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At least 973 records · Page 54

Volatile Element Depletion of the Moon – The Roles of Pre-Cursors, Post-Impact Disk Dynamics, and Core Formation

The compositional and isotopic similarity of Earth’s primitive upper mantle (PUM) and the Moon has bolstered the idea that the Moon was derived from the proto-Earth, but the Moon’s inventory of volatile lithophile elements – Na, K, Rb and Cs – are lower than in Earth’s PUM by a factor of 4 to 5. The abundances of fourteen other volatile elements exhibit siderophile behavior (volatile siderophile elements or VSE; P, As, Cu, Ag, Sb, Ga, Ge, Bi, Pb, Zn, Sn, Cd, In, and Tl) that could be used to evaluate whether the Moon was derived from the proto-Earth, and whether their depletion can be attributed to volatility or core formation. In this study, newly available core-mantle partitioning data are used, together with bulk Moon compositions, protolunar disk dynamics modelling to test the hypothesis that the Moon was derived from PUM-like material. At lunar core formation conditions, As, Sb, Ag, Ge, Bi, Sn are siderophile, whereas P, Cu, Ga, Pb, Zn, Cd, In and Tl are all weakly siderophile or lithophile. Most of the VSE can be explained by a combination of known processes – pre-cursor volatile depletion, melt-gas dynamics and equilibria in the protolunar disk, and core formation. Explaining this whole group of volatile elements may require a combination of mixing and separation of the newly formed Moon from remnant gas rich in the highest volatility VSEs. This large group of volatile elements informs a wide temperature range and offers a powerful test of melt-gas segregation mechanisms in the protolunar disk and lunar formation hypotheses.

Righter, K.↗

Shock absorber servicing tool

A tool to assist in the servicing of a shock absorber wherein the shock absorber is constructed of a pair of aligned gas and liquid filled chambers. Each of the chambers is separated by a movable separator member. Maximum efficiency of the shock absorber is achieved in the locating of a precise volume of gas within the gas chamber and a precise volume of liquid within the liquid chamber. The servicing tool of this invention employs a rod which is to connect with the separator and by observation of the position of the rod with respect to the gauge body, the location of the separator is ascertained even though it is not directly observable.

Koepler, Jack L.↗

Molten Salt Reactor Engineering Study for Off-Gas Management

In previous work published by the current team, the waste processing and waste form options were summarized for molten salt reactors (MSR) (Riley et al., 2018b; Riley et al., 2019). The primary types of waste from an MSR are summarized in Figure S1 and include (1) off-gas streams, (2) salt waste streams, (3) separated salt streams, (4) metal waste streams, (5) carbon waste streams, (6) decommissioning and decontaminating (D&D) waste streams, and (7) operating waste streams, or those that are generated from maintenance procedures. The primary focus of this report will be on management of the off-gas stream as it represents the pressure boundary for fuel-salt MSRs and, thus, is required for fission product confinement during reactor operation and reduction of the source term during a reactor accident.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Deconvolution of gas chromatographic data

The use of deconvolution methods on gas chromatographic data to obtain an accurate determination of the relative amounts of each material present by mathematically separating the merged peaks is discussed. Data were obtained on a gas chromatograph with a flame ionization detector. Chromatograms of five xylenes with differing degrees of separation were generated by varying the column temperature at selected rates. The merged peaks were then successfully separated by deconvolution. The concept of function continuation in the frequency domain was introduced in striving to reach the theoretical limit of accuracy, but proved to be only partially successful.

Howard, S.↗

Liquid Sorption-Enhanced Haber–Bosch Process

The use of a liquid sorbent in a traditional Haber-Bosch process enables significant improvements in energy efficiency and potential cost savings for arguably the most important chemical process on the planet. The approach presented in this report employs an incompressible liquid sorbent that absorbs and releases ammonia (NH 3 ) under specific conditions. To achieve this, we investigate reactions of ammonia and pure phosphoric acid (H 3 PO 4 , PA), which rapidly neutralize to form an equilibrated solution of monoammonium phosphate (MAP) and diammonium phosphate (DAP) that functions as a reversible and regenerable sorbent. Through intimate contact of the gas-phase Haber-Bosch reaction mixture with this liquid absorbent, complete equilibrium uptake may be achieved in an appropriately sized separator, and facile separation occurs through the use of independent liquid and gas phases. Following depressurization and release of the ammonia product, only the incompressible fluid needs to be repressurized and returned to the reactor. This study documents proof-of-concept absorption and desorption experiments carried out in 75 mL batch reactors, predominantly charged with precise MAP and DAP mixtures that equilibrate at process-relevant temperatures and pressures. We then assemble the first thermodynamic relationships that underlie this advantaged separation strategy, validated by reactive force field (ReaxFF) interatomic potential simulations, and benchmarked with traditional separation routes via process modeling and technoeconomic analysis. The scale of energy consumption in the century-old Haber-Bosch process is massive, and the elegant liquid sorption approach reported here offers opportunities to enhance its energy efficiency for the next frontier of ammonia synthesis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Evaluation of Low-Energy Hydrogen Separation Method Using Metal-Organic Frameworks (MOFs) for Closed-Loop ECLSS Air Revitalization (CLEAR)

The State-of-the-Art (SOA) air revitalization architecture onboard the International Space Station (ISS) recovered approximately 50% of the oxygen (O 2 ) from metabolic carbon dioxide (CO 2 ) via the Sabatier process from 2011 to 2017. O 2 recovery is currently constrained by the limited availability of reactant hydrogen (H 2 ) preventing complete conversion of CO 2 to H 2 O. Increasing O 2 recovery within Closed-Loop ECLSS is essential to reducing resupply mass for long-duration manned missions; specifically focusing on water (H 2 O) which supplies H 2 for Sabatier via water electrolysis. Past ground test endeavors at Marshall Space Flight Center (MSFC) have attempted to recover H 2 from Sabatier-produced CH 4 using technologies such as carbon vapor deposition (CVD) and plasma pyrolysis. The byproducts of these technologies can act as a catalyst poison or reactor deadload to the Sabatier reactor. Hydrogen separation techniques must be utilized to maintain the Sabatier catalyst during gas recycling and must be scalable, non-energy intensive, and safe to operate in a habitation setting. Research indicated that metal-organic frameworks (MOFs) could meet these criteria and were tested for their capability to capture the various carbon-based gaseous products of CVD and plasma pyrolysis such as acetylene (C 2 H 2 ), ethylene (C 2 H 4 ), ethane (C 2 H 6 ), and carbon monoxide (CO) which would purify the hydrogen gas stream passing through the MOF. A sub-scale adsorption column was developed by Marshall Space Flight Center to test three MOF candidates against a synthetic gas mixture comprised of process-relevant carbonous gases and hydrogen to evaluate the separation capability of the MOFs. The results of the hydrogen separation capability, isothermal desorption capability, and demonstrated cyclic reuse of the MOF are presented in this paper.

Kagen Crawford↗

A Modular Heat Engine for the Direct Conversion of Natural Gas to Hydrogen and Power using Hydrogen Turbines (Phase I Final Report)

This report describes a novel, modular heat engine comprising of a one-step hydrogen production from natural gas with in-situ CO 2 separation which is amenable for re-use or sequestration. Combining with a hydrogen turbine subsystem, a distributed or central power generation system is conceived. An added hydrogen storage subsystem enables load-following capability. The techno-economics of the overall system compared favorably against current state-of-the-art natural gas combined cycle plants with post-combustion CO 2 capture.

01 COAL, LIGNITE, AND PEAT↗

Generation and delivery device for ozone gas and ozone dissolved in water

The present invention provides an ozone generation and delivery system that lends itself to small scale applications and requires very low maintenance. The system preferably includes an anode reservoir and a cathode phase separator each having a hydrophobic membrane to allow phase separation of produced gases from water. The hydrogen gas, ozone gas and water containing ozone may be delivered under pressure.

Andrews, Craig C.↗

Viking Afterbody Heating Computations and Comparisons to Flight Data

Computational fluid dynamics predictions of Viking Lander 1 entry vehicle afterbody heating are compared to flight data. The analysis includes a derivation of heat flux from temperature data at two base cover locations, as well as a discussion of available reconstructed entry trajectories. Based on the raw temperature-time history data, convective heat flux is derived to be 0.63-1.10 W/sq cm for the aluminum base cover at the time of thermocouple failure. Peak heat flux at the fiberglass base cover thermocouple is estimated to be 0.54-0.76 W/sq cm, occurring 16 seconds after peak stagnation point heat flux. Navier-Stokes computational solutions are obtained with two separate codes using an 8-species Mars gas model in chemical and thermal non-equilibrium. Flowfield solutions using local time-stepping did not result in converged heating at either thermocouple location. A global time-stepping approach improved the computational stability, but steady state heat flux was not reached for either base cover location. Both thermocouple locations lie within a separated flow region of the base cover that is likely unsteady. Heat flux computations averaged over the solution history are generally below the flight data and do not vary smoothly over time for both base cover locations. Possible reasons for the mismatch between flight data and flowfield solutions include underestimated conduction effects and limitations of the computational methods.

Edquist, Karl T.↗

Viking Afterbody Heating Computations and Comparisons to Flight Data

Computational fluid dynamics predictions of Viking Lander 1 entry vehicle afterbody heating are compared to flight data. The analysis includes a derivation of heat flux from temperature data at two base cover locations, as well as a discussion of available reconstructed entry trajectories. Based on the raw temperature-time history data, convective heat flux is derived to be 0.63-1.10 W/cm2 for the aluminum base cover at the time of thermocouple failure. Peak heat flux at the fiberglass base cover thermocouple is estimated to be 0.54-0.76 W/cm2, occurring 16 seconds after peak stagnation point heat flux. Navier-Stokes computational solutions are obtained with two separate codes using an 8- species Mars gas model in chemical and thermal non-equilibrium. Flowfield solutions using local time-stepping did not result in converged heating at either thermocouple location. A global time-stepping approach improved the computational stability, but steady state heat flux was not reached for either base cover location. Both thermocouple locations lie within a separated flow region of the base cover that is likely unsteady. Heat flux computations averaged over the solution history are generally below the flight data and do not vary smoothly over time for both base cover locations. Possible reasons for the mismatch between flight data and flowfield solutions include underestimated conduction effects and limitations of the computational methods.

Edquist, Karl T.↗

Design and Performance of a Gas Chromatograph for Automatic Monitoring of Pollutants in Ambient Air

In recent years, interest in air pollution constituents has focused on carbon monoxide and hydrocarbons as prime components of polluted air. Instrumental methods have been developed, and commercial instruments for continuous monitoring of these components have been available for a number of years. For the measurement of carbon monoxide, non-dispersive infrared spectroscopy has been the accepted tool, in spite of its marginal sensitivity at low parts-per-million levels. For continuously monitoring total hydrocarbons, the hydrogen flame ionization analyzer has been widely accepted as the preferred method. The inadequacy of this latter method became evident when it was concluded that methane is non-reactive and cannot be considered a contaminant even though present at over 1 ppm in the earth's atmosphere. Hence, the need for measuring methane separately became apparent as a means of measuring the reactive and potentially harmful non-methane hydrocarbons fraction. A gas chromatographic method for the measurement of methane and total hydrocarbons which met these requirements has been developed. In this technique, methane was separated on conventional gas chromatographic columns and detected by a hydrogen flame ionization detector (FID) while the total hydrocarbons were obtained by introducing a second sample directly into the FID without separating the various components. The reactive, or non-methane hydrocarbons, were determined by difference. Carbon monoxide was also measured after converting to methane over a heated catalyst to render it detectable by the FID. The development of this method made it possible to perform these measurements with a sensitivity of as much as 1 ppm full scale and a minimum detectability of 20 ppb. Incorporating this technique, criteria were developed by APCO for a second generation continuous automatic instrument for atmospheric monitoring stations.

Villalobos, R.↗

The computation of thermo-chemical nonequilibrium hypersonic flows

Several conceptual designs for vehicles that would fly in the atmosphere at hypersonic speeds have been developed recently. For the proposed flight conditions the air in the shock layer that envelops the body is at a sufficiently high temperature to cause chemical reaction, vibrational excitation, and ionization. However, these processes occur at finite rates which, when coupled with large convection speeds, cause the gas to be removed from thermo-chemical equilibrium. This non-ideal behavior affects the aerothermal loading on the vehicle and has ramifications in its design. A numerical method to solve the equations that describe these types of flows in 2-D was developed. The state of the gas is represented with seven chemical species, a separate vibrational temperature for each diatomic species, an electron translational temperature, and a mass-average translational-rotational temperature for the heavy particles. The equations for this gas model are solved numerically in a fully coupled fashion using an implicit finite volume time-marching technique. Gauss-Seidel line-relaxation is used to reduce the cost of the solution and flux-dependent differencing is employed to maintain stability. The numerical method was tested against several experiments. The calculated bow shock wave detachment on a sphere and two cones was compared to those measured in ground testing facilities. The computed peak electron number density on a sphere-cone was compared to that measured in a flight test. In each case the results from the numerical method were in excellent agreement with experiment. The technique was used to predict the aerothermal loads on an Aeroassisted Orbital Transfer Vehicle including radiative heating. These results indicate that the current physical model of high temperature air is appropriate and that the numerical algorithm is capable of treating this class of flows.

Candler, Graham↗

Developing reactors for electrifying bio-methanation: a perspective from bio-electrochemistry

The integration of microbial synthesis with renewable electricity is an emerging route for both CO 2 utilization and seasonal energy storage in the form of stored bio-electrofuels. The major benefits of electrifying bioreactors include: using highly selective bio-catalysts for CO 2 conversion under mild reaction conditions; decoupling the production of more facile electrochemical intermediates, such as hydrogen, at the electrode from the production of bio-catalyzed multi-electron and/or carbon products, such as methane or acetate; using microbes as robust and self-regenerating catalysts enabling higher efficiency and durability in CO 2 conversion systems compared to inorganic catalysis. In this Perspective, we propose research aimed at developing electro-bioreactor components that will increase the productivity of the reactor while maintaining high energy efficiency and biocompatible reaction conditions to fully realize the benefits of electrified bioreactors. Furthermore, these developments include: flow reactors with tailored 3D electrodes to optimally use the reactor volume, electrocatalysts designed for peak performance in neutral pH electrolytes, high conductivity microbial media, and new membrane separator materials with high ion conductivity and low gas permeability. Production of methane via a hybrid electrical-biological approach is taken as a case study to motivate these developments. Finally, an iterative design–manufacture–test cycle, enabled by additive manufacturing and 3D printing technologies, is proposed to rapidly prototype components prior to large-scale manufacturing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ambient Ion Trapping and Separations for High Throughput Structurally Selective Material Deposition

While ion mobility coupled to mass spectrometry (IMS/MS) has been increasingly adapted to biological analysis, the structural and molecular specificity offered by IMS/MS has untapped potential for creating novel materials (for energy, catalysis, biomolecular switches etc.) with rationally tailored properties by precisely controlling the chemical structure and composition of these materials. While electrochemical and catalytic properties of the bulk material are understood by mass-selective ion-soft-landing, different structures of one molecule can exhibit distinct properties from the bulk. Many biological phenomenon occur at interfaces and are highly structurally specific. IMS/MS offers means to separate molecules in a sample (which is first ionized and released to gas phase from the condensed phase) based on mass and structure. Species thus separated can potentially be deposited onto surfaces with molecular and structural specificity, to perform fundamental investigations for understanding critical interfacial phenomenon. Key performance metrics for IMS/MS analysis are resolution of separations and sensitivity. Recently developed Structures for Lossless Ion Manipulations (SLIM)4 enabled unprecedented resolution in IMS separations. In addition, high sensitivity was enabled in SLIM due to lossless confinement of ions using radio frequency fields. Thus, SLIM enabled extremely long path length separations (up to 0.1 km thus far) providing efficient separation of molecular ions never before achieved (e.g. isotopologues, D&L amino acids). While SLIM has unprecedented analytical separations power/utility, the use of SLIM platform for depositing mobility and mass selected molecular ions has two specific technological challenges: (a) Pulsed nature of IMS separations and their low duty cycle and (b) the need for a low vacuum of ~4 torr for lossless ion confinement. These limitations lead to long deposition times due to loss of ions generated from the sample. Enabling ion confinement at atmospheric pressure will be path-breaking contribution to the fundamental understanding of ion manipulations and separations and will also enable novel science currently precluded due to the inability of the present technologies to confine ions under ambient conditions. Traditionally used radio frequency fields are ineffective in confining ions at high pressures due to ion/neutral collisions. To address these, we propose to (a) develop methods for confining and manipulating ions for lossless IMS separations at atmospheric pressure enabling high sensitivity and throughput and (b) use the high specificity of IMS/MS and high throughput from ambient ion confinement to perform mobility and mass selective ion deposition at atmospheric pressure. Our goal is to enable the study of the fundamental properties of energy/catalysis materials and biomolecules. This project paves the way for high-throughput, mass and structure selective material deposition for highly specific surface creation/functionalization (discussed in Section 2 of the report). Further, the developments reported continue to push the boundaries of this process to ambient conditions (discussed in Section 3 of the report). We conclude with a list of specific intellectual property and publications which have been the outcome of this funded project.

36 MATERIALS SCIENCE↗

Flow Regime Transitions and Pressure Drop in Gas-Liquid Flows through Packed Beds in Microgravity

The Packed Bed Reactor Experiment (PBRE) focused on the hydrodynamics of gas-liquid flow in porous media, specifically on flow regime transition and pressure drop correlation. The reactor included a cylindrical test section of 60 cm in length, 5 cm in diameter and filled with 2 mm spherical glass beads. Liquid water and Nitrogen gas were flowed into a centrifugal phase separator after exiting the test section. Five absolute pressure transducers and two high-speed video cameras spanned the test section to measure the pressure drop and capture flow regime behavior. Video observations, analysis of pressure traces, and pressure drop data were used to identify flow patterns. It was found that the slope of pressure gradient data when plotted versus the gas or liquid Reynolds numbers changed when the flow regime changed. This observation was used to identify the flow regime boundaries. At high liquid flow rates (high interaction regime), dispersed bubble and pulse flow regimes were detected. At low liquid flow rates (low interaction regime), large bubble and gas channeling regimes were observed. The transition from the big bubble regime to the gas channeling regime occurred at a critical gas flow rate independent of the liquid flow rate. Similarly, the transition from the low interaction to the high interaction regime occurred at a critical liquid flow rate. For these different flow regimes, different two-phase flow friction factors and pressure gradient correlations were fitted as a function of the gas and liquid modified Reynolds numbers and Suratman number. It was found that in all the flow regimes the capillary contribution to the pressure drop is significant and can be as high as 90% of the total pressure drop.

Brian Motil↗

Perspective on the oil-dominated gas hydrate plugging conceptual picture as applied to transient Shut-In/Restart

Gas hydrate formation is rarely an issue during continuous production conditions. Unplanned and/or extended shut-downs comprise the majority of scenarios where overlapping concern and uncertainty for gas hydrate blockages exist. To date, most experimental studies and theoretical analysis of gas hydrate formation derive from the steady-state conceptual picture. Yet, significant distinctions induced by phase separation and prolonged cooling suggest an altered conceptual picture is required for transient shut-in/restart operations. To address this outstanding issue, this work presents a conceptual picture for the base case of a non-surface active hydrocarbon undergoing cold restart without enacted mitigation efforts. First, phase separation upon shut-in leads to the localization of gas hydrate ingredients due to fluids density differences and pipeline inclination. Cooling to the seafloor temperature, then, induces gas hydrate film formation at the hydrocarbon interface and maximizes subcooling, resulting in rapid and confined gas hydrate growth occurring upon restart. Furthermore, this ultimately leads to plugging dominated by the deposition of porous, low conversion gas hydrate masses. Direct visual observations and results from Raman spectroscopy, hydrate contact angle and film growth, micromechanical force apparatus, rocking cell, and flow loop studies support the mechanisms outlined within each step. Similar to the influence provided by the original Colorado School of Mines steady-state conceptual picture that was introduced about 15 years ago, this transient counterpart builds a foundation that could inspire new directions of hydrate research and analysis in areas where uncertainty abounds.

02 PETROLEUM↗