Engineering topics

DePaoli, David W.

Publications and source records attributed to DePaoli, David W..

14 records

DOE OSTI2021

Measuring Neptunium Concentration using Optical Spectrometry for the Pu-238 Supply Program

Targets containing 237 Np are irradiated at the High Flux Isotope Reactor at Oak Ridge National Laboratory to produce 238 Pu, as plutonium dioxide (PuO 2 ), a heat source material for use in future NASA space missions. Kilogram quantities of Np are processed yearly and developing methods to efficiently characterize and monitor the Np processing streams with optical spectroscopy and real-time monitoring software is a critical aspect of this effort. Here, we evaluate how ultraviolet/visible/near-infrared (UV-Vis-NIR) absorbance and Raman spectroscopic techniques are applicable to characterizing concentrated Np solutions and provide proof-of-principle and proof-of-concept results for each technique. Both techniques were tested in lab-scale studies and should improve the timeliness of production efforts. However, spectrophotometry is the more mature option and has been successfully demonstrated in a hot cell environment. An overview of the initial findings, a brief demonstration, and areas for future work will be highlighted in this report.

07 ISOTOPE AND RADIATION SOURCES↗

DOE OSTI2021

Lipophilic diglycolamide compounds for extraction of rare earth metals from aqueous solutions

A method for extracting rare earth metals (e.g., lanthanides and/or actinides) from aqueous solution, the method comprising: (i) acidifying an aqueous solution containing said rare earth metals with sulfuric acid to result in an acidified aqueous solution containing 1-12 M concentration of sulfuric acid; and (ii) contacting the acidified aqueous solution with an aqueous-insoluble hydrophobic solution comprising a rare earth extractant molecule dissolved in an aqueous-insoluble hydrophobic solvent to result in extraction of one or more of the rare earth metals into the aqueous hydrophobic solution, wherein the rare earth extractant molecule has the following structure: wherein R1, R2, R3, and R4 are independently selected from hydrocarbon groups containing 1-20 carbon atoms, provided that the total carbon atoms in R1, R2, R3, and R4 is at least 12; and R5 and R6 are independently selected from hydrogen atom and hydrocarbon groups containing 1-3 carbon atoms.

Brigham, Derek↗

DOE OSTI2017

The ultimate mineral processing challenge: Recovery of rare earths, phosphorus and uranium from Florida phosphatic clay

We report phosphate beneficiation in Florida generates more than one tonne of phosphatic clay, or slime, per tonne of phosphate rock produced. Since the start of the practice of large-scale washing and desliming for phosphate beneficiation, more than 2 Gt of slime has accumulated, containing approximately 600 Mt of phosphate rock, 600 kt of rare earth elements (REEs) and 80 million kilograms of uranium. The recovery of these valuable elements from the phosphatic clay is one of the most challenging endeavors in mineral processing, because the clay is extremely dilute, with an average solids concentration of 3 percent, and fine in size, with more than 50 percent having particle size smaller than 2 μm, and it contains nearly 50 percent clay minerals as well as large amounts of magnesium, iron and aluminum. With industry support and under funding from the Critical Materials Institute, the Florida Industrial and Phosphate Research Institute in conjunction with the Oak Ridge National Laboratory undertook the task to recover phosphorus, rare earths and uranium from Florida phosphatic clay. This paper presents the results from the preliminary testing of two approaches. The first approach involves three-stage cycloning using cyclones with diameters of 12.4 cm (5 in.), 5.08 cm (2 in.) and 2.54 cm (1 in.), respectively, to remove clay minerals followed by flotation and leaching. The second approach is a two-step leaching process. In the first step, selective leaching was conducted to remove magnesium, thus allowing the production of phosphoric acid suitable for the manufacture of diammonium phosphate (DAP) in the second leaching step. The results showed that multistage cycloning with small cyclones is necessary to remove clay minerals. Finally, selective leaching at about pH 3.2 using sulfuric acid was found to be effective for removing more than 80 percent of magnesium from the feed with minimal loss of phosphorus.

36 MATERIALS SCIENCE↗

DOE OSTI2017

Rare earths recovery and gypsum upgrade from Florida phosphogypsum

Phosphogypsum is a byproduct created during the production of industrial wet-process phosphoric acid. This study focused on recovering rare earth elements (REEs) from a Florida phosphogypsum sample and investigated the effects of removing detrimental impurities such as phosphorus pentoxide (P 2 O 5 ), uranium (U) and fluorine (F) during the leaching process. Experimental results indicated that REE leaching efficiency increased rapidly, reached a maximum and then began to decrease with sulfuric acid concentrations ranging from 0 to 10 percent and temperatures ranging from 20 to 70 °C. At a sulfuric acid concentration of 5 percent and leaching temperature of 50 °C, REE leaching efficiency obtained a maximum value of approximately 43 percent. Increasing the leaching time or liquid/solid ratio increased the leaching efficiency. The leaching efficiencies of P 2 O 5 , U and F consistently increased with sulfuric acid concentration, temperature, leaching time and liquid/solid ratio within the testing ranges. A fine-grain gypsum concentrate, sized smaller than 40 μm, was separated from leached phosphogypsum through elutriation, in which the P 2 O 5 , U and F content levels were reduced by 99, 70 and 83 percent, respectively, from their content levels in fresh phosphogypsum.

58 GEOSCIENCES↗

DOE OSTI2017

Status Summary of Chemical Processing Development in Plutonium-238 Supply Program

This document summarizes the status of development of chemical processing in the Plutonium-238 Supply Program (PSP) near the end of Demonstration 1. The objective of the PSP is “to develop, demonstrate, and document a production process that meets program objectives and to prepare for its operation” (Frazier et al. 2016).

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2017

Electric-Field-Oriented Growth of Long Hair-Like Silica Microfibrils and Derived Functional Monolithic Solids

We present a “bottom-up” fabrication approach to first grow a new class of inorganic (silica) long hair-like microfibers or microwires and then to form monolithic solid pellet that contains parallel arrays of bundled microfibers with a controlled orientation. During the sol-gel solution processing, reactive precursor species are utilized as molecular “building blocks” for the field-directed assembly growth of microfibers driven by an electric field of pulsed direct current (dc) with controlled frequency. In principle, this reactive electrofibrilation process that combines an external field with a solid-phase nucleation and growth process has no limitation on reactions (such as the one here that involves sol-gel reaction chemistry) and on materials compositions (such as the example silica oxide), thus will enable bulk production of long microfibers of wide variety of inorganic materials (other oxides or metals). Furthermore, we have fabricated uniquely architectured monolithic solid materials containing aligned microfibers by “wet press” of the in-situ grown microfiber structure in the electric field. The consolidated monolithic slabs (1 cm x 1 cm x 3 mm) have shown anisotropic properties and desirable retention of DNA molecule fragments, thus, could serve as a platform stationary-phase materials for future development of capillary electrochromatography for biomolecule separations.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

DOE OSTI2017

Aging Processes of Silver Mordenite and Silver Functionalized Aerogel in Dry Air, Humid Air and NO/N{sub 2}

One major problem in the treatment of nuclear-fuel reprocessing off-gas streams is the loss of capacity of the adsorbents exposed to off-gas streams containing air, I{sub 2} vapor, H{sub 2}O vapor, NO and NO{sub 2} over extended periods of time. These aging processes decrease the adsorption capacity of the reduced silver exchanged mordenite (Ag{sup 0}Z) and silver functionalized silica aerogel (Ag{sup 0}-aerogel) columns during the long processing time of iodine adsorption. Significant work has been performed over the past few years at ORNL on Ag{sup 0}Z and Ag{sup 0}-aerogel aging. The Ag{sup 0}Z and Ag{sup 0}-aerogel were aged in 4 different gas streams at 150 deg. C for periods of time up to 6 months. The aging samples were then loaded with I{sub 2} to determine the capacity loss after the aging. The results are summaries in Tab. 1. It was found that both Ag{sup 0}Z and Ag{sup 0}-aerogel had different amounts of capacity loss in different gases. For example, 40% and 22% capacity loss were observed for Ag{sup 0}Z and Ag{sup 0}-aerogel when aged in dry air for 6 months, while 78% and 43% capacity loss were observed when aged in 1% NO{sub 1} for 2 months. In addition, it was found that Ag{sup 0}Z and Ag{sup 0}-aerogel had a different capacity loss when aged at the same conditions. For example, after aged in 2% NO{sub 2} for 2 months, Ag{sup 0}Z lost 30% iodine capacity, but there was no capacity loss for Ag{sup 0}- aerogel. The differences in capacity loss should be due to different aging processes occurred when Ag{sup 0}Z and Ag{sup 0}- aerogel were exposed to different gases. The mechanisms of the aging processes have not been determined and need to be studied with proper chemical and physical characterization methods. Towards this objective, experimental work is proposed and on-going to obtain data to determine the mechanisms of the aging processes of Ag{sup 0}Z and Ag{sup 0}-aerogel in different aging gas streams. In addition, models will be developed to describe the deactivation process of the adsorbents when exposed to off gases. The deactivation model will be included in the transport models for predicting the adsorption processes over these long-time periods.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2016

Adsorption of iodine on hydrogen-reduced silver-exchanged mordenite: Experiments and modeling

The adsorption process of iodine, a major volatile radionuclide in the off-gas streams of spent nuclear fuel reprocessing, on hydrogen-reduced silver-exchanged mordenite (Ag 0 Z) was studied at the micro-scale. The gas-solid mass transfer and reaction involved in the adsorption process were investigated and evaluated with appropriate models. Optimal conditions for reducing the silver-exchanged mordenite (AgZ) in a hydrogen stream were determined. Kinetic and equilibrium data of iodine adsorption on Ag 0 Z were obtained by performing single-layer adsorption experiments with experimental systems of high precision at 373–473 K over various iodine concentrations. Results indicate approximately 91% to 97% of the iodine adsorption was through the silver-iodine reaction. The effect of temperature on the iodine loading capacity of Ag 0 Z was discussed. In conclusion, the Shrinking Core model describes the data well, and the primary rate controlling mechanisms were macro-pore diffusion and silver-iodine reaction. © 2016 American Institute of Chemical Engineers AIChE J, 2016

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

DOE OSTI2016

Co-adsorption of I{sub 2} and H{sub 2}O on Ag{sup 0}Z and Kinetics of Iodine Silver Reaction

Co-adsorption of iodine and water by reduced silver-exchanged mordenite (Ag{sup 0}Z) is studied to support the development of multi-component adsorption models for the separation and recovery of radio isotopic gases in off-gas streams in nuclear fuel reprocessing. Single-component adsorption equilibrium data of iodine and water were obtained to determine the saturation capacity and evaluate the parameters of the generalized statistical thermodynamic adsorption (GSTA) model being developed for modeling of co-adsorption. Co-adsorption data acquisition is in progress for model validation. Kinetic data were obtained to determine the intra-particle mass transfer and reaction parameters for the adsorption models. In addition, work is in progress to obtain data of the iodine-silver reaction at various conditions to study the reaction kinetics, which will provide insight to the chemisorption process of iodine on Ag{sup 0}Z. (authors)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2015

Foreword [Introductory Remarks - Special Issue on Eighteenth Symposium on Separation Science and Technology for Energy Applications]

This issue contains papers from the Eighteenth Symposium on Separation Science and Technology for Energy Applications, held in Oak Ridge, Tennessee on October 27-30, 2014. Symposia in this series are aimed at bringing together practitioners in diverse fields related to separations to exchange knowledge, both within and among their specialties, on topics related to energy production and conservation. Meetings are typically scheduled every two years and attract over 100 international participants.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

DOE OSTI2015

Dissolution and Separation of Aluminum and Aluminosilicates

The selection of an aluminum alloy for target irradiation affects post-irradiation target dissolution and separations. Recent tests with aluminum alloy 6061 yielded greater than expected precipitation in the dissolver, forming up to 10 wt.% solids of aluminum hydroxides and aluminosilicates. Aluminosilicate dissolution presents challenges in a number of different areas, metals extraction from minerals, flyash treatment, and separations from aluminum alloys. We present experimental work that attempts to maximize dissolution of aluminum metal, along with silicon, magnesium, and copper impurities, through control of temperature, the rate of reagent addition, and incubation time. Aluminum phase transformations have been identified as a function of time and temperature, using X-ray diffraction. Solutions have been analyzed using wet chemical methods and X-ray fluorescence. Our data have been compared with published calculations of aluminum phase diagrams. Approaches are given to enhance the dissolution of aluminum and aluminosilicate phases in caustic solution.

36 MATERIALS SCIENCE↗

DOE OSTI2015

Hydroxylamine Nitrate Decomposition under Non-radiological Conditions

Hydroxylamine nitrate (HAN) is used to reduce Pu(IV) to Pu(III) in the separation of plutonium from uranium. HAN becomes unstable under certain conditions and has been known to explode, causing injury to humans including death. Hence, it is necessary to deactivate HAN once the reduction of plutonium is finished. This report reviews what is known about the chemistry of HAN and various methods to achieve a safe decomposition. However, there are areas where more information is needed to make a decision about the handling of HAN in reprocessing of nuclear fuel. Experiments have demonstrated a number of non-radiolytic ways to safely decompose HAN, including heating in HNO 3 , photolytic oxidation in the presence of H 2 O 2 , and the addition of a metal such as Fe(III) that will oxidize the HAN.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

DOE OSTI2015

Isotherms for Water Adsorption on Molecular Sieve 3A: Influence of Cation Composition

This study is part of our continuing efforts to address engineering issues related to the removal of tritiated water from off-gases produced in used nuclear fuel reprocessing facilities. In the current study, adsorption equilibrium of water on molecular sieve 3A beads was investigated. Adsorption isotherms for water on the UOP molecular sieve 3A were measured by a continuous-flow adsorption system at 298, 313, 333, and 353 K. Experimental data collected were analyzed by the Generalized Statistical Thermodynamic Adsorption (GSTA) isotherm model. The K + /Na + molar ratio of this particular type of molecular sieve 3A was ~4:6. Our results showed that the GSTA isotherm model worked very well to describe the equilibrium behavior of water adsorption on molecular sieve 3A. The optimum number of parameters for the current experimental data was determined to be a set of four equilibrium parameters. This result suggests that the adsorbent crystals contain four energetically distinct adsorption sites. In addition, it was found that water adsorption on molecular sieve 3A follows a three-stage adsorption process. This three-stage adsorption process confirmed different water adsorption sites in molecular sieve crystals. In addition, the second adsorption stage is significantly affected by the K + /Na + molar ratio. In this stage, the equilibrium adsorption capacity at a given water vapor pressure increases as the K + /Na + molar ratio increases.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2015

Generalized gas-solid adsorption modeling: Single-component equilibria

Over the last several decades, modeling of gas–solid adsorption at equilibrium has generally been accomplished through the use of isotherms such as the Freundlich, Langmuir, Tóth, and other similar models. While these models are relatively easy to adapt for describing experimental data, their simplicity limits their generality to be used with many different sets of data. This limitation forces engineers and scientists to test each different model in order to evaluate which one can best describe their data. Additionally, the parameters of these models all have a different physical interpretation, which may have an effect on how they can be further extended into kinetic, thermodynamic, and/or mass transfer models for engineering applications. Therefore, it is paramount to adopt not only a more general isotherm model, but also a concise methodology to reliably optimize for and obtain the parameters of that model. A model of particular interest is the Generalized Statistical Thermodynamic Adsorption (GSTA) isotherm. The GSTA isotherm has enormous flexibility, which could potentially be used to describe a variety of different adsorption systems, but utilizing this model can be fairly difficult due to that flexibility. To circumvent this complication, a comprehensive methodology and computer code has been developed that can perform a full equilibrium analysis of adsorption data for any gas-solid system using the GSTA model. The code has been developed in C/C++ and utilizes a Levenberg–Marquardt’s algorithm to handle the non-linear optimization of the model parameters. Since the GSTA model has an adjustable number of parameters, the code iteratively goes through all number of plausible parameters for each data set and then returns the best solution based on a set of scrutiny criteria. Data sets at different temperatures are analyzed serially and then linear correlations with temperature are made for the parameters of the model. The end result is a full set of optimal GSTA parameters, both dimensional and non-dimensional, as well as the corresponding thermodynamic parameters necessary to predict the behavior of the system at temperatures for which data were not available. It will be shown that this code, utilizing the GSTA model, was able to describe a wide variety of gas-solid adsorption systems at equilibrium.In addition, a physical interpretation of these results will be provided, as well as an alternate derivation of the GSTA model, which intends to reaffirm the physical meaning.

97 MATHEMATICS AND COMPUTING↗