Search NASA⌕ Search

SEARCH · Search NASA

Results for “AMMONIA”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 595 records · Page 33

Low power DC arcjet operation with hydrogen/nitrogen/ammonia mixtures

The effect of gas composition and ambient pressure on arcjet operation was determined. Arcjet operation in different facilities was also compared to determine the validity of tests in small facilities. Volt-ampere characteristics were determined for an arcjet using hydrogen/nitrogen mixtures (simulating both ammonia and hydrazine), hydrogen/nitrogen/ammonia mixtures, and pure ammonia as propellants at various flow rates. The arcjet had a typical performance of 450 sec specific impulse at 1 kW with hydrogen/nitrogen mixures. It was determined that the amount of ammonia present in the gas stream had a significant effect on the arcjet volt-ampere characteristics. Also, hydrogen/nitrogen mixtures simulating ammonia gave arc characteristics approximately the same as those of pure ammonia. Finally, no differences in arc volt-ampere characteristics were seen between low and high ambient pressure operation in the same facility. A 3 to 5 V difference was seen when different facilities were compared, but this difference was probably due to differences in the voltage drops across the current connections, and not due to arcjet operational differences in the two facilities.

Hardy, Terry L.↗

Low power dc arcjet operation with hydrogen/nitrogen/ammonia mixtures

The effect of gas composition and ambient pressure on arcjet operation was determined. Arcjet operation in different facilities was also compared to determine the validity of tests in small facilities. Volt-ampere characteristics were determined for an arcjet using hydrogen/nitrogen mixtures (simulating both ammonia and hydrazine), hydrogen/nitrogen/ammonia mixtures, and pure ammonia as propellants at various flow rates. The arcjet had a typical performance of 450 sec specific impulse at 1 kW with hydrogen/nitrogen mixtures. It was determined that the amount of ammonia present in the gas stream had a significant effect on the arcjet volt-ampere characteristics. Also, hydrogen/nitrogen mixtures simulating ammonia gave arc characteristics approximately the same as those of pure ammonia. Finally, no differences in arc volt-ampere characteristics were seen between low and high ambient pressure operation in the same facility. A 3 to 5 V difference was seen when different facilities were compared, but this difference was probably due to differences in the voltage drops across the current connections, and not due to arcjet operational differences in the two facilities.

Hardy, Terry L.↗

Late Wenlock (middle Silurian) bio-events: Caused by volatile boloid impact/s

Late Wenlockian (late mid-Silurian) life is characterized by three significant changes or bioevents: sudden development of massive carbonate reefs after a long interval of limited reef growth; sudden mass mortality among colonial zooplankton, graptolites; and origination of land plants with vascular tissue (Cooksonia). Both marine bioevents are short in duration and occur essentially simultaneously at the end of the Wenlock without any recorded major climatic change from the general global warm climate. These three disparate biologic events may be linked to sudden environmental change that could have resulted from sudden infusion of a massive amount of ammonia into the tropical ocean. Impact of a boloid or swarm of extraterrestrial bodies containing substantial quantities of a volatile (ammonia) component could provide such an infusion. Major carbonate precipitation (formation), as seen in the reefs as well as, to a more limited extent, in certain brachiopods, would be favored by increased pH resulting from addition of a massive quantity of ammonia into the upper ocean. Because of the buffer capacity of the ocean and dilution effects, the pH would have returned soon to equilibrium. Major proliferation of massive reefs ceased at the same time. Addition of ammonia as fertilizer to terrestrial environments in the tropics would have created optimum environmental conditions for development of land plants with vascular, nutrient-conductive tissue. Fertilization of terrestrial environments thus seemingly preceded development of vascular tissue by a short time interval. Although no direct evidence of impact of a volatile boloid may be found, the bioevent evidence is suggestive that such an impact in the oceans could have taken place. Indeed, in the case of an ammonia boloid, evidence, such as that of the Late Wenlockian bioevents may be the only available data for impact of such a boloid.

Berry, W. B. N.↗

Analysis of the plugging of the systems autonomy demonstration project brassboard filters

A fine gray powder was clogging the brassboard filters. The powder appeared to be residue from a galvanic corrosive attack by ammonia of the aluminum and stainless steel components in the system. The corrosion was caused by water and chlorine that had entered into the system and combined with the ammonia. This combination made an electrolyte and a corrosive agent of the ammonia that attacked the metals in the system. The corroded material traveled through the system with the ammonia and clogged the filters. Key conclusions are: the debris collecting in the filters is a by-product of galvanic corrosion; the debris is principally corroded aluminum and stainless from the system; and galvanic corrosion occurred from water and chlorine that entered the system during normal and/or extreme operating and servicing conditions. Key recommendations are: use only one metal in the ammonia system-titanium, aluminum, or stainless steel; make the system as air-tight as possible (replace fittings with welded joints); and replace electron paramagnetic resonance (EPR) O-rings with neoprene O-rings, and do not use freon to clean system components.

Clay, John C.↗

Photochemical model for NH3 in an early Martian atmosphere

A warm and wet climate scenario for early Mars has been explained by invoking a 5-bar CO2 atmosphere; however, Kasting has shown that CO2 will condense in the Martian atmosphere at these pressures. The formation of CO2 clouds will reduce the convection lapse rate and reduce the magnitude of the greenhouse effect. It is possible that additional greenhouse gases such as methane and ammonia were present in the early Mars atmosphere. We are using a one dimensional photochemical model to estimate the magnitude of the ammonia source required to maintain a given ammonia concentration in a dense CO2 atmosphere. Because CO2 is 2.5 times more efficient at Rayleigh scattering than Earth's N2 atmosphere, we anticipate increased scattering opacities and decreased photolytic destruction rates of ammonia on early Mars. The reduced gravity on Mars means that a 1 bar atmosphere will be approximately 3 times as thick as on Earth. It is possible that ammonia could have been shielded from photolysis by hydrocarbon aerosols which form as a product of methane photolysis.

Brown, L. L.↗

Hydrazine Detection with a Tunable Diode Laser Spectrometer

Several instruments have been developed to measure low concentrations of hydrazine but none completely meet the sensitivity requirements while satisfying additional criteria such as quick response, stable calibration, interference free operation, online operation, reasonable cost, etc. A brief review is presented of the current technology including the electrochemical cell, the ion mobility spectrometer, the mass spectrometer, and the gas chromatograph. A review of the advantages and disadvantages of these instruments are presented here. The review also includes commercially unavailable technology such as the electronic nose and the Tunable Diode Laser (TDL) IR Spectrometer. It was found that the TDL could meet the majority of these criteria including fast response, minimum maintenance, portability, and reasonable cost. An experiment was conducted to demonstrate the feasibility of such a system using an existing (non-portable) instrument. A lead-salt tunable diode laser, cooled to 85 degrees Kelvin was used to record direct absorption and second-derivative spectra of Hydrazine at several pressures to study the sensitivity to low levels of Hydrazine. Spectra of NH3 and CO2 were used for wavelength identification of the scanned region. With a pathlength of 80 m, detection sensitivities of about 1 ppb were achieved for hydrazine in dry nitrogen at a cell pressure of 100 mbar. For spectroscopic detection of Hydrazine, spectral regions including strong Ammonia or Carbon Dioxide lines must be avoided. Strong Hydrazine absorption features were identified at 940/cm showing minimal contribution from Ammonia interferences as suitable candidates for Hydrazine gas detection. For the studies reported here, the particular laser diode could only cover the narrow regions near 962/cm and 965/cm where strong Ammonia interferences were expected. However, the high resolution (0.001/cm) of the TDL spectrometer allowed individual lines of Hydrazine to be identified away from interferences from either Ammonia or Carbon Dioxide, especially at lower pressures. A Hydrazine line was identified at 961.75/cm which was free from Ammonia absorption and would be suitable to monitor hydrazine levels. This paper also shows data on the degradation of the detectivity of Hydrazine with increasing pressure. Several design options for a portable unit are presented, including designs with near IR and Quantum Cascade laser components which do not require liquid nitrogen cooling.

Houseman, John↗

Retrievals of Jovian Tropospheric Phosphine from Cassini/CIRS

On December 30th 2000, the Cassini-Huygens spacecraft reached the perijove milestone on its continuing journey to the Saturnian system. During an extended six-month encounter, the Composite Infrared Spectrometer (CIRS) returned spectra of the Jovian atmosphere, rings and satellites from 10-1400 cm(exp -1) (1000-7 microns) at a programmable spectral resolution of 0.5 to 15 cm(exp -1). The improved spectral resolution of CIRS over previous IR instrument-missions to Jupiter, the extended spectral range, and higher signal-to-noise performance provide significant advantages over previous data sets. CIRS global observations of the mid-infrared spectrum of Jupiter at medium resolution (2.5 cm(exp -1)) have been analysed both with a radiance differencing scheme and an optimal estimation retrieval model to retrieve the spatial variation of phosphine and ammonia fractional scale height in the troposphere between 60 deg S and 60 deg N at a spatial resolution of 6 deg. The ammonia fractional scale height appears to be high over the Equatorial Zone (EZ) but low over the North Equatorial Belt (NEB) and South Equatorial Belt (SEB) indicating rapid uplift or strong vertical mixing in the EZ. The abundance of phosphine shows a similar strong latitudinal variation which generally matches that of the ammonia fractional scale height. However while the ammonia fractional scale height distribution is to a first order symmetric in latitude, the phosphine distribution shows a North/South asymmetry at mid latitudes with higher amounts detected at 40 deg N than 40 deg S. In addition the data show that while the ammonia fractional scale height at this spatial resolution appears to be low over the Great Red Spot (GRS), indicating reduced vertical mixing above the approx. 500 mb level, the abundance of phosphine at deeper levels may be enhanced at the northern edge of the GRS indicating upwelling.

Irwin, P. G. J.↗

Heat cascading regenerative sorption heat pump

A simple heat cascading regenerative sorption heat pump process with rejected or waste heat from a higher temperature chemisorption circuit (HTCC) powering a lower temperature physisorption circuit (LTPC) which provides a 30% total improvement over simple regenerative physisorption compression heat pumps when ammonia is both the chemisorbate and physisorbate, and a total improvement of 50% or more for LTPC having two pressure stages. The HTCC contains ammonia and a chemisorbent therefor contained in a plurality of canisters, a condenser-evaporator-radiator system, and a heater, operatively connected together. The LTPC contains ammonia and a physisorbent therefor contained in a plurality of compressors, a condenser-evaporator-radiator system, operatively connected together. A closed heat transfer circuit (CHTC) is provided which contains a flowing heat transfer liquid (FHTL) in thermal communication with each canister and each compressor for cascading heat from the HTCC to the LTPC. Heat is regenerated within the LTPC by transferring heat from one compressor to another. In one embodiment the regeneration is performed by another CHTC containing another FHTL in thermal communication with each compressor. In another embodiment the HTCC powers a lower temperature ammonia water absorption circuit (LTAWAC) which contains a generator-absorber system containing the absorbent, and a condenser-evaporator-radiator system, operatively connected together. The absorbent is water or an absorbent aqueous solution. A CHTC is provided which contains a FHTL in thermal communication with the generator for cascading heat from the HTCC to the LTAWAC. Heat is regenerated within the LTAWAC by transferring heat from the generator to the absorber. The chemical composition of the chemisorbent is different than the chemical composition of the physisorbent, and the absorbent. The chemical composition of the FHTL is different than the chemisorbent, the physisorbent, the absorbent, and ammonia.

Jones, Jack A.↗

Analysis of Rocket, Ram-Jet, and Turbojet Engines for Supersonic Propulsion of Long-Range Missles. II - Rocket Missile Performance

The theoretical performance of a two-stage ballistic rocket mis having a centerbody and two parallel boosters was investigated for J oxygen and ammonia-fluorine propellants. Both power-plant and missi parameters were optimized to give minimum cost on-the basis of the analysis for a range of 5500 nautical miles. After optimum values were found, each parameter was varied independently to determine its effect on performance of the missile. The missile using the ammonia-fluorine propellant weighs about one half as much as a missile using JP4-oxygen. Based on an expected unit cost of fluorine in quantity production, the ammonia-fluorine missile has a substantially lower relative cost than a JP4-oxygen missile. Optimum chamber pressures for both propellant systems and for both the centerbody and boosters were between 450 and 600 pounds per square inch. High design altitudes for the exhaust nozzle are desirable for both the centerbody and boosters. For the centerbody, the design altitude should be between 45,000 and 60,000 feet, with the value for ammonia-fluorine lower than that for JP4-oxygen. For the boosters, the design altitude should be 20,000 to 30,000 feet, with the value for the ammonia-fluorine. missile higher.

Huff, Vearl N.↗

Investigation of Loop Heat Pipe Survival and Restart After Extreme Cold Environment Exposure

NASA plans human exploration near the South Pole of the Moon, and other locations where the environment is extremely cold. This paper reports on the heat transfer performance of a loop heat pipe (LHP) exposed to extreme cold under the simulated reduced gravitational environment of the Moon. A common method of spacecraft thermal control is to use a LHP with ammonia working fluid. Typically, a small amount of heat is provided either by electrical heaters or by environmental design, such that the LHP condenser temperature never drops below the freezing point of ammonia. The concern is that a liquid-filled, frozen condenser would not restart, or that a thawing condenser would damage the tubing due to the expansion of ammonia upon thawing. This paper reports the results of an experimental investigation of a novel approach to avoid these problems. The LHP compensation chamber (CC) is conditioned such that all the ammonia liquid is removed from the condenser and the LHP is nonoperating. The condenser temperature is then reduced to below that of the ammonia freezing point. The LHP is then successfully restarted.

Golliher, Eric↗

ITCS Test Strip Development and Certification

Internal coolant loops used for International Space Station thermal control must be periodically monitored for system health, including pH, biocide levels and any indication of ammonia. The presence of ammonia, possible via a microleak in the interface between the internal and external thermal control systems, could be a danger to the crew. The Internal Thermal Control System (ITCS) Sampling Kit uses test strips as a colorimetric indicator of pH and concentrations of biocide and free ammonia. This paper describes the challenges in designing an ammonia colorimetric indicator in a variable pH environment, as well as lessons learned, ultimately resulting in a robust test strip to indicate a hazardous ammonia leak.

Carrigan, Caitlin↗

High Power Flex-Propellant Arcjet Performance

A MW-class electrothermal arcjet based on a water-cooled, wall-stabilized, constricted arc discharge configuration was subjected to extensive performance testing using hydrogen and simulated ammonia propellants with the deliberate aim of advancing technology readiness level for potential space propulsion applications. The breadboard design incorporates alternating conductor/insulator wafers to form a discharge barrel enclosure with a 2.5-cm internal bore diameter and an overall length of approximately 1 meter. Swirling propellant flow is introduced into the barrel, and a DC arc discharge mode is established between a backplate tungsten cathode button and a downstream ringanode/ spin-coil assembly. The arc-heated propellant then enters a short mixing plenum and is accelerated through a converging-diverging graphite nozzle. This innovative design configuration differs substantially from conventional arcjet thrusters, in which the throat functions as constrictor and the expansion nozzle serves as the anode, and permits the attainment of an equilibrium sonic throat (EST) condition. During the test program, applied electrical input power was varied between 0.5-1 MW with hydrogen and simulated ammonia flow rates in the range of 4-12 g/s and 15-35 g/s, respectively. The ranges of investigated specific input energy therefore fell between 50-250 MJ/kg for hydrogen and 10-60 MJ/kg for ammonia. In both cases, observed arc efficiencies were between 40-60 percent as determined via a simple heat balance method based on electrical input power and coolant water calorimeter measurements. These experimental results were found to be in excellent agreement with theoretical chemical equilibrium predictions, thereby validating the EST assumption and enabling the utilization of standard TDK nozzle expansion analyses to reliably infer baseline thruster performance characteristics. Inferred specific impulse performance accounting for recombination kinetics during the expansion process implied nearly frozen flow in the nozzle and yielded performance ranges of 800-1100 sec for hydrogen and 400-600 sec for ammonia. Inferred thrust-to-power ratios were in the range of 30-10 lbf/MWe for hydrogen and 60-20 lbf/MWe for ammonia. Successful completion of this test series represents a fundamental milestone in the progression of high power arcjet technology, and it is hoped that the results may serve as a reliable touchstone for the future development of MW-class regeneratively-cooled flex-propellant plasma rockets.

Litchford, Ron J.↗

Close Range Photogrammetry in Space - Measuring the On-Orbit Clearance between Hardware on the International Space Station

When photogrammetrists read an article entitled "Photogrammetry in Space" they immediately think of terrestrial mapping using satellite imagery. However in the last 19 years the roll of close range photogrammetry in support of the manned space flight program has grown exponentially. Management and engineers have repeatedly entrusted the safety of the vehicles and their crews to the results of photogrammetric analysis. In February 2010, the Node 3 module was attached to the port side Common Berthing Mechanism (CBM) of the International Space Station (ISS). Since this was not the location at which the module was originally designed to be located on the ISS, coolant lines containing liquid ammonia, were installed externally from the US Lab to Node 3 during a spacewalk. During mission preparation I had developed a plan and a set of procedures to have the astronauts acquire stereo imagery of these coolant lines at the conclusion of the spacewalk to enable us to map their as-installed location relative to the rest of the space station. Unfortunately, the actual installation of the coolant lines took longer than expected and in an effort to wrap up the spacewalk on time, the mission director made a real-time call to drop the photography. My efforts to reschedule the photography on a later spacewalk never materialized, so rather than having an as-installed model for the location of coolant lines, the master ISS CAD database continued to display an as-designed model of the coolant lines. Fast forward to the summer of 2015, the ISS program planned to berth a Japanese cargo module to the nadir Common Berthing Mechanism (CBM), immediately adjacent to the Node 3 module. A CAD based clearance analysis revealed a negative four inch clearance between the ammonia lines and a thruster nozzle on the port side of the cargo vehicle. Recognizing that the model of the ammonia line used in the clearance analysis was "as-designed" rather than "as-installed", I was asked to determine the real clearance between the ammonia lines and expected position of the thruster bell using existing on-orbit imagery. Imagery of the area of interest, taken several years earlier from the Space Shuttle during a fly-around of the ISS, was found and used to set a stereo pair. Space Vision System Targets and Handrail bolts measured in the ISS analytical coordinate system (ISSACS) prior to launch, were used to obtain an absolute orientation so all photogrammetric measurement's would be in the ISSACS coordinate system. Coordinates for the design location of the edges of the thruster bell, when the cargo vehicle was fully berthed to the ISS, were displayed in 3-D relative to the as-installed ammonia lines. This immediately revealed a positive clearance, which was later quantified to be a minimum of 10" +/0.5". The analysis was completed over a single weekend by a single analyst. Using updated imagery, acquired from the station's robotic arm, a complete as-installed model of the coolant lines was generated from stereo photography and replaced the design model in the master ISS CAD database.

Liddle, Donn↗

An Ensemble Investigation of the Causes for Regional Air-Quality Model Critical Load Exceedances Prediction Variability in European and North American Domains Using Diagnostics From Phase 4 of the Air Quality Model Evaluation International Initiative

We summarize tentative findings from multi air quality model ensembles for the years 2009 and 2010 in Europe (EU), and 2010 and 2016 in North America (NA), under AQMEII-4. The model predictions of sulphur and nitrogen deposition were used to estimate exceedances of critical loads for acidification and eutrophication, to show the extent to which the ensemble members agree in the magnitude and the trend of ecologically meaningful impacts. Model exceedance variability was analyzed using AQMEII-4 diagnostics. Evaluation against concentration and wet deposition observations, coupled with these diagnostics, identified specific process representations as the causes for variability between model predictions and for reduced model performance. All models predicted reductions in ecosystem acidification impacts in North America between the years 2010 and 2016, in accord with SO2 emissions reduction legislation which started in 2010 (SO2 SIP) However, all models in EU and NA domains had net negative biases for wet deposition of sulphur and nitrogen relative to observations. The wet S deposition average mean bias for the NA ensemble was -0.17 eq ha-1 d-1, and for the EU ensemble -1.15 eq ha-1 d-1. The NA daily wet deposition average mean bias for NH4+ was -0.37 eq ha-1d-1; EU -1.19 eq ha-1 d-1. The daily NA wet NO3- deposition average mean bias was -0.24 eq ha-1d-1; EU -0.69 eq ha-1 d-1. The members of the ensemble diverged (factor of 10) in their North American predictions for Ndep and consequently their eutrophication exceedances. The models with the highest eutrophication predictions also predicted the highest levels of gas-phase ammonia dry deposition (standard deviation of ammonia dry deposition flux across ensemble members was larger than the ensemble average). These models also had negative biases of predicted ammonia concentrations; average mean biases of -0.63 (satellite NH3) and -0.85 ppbv (surface NH3) compared to ensemble averages of -0.30 and -0.34 ppbv. Diagnostics showed that these differences resulted from the manner in which bidirectional ammonia fluxes were parameterized within these models. The second largest source of NA eutrophication prediction variability were models with positive biases in particulate ammonium and nitrate concentrations, and higher particle nitrogen deposition levels ( particle ammonium concentration bias +0.35 ug m-3; ensemble bias +0.15 ug m-3). We believe two factors may have led to these latter overestimates: higher levels of fine mode particle nitrate formation compared to other models (due to the use of an inorganic heterogeneous chemistry algorithm which did not take base cation chemistry into account), and updates to particle dry deposition velocities carried out in the absence of concurrent updates to wet scavenging algorithms. The relative importance of dry gas, dry particulate, and wet deposition towards total sulphur and nitrogen deposition totals differed between EU and North American domains, though all models had negative biases in wet deposition as noted above. Parallel and subsequent work suggests that multiphase hydrometeor scavenging may improve model wet deposition performance. An increased research focus is recommended for four model processes: multiphase hydrometeor scavenging, ammonia bidirectional fluxes, base cation chemistry and emissions, and particle dry deposition.

regional air-quality model↗

Project Development of an Electrochemical Denitration and Caustic Generation System for HLW Pretreatment at Hanford - 26350

An engineering-scale electrochemical processing skid is proposed to perform the denitration of Hanford tank waste, which would help to mitigate a key process concern with the direct feed processing of the Hanford Tank Waste Treatment and Immobilization Plant (WTP). The reduction of nitrates and organic compounds in the waste feed will directly reduce hazardous NOx and ammonia gases generated during the vitrification process, which in turn will aid in addressing potential regulatory and safety challenges associated with processing large volumes of tank waste. This paper highlights the past legacy work, project layout, accomplishments from Phase 1 and research and development envisioned for Phase 2. An innovative electrochemical denitration and caustic generation (EDCGe) process was demonstrated for the pretreatment of tank waste at the Savannah River Site (SRS) in the early 2000s. The denitration electrolyzer, off-gas abatement system, and caustic generator electrolyzer are being developed with the intent that the denitration electrolyzer will convert nitrate and nitrite anions to nitrogen gas while also yielding other gaseous byproducts, which may include N2O, NH3, VOCs, and H2. The gaseous byproducts will be managed via a tandem off-gas catalyst-bed treatment system. The caustic generation electrolyzer will recycle NaOH from the feed to produce a clean caustic stream for use within the batching tanks at Hanford, aiding in the preparation of waste for WTP. The reduction in hazardous emissions and improved waste treatment processes provides a robust solution for nuclear waste management, contributing to environmental safety and regulatory compliance. The EDCGe technology is being adapted, modified, and updated for the preparation of the Direct Feed-High Level Waste (DF-HLW) flowsheet at Hanford. Phase 1 demonstrated a bench-scale proof-of-concept for reactions involving the denitration electrolyzer and gas phase abatement of ammonia. The electrochemical technology is drawing on the scientific outcomes that were reported in the legacy work. The results from Phase 1 demonstrated the viability of the EDCGe system in reducing the nitrogen species of simple non-radioactive waste simulants. Commercially available alloys used as electrode materials and membranes are being studied for the denitration and caustic generation electrolyzers. The continuation of this project holds promise for broader applications, such as energy-efficient ammonia production, and contributes significant advancements in nuclear waste management. Additional material discovery has been investigated into ceramic Na super ion conductive (NaSICON) materials and off-gas abatement catalyst discovery. NaSICON is of interest for selective transport of Na within the electrolyzers to make a clean caustic stream. Future integration and optimization efforts, informed by Phase 1 results and ongoing research, will continue to drive advancements in nuclear waste management technology. The technology developed for the EDCGe treatment of tank waste will also have broader potential to inform other fields, such as energy-efficient ammonia production, as well as ammonia abatement catalysis through the lessons learned in electrochemical nitrate reduction. The applications and benefits of this research extend beyond Hanford and the Savannah River Site, supported by a collaborative team of scientists and engineers from national labs, academia, and industry, ensuring a comprehensive approach to solving complex waste treatment challenges. The team is leveraging advanced electrochemical technologies, machine learning, novel catalysts tailored for gaseous nitrogen species, and cutting-edge reactor systems to enhance the process efficiency and effectiveness of the denitration process.

Rodene, Dylan [Savannah River National Laboratory ↗

Liquid Sorption-Enhanced Haber–Bosch Process

The use of a liquid sorbent in a traditional Haber-Bosch process enables significant improvements in energy efficiency and potential cost savings for arguably the most important chemical process on the planet. The approach presented in this report employs an incompressible liquid sorbent that absorbs and releases ammonia (NH 3 ) under specific conditions. To achieve this, we investigate reactions of ammonia and pure phosphoric acid (H 3 PO 4 , PA), which rapidly neutralize to form an equilibrated solution of monoammonium phosphate (MAP) and diammonium phosphate (DAP) that functions as a reversible and regenerable sorbent. Through intimate contact of the gas-phase Haber-Bosch reaction mixture with this liquid absorbent, complete equilibrium uptake may be achieved in an appropriately sized separator, and facile separation occurs through the use of independent liquid and gas phases. Following depressurization and release of the ammonia product, only the incompressible fluid needs to be repressurized and returned to the reactor. This study documents proof-of-concept absorption and desorption experiments carried out in 75 mL batch reactors, predominantly charged with precise MAP and DAP mixtures that equilibrate at process-relevant temperatures and pressures. We then assemble the first thermodynamic relationships that underlie this advantaged separation strategy, validated by reactive force field (ReaxFF) interatomic potential simulations, and benchmarked with traditional separation routes via process modeling and technoeconomic analysis. The scale of energy consumption in the century-old Haber-Bosch process is massive, and the elegant liquid sorption approach reported here offers opportunities to enhance its energy efficiency for the next frontier of ammonia synthesis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Insights into Sustainable Nitrogen Fixation by Gas-phase Spectroscopic Measurements and Global Modeling of Reaction Intermediates in Humid Nitrogen Plasma

In this article, there is growing interest in reacting molecular nitrogen and water to sustainably synthesize fixed forms of nitrogen such as ammonia. In particular, low-temperature plasmas can activate these relatively inert feedstocks at or near room temperature without a catalyst. However, because of the enhanced reactivity and nonequilibrium chemistry, a diverse range of products is formed, and the underlying reaction mechanisms are exceedingly complex. In this work, we studied a simplified reactor consisting of a gaseous plasma containing controlled mixtures of nitrogen gas and water vapor. Densities of key chemical species such as N, H, OH, NH, and NO were measured by emission and laser-based spectroscopy as a function of the relative humidity. A global model was constructed and the reaction network was validated by comparing calculated species densities with experiments. We discover that N, a key initial intermediate for ammonia, strongly decreases in the presence of water vapor, and as a result, ammonia formation becomes limited at high relative humidity. This decrease is surprisingly not because N itself reacts, but because one of its main sources, an excited molecular nitrogen state, is reacted away. In addition, oxidation pathways for nitrogen, which lead to NO and related products, are found to be favored over reduction pathways because the corresponding reverse reactions are less significant. Together, this understanding helps explain previously reported observations of selectivity toward nitrogen oxides over ammonia, particularly at higher relative humidities.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Reinventing wastewater treatment plants: energy neutral treatment and enhanced fertilizer production through a novel resource recovery center

Wastewater treatment plants (WWTPs) are typically energy intensive, mainly due to the secondary treatment processes such as activated sludge (AS) for treatment of organics as well as nutrients like nitrogen. Nitrogen removal presents a big problem for WWTPs. The main form of nitrogen in wastewater is ammonium, and an AS process uses oxygen to convert ammonium into nitrite and nitrate which is then converted to nitrogen through denitrification process. During anaerobic digestion (AD), organic nitrogen gets degraded, resulting in an effluent stream (centrate) with a high nitrogen content, mostly in the form of ammonium. This contributes 15-30% of total nitrogen to the wastewater influent which further increases energy consumption for aeration. The project aims to transform this conventional municipal WWTPs into energy-neutral, resource-recovering facilities by integrating three core technologies: • Cloth Media Filtration (CMF) to replace conventional primary sedimentation (CPS) and increase the diversion of organics from the energy intensive secondary treatment to AD. This results in reduced energy demand for aeration in the secondary process while simultaneously increasing the biogas production in the anaerobic digesters. • Anerobic Digester to increase biogas and ammonia production. • Membrane Evaporation (ME) to recover ammonia from AD centrate and produce marketable fertilizer. The benefits of proposed WWTP process modifications were evaluated using techno economic analysis (TEA) and life cycle assessment (LCA). For CMF portion of the research a statistical analysis was employed to develop data-driven tools that could be used to enhance and optimize its performance in terms of energy savings and effluent quality. The main objective of this project is to reduce the energy demand for secondary treatment at municipal WWTPs by at least 50%, increase anaerobic digester (AD) biogas and ammonia production by 100% and 120%, respectively, and recover 90% of ammonia from the AD. Integrated CMF, AD, and ME was shown to work synergistically toward achieving these decarbonization targets through energy-positive treatment and fertilizer recovery techniques.

42 ENGINEERING↗