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At least 505 records · Page 28

Advanced one-pot deconstruction and valorization of lignocellulosic biomass into triacetic acid lactone using Rhodosporidium toruloides

Abstract Background Rhodosporidium toruloides is capable of co-utilization of complex carbon sources and robust growth from lignocellulosic hydrolysates. This oleaginous yeast is therefore an attractive host for heterologous production of valuable bioproducts at high titers from low-cost, deconstructed biomass in an economically and environmentally sustainable manner. Here we demonstrate this by engineering R. toruloides to produce the polyketide triacetic acid lactone (TAL) directly from unfiltered hydrolysate deconstructed from biomass with minimal unit process operations. Results Introduction of the 2-pyrone synthase gene into R. toruloides enabled the organism to produce 2.4 g/L TAL from simple media or 2.0 g/L from hydrolysate produced from sorghum biomass. Both of these titers are on par with titers from other better-studied microbial hosts after they had been heavily engineered. We next demonstrate that filtered hydrolysates produced from ensiled sorghum are superior to those derived from dried sorghum for TAL production, likely due to the substantial organic acids produced during ensiling. We also demonstrate that the organic acids found in ensiled biomass can be used for direct synthesis of ionic liquids within the biomass pretreatment process, enabling consolidation of unit operations of in-situ ionic liquid synthesis, pretreatment, saccharification, and fermentation into a one-pot, separations-free process. Finally, we demonstrate this consolidation in a 2 L bioreactor using unfiltered hydrolysate, producing 3.9 g/L TAL. Conclusion Many steps involved in deconstructing biomass into fermentable substrate can be combined into a distinct operation, and directly fed to cultures of engineered R. toruloides cultures for subsequent valorization into gram per liter titers of TAL in a cost-effective manner.

59 BASIC BIOLOGICAL SCIENCES↗

Eliminating Impurity Traps in the Silane Process

Redistribution reaction section of silane process progressively separates heavier parts of chlorosilane feedstock until light silane product is available for pyrolysis. Small amount of liquid containing impurities is withdrawn from processing stages in which trapping occurs and passed to earlier processing stage in which impurities tend to be removed via chemical reactions.

Coleman, L. M.↗

Efficient light harvesting and photon sensing via engineered cooperative effects

Abstract Efficient devices for light harvesting and photon sensing are fundamental building blocks of basic energy science and many essential technologies. Recent efforts have turned to biomimicry to design the next generation of light-capturing devices, partially fueled by an appreciation of the fantastic efficiency of the initial stages of natural photosynthetic systems at capturing photons. In such systems extended excitonic states are thought to play a fundamental functional role, inducing cooperative coherent effects, such as superabsorption of light and supertransfer of photoexcitations. Inspired by this observation, we design an artificial light-harvesting and photodetection device that maximally harnesses cooperative effects to enhance efficiency. The design relies on separating absorption and transfer processes (energetically and spatially) in order to overcome the fundamental obstacle to exploiting cooperative effects to enhance light capture: the enhanced emission processes that accompany superabsorption. This engineered separation of processes greatly improves the efficiency and the scalability of the system.

42 ENGINEERING↗

Failure analysis of solid oxide fuel cells nickel-yttria stabilized zirconia anode under siloxane contamination

In this study, the failure process of the solid oxide fuel cell (SOFC) Ni-yttria-stabilized zirconia (YSZ) anode is investigated with D4 siloxane (octamethylcyclotetrasiloxane) contamination. In order to evaluate the influence of the electrochemical reaction on the siloxane deposition process, the SOFC experiments were operated at open circuit voltage (OCV) and 50 mA cm -2 conditions at 800°C. During the failure process, electrochemical, morphology and exhaust gas component analysis testing are conducted at the critical points. An equivalent circuit model and corresponding microstructure parameter calculations for separated physicochemical processes were utilized for the quantitative analysis of the failure process. Further, the results confirm the siloxane chemical adsorption deposition mechanism proposed in previous work. As a result, the failure of the anode was attributed to the gas diffusion blockage by dense silicon dioxide layer formation. The anode failure process with siloxane contamination is faster when the anode is operated under polarization.

25 ENERGY STORAGE↗

Magnetic Separator Enhances Treatment Possibilities

Since the earliest missions in space, NASA specialists have performed experiments in low gravity. Protein crystal growth, cell and tissue cultures, and separation technologies such as electrophoresis and magnetophoresis have been studied on Apollo 14, Apollo 16, STS-107, and many other missions. Electrophoresis and magnetophoresis, respectively, are processes that separate substances based on the electrical charge and magnetic field of a molecule or particle. Electrophoresis has been studied on over a dozen space shuttle flights, leading to developments in electrokinetics, which analyzes the effects of electric fields on mass transport (atoms, molecules, and particles) in fluids. Further studies in microgravity will continue to improve these techniques, which researchers use to extract cells for various medical treatments and research.

Source record↗

Isotopic composition and concentration of sulfur in carbonaceous chondrites

New sulfur isotopic ratio measurements are reported for seven carbonaceous chondrites. Newly developed procedures permit measurement of delta S-33, delta S-34, and delta S-36 at precisions significantly greater than previously reported. A search for S-36 nucleosynthetic anomalies coproduced with anomalies in, for example, Ti-50 and Ca-48 was negative. The high endemic sulfur concentration probably dilutes any S-36 anomaly, and separation of individual sulfur phases may be needed to identify S-36 carrier phases. Large internal isotopic variations are observed, deriving from parent body and possibly nebular processes. Chondrule separates from Allende demonstrate isotopic compositions which vary as a function of diameter. High-temperature gas-solid exchange and a two-component mixing model may account for the observations. High-resolution isotopic data and structural information are reported for organic sulfur compounds separated by chemical extractions. The insoluble organics appear to be of either aliphatic or alicyclic structure and are dominant phases.

Gao, Xia↗

A New Approach to Monitoring Solvent Extraction Processes for the Nuclear Industry

As part of an initiative to steward research, development, and innovation into the nuclear fuel cycle, Idaho National Laboratory is building the Beartooth testbed. Beartooth will include a cascade of centrifugal contactors, glove box lines, solidification, and dissolution equipment to aid in the progression of novel separation techniques and provide hands-on opportunities to early-career separation scientists. Beartooth will incorporate novel monitoring techniques using sensors and machine learning algorithms to inform a process operator of separation conditions. This research is examining monitoring technologies not typically used in nuclear separation processes such as acoustic microphones, accelerometers, infrared cameras, red-green-blue color sensors, among others. These sensors are being examined for their functionality within a separation process and their ability to detect applicable signals. Machine learning methods are being developed to determine their utility in detecting faults and alerting operators of expected and unexpected events. These methods have the potential to impact Safeguards by Design efforts and real-time decision making. This overview will detail preliminary results from acoustic, vibration, and color sensors.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

When SLIPS meets TIPS: An endogenous lubricant-infused surface by taking the diluent as the lubricant

Slippery lubricant-infused porous surfaces (SLIPSs) hold great promise in fields requiring adhesion resistance such as self-cleaning, anti-fouling, anti-icing, and anti-scaling. However, their road to practical application is still blocked by the complicated fabrication process and the restricted coating area. To address these challenges, we propose a new concept of endogenous SLIPS in which the porous structure grows from the solution coating of polypropylene/caprylyl methicone undergoing a thermally induced phase separation (TIPS) process. Caprylyl methicone serves as the diluent during TIPS as well as the lubricant in the SLIPS so that the coating can be fabricated in one step and unrestrictedly. Furthermore, the dissolution and phase separation mechanisms have been revealed by molecular dynamic simulation and in situ microscopic observation. Such SLIPSs exhibits impressive sliding property even for sticky and viscous liquids and exhibit extremely low ice adhesion in anti-icing tests.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hydroxypyridinone-based stabilization of Np(IV) enabling efficient U/Np/Pu separations in the Adapted PUREX process

The classical process to recover uranium (U) and plutonium (Pu) from used nuclear fuel using tributyl phosphate (TBP), namely the Plutonium Uranium Redox EXtraction (PUREX) process, is complicated by the persistent presence of neptunium (Np) and thus requires extra purification steps. The concept of Adapted PUREX seeks to achieve Np recovery by adjusting the valence of the metal more effectively, thereby controlling its behavior more precisely. This study introduces the use of an aqueous hydroxypyridinone chelator, 3,4,3-LI(1,2-HOPO) (abbreviated as HOPO), to dictate the behavior of Np for recovery and meanwhile simplify cumbersome reprocessing steps. The interactions between Np and HOPO were probed mechanistically by way of absorption spectrophotometry, in conjunction with cyclic voltammetry. UV–Vis-NIR spectra illustrated the reduction of NpO 2 2+ to Np 4+ , with a fast reaction rate. Cyclic voltammetry revealed quasi-reversible processes between the oxidized and reduced forms of the ligand and its Np complexes. The corresponding heterogeneous rate constants (k 0 ) were estimated from the peak-to-peak separation potentials (ΔE p ), at ~ 4 – 35 μm/s for both HOPO and NpHOPO, with scan rates of 0.01 – 0.4 V/s. Meanwhile, the electromotive force (E MF ) as well as the change of Gibbs free energy (ΔG) were assessed from the half-wave potential (E 1/2 ), demonstrating the completeness of NpO 2 2+ reduction to Np 4+ by HOPO. The cumulative formation constant of the resulting NpHOPO complex (logβ 101 ) was determined by metal competition titration to be 42.0 ± 0.6, corroborating the extraordinarily high affinity of HOPO to tetravalent metal ions. Here, the prowess of valence control by HOPO and the high stability of the formed complex resulted in enhanced separations of Np from U and of Pu from U, with a maximum separation factor of ~7000 for both, nearly 90- and 10300-fold higher, respectively, than the values obtained using conventional PUREX formulae.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Computation of turbulent flows over backward and forward-facing steps using a near-wall Reynolds stress model

Separation and reattachment of turbulent shear layers is observed in many important engineering applications, yet it is poorly understood. This has motivated many studies on understanding and predicting the processes of separation and reattachment of turbulent shear layers. Both of the situations in which separation is induced by adverse pressure gradient, or by discontinuities of geometry, have attracted attention of turbulence model developers. Formulation of turbulence closure models to describe the essential features of separated turbulent flows accurately is still a formidable task. Computations of separated flows associated with sharp-edged bluff bodies are described. For the past two decades, the backward-facing step flow, the simplest separated flow, has been a popular test case for turbulence models. Detailed studies on the performance of many turbulence models, including two equation turbulence models and Reynolds stress models, for flows over steps can be found in the papers by Thangam & Speziale and Lasher & Taulbee). These studies indicate that almost all the existing turbulence models fail to accurately predict many important features of back step flow such as reattachment length, recovery rate of the redeveloping boundary layers downstream of the reattachment point, streamlines near the reattachment point, and the skin friction coefficient. The main objectives are to calculate flows over backward and forward-facing steps using the NRSM and to make use of the newest DNS data for detailed comparison. This will give insights for possible improvements of the turbulence model.

Ko, Sung HO↗

A geochemical assessment of possible lunar ore formation

The Moon apparently formed without appreciable water or other relatively volatile materials. Interior concentrations of water or other volatile substances appear to be extremely low. On Earth, water is important to the genesis of nearly all types of ores. Thus, some have reasoned that only abundant elements would occur in ore concentrations. The definition and recognition of ores on the Moon challenge the imaginations and the terrestrial perceptions of ore bodies. Lunar ores included solar-wind soaked soils, which contain abundant but dilute H, C, N, and noble gases (including He-3). Oxygen must be mined; soils contain approximately 45 percent (wt). Mainstream processes of rock formation concentrated Si, Mg, Al, Fe, and Ca, and possibly Ti and Cr. The highland surface contains approximately 70 percent (wt) feldspar (mainly CaAl2Si2O8), which can be separated from some highland soils. Small fragments of dunite were collected; dunite may occur in walls and central peaks of some craters. Theoretical extensions of observations of lunar samples suggest that the Moon may have produced ores of trace elements. Some small fragments have trace-element concentrations 10(exp 4) times higher than the lunar average, indicating that effective geochemical separations occurred; processes included fractional crystallization, silicate immiscibility, vaporization and condensation, and sulfide metamorphism. Operations of these processes acting on indigenous materials and on meteoritic material in the regolith could have produced ores. Infalling carbonaceous meteorites and comets have added water and hydrocarbons that may have been cold-trapped. Vesicles in basalts, pyroclastic beads, and reported transient events suggest gag emission from the lunar interior; such gas might concentrate and transport rare elements. Large impacts may disperse ores or produce them through deposition of heat at depth and by vaporization and subsequent condensation. The main problem in assessing lunar resources is the ignorance about the largely unexplored Moon.

Haskin, Larry A.↗

Analysis of Oxygen Liquefaction with Transient Flow Rates for ISRU Systems

Human occupation of lunar and Martian surfaces requires in-situ resource utilization (ISRU) to create a sustainable environment with the limited resources available in space. Fuel and oxidizer generation is essential for developing a refueling capability for spacecraft, significantly reducing the propellant mass required for landing. Liquefaction systems are a key step in producing and storing cryogenic liquids such as oxygen, hydrogen, and methane. All those fluids are critical to propulsion, life support, and other spacecraft systems. NASA has previously confirmed the presence of water on the Moon and an electrolysis process can be used to separate the oxygen from the hydrogen molecules. Oxygen has also been found within lunar regolith and can be separated through ISRU processes. The extracted oxygen gas can then be liquefied inside a storage tank with tube-on-tank heat exchangers for future use as an oxidizer for propellants. While steady state liquefaction performance is easy to model, power limitations and cyclical environments caused by the change in Sun exposure between day and night periods potentially call for transient operations. The following analysis was performed using the Thermal Desktop software to investigate how various transient gaseous oxygen (GOX) flow rates impact the production and storage of liquid oxygen (LOX) in a 1-g liquefaction system. Variations of sinusoidal and exponential step functions were selected to model potential GOX flow rates that could be experienced by ISRU systems on lunar or Martian surfaces. This early computational analysis provides some insight on how transient operations impact oxygen liquefaction systems and helps illustrate operational questions to explore experimentally throughout the design process.

Cryogenic Fluid Management↗

Integrated membrane material design and system synthesis

In designing membrane systems, the synergy between membrane materials and the process design is often overlooked. In this paper, we present a mixed-integer nonlinear programming (MINLP) model for synthesizing membrane systems while simultaneously designing the respective membrane materials for multicomponent gas separation. The approach considers superstructure representations for systems with: (1) same, (2) potentially different, and (3) property-targeting membrane materials. In the first two systems, the selection of membrane material is a decision, while in the final type, membrane permeances are subject to optimization. Physics-based surrogate models are used to describe permeation in crossflow and countercurrent flow permeators. We show that, through a case study of biogas upgrading, our approach obtains high quality solutions. Furthermore, we use the proposed approach while considering permeance-based production cost to find the optimal membrane.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Development of 211 At production at Crocker Nuclear Laboratory (Final Technical Report)

The focus of this effort was the development of the capability to produce and recover 211 At via the process 209 Bi(α, 2n) 211 At at the cyclotron at the Crocker Nuclear Laboratory at UC Davis. This effort required the design and fabrication of an internal production target, the development of a separation and processing area, and upgrades to the cyclotron to increase its reliability. There was a significant delay due to the pandemic lockdown, but ultimately we were able to produce and recover 211 At at the tens of µCi level using a wet chemistry method. Results of the project were presented at conference, but publication of a refereed article has been delayed by some discrepancies in understanding the calibration of total 211 At produced. We plan to repeat the production using internal funding, but first we want to revise our recovery to use a different technique, developed at the Texas A& M Cyclotron Institute.

07 ISOTOPE AND RADIATION SOURCES↗

Delamination recycling of multilayer plastic films: Solvent-assisted separation pathways and recovery of solid polyolefins

Multilayer plastic films are excellent packaging materials due to the bound layers of multiple polymers, with each different polymer contributing to the film properties. Desirable properties lead to continuously growing demand for multilayer films. Multilayer plastic films are typically single-use and, as such, their increased production and disposal have led to waste management problems. Multilayer films are not currently recyclable primarily due to the multiple bound polymers. This work advances delamination as a recycling process to separate and sequester valuable polymers from multilayer films, facilitating the incorporation of these polymers into the circular economy. We effect delamination in a physical process that preserves targeted polymers as solid film, hence retaining their embodied energy. This work documents three different pathways of inducing delamination of multilayer films, with appropriate solvents disrupting adhesion between adjacent layers or dissolving a minor component of the film in less than an hour and at temperatures below 90°C, and where all initial polyethylene is maintained in its solid form throughout the process and is recovered at high purity. Solvent-based delamination is exemplified on commercial multilayer films with majority polyethylene (PE), and polyethylene terephthalate (PET) or ethylene vinyl alcohol copolymer (EVOH) or nylon also present. Solvent-based delamination is an energy-efficient and environmentally friendly recycling process that improves upon dissolution-precipitation recycling, since delamination involves very little dissolution and no precipitation, and is superior to pyrolysis which breaks down the polymers, while delamination keeps polymer chains intact. Furthermore, delamination recycling can contribute to the sustainable use of multilayer films as they continue to protect our food and medicine.

Chemical Recycling↗

Macrovoid-free high performance polybenzimidazole hollow fiber membranes for elevated temperature H 2 /CO 2 separations

Thermally robust membranes are required for H 2 production and carbon capture from hydrocarbon fuel derived synthesis (syn) gas. Polybenzimidaole (PBI) materials have exceptional thermal, chemical and mechanical characteristics and high H 2 perm-selectivity for efficient syngas separations at process relevant conditions. The large gas volumes processed mandate the use of a high-throughput, small footprint hollow fiber membrane (HFM) platform. Here in this work, an industrially attractive spinning protocol is developed to fabricate PBI HFMs with unprecedented H 2 /CO 2 separation performance. A unique dope composition incorporating an acetonitrile diluent is discovered enabling asymmetric macro-void free PBI HFM fabrication using a water coagulant. The influences of dope viscosity, coagulant chemistry, and air gap on HFM morphology are evaluated. Elevated temperature (up to 350 °C) H 2 permeances of 400 GPU with H 2 /CO 2 selectivities > 20 are achieved. This unprecedented separation performance is a ground breaking achievement at temperatures traditionally considered out-of-reach for polymeric membranes.

08 HYDROGEN↗

Radiant Heat Transfer to Absorbing Gases Enclosed Between Parallel Flat Plates with Flow and Conduction

An analysis is presented for obtaining two-dimensional temperature profiles and heat transfer in a radiation-absorbing gray gas of uniform absorptivity under the combined influence of thermal radiation, conduction, and gas flow. The gas is enclosed in a channel of infinite width and finite length formed by two semi-infinite parallel flat plates. These plates are black emitting surfaces, and the ends of the channel are formed by porous black surfaces through which the gas can flow into or out of the channel. These porous black end surfaces are used to simulate the radiation environment external to the channel. First, results are obtained for heat transfer between the plates in the absence of both conduction and flow. These results are found to be in good agreement with those obtained for the same conditions by previous workers. Results are then presented for heat transfer between the plates for the case of a radiating and conducting, but stagnant, gas separating the plates. The effects of the interactions between radiation and conduction are discussed. It was found that the heat transfer for combined radiation and conduction in an absorbing gas is slightly greater than the sum for each process taken separately. Finally, results are given for heat transfer from the plates to a flowing, radiating gas in the absence of conduction. The two plates are at the same temperature, and the gas enters the channel with uniform velocity and temperature. The results obtained for this case indicate that the heat transferred to the flowing gas from the constant temperature surfaces goes through a maximum as the absorptivity of the gas increases. This is in qualitative agreement with earlier results obtained by other investigators. All the results are presented in terms of dimensionless parameters, for the sake of generality, and the derivation of the dimensionless parameters, which are indicative of the effects of conduction and flow is presented.

Gray Gas↗

Chloride Molten Salt Electrolysis Enables Integrated and Energy-Efficient Process for NdFeB Magnet Fabrication

Rare-earth elements (REEs) have been identified by NATO, the USDOE, and USGS as critical materials, i.e., materials which have significant demand yet pose supply-chain risks. Many of the existing processes for separations, metallization, and final parts production used across the REE supply chain involve energy intensive steps. For example, neodymium (Nd or NdPr) is produced using oxyfluoride electrolysis of Nd 2 O 3 , which requires hydrofluoric acid to produce a key electrolyte component (NdF 3 ) and generates undesired perfluorocarbon (PFC) gases. Such challenges make securing a resilient supply chain for NdFeB permanent magnets in countries like the United States prohibitively difficult. Here, we propose a chloride-based MSE process that circumvents these challenges, delivering high-purity NdPr from a (NdPr)Cl 3 feed from upstream REE separations. This eliminates environmentally-damaging steps of oxalate or carbonate precipitation and calcination, and enables superior production rates due to greater solubility of (NdPr)Cl 3 in chloride melts compared to Nd 2 O 3 . We show that CMSE generates high-purity NdPr (99.4 wt.%) while being energy-efficient (~ 6 kWh/kg-Nd). NdPr from CMSE was used to fabricate a NdFeB magnet with an excellent maximum energy product (> 40 MGOe), comparable to commercially available NdFeB magnets. This establishes CMSE as a leading approach for integrated, energy-efficient NdFeB magnet production.

Materials science↗