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At least 667 records · Page 37

Final Project Report (Oct 2014-Dec 2017): Zeolite Membranes for Krypton/Xenon Separation from Spent Nuclear Fuel Reprocessing Off-Gas

The overall focus of this project is to develop and understand SAPO-34 zeolitic membranes that can separate mixtures of radioisotope krypton-85 and xenon released as off-gases during used nuclear fuel recycling. The primary advantage of separating 85 Kr from Xe is to reduce the volume of radioactive waste for storage. The second advantage is the revenue generated from the sale of high-purity Xe. Zeolite membranes are attractive because of their much lower energy requirements relative to cryogenic distillation, and their high resistance to radiation degradation. We report the detailed study of silicoaluminophosphate zeolite SAPO-34 materials and membranes for this application, due to hypothesized favorable molecular sieving properties. In the 3-year Mission Support project, we developed a novel, high-performance, low-energy intensity, lower-cost zeolite membrane process for Kr/Xe separation during SNF processing; and investigated the underlying molecular adsorption and transport processes in both ‘idealized’ and ‘realistic’ operating conditions to develop reliable synthesis-structure-property relationships for such membranes. Adsorption and diffusion measurements on SAPO-34 crystals indicate their potential for use in Kr-Xe separation membranes, but also highlight competing effects of adsorption and diffusion selectivity. SAPO-34 membranes synthesized on α-alumina substrates via steam-assisted conversion seeding and hydrothermal growth are characterized in detail, with Kr permeances 26 GPU and ideal Kr/Xe selectivities >20 at 298 K after thickness reduction. Post-synthesis cation exchange shows large (>50%) increases in selectivity at ambient or slight sub-ambient conditions. In addition, we confirm that SAPO-34 membrane is stable under radiation exposure and the impact of radiation exposure on membrane performance would not be substantial. We also successfully synthesized hollow-fiber SAPO-34 membranes with the same performance levels as the disk-type and tubular membranes. This important development will allow a very compact and low-cost Kr/Xe separation system. Finally, a detailed process calculation for techno-economic analysis was performed by integrating Maxwell-Stefan model into cross-flow membrane system, in order to estimate the required number of membrane stages and the total cost.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

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↗

Ultrasonic in-situ water-cut measurement using ultrasonic oil-water separation for affecting sound speed calibration

An apparatus and method for the separation of an oil-water mixture into its components are described. An acoustic radiation force moves oil droplets to the nodes of an acoustic standing wave generated in a vertical column containing the oil-water mixture. Once the droplets are sufficiently close together, attractive forces become dominant and the droplets may coalesce to form larger droplets, which have greater buoyancy, and separation of the mixture into a layer of oil and a layer of water occurs, not possible by simple gravitational separation. Acoustically-driven oil-water separation may be used for water-cut measurements in oil production wells, since separation of the oil from the water permits accurate sound speed measurements to be made for both the oil and the water, thereby allowing frequent in situ calibrations of the apparatus to determine whether sound speed measurements on the mixture are accurate in the event that one or both of the mixture constituents is changing.

02 PETROLEUM↗

Electrochemical cells with ionic sequestration provided by porous separators

Provided are electrochemical cells including separators permeable to some materials and impermeable to other materials in electrolytes. Also provide are methods of forming such separators. The selective permeability of a separator is achieved by its specific pore diameter and a narrow distribution of this diameter. Specifically, a species responsible for ion transport in an electrochemical cell are allowed to pass through the separator, while another species is blocked thereby preventing degradation of the cell. For example, a species containing lithium ions is allowed to pass in rechargeable cells, while one or more species containing transition metals are blocked. In some embodiments, a separator may include a membrane layer with at least 90% of pores of this having a diameter of between about 0.1 nanometers and 1.0 nanometer. The membrane layer may be a standalone layer or supported by a membrane support.

25 ENERGY STORAGE↗

Treatment of Magnesium-Thorium Alloy Used in Military Defence Equipment by Separation of Thorium and/or Thermal Oxidation - 17009

Magnesium-alloys doped with thorium (Th, 3% by weight and with a total activity content in the alloy of 120 Bq/g) to improve mechanical properties has been used in, among other applications, military equipment such as in the jet-engines in military aircraft. The material cannot, due to the presence of the radioactive Th, be handled as an ordinary scrap metal. It needs to be treated to render a more stable waste form prior to final disposal in which the amount of disposed metallic magnesium is limited due to the pyrophoric properties of such type of materials. By thermally treating the material it is possible to transform the alloy into oxide form (MgO and ThO{sub 2}) which is a much more stable form than metallic. This itself enables a form suitable for final disposal of the material. The oxidation step does however lead to an increase in volume and is therefore not an optimal treatment method. It is possible to treat the metal oxide powder in order to get a better volume reduction such as by super compaction but a better result can be obtained by separating the Th from the alloy, leaving a much smaller volume for final disposal. One way of separating the Th from the metal is by dissolution of metallic material in acid followed by directed precipitation of Th as Th-oxalate. Several parameters such as the choice of acid, metal concentration in the acid solution, pH prior to precipitation and amount of added oxalic acid have been investigated. Another method to separate Th from Mg is to perform a selective dissolution of MgO from an MgO/ThO{sub 2} mixture with HNO{sub 3} leaving only ThO{sub 2} as a residue. These tests had to be preceded with an oxidation of the alloy. The tests show that it is possible to separate Th from the metal alloy by either dissolution followed by precipitation or selective dissolution of MgO from an MgO/ThO{sub 2} mixture. This leads to very effective volume reduction of the waste. For the direct dissolution and precipitation tests typically > 95% of the magnesium can be found in the acid solution while 99.5 % of the Th is found as a solid in the filters. For the oxide dissolution tests typically 98% of the Th can be separated from the bulk material, leaving the acid solution possible to free release and dispose of in the same way as for the previous method. (authors)

36 MATERIALS SCIENCE↗

Separation of Actinides from Lanthanides in Molten Fluorides by the Modulated-Current Electrolysis

Recently, the Molten Salt Reactor (MSR) is taking a renewed attraction as one of the reactor systems highlighted by the Generation IV International Forum. It is a non-classical (liquid fuel) system which can be operated as a breeder within the {sup 232}Th-{sup 233}U fuel cycle with the very interesting breeding factor. The necessary precondition for its proper functionality is the online reprocessing within the MSR's fuel cycle. A lot of effort is given to the development of the on-line pyrochemical reprocessing technology. Among the processes considered to be suitable for this process, the electrochemical separations are highlighted. Within this context, it is necessary to study electrochemical behavior of both fissile material and fission products in the molten salt systems and to develop the processes of their extraction from the system at various stages of the whole cycle. In this contribution, the study of the electrochemical separation of U from Gd in the LiF-CaF{sub 2} molten system by the modulated current electrolysis is presented. The study of MSR-related electrochemistry will continue as a part of the new Czech MSR R and D program. The knowledge of the electrochemical behavior of actinides and lanthanides in molten fluorides is necessary to the development of any electrochemical separation process. In our previous work, electrochemical characteristics of uranium, thorium, as well as that of several lanthanides, were measured in LiF-BeF{sub 2} (the basic melt considered for the MSR concept) and Be-free melts (LiF-NaFKF, LiF-NaF, LiF-CaF{sub 2}), and added to available literature data. If the fluoride carrier melt is electrochemically stable enough, it is possible to deposit the element of interest in its basic, metallic state (e.g. uranium in all types of fluoride melts tested) by the electrolysis. In the case of insufficient electrochemical stability of the fluoride melt in which the actinides and lanthanides are dissolved for the experiments, it is possible to use a reactive working electrode made of a material which creates alloys with the element to be deposited. An alloying reaction can shift the deposition potential in a favorable direction and therefore achieve the separation of an element from the system. The use of reactive electrode can also improve the adhesion of the deposit. When two or more electroactive species are present in the system at the same time, the efficiency of their separation by an electrolysis depends on how different the deposition potentials of these two species are. If we input certain modulation to the electrolytic current, we can improve overall result of an electrolytic experiment.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Demating system for separating an electrical connector assembly

A demating device configured to demate an electrical connector assembly having a first connector and a second connector is provided. The demating device may include a first separating member, a second separating member, and a gripping assembly. Actuation of the first separating member and the second separating member towards one another drives the jaws of the gripping assembly together, therein allowing secure gripping of the electrical connector assembly via the demating device for separation of the first and second connectors.

Stoll, Trevor T.↗

Tailor-Made Microporous Metal–Organic Frameworks for the Full Separation of Propane from Propylene Through Selective Size Exclusion

Adsorptive separation of olefin/paraffin mixtures by porous solids can greatly reduce the energy consumption associated with the currently employed cryogenic distillation technique. Here, the complete separation of propane and propylene by a designer microporous metal–organic framework material is reported. The compound, Y 6 (OH) 8 (abtc) 3 (H 2 O) 6 (DMA) 2 (Y-abtc, abtc = 3,3',5,5'-azobenzene-tetracarboxylates; DMA = dimethylammonium), is rationally designed through topology-guided replacement of inorganic building units. Y-abtc is both thermally and hydrothermally robust, and possesses optimal pore window size for propane/propylene separation. It adsorbs propylene with fast kinetics under ambient temperature and pressure, but fully excludes propane, as a result of selective size exclusion. Multicomponent column breakthrough experiments confirm that polymer-grade propylene (99.5%) can be obtained by this process, demonstrating its true potential as an alternative sorbent for efficient separation of propane/propylene mixtures.

36 MATERIALS SCIENCE↗

Gas Separations using Nanoporous Atomically Thin Membranes: Recent Theoretical, Simulation, and Experimental Advances

Abstract Porous graphene and other atomically thin 2D materials are regarded as highly promising membrane materials for high‐performance gas separations due to their atomic thickness, large‐scale synthesizability, excellent mechanical strength, and chemical stability. When these atomically thin materials contain a high areal density of gas‐sieving nanoscale pores, they can exhibit both high gas permeances and high selectivities, which is beneficial for reducing the cost of gas‐separation processes. Here, recent modeling and experimental advances in nanoporous atomically thin membranes for gas separations is discussed. The major challenges involved, including controlling pore size distributions, scaling up the membrane area, and matching theory with experimental results, are also highlighted. Finally, important future directions are proposed for real gas‐separation applications of nanoporous atomically thin membranes.

2D materials↗

Cation exchange separation of radium and actinium using lactic acid DTPA buffer

The separation of actinium ( 228 Ac) from radium ( 223,228 Ra) on cation exchange resin with a diethylenetriaminpentaacetic acid-lactate buffer solution is demonstrated with series of columns. High yield, high radiopurity (~ 100%) separations of Ac from Ra are feasible with small columns in biologically compatible conditions and pHs. As Ac is eluted before Ra on these columns, further studies were performed to determine if this separation system could be applied to Ra/Ac isotope generators, but these were not successful. In conclusion, the separations presented in this work may be relevant for radiopharmaceutical purifications of 225 Ac which is typically obtained from its 225 Ra parent isotope.

and nuclear chemistry↗

Size-Selective Nanoporous Atomically Thin Graphene Separators for Lithium–Sulfur Batteries

Lithium–sulfur batteries (LSBs) are extensively researched for their high energy densities but are hindered by the lithium polysulfide (LiPS) shuttling effect, which results in poor cyclability. A popular mitigation strategy is separator modification, where a LiPS trapping material is slurry-coated onto a conventional microporous polypropylene (PP) separator. This additional mass and volume unfortunately compromise the overall energy density of the LSB. This study aims to take a separator modification approach that avoids this issue. Nanoporous atomically thin membranes (NATMs) made of graphene are gaining attention for their scalable synthesis, tunable pore size, and negligible pore length. Herein, we apply a well-characterized graphene NATM for reasons similar to those of a size-selective interlayer in LSBs. The tailored pore size of ∼0.7–1.0 nm and atomic thinness facilitate the passage of Li + (solvated ionic diameters ∼0.54–1.26 nm) and blockage of larger LiPS (solvated ionic diameters ∼0.81–1.69 nm) without adding significant impedances or mass. The sulfur confinement is confirmed through scanning electron microscopy and energy-dispersive X-ray spectroscopy elemental analysis of the Li anode. An LSB with a NATM@PP separator shows virtually no capacity loss over 150 cycles, demonstrating efficacy of size-selective molecular sieving using NATMs in LSBs.

battery separator↗

Thermoacoustic Soret separation

In a fluid mixture in a channel with an axial time-averaged temperature gradient, high-amplitude oscillating flow can greatly increase the axial flux of thermal diffusion (Soret) separation of the components of the mixture. The enhancement occurs when the oscillating lateral temperature gradient greatly exceeds the axial gradient, causing a large oscillating concentration that can be favorably time-phased with the oscillating flow. This process can occur even with a negligible pressure oscillation or with a negligible temperature response to pressure, as is the case in most liquid solutions. The thermal boundary condition imposed by realistic solids on thermoacoustic liquids is imperfect, adding mathematical complications that are absent for typical gases, for which the solid surface is temporally isothermal. Compared with gas mixtures, the high Lewis number in typical liquid solutions reduces the separation flux associated with the time-averaged temperature gradient, but it also reduces the remixing associated with the time-averaged mole-fraction gradient. For large enough channels, the second-law separation efficiency is only slightly reduced from that of steady liquid Soret separation.

36 MATERIALS SCIENCE↗

Bioprocessing Separations Consortium: Three-Year Overview - Technical Advances, Process Economics Influence, and State of the Science

The Bioprocessing Separations Consortium solves separations challenges that are unique to bioprocessing. To do this, the Consortium uses two methods: applying existing technologies to new challenges and developing new technologies that may address these unique challenges better than today’s commercial technologies. In its research and development, the Consortium leverages its three core capabilities: materials development and evaluation, process development, and analysis and computation. In its first three years, from 2016 to 2019, the Consortium addressed four critical challenges in biochemical and thermochemical processing. First, the Consortium targeted the fractionation of lignin to enable valorization of this portion of biomass that offers diverse, complex, and valuable building blocks and products. Second, Consortium researchers developed technologies to enable process intensification, which can reduce equipment needs, energy consumption, and waste generation, thereby cutting bioprocessing capital costs and rendering processes more efficient. Third, the Consortium sought to recover carbon from dilute aqueous streams that are common to bioprocessing; recovering dilute carbon can improve process efficiency and economics. Finally, Consortium researchers designed and developed new materials and catalysts to reduce targeted foulants and poisons in bioprocessing streams that can limit the lifetime of downstream catalysts or fermenting microorganisms. Table 1 lists the technologies that were examined and places them in the context of the Consortium’s capabilities, types of bioprocesses, and critical challenges in bioprocessing separations. Overall, across these projects, we have developed separations technologies for 10 bioprocesses, addressed 9 target compounds in bioprocessing, developed 10 materials, and evaluated 4 processes for cost and sustainability.

09 BIOMASS FUELS↗

Novel Polyimide Battery Separator Imbibed with Room-Temperature Ionic Liquids

The journey to Mars will require advancements in many existing technologies, including space power and energy storage systems. According to the 2015 NASA Technology Roadmaps, energy storage is a critical technology area to develop for both terrestrial as well as future long-term space missions. Currently, batteries represent one of the major areas in need of advancement, both in terms of energy density as well as safety. Recently, concerns regarding the fire safety of commercial lithium-ion batteries have prompted efforts to produce nonflammable battery components, namely the electrolyte and separator. Commercial lithium-ion batteries utilize polyolefin separators imbibed with a lithium salt dissolved in cyclic carbonates. This separator/electrolyte combination imparts good ionic conductivities in the range of 10(exp -2) to 10(exp -3) S/cm. However, the cyclic carbonates and polyolefin separator are inherently flammable. Room-temperature ionic liquids (RTILs) appear to be a safer alternative to cyclic carbonates. They offer good ionic conductivities, similar to those observed in cyclic carbonates, but are inherently nonvolatile and nonflammable giving them a safety advantage. Many promising RTILs for battery electrolytes are not compatible with commercial polyolefin separator materials. Polyimide aerogels possess an open-porous, fibrillar network architecture which offers a high degree of porosity (typically greater than 85 porous), required for lithium ion conduction, as well as good mechanical properties. Furthermore, these materials are compatible with all tested RTILs. By creating a polyimide gel and imbibing the gel with a RTIL containing a lithium salt instead of super critically drying them to form aerogels, a nonflammable separator/electrolyte system with conductivities in the range of 1x10(exp -3) S/cm has been demonstrated.

Polyimide↗

Preliminary Analysis of Separation Standards for Urban Air Mobility using Unmitigated Fast-Time Simulation

This research provides a preliminary analysis of various separation standards for Urban Air Mobility (UAM) operations. This study focuses on understanding and analyzing potential conflicts between UAM flights and conflicts between UAM and conventional aircraft. Fast-time simulations are conducted with a projected high-density of UAM traffic scenario and historical conventional non-UAM traffic flying under Instrument Flight Rules (IFR) or Visual Flight Rules (VFR) in Dallas Fort Worth (DFW) airspace. The conflicts are analyzed by examining losses of separation and near mid-air collisions of UAM flights and unmitigated risk of collision. A set of varied separation standards are used to investigate the impact of the new UAM operations on safety. The preliminary conflict analysis results will help inform separation standards development and in airspace and route design activities for future UAM operations.

Urban Air Mobility↗

Polymers with Side Chain Porosity for Ultrapermeable and Plasticization Resistant Materials for Gas Separations

Polymer membranes with ultrahigh CO 2 permeabilities and high selectivities are needed to address some of the critical separation challenges related to energy and the environment, especially in natural gas purification and postcombustion carbon capture. However, very few solution-processable, linear polymers are known today that access these types of characteristics, and all of the known structures achieve their separation performance through the design of rigid backbone chemistries that concomitantly increase chain stiffness and interchain spacing, thereby resulting in ultramicroporosity in solid-state chain-entangled films. Herein, the separation performance of a porous polymer obtained via ring-opening metathesis polymerization is reported, which possesses a flexible backbone with rigid, fluorinated side chains. This polymer exhibits ultrahigh CO 2 permeability (>21 000 Barrer) and exceptional plasticization resistance (CO 2 plasticization pressure > 51 bar). Compared to traditional polymers of intrinsic microporosity, the rate of physical aging is slower, especially for gases with small effective diameters (i.e., He, H 2 , and O 2 ). Overall, this structural design strategy, coupled with studies on fluorination, demonstrates a generalizable approach to create new polymers with flexible backbones and pore-forming side chains that have unexplored promise for small-molecule separations.

36 MATERIALS SCIENCE↗

Tailoring the Pore Size of a Polypropylene Separator with a Polymer Having Intrinsic Nanoporosity for Suppressing the Polysulfide Shuttle in Lithium–Sulfur Batteries

Lithium–sulfur (Li–S) batteries are being considered as one of the most promising candidates for the development of next-generation energy storage technologies. Although much progress has been made over the past decade, the development of Li–S batteries is still held back by a crucial polysulfide-shuttle problem. To address this critical issue, an approach to reduce the pore size of the separator is presented here, to prevent the penetration of soluble polysulfide species. A polymer with intrinsic nanoporosity (PIN) is developed within the micrometer-scale pores of a polypropylene separator. The framework of polypropylene acts as a skeleton to sustain reliable mechanical properties with the thin membrane. Upon the formation of PIN in the pores, the polypropylene separator maintains its thickness. With the thin PIN–polypropylene membrane, the Li–S cells can be operated with a relatively high sulfur loading. The PIN allows the transport of Li + ions, but suppresses the penetration of the polysulfide species. The Li–S batteries with the PIN-modified polypropylene separator exhibit enhanced cycling performance.

25 ENERGY STORAGE↗

Linker Vacancy Engineering of a Robust ftw–type Zr–MOF for Hexane Isomers Separation

Discrimination of physically similar molecules by porous solids represents an important yet challenging task in industrially relevant chemical separations. Precisely controlled pore dimension and/or tailored pore surface functionality are crucial to achieve high-efficiency separation. Metal-organic frameworks (MOFs) are promising candidates for these challenging separations in light of their structural diversity as well as highly adjustable pore dimension/functionality. We report here a microporous, ftw-type Zr-based MOF structure, HIAM-410 (HIAM=Hoffmann Institute of Advanced Materials), built on hexanuclear Zr 6 cluster and pyrene-1,3,6,8-tetracarboxylate (ptc 4– ). Its crystallographic structure has been determined using continuous rotation electron diffraction (cRED) technique combined with Rietveld refinement against powder X-ray diffraction data, aided by low-dose high-resolution transmission electron microscopy (HRTEM) imaging. The compound features exceptional framework stability that is comparable to the prototype MOF UiO-66. Interestingly, the linker vacancies in the pristine MOF structure could be partially restored by post-synthetic linker insertion. Its separation capability of hexane isomers is enhanced substantially upon the linker vacancy engineering. As a result, the restored structure exhibits efficient splitting of monobranched and dibranched hexane isomers at both room temperature and industrially relevant temperature.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗