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At least 199 records · Page 11

Rapidly ramp cryogenic air separation unit without loss of O2 product purity—application for low-carbon fossil-fuel plants

The rapid integration of intermittent renewable sources into the electricity grid is driving the need for low-carbon, fossil-fuel power plant capable of rapid ramping. Therefore, a cryogenic air separation unit (ASU) as part of low-carbon, fossil-fuel power plant should be capable of rapid ramping. However, highly integrated and nonlinear processes of the ASU would significantly restrict this rapid ramping. To overcome this fundamental issue, we study the basic dynamic process of a state-of-the-art double-column ASU. A flow-driven dynamic model was established in Aspen Plus Dynamics, assuming perfect flow controls, to capture the basic dynamics of ramping ASU. We find the vapor-liquid counter-current flow structure in the low-pressure column is critical to the air separation when rapidly ramping the ASU. This flow structure is established based on a complicated heat integration process. It is simplified as an apparent counter-current heat transfer process in this work, which greatly reduces the complexity for studying the dynamics of ASU. For keeping this basic flow structure, the heat integration is maintained as its heat duty follows the ASU load, through several basic feed-forward and feed-back controllers on the critical stream flowrates. Moreover, we find a fundamental issue of mismatched dynamics in the low-pressure column, resulting in a significant loss of O2 product purity when rapidly ramping down the ASU and an obvious fluctuation of O2 product purity. Based on these explorations, we propose a basic control method for rapidly ramping the ASU without loss of O2 product purity. Results show the ASU basic dynamic process successfully ramps at a rate up to 10%/min (40-100% load) while maintaining the O2 product purity within 95.2-95.6 mol%.

Cheng, Mao↗

Group hexavalent actinide separation from lanthanides using sodium bismuthate chromatography

Advanced used nuclear fuel (UNF) reprocessing strategies are limited by the complex radiochemical separations and engineering required to achieve the separation of actinides (An) from neutron scavenging lanthanides (Ln). The accessibility of the hexavalent oxidation state for the actinides (U – Am) provides a pathway to achieving a group hexavalent actinide separation from the trivalent lanthanides and Cm. The solid oxidant and ion exchanger, sodium bismuthate (NaBiO 3 ), has been demonstrated to quantitatively oxidize and separate Am from trivalent Cm in a column chromatographic system. This work expands on the use of NaBiO 3 chromatography to characterize the adsorption, kinetic, and elution behavior of U, Pu, and Eu. Separation factors over 200 with rapid kinetics were observed at dilute nitric acid concentrations with a complete An/Ln separation achieved in under an hour. In conclusion, the adsorption and chromatographic behavior of key fission products present in various reprocessing raffinates was characterized which demonstrated potential application of a NaBiO 3 -based separation following a TRUEX process.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

The autocorrelation function of the North Pole dust

The angular scales on which local interstellar dust is distributed are so far rather unknown as are the geometrical shapes of the dust features. From the about 5000 color excesses resulting from a north polar survey with 4 to 5 stars per square degree the two-point autocorrelation function is derived for separations ranging from 10 min to 3 deg. For intercloud lines of sight, -0.020 is less than E(b - y) is less than -0.010 mag, the average cross products (E sub 1 x E sub 2)(sub theta) show no variation with separation theta(1,2) whereas products of cloud column densities, 0.030 is less than E(b - y) is less than 0.040 mag, seem to prefer discrete separations either less than 20 min, around 75 min, or finally at about 150 min. Surprisingly the two point autocorrelation function omega(sub E) = E(sub 1) x E(sub 2)/E squared - 1 equals 0 except for any separation except theta = 0. Omega(sub E)(theta)'s absence of variation is unexpected because omega(sub H)(theta) is known to vary exponentially above b = 40 deg for separations less than 3 deg. Atomic hydrogen and dust may thus not be entirely mixed or the moments (E sub 1 x E sub 2)(sub theta) may not characterize the dust distribution.

Knude, Jens↗

Neural-network dedicated processor for solving competitive assignment problems

A neural-network processor for solving first-order competitive assignment problems consists of a matrix of N x M processing units, each of which corresponds to the pairing of a first number of elements of (R sub i) with a second number of elements (C sub j), wherein limits of the first number are programmed in row control superneurons, and limits of the second number are programmed in column superneurons as MIN and MAX values. The cost (weight) W sub ij of the pairings is programmed separately into each PU. For each row and column of PU's, a dedicated constraint superneuron insures that the number of active neurons within the associated row or column fall within a specified range. Annealing is provided by gradually increasing the PU gain for each row and column or increasing positive feedback to each PU, the latter being effective to increase hysteresis of each PU or by combining both of these techniques.

Eberhardt, Silvio P.↗

Streamlining and Simplifying the Chemical Separationof Berkelium (249Bk) from Other Actinides/Lanthanides andFission Products

Abstract Separation of an individual heavy actinide from other actinides, lanthanides, and coproduced fission products is challenging not only because of their similarity in chemistry but also because the chemistry of heavy actinides is largely unknown. At present, the cation-exchange chromatography with α-hydroxyisobutyric acid (CX-AHIB) method is used to isolate milli- to picogram quantities of heavy actinides (i.e., 249Bk, 252Cf, 254Es, and 257Fm). This method allows simultaneous separation of these actinides; however, isolating a clean individual product with a high yield has proven challenging. The process is also very slow and labor-intensive and requires precise control of various chemical conditions, such as pH, temperature, and AHIB concentration. Developing a separation scheme for heavy actinides requires identifying their unique feature and then harnessing this feature in the separation process design. The unique characteristic of Bk4+ is that it does not adsorb onto anion exchange resin columns, unlike other tetravalent actinides. This article discusses what makes Bk unique and how this discovery led to a new method for separating Bk from adjacent actinides, lanthanides, and coproduced fission products. The method employed two different resin columns in tandem to separate unwanted actinides from 249Bk, followed by fine cleanup of 249Bk. The advantages of the new Bk method over the CX-AHIB method in Bk production are discussed, and the performance and robustness of the proposed method were assessed in two recent production campaigns.

Chemistry↗

Simultaneous Separation of Protactinium-230 and Uranium-230 Isotopes from a Proton-Irradiated Thorium Matrix

The use of radioisotopes in cancer therapy is becoming increasingly important. As a potential candidate for targeted alpha therapy, 230 U (t 1/2 = 20.8 d), the decay daughter of 230 Pa (t 1/2 = 17.4 d) is currently being investigated for cancer treatment. For radioisotopes to be used in biomedicine, they must be radiochemically pure and free from carrier interference. This can be challenging given their short half-life. Thus, in this study, radiological separation methods for harvesting isotopes for use in biomedicine must be simple, fast, and capable of obtaining the required purity levels. Herein, we demonstrate a new rapid method for the separation of 230 U and 230 Pa from a proton-irradiated 232 Th metal target and from coproduced fission products with high recovery and purity. A dual-column approach was used, in which the first column was an anion exchange (AX) column and the second column was a DGA column. The MP-1 AX resin was used for the primary separation of the three major components (U, Pa, and Th, as well as fission products), and the DGA column was used for further purification of the separated 230 U. The method is simple and allows for straightforward separation of U, Pa, Th, and fission products; also, the entire process from target dissolution to shipment of 230 U could be completed in 3 days with an overall 230 U recovery yield of 96 ± 3%. Additionally, separated 230 Pa fractions can be used to harvest ingrown 230 U after initial separation.

DGA resin↗

An optimization approach for cryogenic distillation-based protium removal systems in magnetic fusion energy fuel cycles

Tritium inventory reduction for fusion power plants is central to the successful adoption of fusion energy. The advent of direct internal recycling in deuterium-tritium fusion fuel cycle design has led to significant reduction in startup tritium inventory estimates for fusion power plants but requires an isotope rebalancing and protium removal (IRPR) system to ensure acceptable isotopic fuel composition. Cryogenic distillation is a potential solution for near-term deployment in an IRPR system due to its demonstrated performance in similar operating regimes. Using protium removal in the fuel cycle as the primary performance metric, this paper presents an optimization methodology for a single-column continuous cryogenic distillation-based IRPR system for a 500 MW fus magnetic fusion device. Distillation column optimization was performed using the CryOgenic Distillation For Isotopic Separation of Hydrogen (CODFISH) code developed at Savannah River National Laboratory. The distillation column design presented maximizes direct recycling of hydrogen isotopes from the fusion chamber exhaust to the fueling system while minimizing IRPR system steady-state tritium inventory. The optimized IRPR distillation column presented achieves direct recycling of 60 % of the hydrogen isotopes in the fusion chamber exhaust with an estimated steady-state system tritium inventory <30 g. In conclusion, the optimized IRPR distillation column operation was then used to estimate the design requirements for a detritation column to treat the IRPR system effluent stream.

CryOgenic distillation↗

Doubly Interpenetrated Metal-Organic Framework of pcu Topology for Selective Separation of Propylene from Propane

We report that adsorptive separation is an appealing alternative technology to reduce the high energy and capital cost of the distillation separation of propylene/propane; however, it is very challenging to realize. A new flexible metal-organic framework (MOF) material [Zn 2 (BDC-Cl) 2 (Py 2 TTz)] with a doubly interpenetrated pillared paddle wheel structure of pcu (primitive cubic) topology has been realized for this difficult separation for the first time. Through a judicious choice of linkers, the framework has small pore apertures that lead to much more propylene adsorption than propane. The selective adsorption relies on the sieving effect of the flexible framework. The column breakthrough experiment further demonstrated that efficient separation can be achieved under dynamic conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

On-Chip Microfluidic Components for In Situ Analysis, Separation, and Detection of Amino Acids

The Astrobiology Analytical Laboratory at GSFC has identified amino acids in meteorites and returned cometary samples by using liquid chromatography-electrospray ionization time-of-flight mass spectrometry (LCMS). These organic species are key markers for life, having the property of chirality that can be used to distinguish biological from non-biological amino acids. One of the critical components in the benchtop instrument is liquid chromatography (LC) analytical column. The commercial LC analytical column is an over- 250-mm-long and 4.6-mm-diameter stainless steel tube filled with functionized microbeads as stationary phase to separate the molecular species based on their chemistry. Miniaturization of this technique for spaceflight is compelling for future payloads for landed missions targeting astrobiology objectives. A commercial liquid chromatography analytical column consists of an inert cylindrical tube filled with a stationary phase, i.e., microbeads, that has been functionalized with a targeted chemistry. When analyte is sent through the column by a pressurized carrier fluid (typically a methanol/ water mixture), compounds are separated in time due to differences in chemical interactions with the stationary phase. Different species of analyte molecules will interact more strongly with the column chemistry, and will therefore take longer to traverse the column. In this way, the column will separate molecular species based on their chemistry. A lab-on-chip liquid analysis tool was developed. The microfluidic analytical column is capable of chromatographically separating biologically relevant classes of molecules based on their chemistry. For this analytical column, fabrication, low leak rate, and stationary phase incorporation of a serpentine microchannel were demonstrated that mimic the dimensions of a commercial LC column within a 5 10 1 mm chip. The microchannel in the chip has a 75- micrometer-diameter oval-shaped cross section. The serpentine microchannel has four different lengths: 40, 60, 80, and 100 mm. Functionized microbeads were filled inside the microchannel to separate molecular species based on their chemistry.

Zheng, Yun↗

In-situ polymerized PLOT columns III: divinylbenzene copolymers and dimethacrylate homopolymers

Studies of divinylbenzene copolymers and dimethacrylate homopolymers indicate that the polymer pore size controls the separation of water and ammonia on porous-layer-open-tubular (PLOT) columns. To a lesser degree, the polarity of the polymers also affects the separation of a water-ammonia gas mixture. Our results demonstrate that the pore size can be regulated by controlling the cross-linking density or the chain length between the cross-linking functional groups. An optimum pore size will provide the best separation of water and ammonia.

NASA Discipline Exobiology↗

Extraction of radium and actinium with dibenzo-21-crown-7 resin and Rose Bengal

The extraction of 224 Ra and 228 Ac with dibenzo-21-crown-7 resin was studied in solutions with Rose Bengal and identical solutions without Rose Bengal (blanks) from pH 3 to 12. Batch studies demonstrated that actinium is extracted at high pH (> 10) from both solutions but with a significantly higher extraction from the Rose Bengal solutions (maximum extraction ~ 60,000) than the blank solutions (maximum extraction ~ 2,000). In the Rose Bengal solutions, there was a weak extraction of actinium at lower pH (4–10) as well. There was no uptake of radium from the blank solutions, and a weak extraction at all pH levels from the Rose Bengal solutions. Kinetics studies were performed for actinium only, as radium had no significant extraction. Two column studies are demonstrated for the separation of radium from actinium. These separations are moderately effective with ~ 78% of the actinium recovered with no detectable radium.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

An Automated Ultraclean Ion Exchange Separation Method for the Determinations of 232Th and 238U in Copper using Inductively Coupled Plasma Mass Spectrometry

This work presents a novel automated analytical method developed for high throughput ultrasensitive determinations of Th and U in copper using inductively coupled plasma mass spectrometry (ICP-MS). The method is based on the use of ultra clean sample preparation procedures including the use of a fully automated off-line chromatography system for the extraction and pre-concentration of the analytes prior to ICP-MS analysis. The separation system is equipped with a single reusable chromatographic column that, with the rigorously clean procedures developed herein, provided a low carryover, low background, and reproducible automated separation method. Isotope dilution methods were used for quantitation. Method Detection Limits (MDLs) of 3.7 and 9.4 fg·g-1 were obtained for the quantitation of 232Th and 238U in copper, respectively, corresponding to activities of 0.0148 and 0.116 microBq·kg-1 for 232Th and 238U, respectively. The analytical method provided high and reproducible tracer recoveries. The use of an automated system significantly reduced the extremely tedious active work time required for the chemist (by ca. 80%) relative to manually performing the separation. This method could be adapted to other critical sample matrices requiring the utmost in high throughput clean chemistry procedures for automated ultrasensitive analyses.

Arnquist, Isaac J.↗

Buffer Effects in the Solubility, Nucleation and Growth of Chicken Egg White Lysozyme

The growth of protein crystals is important for determination of their three-dimensional structure, which relates to their biochemical functions and to the practical goal of designing pharmaceuticals to modify that function. While many proteins have been successfully crystallized by a variety of methods, there is still limited understanding of the process of nucleation and growth of even the simplest proteins. Chicken egg-white lysozyme (CEWL) is readily crystallized under a variety of conditions, and studies underway at MSFC are designed to elucidate the mechanisms by which the crystals nucleate and grow. We have investigated the effect of buffer choice on the solubility, nucleation and growth of CEWL. CEWL was purified by dialysis against a .05M phosphate buffer and chromatographic separation from contaminants in a sepharose column. Solubility studies were made as a function of buffer concentration for phosphate and formate buffers, and the nucleation and growth of crystals at 10 C was studied as a function of pH for oxalate, succinate, formate, butyrate, carbonate, phosphate and acetate buffer solutions. The solubility data support the conclusion that there is a solubility minimum as a function of buffer concentration for amphiphilic molecules, while no minimum is observed for a phosphate buffer. Nucleation is suppressed at pH greater than pKa for all buffers except phosphate. The aspect ratio of the (110) faces is shown to be a function of crystal size, rather than pH.

Gibson, Ursula J.↗

Compound Specific Hydrogen Isotope Composition of Type II and III Kerogen Extracted by Pyrolysis-GC-MS-IRMS

The use of Hydrogen (H) isotopes in understanding oil and gas resource plays is in its infancy. Described here is a technique for H isotope analysis of organic compounds pyrolyzed from oil and gas shale-derived kerogen. Application of this technique will progress our understanding. This work complements that of Pernia et al. (2013, this meeting) by providing a novel method for the H isotope analysis of specific compounds in the characterization of kerogen extracted by analytically diverse techniques. Hydrogen isotope analyses were carried out entirely "on-line" utilizing a CDS 5000 Pyroprobe connected to a Thermo Trace GC Ultra interfaced with a Thermo MAT 253 IRMS. Also, a split of GC-separated products was sent to a DSQ II quadrupole MS to make semi-quantitative compositional measurements of the extracted compounds. Kerogen samples from five different basins (type II and III) were dehydrated (heated to 80 C overnight in vacuum) and analyzed for their H isotope compositions by Pyrolysis-GC-MS-TC-IRMS. This technique takes pyrolysis products separated via GC and reacts them in a high temperature conversion furnace (1450 C) which quantitatively forms H2, following a modified method of Burgoyne and Hayes, (1998, Anal. Chem., 70, 5136-5141). Samples ranging from approximately 0.5 to 1.0mg in size, were pyrolyzed at 800 C for 30s. Compounds were separated on a Poraplot Q GC column. Hydrogen isotope data from all kerogen samples typically show enrichment in D from low to high molecular weight compounds. Water (H2O) average deltaD = -215.2 (V-SMOW), ranging from -271.8 for the Marcellus Shale to -51.9 for the Polish Shale. Higher molecular weight compounds like toluene (C7H8) have an average deltaD of -89.7 0/00, ranging from -156.0 for the Barnett Shale to -50.0 for the Monterey Shale. We interpret these data as representative of potential H isotope exchange between hydrocarbons and sediment pore water during formation within each basin. Since hydrocarbon H isotopes readily exchange with water, these data may provide some useful information on gas-water or oil-water interaction in resource plays, and further as a possible indicator of paleo-environmental conditions. Alternatively, our data may be an indication of H isotope exchange with water and/or acid during the kerogen isolation process. Either of these interpretations will prove useful when deciphering H isotope data derived from kerogen analysis. More experiments are planned to discern these two or other possible scenarios.

Socki, Richard A.↗

Hydrogen (H) Isotope Composition of Type II Kerogen Extracted by Pyrolysis-GC-MS-IRMS: Terrestrial Shale Deposits as Martian Analogs

Described here is a technique for H isotope analysis of organic compounds pyrolyzed from kerogens isolated from gas‐ and liquids‐rich shales. Application of this technique will progress the understanding of the use of H isotopes not only in potential kerogen occurrences on Mars, but also in terrestrial oil and gas resource plays. H isotope extraction and analyses were carried out utilizing a CDS 5000 Pyroprobe connected to a Thermo Trace GC interfaced with a Thermo MAT 253 IRMS. Also, a split of GC‐separated products was sent to a DSQ II quadrupole MS to make qualitative and semi‐quantitative compositional measurements of these products. Kerogen samples from five different basins (type II and II‐S) were dehydrated (heated to 80 C overnight under vacuum) and analyzed for their H isotope compositions by Pyrolysis‐GC‐MS‐TC‐IRMS. This technique takes pyrolysis products separated via GC and reacts them in a high temperature conversion furnace (1450 C), which quantitatively forms H2. Samples ranging from ~0.5 to 1.0mg in size, were pyrolyzed at 800 C for 30s. and separated on a Poraplot Q GC column. H isotope data from all kerogen samples typically show enrichment in D from low to high molecular weight. H2O average delta D = ‐215.2 per mille (V‐SMOW), ranging from ‐ 271.8 per mille for the Marcellus Shale to ‐51.9 per mille for a Polish shale. Higher molecular weight compounds like toluene (C7H8) have an average delta D of ‐89.7 per mille, ranging from ‐156.0 per mille for the Barnett Shale to ‐50.0 per mille for the Monterey Shale. We interpret these data as representative of potential H isotope exchange between hydrocarbons and sediment pore water during basin formation. Since hydrocarbon H isotopes readily exchange with water, these data may provide some useful information on gas‐water or oil‐water interaction in resource plays, and further as a possible indicator of paleoenvironmental conditions. Alternatively, our data may be an indication of H isotope exchange with water and/or acid during the kerogen isolation process. Either of these interpretations will prove useful when deciphering H isotope data derived from kerogen analyses. Understanding the role that these H‐bearing compounds play in terrestrial shale paleo‐environmental reconstruction may also prove useful as analogs for understanding the interactions of water and potential kerogen/organic compounds on the planet Mars.

Socki, Richard A.↗

From ash to oxides: Recovery of rare-earth elements as a step towards valorization of coal fly ash waste

Coal fly ash (CFA) is both a valuable waste material and a potential source of environmental contamination. The inclusion of metals such as rare-earth elements offer a possible incentive towards waste valorization if the metals can be extracted and recovered in an economical manner. Rare-earth elements (REEs) have many technological applications and are critically important in the manufacture of electric vehicles, communication devices, and industrial magnets. However, the global supply of rare-earth elements has faced shortages and price shocks. Current methods for separating and isolating individual rare-earth elements use large amounts of energy and organic solvents, raising concerns over environmental impacts. These factors have led to the investigation of nontraditional sources and separation techniques for these elements. Here, we describe a column-based system that uses a newly developed ligand-associated organosilica sorbent to concentrate and separate rare-earth elements from fly ash leachate. The fly ash used in this study originally contained 0.024 wt% rare-earth elements and the final oxide powder after enrichment contained > 10 wt% rare-earth elements, which is a enrichment of > 400 times. This process requires no additional organic solvents after the sorbent media has been synthesized, offering an alternative to the current standard using solvent extraction for rare-earth element recovery.

42 ENGINEERING↗

Compact automated apparatus for rapid astatine recovery from nitric acid media: Design, application, and impurity characterization

We report automation of irradiated bismuth target dissolution and astatine recovery from nitric acid media has been achieved at Texas A&M University. This process can be controlled remotely; it does not require any chemical treatment or evaporation of dissolution solution prior to the separation of above-mentioned elements on an extraction chromatography column, making the final product ready within 20 min. The accompanying radio-impurities have been identified and successfully separated from astatine, leading to greater than 99% radiopurity of the desired fractions. The system consists of only one pump and a set of LabVIEW controlled valves, and allows the connection of up to 10 different columns, providing the opportunity to prepare a variety of air dry columns, which can be different column geometries, containing astatine ready for further chemistry or shipment to desired facilities.

42 ENGINEERING↗

Methods for separating components

Method for concentrating components through a distillation column are disclosed. A process stream is provided containing hydrocarbons, carbon dioxide, and water. The process stream is passed into the distillation column at a bottom portion of the distillation column. The process stream is fractionally distilled in the distillation column, forming an overhead vapor stream, a middle fluid stream, and a bottoms liquid stream. The middle fluid stream is removed from a middle location of the distillation column. The bottoms liquid stream is removed from the distillation column. The overhead vapor stream is removed from the distillation column. The middle fluid stream consists of a first portion of the carbon dioxide and a first portion of the hydrocarbons. The bottoms liquid stream consists of a second portion of the hydrocarbons as a first phase and substantially all the water as a second phase.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗