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At least 505 records · Page 28

Three stage gas dilution system for calibration of air quality instrumentation

Tests were conducted on a three stage gas dilution system to evaluate the performance of the system for preparation of gas mixtures in the range of concentrations from 1 to 200 ppm. The test gas used in the evaluation was carbon monoxide. Mixtures of carbon monoxide and air were prepared in the gas dilution system and analyzed on stream with a commercially available infrared CO detector. Results showed the gas dilution system to be accurate to within 5, 3, and 2 percent in the respective ranges of 1-20 ppm, 20-50 ppm, and 50-200 ppm.

Gregory, G. L.↗

Thermal Theory of Combustion and Explosion: Theory of Normal Flame Propagation - 3

The technical memorandum covers experimental data on flame propagation, the velocity of flame propagation, analysis of the old theoretical views of flame propagation, confirmation of the theory for simple reactions (theory of combustion of explosive substances and in particular nitroglycol), and check of the theory by example of a chain oxidizing reaction (theory of flame propagation in carbon monoxide, air and carbon monoxide - oxygen mixtures).

Semenov, N. N.↗

On-site manufacture of propellant oxygen from lunar resources

The Aerojet Carbothermal Process for the manufacture of oxygen from lunar resources has three essential steps: the reduction of silicate with methane to form carbon monoxide and hydrogen; the reduction of carbon monoxide with hydrogen to form methane and water; and the electrolysis of water to form oxygen and hydrogen. This cyclic process does not depend upon the presence of water or water precursors in the lunar materials; it will produce oxygen from silicates regardless of their precise composition and fine structure. Research on the first step of the process was initiated by determining some of the operating conditions required to reduce igneous rock with carbon and silicon carbide. The initial phase of research on the second step is completed; quantitative conversion of carbon monoxide and hydrogen to methane and water was achieved with a nickel-on-kieselguhr catalyst. The equipment used in and the results obtained from these process studies are reported in detail.

Rosenberg, Sanders D.↗

Modeling of the HiPco process for carbon nanotube production. I. Chemical kinetics

A chemical kinetic model is developed to help understand and optimize the production of single-walled carbon nanotubes via the high-pressure carbon monoxide (HiPco) process, which employs iron pentacarbonyl as the catalyst precursor and carbon monoxide as the carbon feedstock. The model separates the HiPco process into three steps, precursor decomposition, catalyst growth and evaporation, and carbon nanotube production resulting from the catalyst-enhanced disproportionation of carbon monoxide, known as the Boudouard reaction: 2 CO(g)-->C(s) + CO2(g). The resulting detailed model contains 971 species and 1948 chemical reactions. A second model with a reduced reaction set containing 14 species and 22 chemical reactions is developed on the basis of the detailed model and reproduces the chemistry of the major species. Results showing the parametric dependence of temperature, total pressure, and initial precursor partial pressures are presented, with comparison between the two models. The reduced model is more amenable to coupled reacting flow-field simulations, presented in the following article.

Evaluation Studies↗

Exhaust emission survey of an F100 afterburning turbofan engine at simulated altitude flight conditions

Emissions of carbon monoxide, total oxides of nitrogen, unburned hydrocarbons, and carbon dioxide from an F100, afterburning, two spool turbofan engine at simulated flight conditions are reported. For each flight condition emission measurements were made for two or three power levels from intermediate power (nonafterburning) through maximum afterburning. The data showed that emissions vary with flight speed, altitude, power level, and radial position across the nozzle. Carbon monoxide emissions were low for intermediate power (nonafterburning) and partial afterburning, but regions of high carbon monoxide were present downstream of the flame holder at maximum afterburning. Unburned hydrocarbon emissions were low for most of the simulated flight conditions. The local NOX concentrations and their variability with power level increased with increasing flight Mach number at constant altitude, and decreased with increasing altitude at constant Mach number. Carbon dioxide emissions were proportional to local fuel air ratio for all conditions.

Moss, J. E.↗

Propulsion systems using in situ propellants for a Mars Ascent Vehicle

The indigenous propellants of oxygen and carbon monoxide were studied for use in a Mars Ascent Vehicle (MAV). Both the oxygen and carbon monoxide were evaluated as turbine working fluids for a full expander engine cycle used in the MAV. Two oxygen working fluid engines and four carbon monoxide engines were investigated. The maximum hot-gas-side wall temperature was limited to either 445 K (800R) or 556 K (1000 R) over a range of working fluid mass flows. An engine thrust of 44.5 kN (1,000 lb(sub f)) was assumed. The engine characteristics of coolant inlet pressure, total engine length, specific impulse, pump efficiencies, and turbine power required were optimized. Of the six engines evaluated, the study showed that either type of working fluid was feasible for a MAV engine. Using carbon monoxide as the working fluid resulted in the best engine characteristics.

Wadel, Mary F.↗

Propulsion systems using in situ propellants for a Mars ascent vehicle

The indigenous propellants of oxygen and carbon monoxide were studied for use in a Mars Ascent Vehicle (MAV). Both the oxygen and carbon monoxide were evaluated as turbine working fluids for a full expander engine cycle used in the MAV. Two oxygen working fluid engines and four carbon monoxide engines were investigated. The maximum hot-gas-side wall temperature was limited to either 445 K (800 R) or 556 K (1000 R) over a range of working fluid mass flows. An engine thrust of 44.5 kN (1,000 lb(sub f)) was assumed. The engine characteristics of coolant inlet pressure, total engine length, specific impulse, pump efficiencies, and turbine power required were optimized. Of the six engines evaluated, the study showed that either type of working fluid was feasible for a MAV engine. Using carbon monoxide as the working fluid resulted in the best engine characteristics.

Wadel, Mary F.↗

Solar reduction of carbon dioxide on copper-tin electrocatalysts with energy conversion efficiency near 20%

Abstract Copper catalysts modified with tin have been demonstrated to be selective for the electroreduction of carbon dioxide to carbon monoxide. However, such catalysts require the precise control of tin loading amount. Here, we develop a copper/tin-oxide catalyst with dominant tin oxide surface being formed via a spontaneous exchange reaction between sputtered tin and copper oxide. Even though the surface of this catalyst is tin-rich, it achieves an excellent performance towards carbon monoxide production in a flow cell. This contrasts with copper/tin-oxide prepared via atomic layer deposition since it yields selectivity towards carbon monoxide only on a copper-rich surface. Mechanism studies reveal that the tin sites on the tin-rich copper/tin-oxide surface achieve a suitable binding with adsorbed carbon monoxide under the presence of copper. Powered by a triple-junction solar cell, the copper/tin-oxide based electrolyzer sets a new benchmark solar-to-chemical energy conversion efficiency of 19.9 percent with a Faradaic efficiency of 98.9 percent towards carbon monoxide under simulated standard air mass 1.5 global illumination.

14 SOLAR ENERGY↗

One‐Pot Synthesis of Xanthone by Carbonylative Suzuki Coupling Reaction

Abstract Xanthone derivatives have a dibenzo‐y‐pyrone scaffold which has gained great interest in Medicinal Chemistry due to their diverse biological activities. Usually, its synthesis requires multi‐step synthetic routes using harsh conditions and high catalyst loadings. In this communication, we report for the first time a one‐pot synthesis of the xanthone scaffold based on a carbonylative Suzuki coupling. Iodophenol and (2‐methoxyphenyl)boronic acid were coupled under carbon monoxide, generated from a carbon monoxide surrogate. An experimental data‐based model was built to guide the reaction optimization. The optimized conditions were 1 mol% of a pincer complex as palladium catalyst, 5 equivalents of K 2 CO 3 as base, and DMF:water (7 : 3) as solvent. The robustness of the synthetic method, namely in terms of the reactants scope, was also evaluated. This approach provided the xanthone scaffold in high yields and provided a deep insight into the carbonylative Suzuki couplings.

Loureiro, Daniela R. P.↗

Oxidative Grafting for Catalyst Synthesis in Surface Organometallic Chemistry

The development of new methods of catalyst synthesis with the potential to generate active site structures orthogonal to those accessible by traditional protocols is of great importance for discovering new materials for addressing challenges in the evolving energy and chemical economy. Here, in this work, the generality of oxidative grafting of organometallic and well-defined molecular metal precursors onto redox-active surfaces such as manganese dioxide (MnO 2 ) and lithium manganese oxide (LiMn 2 O 4 ) is investigated. Nine molecular metal precursors are explored, spanning groups 4–11 and each of the three periods of the transition metal series. The byproducts of the oxidative grafting reaction, a mixture of protodemetalation and ligand homocoupling for several organometallic precursors, was found to provide insights into the mechanism of the grafting reaction, suggesting oxidation of both the metal d-orbitals, as well as the metal–carbon σ-bonds, resulting in ejection of the ligand radical fragment. Analysis of the supported structures and oxidation state by X-ray absorption spectroscopy (XAS) and X-ray photoelectron spectroscopy (XPS) suggests that several of the chemisorbed metal ions are intercalated into interstitial vacancies of the surface structure while other complexes form intact molecular fragments on the surface. Proof of concept for the use of this metalation protocol to generate diverse, metal-dependent catalytic performance is demonstrated by the application of these materials in the conversion of cyclohexane to K/A oil (cyclohexanol and cyclohexanone) with tert-butyl hydroperoxide, as well as in the low-temperature (T ≤ 50 °C) oxidation of carbon monoxide to carbon dioxide.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Results of the 2018 Wood Stove Design Challenge

The 2018 Wood Stove Design Challenge was an international design competition which sought to identify top performing residential wood stoves based on automation. To prepare for the event, the Northeast States for Coordinated Air Use Management (NESCAUM) developed a testing protocol that challenged the stoves by testing them in more field-like conditions—capturing emissions from start-up, reloading a stove, and the use of larger piece sizes. Flue gas emissions were measured using a combination of in-stack and novel dilution sampling methods, as the event occurred on the National Mall in Washington D.C. in a non-laboratory setting. Particulate matter (PM), carbon monoxide (CO), carbon dioxide (CO2), and methane (CH4) were measured from three stoves in real-time. A combustion efficiency was also calculated for each stove in real-time. Measured PM emission rates ranged between 1.8 and 8.0 g/hr for all stoves and operating conditions, with the highest emissions being measured during cold start in all cases. The test average PM emission rates were 2.4, 4.0, and 2.4 g/hr for stoves A, B, and C, respectively. Results showed emissions measured during transient operations, which are often excluded in current certification methods, can be significantly higher than steady-state periods—echoing other studies and highlighting the importance of testing in various operational modes for more realistic emission estimates. Additionally, the stoves had overall CO emission rates of 48.8, 284.8, and 100.8 g/hr, for stoves A, B and C, respectively. Calculated PM and CO emission factors overall were low considering the testing protocol sought to follow more challenging yet realistic practices in terms of fuel loading and operating procedures. The overall estimated combustion efficiency for stoves A, B, and C was 85%, 78%, 76%, respectively and in all cases was lowest during the cold start period.This report details the successfully proposed and assembled instrumentation that was relatively portable for field-site testing and the results of the emissions measurements for the 2018 Wood Stove Design Challenge competition. Overall, the repeatability of each stove was favorable with coefficients of variation (COV) ranging from 7 to 15% for measured PM concentrations.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Cleaner Cooking: Exploring Tools to Measure and Understand the Long-term Adoption and Environmental Significance of Cookstoves in India

About 40% of the world’s population, or roughly 3 billion people, rely on solid biomass fuels like coal, wood, dung, and crop residues to cook and meet their household energy needs. This outdated energy system has severe social, health, and environmental implications. Women are disproportionately affected as they predominantly bear the burden of cooking and collecting fuelwood, which exacerbates the “time poverty” trap that restricts them from participating in economic and educational activities. Exposure to indoor solid fuel combustion, also known as household air pollution, is responsible for 3-4 million premature deaths per year and is a leading risk factor for chronic obstructive pulmonary disease, childhood pneumonia, stroke, ischemic heart disease, and lung cancer. Solid-fuel cooking contributes to 16% of global ambient air pollution, emitting CO 2 and other climate-forcing pollutants like carbon monoxide, black carbon, and methane.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

A formaldehyde and nitrogen dioxide toxics monitor for environmental justice

DOE’s Integrated Field Laboratories (IFLs) require a vast array of measurements to measure urban air quality. Nitrogen dioxide (NO2) and formaldehyde (HCHO) are ubiquitous pollutants with numerous sources, most notably vehicle exhaust. High-spatial density measurements are critical to understanding how certain neighborhoods are more adversely impacted by pollutants. This report describes the results of a Phase I SBIR project to develop and demonstrate a rapid, affordable, low-power monitor to provide high spatial resolution mobile measurements of formaldehyde and nitrogen dioxide at street-level, where people live and walk. The spatial density will be achieved via rapid measurements on a mobile platform. This sensor will quantify spatial disparities in cities of the toxics, HCHO and NO2, as well as carbon monoxide and carbon dioxide for better source identification. These species are detected in the mid infrared by laser absorption spectroscopy, and fiberoptics are used. Tasks accomplished include identification and testing of the appropriate spectroscopic regions; coupling of laser light into a fiberoptic system; development of software to control miniature electronics to scan and control two lasers simultaneously; coupling of the mid infrared fiber into a multipass cell for enhanced pathlength and sensitivity; characterization of sources of instrument noise; and design work for a Phase II prototype.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Modeled and observed properties related to the direct aerosol radiative effect of biomass burning aerosol over the southeastern Atlantic

Biomass burning smoke is advected over the southeastern Atlantic Ocean between July and October of each year. This smoke plume overlies and mixes into a region of persistent low marine clouds. Model calculations of climate forcing by this plume vary significantly in both magnitude and sign. NASA EVS-2 (Earth Venture Suborbital-2) ORACLES (ObseRvations of Aerosols above CLouds and their intEractionS) had deployments for field campaigns off the west coast of Africa in 3 consecutive years (September 2016, August 2017, and October 2018) with the goal of better characterizing this plume as a function of the monthly evolution by measuring the parameters necessary to calculate the direct aerosol radiative effect. Here, this dataset and satellite retrievals of cloud properties are used to test the representation of the smoke plume and the underlying cloud layer in two regional models (WRF-CAM5 and CNRM-ALADIN) and two global models (GEOS and UM-UKCA). The focus is on the comparisons of those aerosol and cloud properties that are the primary determinants of the direct aerosol radiative effect and on the vertical distribution of the plume and its properties. The representativeness of the observations to monthly averages are tested for each field campaign, with the sampled mean aerosol light extinction generally found to be within 20 % of the monthly mean at plume altitudes. When compared to the observations, in all models, the simulated plume is too vertically diffuse and has smaller vertical gradients, and in two of the models (GEOS and UM-UKCA), the plume core is displaced lower than in the observations. Plume carbon monoxide, black carbon, and organic aerosol masses indicate underestimates in modeled plume concentrations, leading, in general, to underestimates in mid-visible aerosol extinction and optical depth. Biases in mid-visible single scatter albedo are both positive and negative across the models. Observed vertical gradients in single scatter albedo are not captured by the models, but the models do capture the coarse temporal evolution, correctly simulating higher values in October (2018) than in August (2017) and September (2016). Uncertainties in the measured absorption Ångstrom exponent were large but propagate into a negligible (<4 %) uncertainty in integrated solar absorption by the aerosol and, therefore, in the aerosol direct radiative effect. Model biases in cloud fraction, and, therefore, the scene albedo below the plume, vary significantly across the four models. The optical thickness of clouds is, on average, well simulated in the WRF-CAM5 and ALADIN models in the stratocumulus region and is underestimated in the GEOS model; UM-UKCA simulates cloud optical thickness that is significantly too high. Overall, the study demonstrates the utility of repeated, semi-random sampling across multiple years that can give insights into model biases and how these biases affect modeled climate forcing. The combined impact of these aerosol and cloud biases on the direct aerosol radiative effect (DARE) is estimated using a first-order approximation for a subset of five comparison grid boxes. A significant finding is that the observed grid box average aerosol and cloud properties yield a positive (warming) aerosol direct radiative effect for all five grid boxes, whereas DARE using the grid-box-averaged modeled properties ranges from much larger positive values to small, negative values. It is shown quantitatively how model biases can offset each other, so that model improvements that reduce biases in only one property (e.g., single scatter albedo but not cloud fraction) would lead to even greater biases in DARE. Across the models, biases in aerosol extinction and in cloud fraction and optical depth contribute the largest biases in DARE, with aerosol single scatter albedo also making a significant contribution.

54 ENVIRONMENTAL SCIENCES↗

Gaseous exhaust emissions from a J-58 engine at simulated supersonic flight conditions

Emissions of total oxides of nitrogen, unburned hydrocarbons, carbon monoxide, and carbon dioxide from a J-58 engine at simulated flight conditions of Mach 2.0, 2.4, and 2.8 at 19.8 km altitude are reported. For each flight condition, measurements were made for four engine power levels from maximum power without afterburning through maximum afterburning. These measurements were made 7 cm downstream of the engine primary nozzle using a single point traversing gas sample probe. Results show that emissions vary with flight speed, engine power level, and with radial position across the exhaust.

Holdeman, J. D.↗

The Viking carbon assimilation experiments - Interim report

A synthesis of organic matter from atmospheric carbon monoxide or carbon dioxide, or both, appears to take place in the surface material of Mars at a low rate. The synthesis appears to be thermolabile and to be inhibited by moisture.

Horowitz, N. H.↗