Synthesis of formaldehyde from CO sub 2 and H sub 2.
Formaldehyde synthesis from carbon dioxide and hydrogen via methane partial oxidation, discussing role in carbohydrates synthesis from spacecrew gaseous metabolic wastes
Budininkas, P.↗
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Prediction of hydrodynamics and chemistry of confined turbulent methane-air flames with attention to formation of oxides of nitrogen
A formulation of the governing partial differential equations for fluid flow and reacting chemical species in a tubular combustor is presented. A numerical procedure for the solution of the governing differential equations is described, and models for chemical equilibrium and chemical kinetics calculations are presented. The chemical equilibrium model is used to characterize the hydrocarbon reactions. The chemical kinetics model is used to predict the concentrations of the oxides of nitrogen. The combustor consists of a cylindrical duct of varying cross sections with concentric streams of gaseous fuel and air entering the duct at one end. Four sample cases with specified inlet and boundary conditions are considered, and the results are discussed
Elghobashi, S.↗
Steam Methane Reformation Testing for Air-Independent Solid Oxide Fuel Cell Systems
Recently, NASA has been looking into utilizing landers that can be propelled by LOX-CH (sub 4), to be used for long duration missions. Using landers that utilize such propellants, also provides the opportunity to use solid oxide fuel cells as a power option, especially since they are able to process methane into a reactant through fuel reformation. One type of reformation, called steam methane reformation, is a process to reform methane into a hydrogen-rich product by reacting methane and steam (fuel cell exhaust) over a catalyst. A steam methane reformation system could potentially use the fuel cell's own exhaust to create a reactant stream that is hydrogen-rich, and requires less internal reforming of the incoming methane. Also, steam reformation may hold some advantages over other types of reforming, such as partial oxidation (PROX) reformation. Steam reformation does not require oxygen, while up to 25 percent can be lost in PROX reformation due to unusable CO (sub 2) reformation. NASA's Johnson Space Center has conducted various phases of steam methane reformation testing, as a viable solution for in-space reformation. This has included using two different types of catalysts, developing a custom reformer, and optimizing the test system to find the optimal performance parameters and operating conditions.
Mwara, Kamwana N.↗
The Behavior of Methane-Air Partially Premixed Flames Under Normal- and Zero-G Conditions
Partially premixed flames (PPFs) represent a class of hybrid flames containing multiple reaction zones. These flames are established when less than stoichiometric quantity of oxidizer is molecularly mixed with the fuel stream before entering the reaction zone where additional oxidizer is available for complete combustion. This mode of combustion can be used to exploit the advantages of both nonpremixed and premixed flames regarding operational safety, lower pollutant emissions and flame stabilization. A double flame containing a fuel-rich premixed reaction zone, which is anchored by a nonpremixed reaction zone, is one example of a partially premixed flame. A triple flame is also a PPF that contains three reaction zones, namely, a fuel-rich premixed zone, a fuel-lean premixed zone, and a nonpremixed reaction zone. Herein we focus on two aspects of our investigation, one involving the development of optical diagnostics that can be used on a microgravity rig, which has been recently fabricated, and the other on the numerically predicted differences between normal- and zero-gravity PPFs. Both the measurements and simulations examine the detailed structure of methane-air PPFs stabilized on a Wolfhard-Parker slot burner.
Puri, Ishwar K.↗
A high pressure modulated molecular beam mass spectrometric sampling system
The current state of understanding of free-jet high pressure sampling is critically reviewed and modifications of certain theoretical and empirical considerations are presented. A high pressure, free-jet expansion, modulated molecular beam, mass spectrometric sampling apparatus was constructed and this apparatus is described in detail. Experimental studies have demonstrated that the apparatus can be used to sample high temperature systems at pressures up to one atmosphere. Condensible high temperature gaseous species have been routinely sampled and the mass spectrometric detector has provided direct identification of sampled species. System sensitivity is better than one tenth of a part per million. Experimental results obtained with argon and nitrogen beams are presented and compared to theoretical predictions. These results and the respective comparison are taken to indicate acceptable performance of the sampling apparatus. Results are also given for two groups of experiments related to hot corrosion studies. The formation of gaseous sodium sulfate in doped methane-oxygen flames was characterized and the oxidative vaporization of metals was studied in an atmospheric pressure flowing gas system to which gaseous salt partial pressures were added.
Stearns, C. A.↗
Sources and geochemical evolution of cyanide and formaldehyde
The major source of cyanide has, in current paleoatmospheric models, been assumed to be the reaction of photodissociated thermospheric nitrogen with a limiting supply of stratospheric methane. Formaldehyde may be produced with more ease from an atmosphere of carbon dioxide as the dominant carbon species, and from carbonate in solution or sorbed in double layer hydroxide minerals. Potentially more important sources for cyanide and other carbon containing molecules are the partially photoprotected northern and southern auroral ovals where continuous currents reaching several mega-amperes induce ion-molecule reactions, extending into the lower stratosphere. In simulated environments of this kind, the cyanide ion is known to be produced from oxidized carbon species potentially more abundant than methane. Rainout of cyanide and formaldehyde place them in two different geochemical reaction reservoirs. In the anoxic Archean hydrosphere, about 1mM in Fe2(+), the cyanide ion would have been efficiently converted to the stable ferrocyanide complex Fe(CN) sub 6(4-), protecting it from the commonly considered fate of decomposition by hydrolysis, and eventually incorporating it in pyroaurite type minerals, most efficiently in green rust where it converts to insoluble ferriferrocyanide, prussian blue.
Arrhenius, G.↗
Advanced Small Rocket Chambers. Basic Program and Option 2: Fundamental Processes and Material Evaluation
Propellants, chamber materials, and processes for fabrication of small high performance radiation cooled liquid rocket engines were evaluated to determine candidates for eventual demonstration in flight-type thrusters. Both storable and cryogenic propellant systems were considered. The storable propellant systems chosen for further study were nitrogen tetroxide oxidizer with either hydrazine or monomethylhydrazine as fuel. The cryogenic propellants chosen were oxygen with either hydrogen or methane as fuel. Chamber material candidates were chemical vapor deposition (CVD) rhenium protected from oxidation by CVD iridium for the chamber hot section, and film cooled wrought platinum-rhodium or regeneratively cooled stainless steel for the front end section exposed to partially reacted propellants. Laser diagnostics of the combustion products near the hot chamber surface and measurements at the surface layer were performed in a collaborative program at Sandia National Laboratories, Livermore, CA. The Material Sample Test Apparatus, a laboratory system to simulate the combustion environment in terms of gas and material temperature, composition, and pressure up to 6 Atm, was developed for these studies. Rocket engine simulator studies were conducted to evaluate the materials under simulated combustor flow conditions, in the diagnostic test chamber. These tests used the exhaust species measurement system, a device developed to monitor optically species composition and concentration in the chamber and exhaust by emission and absorption measurements.
Jassowski, Donald M.↗
Prediction of hydrodynamics and chemistry of confined turbulent methane-air frames in a two concentric tube combustor
A formulation of the governing partial differential equations for fluid flow and reacting chemical species in a two-concentric-tube combustor is presented. A numerical procedure for the solution of the governing differential equations is described and models for chemical-equilibrium and chemical-kinetics calculations are presented. The chemical-equilibrium model is used to characterize the hydrocarbon reactions. The chemical-kinetics model is used to predict the concentrations of the oxides of nitrogen. The combustor considered consists of two coaxial ducts. Concentric streams of gaseous fuel and air enter the inlet duct at one end; the flow then reverses and flows out through the outer duct. Two sample cases with specified inlet and boundary conditions are considered and the results are discussed.
Markatos, N. C.↗
Heterogeneous Photocatalytic Oxidation of Atmospheric Trace Contaminants
Heterogeneous photocatalysis involves the use of a light-activated catalyst at room temperature in order to carry out a desired reaction. In the presence of molecular oxygen, illumination of the n-type semiconductor oxide titanium dioxide (TiO2) provides for production of highly active forms of oxygen, such as hydroxyl radicals, which are able to carry out the complete oxidative destruction of simple hydrocarbons such as methane, ethane, ethylene, propylene, and carbon monoxide. This broad oxidation potential, coupled with the ability with sufficient residence time to achieve complete oxidation of simple hydrocarbon contaminants to carbon dioxide and water, indicated that heterogeneous photocatalysis should be examined for its potential for purification of spacecraft air. If a successful catalyst and photoreactor could be demonstrated at the laboratory level, such results would allow consideration of photocatalysts as a partial or complete replacement of adsorption systems, thereby allowing for reduction in lift-off weight of a portion of the life support system for the spacecraft, or other related application such as a space station or a conventional commercial aircraft. The present research was undertaken to explore this potential through achievement of the following plan of work: (a) ascertain the intrinsic kinetics of conversion of pollutants of interest in spacecraft, (b) ascertain the expected lifetime of catalysts through examination of most likely routes of catalyst deactivation and regeneration, (c) model and explore experimentally the low pressure drop catalytic monolith, a commercial configuration for automotive exhaust control, and (d) examine the kinetics of multicomponent conversions. In the recent course of this work, we have also discovered how to increase catalyst activity via halide promotion which has allowed us to achieve approximately 100% conversion of an aromatic contaminant (toluene) in a very short residence time of 5-6 milliseconds.
Ollis, David F.↗
Heterogeneous Photocatalytic Oxidation of Atmospheric Trace Contaminants
Heterogeneous photocatalysis involves the use of a light-activated catalyst at room temperature in order to carry out a desired reaction. In the presence of molecular oxygen, illumination of the n-type semiconductor oxide titanium dioxide (TiO2) provides for production of highly active forms of oxygen, such as hydroxyl radicals, which are able to carry out the complete oxidative destruction of simple hydrocarbons such as methane, ethane, ethylene, propylene, and carbon monoxide. This broad oxidation potential, coupled with the ability with sufficient residence time to achieve complete oxidation of simple hydrocarbon contaminants to carbon dioxide and water, indicated that heterogeneous photocatalysis should be examined for its potential for purification of spacecraft air. If a successful catalyst and photoreactor could be demonstrated at the laboratory level, such results would allow consideration of photocatalysts as a partial or complete replacement of adsorption systems, thereby allowing for reduction in lift-off weight of a portion of the life support system for the spacecraft, or other related application such as a space station or a conventional commercial aircraft. The present research was undertaken to explore this potential through achievement of the following plan of work: (a) ascertain the intrinsic kinetics of conversion of pollutants of interest in spacecraft, (b) ascertain the expected lifetime of catalysts through examination of most likely routes of catalyst deactivation and regeneration (c) model and explore experimentally the low pressure drop catalytic monolith, a commercial configuration for automotive exhaust control (d) examine the kinetics of multicomponent conversions. In the recent course of this work, we have also discovered how to increase catalyst activity via halide promotion which has allowed us to achieve approximately 100% conversion of an aromatic contaminant (toluene) in a very short residence time of 5-6 milliseconds.
Ollis, David F.↗
Xenon Fractionation, Hydrogen Escape, and the Oxidation of the Earth
Xenon in Earth's atmosphere is severely mass fractionated and depleted compared to any plausible solar system source material, yet Kr is unfractionated. These observations seem to imply that Xe has escaped from Earth. But to date no process has been identified that can cause Xe, which is heavier than Kr, to escape while Kr does not. Vigorous hydrodynamic hydrogen escape can produce mass fractionation in heavy gases. The required hydrogen flux is very high but within the possible range permitted by solar Extreme Ultraviolet radiation (EUV, which here means radiation at wavelengths short enough to be absorbed efficiently by hydrogen) heating when Earth was on the order of 100 Myrs old or younger. However this model cannot explain why Xe escapes but Kr does not. Recently, what appears to be ancient atmospheric xenon has been recovered from several very ancient (3-3.5 Ga) terrestrial hydrothermal barites and cherts. What is eye-catching about this ancient Xe is that it is less fractionated that Xe in modern air. In other words, it appears that a process was active on Earth some 3 to 3.5 billion years ago that caused xenon to fractionate. By this time the Sun was no longer the EUV source that it used to. If xenon was being fractionated by escape — currently the only viable hypothesis — it had to be in the less unfamiliar context of Earth’s Archean atmosphere and under rather modest levels of EUV forcing. This requires a new model. Here we address the circumstances in which Xe, but not Kr, could escape from Earth as an ion. In a hydrodynamically escaping hydrogen wind the hydrogen is partially photo-ionized. The key concepts are that ions are much more strongly coupled to the escaping flow than are neutrals (so that a relatively modest flow of H and H+ to space could carry Xe+ along with it), and that xenon alone among the noble gases is more easily ionized than hydrogen. This sort of escape is possible if not prevented by a planetary magnetic field. The best prospects for Earth are therefore escape along the polar field lines, although a very weak or absent magnetic field would likely work as well. As applied to the Archean Earth the discussion will be constrained by diffusion-limited hydrogen escape. The extended history of hydrogen escape implicit in Xe escape in the Archean is consistent with suggestions that hydrogen escape from the anoxic Archean atmosphere was considerable, because biogenic methane is expected to have been rather abundant. Hydrogen escape plausibly played the key role in creating oxidizing condition at the surface of the Earth and setting the stage for the creation of an O2 atmosphere.
photo-ionized gases↗
Solar wind and terrestrial atmosphere effects on lunar sample surface composition
Samples returned from the Apollo missions have been shown to have undergone a partial surface oxidation with the degree of oxidation being dependent on the intensity and duration of exposure to a terrestrial or other oxidizing atmosphere. Exposure to atomic hydrogen at room temperature, or molecular hydrogen above 100 C results in a surface reduction. The adsorption of water vapor on a test sample was found to be only slightly dependent on the state of surface oxidation, a situation consistent with the formation of hydroxyl groups on the surface when a sample is exposed to hydrogen. That hydroxyl groups are indeed formed is substantiated by the release of water vapor (and by release of heavy water following exposure to deuterium), indicating that water vapor can be synthesized from solar wind hydrogen and sample oxygen. Observations of trace amounts of methane indicate that the reduction process is by no means restricted to the formation of water vapor.
Cadenhead, D. A.↗
Laser-Induced Fluorescence Measurements and Modeling of Nitric Oxide in Counterflow Diffusion Flames
The feasibility of making quantitative nonintrusive NO concentration ([NO]) measurements in nonpremixed flames has been assessed by obtaining laser-induced fluorescence (LIF) measurements of [NO] in counterflow diffusion flames at atmospheric and higher pressures. Comparisons at atmospheric pressure between laser-saturated fluorescence (LSF) and linear LIF measurements in four diluted ethane-air counterflow diffusion flames with strain rates from 5 to 48/s yielded excellent agreement from fuel-lean to moderately fuel-rich conditions, thus indicating the utility of a model-based quenching correction technique, which was then extended to higher pressures. Quantitative LIF measurements of [NO] in three diluted methane-air counterflow diffusion flames with strain rates from 5 to 35/s were compared with OPPDIF model predictions using the GRI (version 2.11) chemical kinetic mechanism. The comparisons revealed that the GRI mechanism underpredicts prompt-NO by 30-50% at atmospheric pressure. Based on these measurements, a modified reaction rate coefficient for the prompt-NO initiation reaction was proposed which causes the predictions to match experimental data. Temperature measurements using thin filament pyrometry (TFP) in conjunction with a new calibration method utilizing a near-adiabatic H2-air Hencken burner gave very good comparisons with model predictions in these counterflow diffusion flames. Quantitative LIF measurements of [NO] were also obtained in four methane-air counterflow partially-premixed flames with fuel-side equivalence ratios (phi(sub B)) of 1.45, 1.6, 1.8 and 2.0. The measurements were in excellent agreement with model predictions when accounting for radiative heat loss. Spatial separation between regions dominated by the prompt and thermal NO mechanisms was observed in the phi(sub B) = 1.45 flame. The modified rate coefficient proposed earlier for the prompt-NO initiation reaction improved agreement between code predictions and measurements in the region where prompt-NO dominates. Finally, LIF measurements of NO were obtained in counterflow diffusion flames at 2 to 5 atm. Comparisons between [NO] measurements and predictions show that the GRI mechanism underpredicts prompt-NO by a factor of two to three at all pressures. In general, the results indicate a need for refinement of the CH chemistry, especially the pressure-dependent CH formation and destruction reactions.
Ravikrishna, Rayavarapu V.↗
Effects of confinement on partially premixed flames
Partially premixed combustion is an intermediate regime between the limiting cases of premixed and nonpremixed combustion. Although combustion problems are generally approached from one of these two limiting cases, there are many practical situations where flames cannot be considered as purely premixed or nonpremixed, and thus the partially premixed approach must be used. In partially premixed combustion, mechanisms from the premixed and nonpremixed regimes can coexist, and as a result some interesting new phenomena can arise. One such phenomenon is the flame stabilization in laminar mixing layers by triple flames. One of the first observations of triple flames was made by Phillips (1965), who investigated a triple flame propagating in a methane mixing layer. Kioni et al. (1993) also examined triple flames both experimentally and numerically. There have also been numerous analytical studies on the shape and propagation of triple flames under various assumptions by Dold (1989), Dold et al. (1991), and Hartley and Dold (1991). In terms of modeling, Muller et al. (1994) have combined the flamelet formulations for premixed and nonpremixed combustion in order to treat lifted diffusion flames. One common feature in the analytical and numerical studies mentioned above is the assumption of zero heat release, which is necessary to make the problem tractable. The effect of heat release on triple flames was investigated by Ruetsch et al. (1995), where for the unconfined case, flame speeds larger than their premixed counterparts were found. One of the most important practical situations in which these conditions arise is in lifted turbulent jet diffusion flames. At a critical velocity the burning zone of a fuel jet lifts off from the nozzle, moves to increasing distances as the jet velocity increases, and finally blows off. The mechanisms that control these phenomena, i.e. that determine the stability of these flames, are still not understood. In addition to regions where diffusion flame stabilization takes place, partially premixed conditions also exist during the ignition process in nonpremixed systems. Numerical simulations by Reveillon et al. (1994) of the ignition process in a weakly stirred mixture of fuel and oxidizer show that triple flames propagate along lines of stoichiometric mixture fraction throughout the fluid. In addition, Peters (1994) notes that NO(x) emissions are likely to be large in such transient cases, and therefore an understanding of triple flames can provide information concerning pollutant formation. This study extends the work previously done and examines the effects of lateral confinement on partially premixed flames. Once again, we study both the flame structure and propagation.
Ruetsch, G. R.↗