, NO emission exceeded N₂O emission. Liming of a spruce plot resulted in a reduction of NO emission rates (monthly means: 15–140 µg NO-N m^-2 h^-1) by 25-30% as compared to the control spruce plot. On the other hand, liming of a spruce plot significantly enhanced over the entire observation period N₂O emission rates (monthly means: 6.2–22.1 µg N₂O-N m^-2 h^-1). Contrary to the spruce stand, mean monthly N₂O emission rates from soil of the beech plot (range: 7.9–102 µg N₂O-N m^-2 h^-1) were generally significantly higher than NO emission rates (range: 6.1–47.0 µg NO-N m^-2 h^-1). Results obtained from measuring campaigns in three different pine forest ecosystems revealed mean N₂O emission rates between 6.0 and 53.0 µg N₂O-N m^-2 h^-1 and mean NO emission rates between 2.6 and 31.1 µg NO-N m^-2 h^-1. The NO and N₂O flux rates reported here for the different measuring sites are high compared to other reported fluxes from temperate forests. Ratios of NO/N₂O emission rates were >> 1 for the spruce control and limed plot of the Höglwald site and << 1 for the beech plot. The pine forest ecosystems showed ratios of NO/N₂O emission rates of 0.9 ± 0.4. These results indicate a strong differentiating impact of tree species on the ratio of NO to N₂O emitted from soil.     

The potential of di-methyl ether (DME) as an alternative fuel for compression-ignition engines: A review

This paper reviews the properties and application of di-methyl ether (DME) as a candidate fuel for compression-ignition engines. DME is produced by the conversion of various feedstock such as natural gas, coal, oil residues and bio-mass. To determine the technical feasibility of DME, the review compares its key properties with those of diesel fuel that are relevant to this application. DME’s diesel engine-compatible properties are its high cetane number and low auto-ignition temperature. In addition, its simple chemical structure and high oxygen content result in soot-free combustion in engines. Fuel injection of DME can be achieved through both conventional mechanical and current common-rail systems but requires slight modification of the standard system to prevent corrosion and overcome low lubricity. The spray characteristics of DME enable its application to compression-ignition engines despite some differences in its properties such as easier evaporation and lower density. Overall, the low particulate matter production of DME provides adequate justification for its consideration as a candidate fuel in compression-ignition engines. Recent research and development shows comparable output performance to a diesel fuel led engine but with lower particulate emissions. NO_x emissions from DME-fuelled engines can meet future regulations with high exhaust gas recirculation in combination with a lean NO_x trap. Although more development work has focused on medium or heavy-duty engines, this paper provides a comprehensive review of the technical feasibility of DME as a candidate fuel for environmentally-friendly compression-ignition engines independent of size or application.     

A review on the mechanical and electrical properties of graphite and modified graphite reinforced polymer composites

Carbon materials particularly in the form of sparkling diamonds have held mankind spellbound for centuries, and in its other forms, like coal and coke continue to serve mankind as a fuel material, like carbon black, carbon fibers, carbon nanofibers and carbon nanotubes meet requirements of reinforcing filler in several applications. All these various forms of carbon are possible because of the element's unique hybridization ability. Graphene (a single two-dimensional layer of carbon atoms bonded together in the hexagonal graphite lattice), the basic building block of graphite, is at the epicenter of present-day materials research because of its high values of Young's modulus, fracture strength, thermal conductivity, specific surface area and fascinating transport phenomena leading to its use in multifarious applications like energy storage materials, liquid crystal devices, mechanical resonators and polymer composites. In this review, we focus on graphite and describe its various modifications for use as modified fillers in polymer matrices for creating polymer-carbon nanocomposites.