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At least 127 records · Page 7

Ambient ammonia measurements using laser photo-acoustic spectroscopy

Ammonia concentrations reached minimal levels (approximately 0.1 ppb) in early winter, followed by a sudden later winter increase. A direct relationship between ambient ammonia levels and air temperature was inferred from the data (linear correlation coefficient r=0.53). Ammonia concentrations were determined to be directly related to the absolute humidity of the air (r=0.72); a weaker relationship between ammonia concentrations and relative humidity was discovered (r=0.37). The data also indicated that ammonia levels were generally higher within continental air masses than those of maritime origin. Soil parameters such as pH and moisture content were found to have a major bearing on the release of gaseous ammonia from soils in the region.

Aldridge, M. D., III↗

Calorimetric studies of the ammonia-water system with application to the outer solar system

A series of heating experiments was performed on the condensed ammonia-water system using a differential scanning calorimeter (DSC). The water-rich samples were cooled quickly to below 130 K, then heated at a variety of rates. Rather than a single peritectic melt at 176 K, expected for the equilibrium system of water ice and ammonia dihydrate, four enthalpic transitions were repeatedly seen in the temperature range 150-176 K. These transitions are generally consistent with the earlier calorimetric results of Van Kasteren (1973), who interpreted the lowest temperature exotherm as crystallization of an amorphous ammonia-water compound formed during cooling. We propose that both sets of experiments are seeing the crystallization of ammonia monohydrate, which is metastable relative to the dihydrate, followed by partial remelting and crystallization of dihydrate upon further heating. The apparent stability of the monohydrate in the dihydrate equilibrium field implies a potentially complex behavior of ammonia-water ices in satellites. Possible self-heating of the mixture by several tens of degrees up to the 170 K eutectic could make mobilization of ammonia-water liquids in icy satellite interiors energetically easier than previously thought.

Yarger, Jeffery↗

An Exposure Prevention Plan for an Anhydrous Ammonia Handling System

In July of 1996, the Industrial Hygiene Team of the Environmental Management Office at NASA Lewis Research Center was contacted by the Space Station Program Office to conduct ammonia awareness training for a team of engineers and technicians. The team was tasked with assembling and operating an ammonia handling system for testing of a photovoltaic radiator at the NASA Plum Brook Station Space Power Facility. The ammonia handling system supports a radiator designed to radiate excess heat from a photovoltaic array module used to provide power to the International Space Station. The system would consist of a hazardous materials trailer equipped with an anhydrous ammonia tank, heater, accumulator, chiller, and flow bench. Meetings were held with representatives from the Space Station Program Office, the engineers and Plum Brook safety personnel. Guidance was also provided by representatives from Kennedy Space Center. Determinations were made concerning the locations and types of potential exposures and a plan was developed which included training, personal protective equipment, engineering controls and emergency response. Various organizations including the Plum Brook Safety Committee, the Lewis Environmental Management Office, the Test Readiness Review Board and the Program Office all had requirements that had to be met in order to satisfy themselves that all personnel involved in the operation of the system would be safe. What resulted was a comprehensive plan that provided more than adequate safety measures and succeeded in protecting all personnel from the hazards of the ammonia system. Testing of the photovoltaic radiator was successful and although ammonia leaks were detected and maintenance of the system was ongoing, no one was injured. It was felt that the training and controls in place allowed for a comfort level that did not interfere with the operations.

Cathy L Padolewski↗

Comparison of Thermal Performance Characteristics of Ammonia and Propylene Loop Heat Pipes

In this paper, experimental work performed on a breadboard Loop Heat Pipe (LHP) is presented. The test article was built by DCI for the Geoscience Laser Altimeter System (GLAS) instrument on the ICESat spacecraft. The thermal system requirements of GLAS have shown that ammonia cannot be used as the working fluid in this LHP because GLAS radiators could cool to well below the freezing point of ammonia. As a result, propylene was proposed as an alternative LHP working fluid since it has a lower freezing point than ammonia. Both working fluids were tested in the same LHP following a similar test plan in ambient conditions. The thermal performance characteristics of ammonia and propylene LHP's were then compared. In general, the propylene LHP required slightly less startup superheat 5nd less control heater power than the ammonia LHP, The thermal conductance values for the propylene LHP were also lower than the ammonia LHP. Later, the propylene LHP was tested in a thermal vacuum chamber. These tests demonstrated that propylene could meet the GLAS thermal design requirements. Design guidelines were proposed for the next flight-like Development Model (DM) LHP for thermal control of the GLAS instrument.

Kaya, Tarik↗

Numerical Study of Ammonia Leak and Dispersion in the International Space Station

Release of ammonia into the International Space Station (ISS) cabin atmosphere can occur if the water/ammonia barrier breach of the active thermal control system (ATCS) interface heat exchanger (IFHX) happens. After IFHX breach liquid ammonia is introduced into the water-filled internal thermal control system (ITCS) and then to the cabin environment through a ruptured gas trap. Once the liquid water/ammonia mixture exits ITCS, it instantly vaporizes and mixes with the U.S. Laboratory cabin air that results in rapid deterioration of the cabin conditions. The goal of the study is to assess ammonia propagation in the Station after IFHX breach to plan the operation procedure. A Computational Fluid Dynamics (CFD) model for accurate prediction of airflow and ammonia transport within each of the modules in the ISS cabin was developed. CFD data on ammonia content in the cabin aisle way of the ISS and, in particular, in the Russian On- Orbit Segment during the period of 15 minutes after gas trap rupture are presented for four scenarios of rupture response. Localized effects of ammonia dispersion and risk mitigation are discussed.

Son, Chang H.↗

Analysis of Saturn's Thermal Emission at 2.2-cm Wavelength: Spatial Distribution of Ammonia Vapor

This work focuses on determining the latitudinal structure of ammonia vapor in Saturn's cloud layer near 1.5 bars using the brightness temperature maps derived from the Cassini RADAR (Elachi et al., 2004) instrument, which works in a passive mode to measure thermal emission from Saturn at 2.2-cm wavelength. We perform an analysis of five brightness temperature maps that span epochs from 2005 to 2011, which are presented in a companion paper by Janssen et al. (2013a, this issue). The brightness temperature maps are representative of the spatial distribution of ammonia vapor, since ammonia gas is the only effective opacity source in Saturn's atmosphere at 2.2-cm wavelength. Relatively high brightness temperatures indicate relatively low ammonia relative humidity (RH), and vice versa. We compare the observed brightness temperatures to brightness temperatures computed using the Juno atmospheric microwave radiative transfer (JAMRT) program which includes both the means to calculate a tropospheric atmosphere model for Saturn and the means to carry out radiative transfer calculations at microwave frequencies. The reference atmosphere to which we compare has a 3x solar deep mixing ratio of ammonia (we use 1.352x10(exp -4) for the solar mixing ratio of ammonia vapor relative to H2; see Atreya, 2010) and is fully saturated above its cloud base. The maps are comprised of residual brightness temperatures-observed brightness temperature minus the model brightness temperature of the saturated atmosphere.

Atmospheres↗

Co-Adsorption of Ammonia and Formaldehyde on Regenerable Carbon Sorbents for the Primary Life Support System (PLSS)

Results are presented on the development of a reversible carbon sorbent for trace-contaminant (TC) removal for use in Extravehicular Activities (EVAs), and more specifically in the Primary Life Support System (PLSS). The current TC-control technology involves the use of a packed bed of acid-impregnated granular charcoal, which is deemed non-regenerable, while the carbon-based sorbent under development in this project can be regenerated by exposure to vacuum at room temperature. Data on concurrent sorption and desorption of ammonia and formaldehyde, which are major TCs of concern, are presented in this paper. A carbon sorbent was fabricated by dry impregnation of a reticulated carbon-foam support with polyvinylidene chloride, followed by carbonization and thermal oxidation in air. Sorbent performance was tested for ammonia and formaldehyde sorption and vacuum regeneration, with and without water present in the gas stream. It was found that humidity in the gas phase enhanced ammonia-sorption capacity by a factor larger than two. Co-adsorption of ammonia and formaldehyde in the presence of water resulted in strong formaldehyde sorption (to the point that it was difficult to saturate the sorbent on the time scales used in this study). In the absence of humidity, adsorption of formaldehyde on the carbon surface was found to impair ammonia sorption in subsequent runs; in the presence of water, however, both ammonia and formaldehyde could be efficiently removed from the gas phase by the sorbent. The efficiency of vacuum regeneration could be enhanced by gentle heating to temperatures below 60 deg.

Wojtowicz, Marek A.↗

The International Space Station (ISS) Port 1 (P1) External Active Thermal Control System (EATCS) Ammonia Leak

From 2011 to 2017, the crew onboard the International Space Station (ISS) was at risk of dire consequences due to an external ammonia leak. Ammonia is used in the External Active Thermal Control System (EATCS) to cool the pressurized modules and external electrical systems. Engineers at NASA's Johnson Space Center (JSC) initially detected the leak in one of two cooling loops by monitoring the system ammonia inventory decay over time. White flakes seen on High Definition (HD) cameras were also thought to be associated with the leakage but not confirmed. Initially, the leak was small enough that the ammonia inventory and system operations were not in jeopardy. However, the leak began to accelerate to the point where troubleshooting and corrective action were vital to the sustainability of the ISS. Therefore, it became imperative that the leak be located and repaired for ISS operations to continue. No tools were readily available on the ISS to locate such a leak when it was initially detected, however NASA engineers were already in the process of developing a new device for this purpose called the Robotic External Leak Locator (RELL). The RELL is a robotic instrument package with a mass spectrometer and an ion pressure gauge. Initial checkout operations with RELL happened to coincide with the increasing leak, and ammonia vapors were measured around the P1 EATCS Radiator #3 flexible jumper hoses. The leak stopped after the radiator and its flexible hoses were remotely isolated from the loop and the ammonia from the isolated segment was vented to space. Astronauts conducted a spacewalk that successfully removed the hoses, which were returned to ground for further investigation. The purpose of this paper is to review the leak detection and isolation efforts, investigation results, lessons learned and the recovery plan.

Cowan, Darnell T.↗

The International Space Station (ISS) Port 1 (P1) External Active Thermal Control System (EATCS) Ammonia Leak

From 2011 to 2017, the crew onboard the International Space Station (ISS) was at risk of dire consequences due to an external ammonia leak. Ammonia is used in the External Active Thermal Control System (EATCS) to cool the pressurized modules and external electrical systems. Engineers at NASA's Johnson Space Center (JSC) initially detected the leak in one of two cooling loops by monitoring the system ammonia inventory decay over time. White flakes seen on High Definition (HD) cameras were also thought to be associated with the leakage but not confirmed. Initially, the leak was small enough that the ammonia inventory and system operations were not in jeopardy. However, the leak began to accelerate to the point where troubleshooting and corrective action were vital to the sustainability of the ISS. Therefore, it became imperative that the leak be located and repaired for ISS operations to continue. No tools were readily available on the ISS to locate such a leak when it was initially detected, however NASA engineers were already in the process of developing a new device for this purpose called the Robotic External Leak Locator (RELL). The RELL is a robotic instrument package with a mass spectrometer and an ion pressure gauge. Initial checkout operations with RELL happened to coincide with the increasing leak, and ammonia vapors were measured around the P1 EATCS Radiator #3 flexible jumper hoses. The leak stopped after the radiator and its flexible hoses were remotely isolated from the loop and the ammonia from the isolated segment was vented to space. Astronauts conducted a spacewalk that successfully removed the hoses, which were returned to ground for further investigation. The purpose of this paper is to review the leak detection and isolation efforts, investigation results, lessons learned and the recovery plan.

Cowan, Darnell T.↗

The International Space Station (ISS) Port 1 (P1) External Active Thermal Control System (EATCS) Ammonia Leak

Ammonia is used in the Starboard 1 (S1) and Port 1 (P1) External Active Thermal Control System (EATCS) to cool the pressurized modules, and some of the external electrical power distribution hardware. Leaks that develop in these critical cooling systems that deplete in-line tanks can ultimately result in loss of cooling, which can have devastating impacts to the mission, science and crew onboard the ISS. A slow ammonia leak was initially observed from the P1 EATCS in 2011, but later in 2013 the leak rate began to accelerate. The ammonia inventory eventually began to decay exponentially, raising concerns that the inventory could drop to levels where the system would not be operational.The Robotic External Leak Locator (RELL) was built and launched to the ISS to detect and help locate ammonia leaks using the ISS Robotic Arm and remote ground operator control without constant crew involvement. RELL pinpointed the ammonia leak to the two flexible jumper hose assemblies connecting one of two fluid loops in one of the three deployable radiators to the P1 EATCS. The ammonia inside the two hose assemblies and that radiator fluid loop was isolated and vented to space in 2017. This stopped the leak and an Extravehicular Activity was conducted to remove the two hose assemblies so they could be returned to ground for further Test, Teardown and Evaluation (TT&E). The purpose of this presentation is to discuss this leakage scenario and the TT&E efforts.

Cowan, Darnell T.↗

Stable ammonia absorbents

The present disclosure relates to systems and methods of making ammonia using stable ammonia absorbents. The system and method for producing ammonia, comprises a reactor comprising a catalyst that converts at least a portion of nitrogen feed gas and at least a portion of hydrogen feed gas to ammonia (NH3) forming a reaction mixture comprising the ammonia, unreacted nitrogen, and unreacted hydrogen. An absorber configured to selectively absorb ammonia from the reaction mixture at a temperature of about 180 deg. C. to 330 deg. C. and a pressure of about 1-20 bar, the absorber comprising a solid absorbent. Preferably the solid absorbent is at least one metal halide and a solid support. The unabsorbed ammonium, the unreacted nitrogen, and unreacted hydrogen gas are recycled to the reactor.

Cussler, Edward↗

In-Situ Species Concentration Measurements in Ammonia-Mix Flames Using FTIR Spectroscopy

Hydrogen and ammonia represent two carbon-free fuel sources that could be used in place of current fossil energy sources in combustion systems. To develop optimized ammonia combustion systems, validated modeling tools are needed. In the open literature, it has been shown that the complex chemistry associated with fuel-bound nitrogen contained in ammonia differs greatly from natural gas or hydrogen combustion. As a result, several new chemical kinetic mechanisms have been developed. Many of these mechanisms have been validated experimentally, however this has primarily focused on bulk parameters such as laminar flame speed and ignition delay time. Critically, high quality measurements of species concentrations are needed under controlled conditions which are easily represented by simple models. In this paper, direct, in-situ measurements of species concentrations and gas temperature are performed in a laminar flat-flame burner. This arrangement enables comparison with 1D model predictions, better isolating chemical kinetics from the fluid dynamics. Quantitative species concentrations are determined by absorption spectroscopy using an FTIR spectrometer. Fuel compositions representative of cracked ammonia (NH3/H2) and ammonia-natural gas (NH3/CH4) are considered for rich and lean equivalence ratios. A major focus of the paper is on the selection of spectral features for nitric oxide and ammonia and correcting for large amounts of baseline H2O absorption.

Bedick, Clinton↗

Benchmarking plasma and electrolysis decomposition technologies for ammonia to power generation

Ammonia is a promising energy and hydrogen carrier due to its ease of liquification, high hydrogen content, and potential to be synthesized without carbon feedstocks. Despite its widespread use in agriculture, the utilization of ammonia to deliver hydrogen or for direct power generation is still under development. Sometimes referred to as “cracking”, the standard approach for recovering hydrogen from ammonia relies on harsh reaction conditions that limit its suitability for low-carbon transitions. Here, this work investigates the technology development status and potential cost of plasma and electrolysis-based ammonia decomposition, benchmarks them with thermal-chemical decomposition, and further compares them with direct ammonia-to-power solid oxide fuel cell systems. Results suggest that in order to reach cost parity with cracking technologies, plasma-based decomposition must achieve one order of magnitude improvement in energy efficiency (to 10 kWh/kg or lower), while electrolysis decomposition must achieve enhanced durability using cheap electrolytes.

30 DIRECT ENERGY CONVERSION↗

Electrolyte Engineering for Efficient Electrochemical Nitrate Reduction to Ammonia on a Titanium Electrode

Nitrates from agricultural runoff and industrial waste streams are a notorious waste product and hazardous pollutant. Traditional electrochemical water remediation approaches aim to solve this problem by converting nitrates to environmentally benign N 2 while minimizing the production of environmentally hazardous side products such as ammonia and nitrous oxide in a process known as “denitrification”. We modify this concept and outline an opportunity to optimize the conversion of nitrates into ammonia, which is also a key commodity product used as a fertilizer, potential fuel, and chemical precursor. The electrochemical conversion of nitrates to ammonia recycles the fixed nitrogen and offers an appealing and supplementary alternative to the energy- and resource-intensive Haber-Bosch process. In this study, we investigated the effect of varying electrochemical conditions (pH, nitrate concentration, and applied potential) on the selective reduction of nitrate to ammonia at a titanium cathode. We observed that high concentrations of both protons and nitrate ions are needed to achieve high selectivity, reaching a peak of 82% Faradaic efficiency to ammonia at an applied potential of -1 V versus RHE and a partial current density to NH 3 of -22 mA/cm 2 , using 0.4 M [NO 3 – ] at pH ~0.77. The Ti electrode, as a poor hydrogen evolution catalyst with notable corrosion resistance, provides a large window of operating conditions to achieve high selectivity in the reduction of nitrate anions. Stability of the system was evaluated, and we found a high Faradaic efficiency throughout the course of an 8 h experiment. After electrochemical testing, titanium hydride was observed at the cathode surface. We also show a preliminary technoeconomic study, indicating that it may be feasible to employ an electrochemical strategy for the production of ammonium nitrate.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

On the Structural Transformation of Ni/BaH 2 During a N 2 -H 2 Chemical Looping Process for Ammonia Synthesis: A Joint In Situ Inelastic Neutron Scattering and First-Principles Simulation Study

The demand for decarbonizing the ammonia industry by using renewable energy has invoked increasing research interests into catalyst development for effective N 2 reduction under mild conditions. Hydride-based materials are among some of the emerging catalysts for ammonia synthesis at ambient pressure and low temperatures (< 673 K). A recent chemical looping process based on Ni/BaH 2 showed the most promise as it can realize ammonia production at a temperature as low as 373 K and under ambient pressure. However, the chemical transformation of the hydride catalyst at the molecular level remains unclear in this process. Here, we report detailed in situ neutron spectroscopy and diffraction investigations along with first-principles simulations on the structural transformation of Ni/BaH 2 during the nitridation and hydrogenation steps in the chemical looping process for ammonia synthesis. It was shown that a ball-milling process of the starting Ni/BaH 2 could significantly decrease the size of BaH 2 and increase the density of defects, thus potentially enhancing the reactivity of the hydride. The evolution from BaH 2 to barium imide (BaNH) was evidenced in the inelastic neutron scattering (INS) and neutron diffraction results during the N 2 reaction step. During the hydrogenation study, in addition to the recovery of BaH 2 , a possible intermediate species, N-deficient barium imide, was also detected. In comparing the N 2 and H 2 reaction steps, the neutron results indicate that the hydrogenation step appears more difficult than the nitridation step, confirming the facile N 2 fixation property of Ni/BaH 2 catalyst in ammonia synthesis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Challenges in Kinetic modeling of ammonia pyrolysis

Ammonia pyrolysis reactions have implications for its ignition and oxidation in engines and gas turbines. In the present work, the chemistry of ammonia pyrolysis is investigated by kinetic modeling and theory. Rate constants for key reactions are carefully evaluated based on available experimental and theoretical results. The high pressure limit k1,∞ for NH 2 + H (+M) &rlarr; NH 3 (+M) (R1) is calculated to be essentially the collision frequency, indicating that dissociation of ammonia in combustion processes will be at or close to the low pressure limit even at engine and gas turbine conditions. The chemical kinetic model is validated against reported shock tube measurements of NH 3 , NH 2 , and NH in ammonia pyrolysis. Predictions are in good agreement with observations for dilute conditions (≤ 0.5% NH 3 ), but the model appears to underpredict the NH 3 consumption rate at longer times in less dilute mixtures. At short reaction times, thermal dissociation of NH3, together with the NH 3 + H reaction, controls conversion. At longer times, secondary reactions involving NH 2 and NH become important due to their impact on the radical pool. Predictions become sensitive to formation and consumption of diazene (tHNNH and cHNNH). Several of the key steps in the ammonia pyrolysis mechanism are radical-radical reactions that are difficult to measure accurately and challenging to calculate theoretically, and a more comprehensive experimental characterization is desirable to support further model development.

10 SYNTHETIC FUELS↗

Ammonia separation from N 2 and H 2 over LTA zeolitic imidazolate framework membranes

LTA type zeolitic imidazolate framework membranes denoted as ZIF-21 were synthesized and evaluated for the separation of a commodity chemical, ammonia, from nitrogen and hydrogen. Membranes were grown using secondary seeded growth. Ammonia permeances were as high as 1727 GPU, with NH 3 /N 2 , and NH 3 /H 2 ideal selectivities of 35, and 12 respectively. ZIF-21 membranes were also evaluated for gas mixtures composed of 13.8:86.2 NH 3 /N 2 and NH 3 /H 2 , with mixture separation selectivities as high as 7.6 for NH 3 /N 2 . Differences in adsorption, and diffusivities were identified as the key separation mechanisms. Specifically, for both gas pairs the polar-polar interaction between ammonia and the linker polar channels, led to the preferential adsorption of ammonia, and therefore favored thermodynamically the separation of ammonia from nitrogen and hydrogen. In addition, for NH 3 /N 2 gas pair, differences in diffusivities was a contributing separation mechanism. For NH 3 /H 2 gas pair, due to the faster hydrogen diffusivity, the kinetic contribution was a strong competing separation mechanism.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Compact ammonia reforming at low temperature using catalytic membrane reactors

Ammonia is a leading carrier for the storage and transport of renewable hydrogen, but its deployment requires scalable technologies for efficient decomposition and purification. In this work, we report on the efficient delivery of high purity hydrogen from ammonia decomposition using a catalytic membrane reactor (CMR). Improvements to the electroless plating process reduced the Pd membrane thickness by >35%, resulting in commensurate increases in hydrogen permeance without sacrificing selectivity. To increase throughput a commercial Ru/Al 2 O 3 catalyst was added to the lumen, and the CMR could process ammonia flowrates 10–50 times higher than an equivalent packed bed reactor while maintaining the same level of conversion. It is shown that the earth-abundant zeolite clinoptilolite could reduce ammonia impurities in the permeated H 2 to the levels required by PEM fuel cells (<25 ppb). Performance increased significantly across a >500-h durability test due to improvements in membrane permeability. Finally, the results show that CMRs are a viable technology for distributed production of hydrogen from ammonia.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗