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At least 127 records · Page 7

Tethered oxygen turns methane into methanol

Precise control of the oxidant — that is, preventing overoxidation — is the missing link in low-temperature methane upgrading. Now, the electro-splitting of carbonate on rutile IrO 2 is shown to cover the surface with on-top oxygen adatoms that act as tethered, single-step hydrogen abstractors. One subset can pull the hydrogen from methane to form a methoxy intermediate, while the neighbouring site can protonate this intermediate to form methanol. Together, this mechanism delivers a room-temperature conversion of methane to methanol with >90% selectivity.

climate-change mitigation↗

Platinum and CeO 2-x Occlusion Electrodeposition at Unsupported Vulcan XC-72R for Methanol and Ethanol Oxidation Reactions in Alkaline Media

Abstract Platinum was electrodeposited in a slurry solution of CeO2 and Vulcan XC-72R to produce Pt/CeO2-x/Vulcan XC-72R catalysts by using the Rotating Disk Slurry Electrodeposition (RoDSE) Technique. The activity of the catalysts was measured towards methanol and ethanol oxidation reactions in alkaline conditions by cyclic voltammetry and chronoamperometry. The electrochemical results were compared to those obtained on commercial catalysts. Pt/CeO2-x/Vulcan XC-72R (with ~ 26 wt.% Pt) catalyst was the most active for both alcohol oxidation reactions when compared to commercial 40 wt.% and 20% /Vulcan XC-72R (ETEK) catalysts. The mass activity increases 2.0x and 2.4x for methanol and ethanol oxidation reactions when compare with 40 and 20 Pt wt. % commercial catalysts, respectively. The Pt/CeO2-x/Vulcan XC-72R catalysts contained Pt nanoparticles growth within the cerium oxide through an occlusion electrodeposition method. These effects were systematically investigated using X-ray Diffraction (XRD), High Resolution Transmission Electron Microscopy (HR-TEM), and X-ray Photoelectron Spectroscopy (XPS).

Suleiman Mahmoud, Amal↗

Photoionization of methanol and formaldehyde

Photoions produced in methanol and formaldehyde by radiation in the spectral region 450-1150 A were analyzed mass spectrometrically, and their relative yields were determined as a function of wavelength. First ionization potentials were determined, and the ion yield curves were interpreted in terms of ionization processes in conjunction with other data. Fragment ions were detected on mass numbers of 31, 30, 29, 15, and 14 for methanol, and 29, 2, and 1 for formaldehyde. The associated appearance potentials were determined and were used to calculate heats of formation of the ions CH2OH(+) and HCO(+), and the radicals CH3, CH2, and HCO.

Warneck, P.↗

Cracking of Ti-6Al-4V in methanol solutions containing sulfates.

Whether cracking of unnotched Ti-6Al-4V specimens occurs in methanol containing H2SO4, Li2SO4, or Fe2(SO4)3 is a function of the age of the solution and the concentration of the sulfate. With H2SO4 concentrations of 0.10 N to 0.25 N, the methanol solutions lose their ability to crack the specimens with time after mixing and prior to exposure. The aging time required to inhibit the cracking varies inversely with the water content of the solution. With larger quantities of H2SO4, 0.5 N and 1 N, no cracking is observed. Interpretations of Raman spectroscopic studies of the aging solution suggests that the nature of the O-H group may play a role in the crack initiation or inhibiting mechanism.

Haney, E. G.↗

Two new methanol transitions in Orion A

Emission from the 11(1) - 10(2) (A-) and 5(0) - 4(1) (E) transitions of CH3OH at rest frequencies of 76,247.4 and 76,509.9 MHz, respectively, has been detected toward Orion A. The velocity widths of the two transitions are estimated to be approximately 3 km/s, which is consistent with other methanol lines in Orion. It is noted that the 117.5-kayser upper-state energy of the 11(1) - 10(2) (A-) transition is the highest yet reported for methanol in any source. The observed intensity is shown to be consistent with the 90-K thermal excitation model that seems to be appropriate for all other reported CH3OH lines in Orion A. Total column densities of 3 x 10 to the 16th per sq cm for the 11(1) - 10(2) (A-) transition and of 2 x 10 to the 16th per sq cm for the 5(0) - 4(1) (E) transition are calculated.

Jennings, D. E.↗

Alumina-supported Pd-Ag catalysts for low-temperature CO and methanol oxidation

Pd-Ag bimetallic catalysts, supported on gamma-Al2O3, have been evaluated as exhaust catalysts for methanol-fueled vehicles. Laboratory studies have shown that a 0.01% Pd-5% Ag catalyst has greater CO and CH3OH oxidation activity than either 0.01% Pd or 5% Ag catalysts alone. Moreover, Pd and Ag interact synergistically in the bimetallic catalyst to produce greater CO and CH3OH oxidation rates and lower yields of methanol partial oxidation products than expected from a mixture of the single-component catalysts. The Pd-Ag synergism results from Pd promoting the rate of O2 adsorption and reaction with CO and CH3OH on Ag. Rate enhancement by the bimetallic catalyst is greatest at short reactor residence times where the oxygen adsorption rate limits the overall reaction rate.

Mccabe, R. W.↗

The contribution of methanol to the 3.4 micron feature in comets

With the advent of improved detectors and improved moderate resolution spectrometers several interesting features have been seen in the infrared spectra of comets. In particular, an emission excess at 3.52 microns was observed in several comets, and has recently been tentatively assigned to the nu 3 band of methanol (CH3OH). Using a developed model it is possible to calculate the relative strengths of the CH3OH features. The 3.52 microns emission strengths were used in a number of comets to retrieve methanol amounts, and the model was used to predict the fraction of the 3.4 micron flux which is contributed by the species. Implications for cometary formation are discussed.

Reuter, Dennis C.↗

The contribution of methanol to the 3.4 micron emission feature in comets

A fluorescence model for cometary emission in the nu2, nu3, and nu9 bands of methanol is described. This model is used in conjunction with observed spectra of several comets to determine the possible contribution of CH3OH to the frequently seen 3.4-micron 'cometary organic' feature. For Comets P/Halley and Wilson, methanol production rates are retrieved from the flux in the nu3 band centered at about 3.52 microns.

Reuter, Dennis C.↗

Serendipitous images of methanol in Comet Levy (1900 XX)

Reuter's (1992) model of the IR fluorescence of methanol is used to retrieve a methanol production rate of 3 +/- 1 x 10 exp 26/s and an abundance relative to water of about 0.1 percent. It is argued that calibration is of paramount importance and that a near-simultaneous spectrum is necessary for achieving a reliable estimate of the continuum underlying the emission feature.

Hoban, Susan↗

Deployment of a Fast-GCMS System to Measure C2 to C5 Carbonyls, Methanol and Ethanol Aboard Aircraft

Through funding of this proposal, a fast response gas chromatograph/mass spectrometer (FGCMS) instrument to measure less than or equal to C4 carbonyl compounds and methanol was developed for the NASA GTE TRACE-P (Global Tropospheric Experiment, Transport And Chemical Evolution Over The Pacific) mission. The system consists of four major components: sample inlet, preconcentration system, gas chromatograph (GC), and detector. The preconcentration system is a custom-built cryogen-conservative system. The GC is a compact, custom-built unit that can be temperature programmed and rapidly cooled. Detection is accomplished with an Agilent Technologies 5973 mass spectrometer. The FGCMS instrument provides positive identification because the compounds are chromatographically separated and mass selected. During TRACE-P, a sample was analyzed every 5 minutes. The FGCMS limit of detection was between 5 and 75 pptv, depending on the compound. The entire instrument package is contained in a standard NASA instrument rack (106 cm x 61 cm x 135 cm), consumes less than 1200 watts and is fully automated with LabViEW 6i. Methods were developed or producing highly accurate gas phase standards for the target compounds and for testing the system in the presence of potential interferents. This report presents data on these tests and on the general overall performance of the system in the laboratory and aboard the DC-8 aircraft during the mission. Vertical profiles for acetaldehyde, methanol, acetone, propanal, methyl ethyl ketone, and butanal from FGCMS data collected over the entire mission are also presented.

Apel, Eric C.↗

Power generation in fuel cells using liquid methanol and hydrogen peroxide

The invention is directed to an encapsulated fuel cell including a methanol source that feeds liquid methanol (CH.sub.3 OH) to an anode. The anode is electrical communication with a load that provides electrical power. The fuel cell also includes a hydrogen peroxide source that feeds liquid hydrogen peroxide (H.sub.2 O.sub.2) to the cathode. The cathode is also in communication with the electrical load. The anode and cathode are in contact with and separated by a proton-conducting polymer electrolyte membrane.

Narayanan, Sekharipuram R.↗

Nano-Engineered Catalysts for Direct Methanol Fuel Cells

Nano-engineered catalysts, and a method of fabricating them, have been developed in a continuing effort to improve the performances of direct methanol fuel cells as candidate power sources to supplant primary and secondary batteries in a variety of portable electronic products. In order to realize the potential for high energy densities (as much as 1.5 W h/g) of direct methanol fuel cells, it will be necessary to optimize the chemical compositions and geometric configurations of catalyst layers and electrode structures. High performance can be achieved when catalyst particles and electrode structures have the necessary small feature sizes (typically of the order of nanometers), large surface areas, optimal metal compositions, high porosity, and hydrophobicity. The present method involves electrodeposition of one or more catalytic metal(s) or a catalytic-metal/polytetrafluoroethylene nanocomposite on an alumina nanotemplate. The alumina nanotemplate is then dissolved, leaving the desired metal or metal/polytetrafluoroethylene-composite catalyst layer. Unlike some prior methods of making fine metal catalysts, this method does not involve processing at elevated temperature; all processing can be done at room temperature. In addition, this method involves fewer steps and is more amenable to scaling up for mass production. Alumina nanotemplates are porous alumina membranes that have been fabricated, variously, by anodizing either pure aluminum or aluminum that has been deposited on silicon by electronbeam evaporation. The diameters of the pores (7 to 300 nm), areal densities of pores (as much as 7 x 10(exp 10)sq cm), and lengths of pores (up to about 100 nm) can be tailored by selection of fabrication conditions. In a given case, the catalytic metal, catalytic metal alloy, or catalytic metal/ polytetrafluoroethylene composite is electrodeposited in the pores of the alumina nanotemplate. The dimensions of the pores, together with the electrodeposition conditions, determine the sizes and surface areas of the catalytic particles. Hence, the small features and large surface areas of the porosity translate to the desired small particle size and large surface area of the catalyst (see figure). When polytetrafluoroethylene is included, it is for the purpose of imparting hydrophobicity in order to prevent water from impeding the desired diffusion of gases through the catalyst layer. To incorporate polytetrafluoroethylene into a catalytic-metal/polytetrafluoroethylene nanocomposite, one suspends polytetrafluoroethylene nanoparticles in the electrodeposition solution. The polytetrafluoroethylene content can be varied to obtain the desired degree of hydrophobicity and permeability by gas.

Myung, Nosang↗

Low-Pt-Content Anode Catalyst for Direct Methanol Fuel Cells

Combinatorial experiments have led to the discovery that a nanophase alloy of Pt, Ru, Ni, and Zr is effective as an anode catalyst material for direct methanol fuel cells. This discovery has practical significance in that the electronic current densities achievable by use of this alloy are comparable or larger than those obtained by use of prior Pt/Ru catalyst alloys containing greater amounts of Pt. Heretofore, the high cost of Pt has impeded the commercialization of direct methanol fuel cells. By making it possible to obtain a given level of performance at reduced Pt content (and, hence, lower cost), the discovery may lead to reduction of the economic impediment to commercialization.

Narayanan, Sekharipuram↗

Dynamics of Water Absorption and Evaporation During Methanol Droplet Combustion in Microgravity

The combustion of methanol droplets is profoundly influenced by the absorption and evaporation of water, generated in the gas phase as a part of the combustion products. Initially there is a water-absorption period of combustion during which the latent heat of condensation of water vapor, released into the droplet, enhances its burning rate, whereas later there is a water-evaporation period, during which the water vapor reduces the flame temperature suffciently to extinguish the flame. Recent methanol droplet-combustion experiments in ambient environments diluted with carbon dioxide, conducted in the Combustion Integrated Rack on the International Space Station (ISS), as a part of the FLEX project, provided a method to delineate the water-absorption period from the water-evaporation period using video images of flame intensity. These were obtained using an ultra-violet camera that captures the OH* radical emission at 310 nm wavelength and a color camera that captures visible flame emission. These results are compared with results of ground-based tests in the Zero Gravity Facility at the NASA Glenn Research Center which employed smaller droplets in argon-diluted environments. A simplified theoretical model developed earlier correlates the transition time at which water absorption ends and evaporation starts. The model results are shown to agree reasonably well with experiment.

Hicks, Michael C.↗

Methanol Droplet Combustion in Oxygen-Inert Environments in Microgravity

The Flame Extinguishment (FLEX) experiment that is currently underway in the Combustion Integrated Rack facility onboard the International Space Station is aimed at understanding the effects of inert diluents on the flammability of condensed phase fuels. To this end, droplets of various fuels, including alkanes and alcohols, are burned in a quiescent microgravity environment with varying amounts of oxygen and inert diluents to determine the limiting oxygen index (LOI) for these fuels. In this study we report experimental observations of methanol droplets burning in oxygen-nitrogen-carbon dioxide and oxygen-nitrogen-helium gas mixtures at 0.7 and 1 atmospheric pressures. The initial droplet size varied between approximately 1.5 mm and 4 mm to capture both diffusive extinction brought about by insufficient residence time at the flame and radiative extinction caused by excessive heat loss from the flame zone. The ambient oxygen concentration varied from a high value of 30% by volume to as low as 12%, approaching the limiting oxygen index for the fuel. The inert dilution by carbon dioxide and helium varied over a range of 0% to 70% by volume. In these experiments, both freely floated and tethered droplets were ignited using symmetrically opposed hot-wire igniters and the burning histories were recorded onboard using digital cameras, downlinked later to the ground for analysis. The digital images yielded droplet and flame diameters as functions of time and subsequently droplet burning rate, flame standoff ratio, and initial and extinction droplet diameters. Simplified theoretical models correlate the measured burning rate constant and the flame standoff ratio reasonably well. An activation energy asymptotic theory accounting for time-dependent water dissolution or evaporation from the droplet is shown to predict the measured diffusive extinction conditions well. The experiments also show that the limiting oxygen index for methanol in these diluent gases is around 12% to 13% oxygen by volume.

Nayagam, Vedha↗

Pyrotechnically Actuated Gas Generator Utilizing Aqueous Methanol

A gas-generating device was developed to supplement the ram-air inflation of a supersonic ballute. The device is designed to initially pressurize the ballute following deployment, exposing and orienting its ram-air inlets to free-stream air for complete inflation. The supplemental pressurization decreases the total inflation time, and increases the likelihood of a successful inflation. The device contains a reservoir filled with an aqueous mixture of methanol that, when released in to the interior of the ballute, rapidly vaporizes due to the low ambient pressure. Upon activation of the device, a pair of redundant ring mechanisms initiate pyrotechnic charges that pressurize and rupture the reservoir, resulting in ejection of the methanol in to the ballute. In addition to its role in inflation, the device serves as the structural connection to the ballute. Analytical models were developed for the inflation capability of the device, which were verified using vacuum chamber testing of developmental hardware. Static, deployment, and environmental testing demonstrated the functionality of the ring mechanism and reservoir under several temperature and pressure conditions. Finally, the device was successfully operated during the first Supersonic Flight Dynamics Test (SFDT) of NASA's Low Density Supersonic Decelerator (LDSD) project. The design architecture is scalable to accommodate different quantities of gas generation, can be adjusted to operate in a variety of temperature and atmospheric pressure regimes, and provides a robust device that may be installed with minimal risk to personnel or hardware.

IA↗

Sublimation of Laboratory Ices Millimeter/Submillimeter Experiment (SubLIME): Structure-Specific Identifications of Products from UV-photolyzed Methanol Ice

Submillimeter/far-IR spectroscopy was used to detect and quantify organic molecules sublimated after the ultraviolet photolysis (at 12 K) and warm-up (up to 300 K) of a methanol (CH3OH) ice sample. Eleven sublimated photoproducts were uniquely identified: carbon monoxide (CO), formaldehyde (H2CO), ketene (C2H2O), acetaldehyde (CH3CHO), ethylene oxide (CH2OCH2), vinyl alcohol (CH2CHOH), ethanol (CH3CH2OH), dimethyl ether (CH3OCH3), methyl formate (HCOOCH3), glycolaldehyde (HOCH2CHO), and acetone ((CH3)2CO). Two additional products were detected in the photolyzed ice by Fourier-transform infrared (FTIR) spectroscopy: carbon dioxide (CO2) and methane (CH4). The rotational temperatures and gas densities were calculated for the organics containing two or more C atoms via a rotation diagram analysis, and the gas-phase submillimeter/far-IR technique was used in tandem with mass spectrometry and FTIR spectroscopy of the ice during photolysis. The abundance ratios of the sublimated species (normalized to methanol) were compared to those observed in hot cores (Orion-KL, Sagittarius B2(N), and IRAS 16293-2422(B)) and in comets C/2014 Q2 (Lovejoy) and 67P/Churyumov–Gerasimenko.

K M Yocum↗

Sublimation of Laboratory Ices Millimeter/Submillimeter Experiment (SubLIME): Structure-Specific Identifications of Products from UV-photolyzed Methanol Ice

Submillimeter/far-IR spectroscopy was used to detect and quantify organic molecules sublimated after the ultraviolet photolysis (at 12 K) and warm-up (up to 300 K) of a methanol (CH3OH) ice sample. Eleven sublimated photoproducts were uniquely identified: carbon monoxide (CO), formaldehyde (H2CO), ketene (C2H2O), acetaldehyde (CH3CHO), ethylene oxide (CH2OCH2), vinyl alcohol (CH2CHOH), ethanol (CH3CH2OH), dimethyl ether (CH3OCH3), methyl formate (HCOOCH3), glycolaldehyde (HOCH2CHO), and acetone ((CH3)2CO). Two additional products were detected in the photolyzed ice by Fourier-transform infrared (FTIR) spectroscopy: carbon dioxide (CO2) and methane (CH4). The rotational temperatures and gas densities were calculated for the organics containing two or more C atoms via a rotation diagram analysis, and the gas-phase submillimeter/far-IR technique was used in tandem with mass spectrometry and FTIR spectroscopy of the ice during photolysis. The abundance ratios of the sublimated species (normalized to methanol) were compared to those observed in hot cores (Orion-KL, Sagittarius B2(N), and IRAS 16293-2422(B)) and in comets C/2014 Q2 (Lovejoy) and 67P/Churyumov–Gerasimenko.

K. M. Yocum↗