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At least 19 records

Design and Operation of an Electrochemical Methanol Concentration Sensor for Direct Methanol Fuel Cell Systems

The development of a 150-Watt packaged power source based on liquid feed direct methanol fuel cells is being pursued currently at the Jet propulsion Laboratory for defense applications. In our studies we find that the concentration of methanol in the fuel circulation loop affects the electrical performance and efficiency the direct methanol fuel cell systems significantly. The practical operation of direct methanol fuel cell systems, therefore, requires accurate monitoring and control of methanol concentration. The present paper reports on the principle and demonstration of an in-house developed electrochemical sensor suitable for direct methanol fuel cell systems.

Narayanan, S. R.

Recent Studies on Methanol Crossover in Liquid-Feed Direct Methanol Fuel Cells

In this work, the effects of methanol crossover and airflow rates on the cathode potential of an operating direct methanol fuel cell are explored. Techniques for quantifying methanol crossover in a fuel cell and for separating the electrical performance of each electrode in a fuel cell are discussed. The effect of methanol concentration on cathode potential has been determined to be significant. The cathode is found to be mass transfer limited when operating on low flow rate air and high concentrations of methanol. Improvements in cathode structure and operation at low methanol concentration have been shown to result in improved cell performance.

Valdez, T. I.

Pressure Effects on Combustion of Methanol and Methanol-Docecanol Droplets

The objective of this research is to improve understanding of the combustion of binary fuel mixtures in the vicinity of the critical point. Fiber-supported single droplets and two-droplet arrays of methanol and of mixtures of methanol and 1-dodecanol, initially 0.9 mm in diameter, were burned in room-temperature air at pressures from 0.1 MPa to 9.0 MPa in the NASA Lewis 2.2-second drop tower. The work is a continuation of a collaborative Japan-US research effort designed to increase knowledge of high-pressure combustion of fuel sprays, relevant to application in propulsive and power-production devices such as Diesel engines. Some previous publications from this cooperative program may be cited. All of the previous experiments concerned alkanes and alkane mixtures. The new research reported here addresses alcohols and alcohol mixtures, to ascertain the degree to which previous results for alkanes extend to alcohols. There have been many previous experimental studies of methanol droplet combustion and a few of alcohol mixtures, but not at the high pressures of interest here. There is some experimental information on methanol droplet combustion at elevated pressure but none on the alcohol mixtures extending to critical pressures, as in the present study.

Okai, K.

Studies on Methanol Crossover in Liquid-Feed Direct Methanol Pem Fuel Cells

The performance of liquid feed direct methanol fuel cells using various types of Nafion membranes as the solid polymer electrolyte have been studied. The rate of fuel crossover and electrical performance has been measured for cells with Nafion membranes of various thicknesses and equivalent weights. The crossover rate is found to decrease with increasing thickness and applied current. The dependence of crossover rate on current density can be understood in terms of a simple linear diffusion model which suggests that the crossover rate can be influenced by the electrode structure in addition to the membrane. The studies suggest that Nafion EW 1500 is a very promising alternate to Nafion EW 1100 for direct methanol fuel cells.

Methanol Pem Fuel

Evaluation of dissociated and steam-reformed methanol as automotive engine fuels

Dissociated and steam reformed methanol were evaluated as automotive engine fuels. Advantages and disadvantages in using methanol in the reformed rather than liquid state were discussed. Engine dynamometer tests were conducted with a four cylinder, 2.3 liter, spark ignition automotive engine to determine performance and emission characteristics operating on simulated dissociated and steam reformed methanol (2H2 + CO and 3H2 + CO2 respectively), and liquid methanol. Results are presented for engine performance and emissions as functions of equivalence ratio, at various throttle settings and engine speeds. Operation on dissociated and steam reformed methanol was characterized by flashback (violent propagation of a flame into the intake manifold) which limited operation to lower power output than was obtainable using liquid methanol. It was concluded that: an automobile could not be operated solely on dissociated or steam reformed methanol over the entire required power range - a supplementary fuel system or power source would be necessary to attain higher powers; the use of reformed mechanol, compared to liquid methanol, may result in a small improvement in thermal efficiency in the low power range; dissociated methanol is a better fuel than steam reformed methanol for use in a spark ignition engine; and use of dissociated or steam reformed methanol may result in lower exhaust emissions compared to liquid methanol.

Lalk, T. R.

Methanol Uptake by Low Temperature Aqueous Sulfuric Acid Solutions

The global methanol budget is currently unbalanced, with source terms significantly larger than the sinks terms. To evaluate possible losses of gaseous methanol to sulfate aerosols, the solubility and reactivity of methanol in aqueous sulfuric acid solutions representative of upper tropospheric and lower stratospheric aerosols is under investigation. Methanol will partition into sulfate aerosols according to its Henry's law solubility. Using standard uptake techniques in a Knudsen cell reactor, we have measured the effective Henry's law coefficient, H*, for cold (196 - 220 K) solutions ranging between 45 and 70 wt % H2SO4. We have found that methanol solubility ranges from approx. 10(exp 5) - 10(exp 7) M/atm for UT/LS conditions. Solubility increases with decreasing temperature and with increasing sulfuric acid content. Although methanol is slightly more soluble than are acetone and formaldehyde, current data indicate that uptake by clean aqueous sulfuric acid particles will not be a significant sink for methanol in the UT/LS. These solubility measurements include uptake due to physical solvation and any rapid equilibria which are established in solution. Reaction between primary alcohols and sulfuric acid does occur, leading to the production of alkyl sulfates. Literature values for the rate of this reaction suggest that formation of CH3OSO3H is not significant over our experimental time scale for solutions below 80 wt % H2SO4. To confirm this directly, results obtained using a complementary equilibrium measurement technique will also be presented.

Iraci, L. T.

The Production and Potential Detection of Hexamethylenetetramine-Methanol in Space

Numerous laboratory studies of astrophysical ice analogues have shown that their exposure to ionizing radiation leads to the production of large numbers of new, more complex compounds, many of which are of astrobiological interest. We show here that the irradiation of astrophysical ice analogues containing H2O, CH3OH, CO, and NH3 yields quantities of hexamethylenetetramine-methanol (hereafter HMT-methanol; C7N4H14O) that are easily detectible in the resulting organic residues. This molecule differs from simple HMT, which is known to be abundant in similar ice photolysis residues, by the replacement of a peripheral H atom with a CH2OH group. As with HMT, HMT-methanol is likely to be an amino acid precursor. HMT has tetrahedral (T(d)) symmetry, whereas HMT-methanol has C1 symmetry. We report the computed expected infrared spectra for HMT and HMT-methanol obtained using ab initio quantum chemistry methods and show that there is a good match between the observed and computed spectra for regular HMT. Since HMT-methanol lacks the high symmetry of HMT, it produces rotational transitions that could be observed at longer wavelengths, although establishing the exact positions of these transitions may be challenging. It is likely that HMT-methanol represents an abundant member of a larger family of functionalized HMT molecules that may be present in cold astrophysical environments.

Materese, Christopher K.

California methanol assessment. Volume 2: Technical report

Energy feedstock sources for methanol; methanol and other synfuels; transport, storage, and distribution; air quality impact of methanol use in vehicles, chemical methanol production and use; methanol utilization in vehicles; methanol utilization in stationary applications; and environmental and regulatory constraints are discussed.

Otoole, R.

Solubility of methanol in low-temperature aqueous sulfuric acid and implications for atmospheric particle composition

Using traditional Knudsen cell techniques, we find well-behaved Henry's law uptake of methanol in aqueous 45 - 70 wt% H2SO4 solutions at temperatures between 197 and 231 K. Solubility of methanol increases with decreasing temperature and increasing acidity, with an effective Henry's law coefficient ranging from 10(exp 5) - 10(exp 8) M/atm. Equilibrium uptake of methanol into sulfuric acid aerosol particles in the upper troposphere and lower stratosphere will not appreciably alter gas-phase concentrations of methanol. The observed room temperature reaction between methanol and sulfuric acid is too slow to provide a sink for gaseous methanol at the temperatures of the upper troposphere and lower stratosphere. It is also too slow to produce sufficient quantities of soluble reaction products to explain the large amount of unidentified organic material seen in particles of the upper troposphere.

Iraci, Laura T.

CO, Water, and Tentative Methanol in η Carinae Approaching Periastron

The complex circumstellar environment around the massive binary and luminous blue variable η Carinae is known to harbor numerous light molecules, emitting most strongly in rotational states with upper level energies to ∼300 K. In circumstellar gas, the complex organic molecule methanol (CH3OH) has been found almost exclusively around young stellar objects, and thus regarded as a signpost of recent star formation. Here we report the first potential detection of methanol around a highly evolved high-mass star, while using the Atacama Large Millimeter Array to investigate molecular cloud conditions traced by CO (2–1) in an orbit phase preceding the 2020 periastron. The methanol emission originates from hot (T(gas) ≃ 700 K) material, ∼2″ (0.02 pc) across, centered on the dust-obscured binary, and is accompanied by prominent absorption of continuum radiation in a cooler (T(gas) ≃ 110 K) layer of gas. We also report a first detection of water in Herschel observations at 557 and 988 GHz. The methanol abundance is several to 50 times higher than observed toward several lower-mass stars, while water abundances are similar to those observed in cool, dense molecular clouds. The very high methanol: water abundance ratio in the core of η Car may suggest methanol formation processes similar to Fischer–Tropschtype catalytic reactions on dust grains. These observations prove that complex molecule formation can occur in a chemically evolved massive stellar environment, given sufficient gas densities and shielding conditions as may occur in material around massive interacting companions and merger remnants.

Patrick W Morris

Predicted exhaust emissions from a methanol and jet fueled gas turbine combustor

A computer model of a gas turbine combustor has been used to predict the kinetic combustion and pollutant formation processes for methanol and simulated jet fuel. Use of the kinetic reaction mechanisms has also allowed a study of ignition delay and flammability limit of these two fuels. The NOX emissions for methanol were predicted to be from 69 to 92% lower than those for jet fuel at the same equivalence ratio which is in agreement with experimentally observed results. The high heat of vaporization of methanol lowers both the combustor inlet mixture temperatures and the final combustion temperatures. The lower combustion temperatures lead to low NOX emissions while the lower inlet mixture temperatures increase methanol's ignition delay. This increase in ignition delay dictates the lean flammability limit of methanol to be 0.8, while jet fuel is shown to combust at 0.4.

Adelman, H. G.

Low Crossover Polymer Electrolyte Membranes for Direct Methanol Fuel Cells

Direct Methanol Fuel Cells (DMFC's) using polymer electrolyte membranes are promising power sources for portable and vehicular applications. State of the art technology using Nafion(R) 117 membranes (Dupont) are limited by high methanol permeability and cost, resulting in reduced fuel cell efficiencies and impractical commercialization. Therefore, much research in the fuel cell field is focused on the preparation and testing of low crossover and cost efficient polymer electrolyte membranes. The University of Southern California in cooperation with the Jet Propulsion Laboratory is focused on development of such materials. Interpenetrating polymer networks are an effective method used to blend polymer systems without forming chemical links. They provide the ability to modify physical and chemical properties of polymers by optimizing blend compositions. We have developed a novel interpenetrating polymer network based on poly (vinyl - difluoride)/cross-linked polystyrenesulfonic acid polymer composites (PVDF PSSA). Sulfonation of polystyrene accounts for protonic conductivity while the non-polar, PVDF backbone provides structural integrity in addition to methanol rejection. Precursor materials were prepared and analyzed to characterize membrane crystallinity, stability and degree of interpenetration. USC JPL PVDF-PSSA membranes were also characterized to determine methanol permeability, protonic conductivity and sulfur distribution. Membranes were fabricated into membrane electrode assemblies (MEA) and tested for single cell performance. Tests include cell performance over a wide range of temperatures (20 C - 90 C) and cathode conditions (ambient Air/O2). Methanol crossover values are measured in situ using an in-line CO2 analyzer.

Prakash, G. K. Surya

First Detection of Methanol in a Class O Protostellar Disk

We report the detection of emission from methanol in a compact source coincident with the position of the L1157 infrared source, which we attribute to molecules in the disk surrounding this young, Class O protostellar object. In addition, we identify a spectral feature in the outflow corresponding to an ethanol transition. Using the Caltech Owens Valley Millimeter Array with a synthesized beam size of 2", we detect spatially unresolved methanol in the 2(sub k) - 1(sub k) transitions at 3mm, which is coincident in position with the peak of the continuum emission. The gas phase methanol could be located in the central region (< 100 AU radius) of a flat disk, or in an extended heated surface layer (approx. 200 AU radius) of a flared disk. The fractional abundance of methanol X(CH3OH) is approx. 2 x l0(exp -8) in the flat disk model, and 3 x l0(exp -7) for the flared disk. The fractional abundance is small in the disk as a whole, but considerably larger in the warm portions. This difference indicates that substantial chemical processing probably takes place in the disk via depletion and desorption. The methanol desorbed from the grains in the warm surface layers returns to the icy grain mantles in the cooler interior of the disk, where it is available to become part of the composition of solar system-like bodies, such as comets, formed in the outer circumstellar region. This first millimeter-wavelength detection of a complex organic molecule in a young protostellar disk has implications for disk structure and chemical evolution and for potential use as a temperature probe. The research of TV and WL was conducted at the Jet Propulsion Laboratory, California Institute of Technology with support from the National Aeronautics and Space Administration.

Velusamy, T.

Methanol Uptake By Low Temperature Aqueous Sulfuric Acid Solutions

To evaluate the role of upper tropospheric and lower stratospheric aerosols in the global budget of methanol, the solubility and reactivity of CH3OH in aqueous sulfuric acid solutions are under investigation. Using standard uptake techniques in a Knudsen cell reactor, we have measured the effective Henry's law coefficient, H(*), for methanol dissolution into 45 to 70 percent by weight H2SO4. We find that methanol solubility ranges from 10(exp 5) to 10(exp 8) M/atm and increases with decreasing temperature and with increasing sulfuric acid content. These solubility measurements include uptake due to physical solvation and all rapid equilibria which are established in solution. Our data indicate that simple uptake by aqueous sulfuric acid particles will not be a significant sink for methanol in the UT/LS. These results differ from those recently reported in the literature, and an explanation of this disparity will be presented. In addition to solvation, reaction between primary alcohols and sulfuric acid does occur, leading to the production of alkyl sulfates. Literature values for the rate of this reaction suggest that formation of CH3OSO3H may proceed in the atmosphere but is not significant under our experimental conditions. Results obtained using a complementary equilibrium measurement technique confirm this directly. In addition, the extent of methanol sequestration via formation of mono- and dimethylsulfate will be evaluated under several atmospheric conditions.

Iraci, Laura T.

Heterogeneous Chemistry Involving Methanol in Tropospheric Clouds

In this report we analyze airborne measurements to suggest that methanol in biomass burning smoke is lost heterogeneously in clouds. When a smoke plume intersected a cumulus cloud during the SAFARI 2000 field project, the observed methanol gas phase concentration rapidly declined. Current understanding of gas and aqueous phase chemistry cannot explain the loss of methanol documented by these measurements. Two plausible heterogeneous reactions are proposed to explain the observed simultaneous loss and production of methanol and formaldehyde, respectively. If the rapid heterogeneous processing of methanol, seen in a cloud impacted by smoke, occurs in more pristine clouds, it could affect the oxidizing capacity of the troposphere on a global scale.

Tabazadeh, A.