Correlating the Reverse Water–Gas Shift Reaction with Surface Chemistry: The Influence of Reactant Gas Exposure to Ni(100)
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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
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Theoretical model of vertical distributions of CO and CH4 in the mesosphere and upper stratosphere.
Carbon compounds (CO and CO2) and methane are added to an existing computer program (Shimazaki and Laird, 1970, 1972), which calculates diurnal variations in density distributions of pure oxygen compounds, hydrogen compounds, and nitrogen compounds. For the present model calculations, the original program was modified to calculate the steady-state profiles for all constituents, and then these solutions were used as the initial condition for solving the time-dependent equations. The effects of chemical reactions and vertical eddy diffusion transport on the CH4 and CO concentrations above 40 km, where one-dimensional treatment may not be too inappropriate, are discussed. Some of the 15 constituents included in the computer program interact with CO and CH4 chemically, and CH4 is more sensitive to the eddy diffusion coefficient than any other constituent. Therefore it is easier to determine the most appropriate profile of the eddy diffusion coefficient by comparing the model profile with the observations for CH4.
Shimazaki, T.↗
Collisional Removal of OH (X (sup 2)Pi, nu=7) by O2, N2, CO2, and N2O
Collisional removal rate constants for the OH (X 2PI, nu = 7) radical are measured for the colliders O2, CO2, and N2O, and an upper limit is established for N2. OH(nu = 4) molecules, generated in a microwave discharge flow cell by the reaction of hydrogen atoms with ozone, are excited to v = 7 by the output of a pulsed infrared laser via direct vibrational overtone excitation. The temporal evolution of the P = 7 population is probed as a function of the collider gas partial pressure by a time-delayed pulsed ultraviolet laser. Fluorescence from the B 21 + state is detected in the visible spectral region.
Knutsen, Karen↗
Spontaneous Raman Scattering (SRS) System for Calibrating High-Pressure Flames Became Operational
A high-performance spontaneous Raman scattering (SRS) system for measuring quantitative species concentration and temperature in high-pressure flames is now operational. The system is located in Glenn s Engine Research Building. Raman scattering is perhaps the only optical diagnostic technique that permits the simultaneous (single-shot) measurement of all major species (N2, O2, CO2, H2O, CO, H2, and CH4) as well as temperature in combustion systems. The preliminary data acquired with this new system in a 20-atm hydrogen-air (H2-air) flame show excellent spectral coverage, good resolution, and a signal-to-noise ratio high enough for the data to serve as a calibration standard. This new SRS diagnostic system is used in conjunction with the newly developed High- Pressure Gaseous Burner facility (ref. 1). The main purpose of this diagnostic system and the High-Pressure Gaseous Burner facility is to acquire and establish a comprehensive Raman-scattering spectral database calibration standard for the combustion diagnostic community. A secondary purpose of the system is to provide actual measurements in standardized flames to validate computational combustion models. The High-Pressure Gaseous Burner facility and its associated SRS system will provide researchers throughout the world with new insights into flame conditions that simulate the environment inside the ultra-high-pressure-ratio combustion chambers of tomorrow s advanced aircraft engines.
Nguyen, Quang-Viet↗
Coordinated Modeling of Electric Grid and Natural Gas Network Operations
Presentation based upon full report of a Colorado case study and coordination framework, which is available at https://www.nrel.gov/docs/fy20osti/77096.pdf. JISEA analysts Brian Sergi, Omar Guerra, and Bri-Mathias Hodge will present on recent JISEA work on coordination between the natural gas and electricity sectors. Power and gas are becoming increasingly interdependent but weren't designed to function together. How does greater coordination impact system operations with different levels of solar and wind penetrations? This free JISEA presentation will take place in a Webinar on Tuesday, May 11, 2021 at 12 p.m.: Learn how greater coordination between the natural gas and electricity sectors impacts system operations with different levels of solar and wind penetrations. Presentation information includes: Historical and projected data for natural gas consumption and power generation in the United States as demonstrated by 2014 East Coast Polar Vortex, 2021 Texas Winter Storm Uri. Showing coupling points, FERC identified need for better coordination, different levels of coordination (decision making and optimization control), coordination framework. Case study on Colorado Front Range, ramping requirements and gas nominations, real-time dispatch (June and December scenarios), results of analysis of impacts of coordination on unserved load. Total real-time gas offtakes by node, impacts on unserved gas, effect on CO2 emissions. Discussions on clusions drawn from Colorado Case study expanded co-simulation via HELICS, objectives of the HELICS+ natural gas use case, modeling of hydrogen blending, techno economic assessment of blending, and blending impacts on energy content and pressure.
analysis↗
Methane Pyrolysis for CO2-free H2 and Carbon Nanomaterials - CRADA 576 (Final Report)
In this CRADA project we continued to develop the Pacific Northwest National Laboratory (PNNL) patent-pending Regenerable Catalytic Pyrolysis (ReCaP) process technology for producing CO 2 -free hydrogen (H 2 ) from inexpensive and domestically-abundant natural gas (NG), while simultaneously reducing H 2 ’s net production cost to $\$$1.0/kg through the sale of valuable crystalline solid carbon co-product. Producing clean hydrogen at this price is a DOE Hydrogen Energy Earthshot goal. This effort builds on our prior catalyst and processing advances made thermocatalytic decomposition of methane (TCD). The additional scope performed here accelerated the commercial deployment of TCD for CO 2 -free H 2 and valuable solid carbon nanotubes (CNT) co-product, by i) scaling up the production of CNT co-product using a fluidized bed reactor (25 g catalyst scale versus the 1 g catalyst scale demonstrated prior), ii) producing approximately 1 kg of CNT byproduct, produced via multiple cycles of TCD, carbon-catalyst separation, and catalyst re-synthesis, to enable the production of sufficient quantities of solid carbon so as to explore its market potential, iii) understanding the quality of the co-product CNTs, produced at larger scale, using advanced characterization, and iv) beginning to explore multiple promising high volume carbon product applications (e.g., aluminum and polymer composites, steel additive, and cement reinforcement applications). We are in discussions with Department of Energy and potential commercial partners to continue funding of this effort with the goal to facilitate eventual commercial deployment.
08 HYDROGEN↗
Kinetics of hydrogen-oxygen and methane-oxygen ignition sensitized by NO or NO2
In a study of methane ignition sensitized by NO2, the induction period chemical kinetics were examined by monitoring reactants and intermediates (CH4, NO2, OH, NO, CO, CO2, and H2O) prior to ignition. Data were obtained at pressure of 2-4 atm, temperatures of 1300-1900 K, equivalence ratios of 0.5-1.0, and NO2 up to 3.4 mole %. A tentative NO2 sensitization mechanism was deduced from the analysis of photometric observations and the comparison of computer modeling with observations.
Slack, M. W.↗
Fixed-Bed Columns for Adsorption of C2H2 in Metal Organic Frameworks for Hydrogen Recovery in Long-Duration Human Space Flight
To live and work in space, astronauts must have a breathable atmosphere. Current life support system technology utilizes the electrolysis of water to recover O2 as the main method of Oxygen recovery. In addition, the Sabatier Reaction is used to recover H2O from the CO2 produced by human respiration. The current atmosphere revitalization architecture onboard the International Space Station (ISS) has an efficiency of approximately 54% oxygen recovery. Therefore, these systems require substantial resupplies of water to sustain this environment, which make long-duration space flight missions, such as Martian transit, expensive and difficult. In order to support these missions, oxygen recovery must exceed 75-90% efficiency. Additional research has shown that with the addition of a Plasma Pyrolysis system, CH4 produced by the Sabatier reaction may be broken down into H2 and C2H2 and the H2 may be recycled. However, the Hydrogen must be separated from the highly volatile C2H2. There are many potential separation methods. A promising method includes the adsorption of the C2H2 into Metal Organic Frameworks (MOFs) using Vacuum Swing Adsorption. Due to the fragile nature of the MOFs and hazards present in producing C2H2, the columns must have a design that is compatible to both materials and that has the potential to operate in extraterrestrial environments. Successful design and testing of this Hydrogen separation system would allow the PPA to be fully integrated into the current oxygen regeneration system, resulting in a theoretical O2 recovery of 91.3%.
Hannah K Davis↗
Implications of the hypohydrous history of Mars
The extent to which fluvial processes occurred in Mars is considered with reference to the oxidation of soil organics by the gamma-Fe2O3/H2O2 system. Data from the Viking biology experiments suggest that the acidity of gamma-Fe2O3 controls the ionization of hydrogen peroxide - that is, in acid conditions and in the presence of large concentrations of formate, gamma-Fe2O3 reacts efficiently with peroxide to oxidize formate to CO2 and H2O. Fe3O4, alpha-Fe2O3, and calcite are basic and block the oxidation of formate. The properties of this system are consistent with the hypothesis that Mars has been under a severe regime of dryness.
Oyama, V. I.↗
Possible Climate Histories of Venus Type Worlds
There are two well-known scenarios for Venus’ climate evolution. In one Venus had a long-lived magma ocean phase in its first 100Myr with a steam and CO2 dominated atmosphere. The faint young sun with its high XUV flux would cause photodissociation of the steam atmosphere and hydrodynamic escape would cause most of the hydrogen to escape & left-over oxygen would be absorbed by the magma ocean. Hence Venus would have started out hot and dry and the high D/H ratio measured by Pioneer Venus would be from this period of water loss. The other scenario is that Venus’ magma ocean lifetime would have been roughly the same length of time as Earth’s (~1Myr) and water would have condensed on its surface in its early history and had a short period of habitability before increasing solar insolation through time drove it into a runaway greenhouse. However, results from 2016 showed that if Venus remains in the slowly rotating climate dynamics regime (as seen in exoplanet related climate studies) its cloud albedo feedback would have kept it temperate for possibly billions of years. The only way to confirm which one of these scenarios occurred for Venus is to visit it and make the necessary measurements of noble and volatile gases. But exoplanet observations of young exo-Venus type worlds around young F,G,K dwarf stars may constrain which scenario is more probable for a population of such planets. We present a vision of Venus’ climate history that places it and its exoVenus cousins in an ‘Optimistic Venus Zone’ for ~3 billion years within the conventionally named ‘Venus Zone’ and hence encourage the exoplanet communit as possible habitable environments.
Way, M. J.↗
Combined Experimental and Modeling Study of the Interactions of Acid Gas with Common Spacecraft Surfaces for Fire Safety Applications
A fire in a spacecraft poses detrimental consequences and risks mission success in addition to crew safety. This is compounded during long-duration missions when the crew has limited options to recover from a fire. A common spacecraft fire concern is the smoldering of wire insulation, typically made from Polyvinyl chloride (PVC) or Polytetrafluoroethylene (PTFE). This creates acid gases such as Hydrogen Chloride (HCl), Hydrogen Fluoride (HF) and Hydrogen Cyanide (HCN). These poisonous gases are hazardous to the crew. They also interact with common surfaces within the spacecraft more than dominant combustion products such as CO2 and H2O. This makes them more difficult to track for potential fire detection techniques, or for postfire clean-up. It is imperative to be able to understand and predict the fate of these poisonous species in a microgravity environment in order to design a safe vehicle. HCl interacts with a number of materials inside a spacecraft. Primary among these materials is aluminum, which is abundantly used due to its strong and light weight nature. Aluminum has a natural oxide layer that protects it from corrosion but is typically treated to enhance this oxide layer. Among these treatments is a chromate conversion coating (CCC), which provides a thin enough protective oxide layer to still conduct electricity, and a traditional anodized material that has a thicker oxide layer that does not conduct electricity. Nomex is another common material found inside a spacecraft. It is a flame-resistant woven polymer that is related to nylon. This commercially available material is used for cargo storage bags and as a fire barrier. Physics-based models were developed to predict the uptake of HCl by these materials. The ultimate objective of these models is to predict the fate of HCl within the spacecraft so that sensors can be placed in meaningful locations in future missions based on the model predictions. To support these modeling efforts, experiments were performed in a cast acrylic test cell that measured the difference between the inlet and outlet concentration of HCl after inserting a sample rod of the test material. Different uptake capacities were realized for each type of sample tested. A computational fluid dynamics model (CFD) model of the reactor was then constructed that used a one-step global reaction rate with calibratable reaction (or kinetic) constants. These constants were calibrated to match the HCl uptake on the CCC aluminum samples, and the same kinetic constants were then tested for the stock and anodized aluminum samples. Model predictions matched the experimental data for the stock aluminum, and to a much lesser extent, the anodized aluminum. The model was additionally validated at different flow rates, sample surface areas, and inlet concentrations, and showed good agreement for all stock and CCC samples. The model did not accurately predict the HCl uptake in the anodized samples compared to the other two types of aluminum. Adjusting the kinetic constants and transport properties did little to improve the prediction. X-Ray Photoelectron Spectroscopy (XPS) was used to determine that the oxide layer thickness of anodized aluminum is approximately 5,000 nm, compared to 250 nm for CCC and 50 nm for stock. XPS also revealed presence of chlorine further down in the aluminum oxide layer in anodized samples than CCC and stock samples after the samples were saturated with HCl, indicating that accounting for diffusion of HCl into the oxide layer is important for accurate prediction of HCl uptake onto anodized aluminum. Consequently, a multi-scale model was developed and tested. First, a single pore inside the anodized aluminum oxide layer was modeled and is referred to as the pore-scale model. In this model, HCl diffused through the pore and reacted with the aluminum oxide pore wall to create aluminum chloride. The sample was then saturated when the mass transfer resistance through the growing aluminum chloride layer became too large for the HCl to reach the aluminum oxide wall and continue the reaction. This pore-scale model was coupled to the reactor-scale model using a concentration-dependent diffusion coefficient, resulting in much more accurate predictions (approximately half the sum square error of the aforementioned reactor-scale model that produced good agreement for stock and CCC) for a variety of operating conditions. The amount of water vapor or relative humidity (RH) in the flow during a reactor experiment was determined to influence HCl uptake. Experiments were performed to understand the interaction of gaseous HCl with aluminum surfaces in the presence of water vapor. The results show that increasing levels of RH increased the capacity of aluminum to adsorb HCl but decreased the capacity of Nomex to uptake HCl. A series of tests were performed on individual aluminum samples after they had been saturated with a fixed concentration of HCl in dry air conditions with the goal of determining how their HCl uptake capacity changes after various treatments with water relative to the original saturation tests. HCl-saturated aluminum samples subjected to a second dry air flow at the same HCl concentration as the original test had an uptake of 23.5% of the original sample with no treatment in between. Saturated aluminum samples subjected to an air flow with a RH of 90% in between tests had an uptake of 35.6% of the original. Saturated aluminum samples submerged in distilled water for 12 hours in between tests had an uptake of 82.2% of the original sample. Previously saturated aluminum tested with HCl and a 50% RH air flow resulted in similar uptake characteristics in multiple repeated tests. The experiments show the profound effect water vapor has on HCl uptake onto aluminum surfaces. In the samples subjected to water vapor or liquid water, capillary condensation and capillary diffusion alters the transport of HCl significantly. A model was proposed that developed a relationship between RH and the coefficient of HCl diffusion in aluminum chloride. This produced an “S-shaped” curve with diffusion coefficient as a function of RH, with 45% RH represented as the point where the diffusion coefficient is halfway between no water saturation and 100% water saturation in the aluminum chloride product layer. No difference in uptake characteristics for the experiment or model were realized between 50% and 62% RH. The results from the large-scale microgravity experiment, Saffire, are discussed as they pertain to the fate of HCl throughout a spacecraft. HCl was released, both as a standalone event, and in concurrence with the burning of a structured cloth. These events only produced a small response in the far field HCl sensor, while a PMMA burn that did not produce HCl had a significantly greater response. A ground-based large-scale facility was constructed to flow acid gas at the scale and configuration realized in the Saffire experiments. A CFD model of this duct was constructed to test kinetic parameters developed in this work at a larger scale and different geometric configuration and to predict the results of the large-scale facility. The models developed in this work were used to interpret the results of the microgravity tests and lead the discussion on what further experiments and models are needed in order to predict the fate of acid gas in a spacecraft environment. To summarize, the major contributions of this work are as follows: the capacity to uptake HCl, with and without the presence of water vapor, was measured for a variety of real spacecraft surfaces. Several different models (single reactor-scale, multiscale, spacecraft-scale) were developed and with the aid of modeling, the rate of uptake for those surfaces was also predicted and validated. The kinetic parameters determined from the small-scale reactor experiments and models were used to predict large-scale and microgravity tests. Conclusions from this research will be used in the design of spacecraft vehicles and large-scale microgravity fire safety experiments. The models built by this work will aid designers in sensor placement and could be used to predict acid gas transport from fires in partial gravity, as would be seen in Lunar and Martian habitats.
fire safety↗
Coordination Chemistry of Phosphine Ligands with Pendant Amines
Phosphine ligands with pendant amines have played an important role in the development of molecular electrocatalyst for H2 oxidation and production and for other potential energy storage and utilization reactions, such as CO2 and O2 reduction and NH3 oxidation. The pendant amines facilitate substrate binding, heterolytic bond cleavage and formation, intra- and intermolecular proton transfers, the formation of dihydrogen and hydrogen bonds, and provide a physical mechanism for coupling electron and proton transfer reactions. The structures of the phosphine ligands determine the ability of the pendant amines to participate in these different catalytic steps and the stability of the electrocatalysts as they are cycled between different oxidation states. These different features are illustrated by a detailed comparison of Mn, Fe, and Ni electrocatalysts for H2 oxidation that contain diphosphine ligands with pendant amines.
Phosphine, amines, electrocatalyst, dihydrogen, me↗
External insulator for liquid hydrogen tanks
With optimized insulation thickness, tank temperatures were always below 311 K (100 F). This conclusion indicated that an aluminum tank could be used with an optimized insulation system if desired. The N2 purged systems were always lighter than CO2 purged systems. The lower condensation temperature was the controlling factor. Closed cell foam systems were lightest. Closed cell foams, in spite of their need for protective outer insulation, produced insulation systems which were lighter than systems which allowed cryodeposition. Foam system durability established for TMAX = 316 K (110 F). Tests for a subsonic application established this durability; higher temperature limit foam durability was unknown at this. An increase in foam TMAX from 316 K (110 F) to 450 K (350 F) potentially decreased TPS mass by 25 percent.
Sharpe, E. L.↗
A comparative study of the early terrestrial atmospheres
The CO2 abundance required for maintenance of the climatic conditions speculated to have existed 4 billion years ago on the earth, Mars, and Venus is presently sought by means of a one-dimensional radiative-convective atmospheric model. It is ascertained on this basis that the terrestrial and Martian atmospheres were highly stable, and unlikely to proceed to a moist or runaway greenhouse state even if CO2 partial pressure were equivalent to 100 bars on earth. The proximity of Venus to the sun rendered its atmosphere highly susceptible to rapid water vapor photodissociation and hydrogen escape.
Durham, Richard↗
BENCH-SCALE DEVELOPMENT OF A TRANSFORMATIVE MEMBRANE PROCESS FOR PRE-COMBUSTION CO 2 CAPTURE
This final technical report describes work conducted by Membrane Technology and Research, Inc. (MTR) for the Department of Energy, National Energy Technology Laboratory (DOE NETL) on development of the second generation (Gen-2) Proteus™ membrane modules and a pre-combustion membrane process for carbon dioxide (CO 2 ) capture from an Integrated Gasification Combined Cycle (IGCC) plant for power generation (award number DE-FE0031632). The work was conducted from October 1, 2018 through March 30, 2022. The overall goal of this project was to bring a Gen-2 version of the H2-selective Proteus membrane to bench-scale module (component) testing with real syngas. MTR was assisted in this project by Susteon, a technology development company with extensive experience in gasification processes, and the University of North Dakota Energy & Environmental Research Center (EERC), who provided the host site for the slipstream field testing. This report details the work conducted to optimize the Gen-2 Proteus membrane and develop modules capable of operation at 200°C; demonstrate membrane module performance processing coal-derived syngas during a field test at EERC; and optimize integration of a dual-membrane process into an IGCC with carbon capture. Work for this project included membrane optimization and scale-up, module component screening and fabrication of high-temperature lab- and bench-scale modules, design and fabrication of a bench-scale field test membrane skid, operation of the field test skid processing coal-derived syngas at EERC, and a detailed techno-economic analysis (TEA) of the MTR dual-membrane process for IGCC power plant pre-combustion CO 2 capture. This project validated recent membrane technology advancements, mitigates risk in future scale-up activities, and moved the membrane pre-combustion capture technology from TRL-4 to TRL-5. Key results for each major task are discussed in the report.
10 SYNTHETIC FUELS↗
Integrated Capture and Conversion of CO 2 to Methane Using a Water-lean, Post-Combustion CO 2 Capture Solvent
Integrated Carbon Capture and Conversion of CO 2 into materials (IC3M) is an attractive solution to meet the global energy demand, reduce our dependence on fossil fuels and lower CO 2 emissions. In this work, using a water-lean post combustion capture solvent, (N-(2-ethoxyethyl)-3-morpholinopropan-1-amine) (2-EEMPA), >90% conversion of captured CO2 to hydrocarbons, mostly methane, is achieved in the presence of a heterogenous Ru catalysts under relatively mild reaction conditions (170 °C and <15 bar H 2 pressure). The catalytic performance was better in 2-EEMPA than aqueous 5M monoethanol amine (MEA). Operando NMR study showed in-situ formation of N-formamide intermediate, which underwent further hydrogenation to form methane and other higher hydrocarbons. The technoeconomic analyses (TEA) showed that the proposed integrated process can potentially improve the thermal efficiency by 5% and reduce the total capital investment and minimum synthetic natural gas (SNG) selling price by 32% and 12% respectively compared to conventional Sabatier process, highlighting the energetic and economic benefits of integrated capture and conversion. Methane derived from CO 2 and renewable H 2 source is an attractive fuel, and it has a great potential as a renewable hydrogen carrier as an environmentally responsible carbon capture and utilization approach.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Expanded capabilities of the Extended Duration Orbiter
The Extended Duration Orbiter (EDO) is presented emphasizing the ability of the program to enhance the stay times of Spacelab, Spacehab, and Commercially Developed Space Facility missions. An overview of EDO is given with particular attention given to the modifications required for the implementation of Environmental Control and Life Support Systems specific to the Space Shuttle. The configuration, operation, and location of proposed regenerative CO2 removal, N2 supply, improved waste-collection, and power-reactant storage and distribution systems are described in detail. The EDO also includes a trash compactor, additional cryogenic hydrogen and oxygen, extra gaseous nitrogen, and a method for reducing stowed lithium hydroxide. The first utilization of the EDO system is a 13-day mission on the space shuttle Columbia planned for March 1992.
Cerna, Peter J.↗
Simulation of 12-bed vacuum pressure-swing adsorption for hydrogen separation from methanol-steam reforming off-gas
This study focuses on analysis of a 12-bed vacuum pressure-swing adsorption (VPSA) process capable of purifying hydrogen from a ternary mixture (H 2 /CO 2 /CO 75/24/1 mol%) derived from methanol-steam reforming. The process produces 9 kmol H 2 /h with less than 2 ppm and 0.2 ppm of CO2 and CO, respectively, to supply a polymer electrolyte membrane fuel cell. The process model is developed in Aspen Adsorption® using the “uni-bed” approach. A parametric study of H 2 purity and recovery with respect to adsorption pressure, adsorbent height, activated carbon:zeolite ratio, feed composition, and number of beds is performed. Results show 12-bed VPSA can meet the H 2 purity goals, with H 2 recovery as high as 75.75%. Adsorption occurs at 7 bar, the column height is 1.2 m, and the adsorbent ratio is 70%:30%. Furthermore, a 4-bed VPSA can achieve the same purity goals as the 12-bed process, but H 2 recovery decreases to 61.34%.
03 NATURAL GAS↗