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At least 163 records · Page 9

Wet oxidation as a waste treatment in closed systems

The chemistry of the wet oxidation process has been investigated in relation to production of plant nutrients from plant and human waste materials as required for a closed life-support system. Hydroponically grown lettuce plants were used as a model plant waste and oxygen gas was used as oxidant. Organic nitrogen content was decreased 88-100% depending on feed material. Production of ammonia and nitrogen gas account for all of the observed decrease in organic nitrogen content. No nitrous oxide (N2O) was detected. The implications of these results for closed life-support systems are discussed.

Onisko, B. L.↗

Wet Oxidation as a Waste Treatment Method in Closed Systems

The chemistry of the wet oxidation process was investigated in relation to production of plant nutrients from plant and human waste materials as required for a closed life support system. Hydroponically grown lettuce plants were used as a model plant waste, and oxygen gas was used as an oxidant. Organic nitrogen content was decreased 88-100%, depending on feed material. Production of ammonia and nitrogen gas accounted for all of the observed decrease in organic nitrogen content. No nitrous oxide (N2O) was detected. The implications of these results for closed life support systems are discussed.

Onisko, B. L.↗

Lower power dc arcjet operations with hydrogen hydrogen/nitrogen propellant mixtures

The arcjet assembly from a flight model system was modified with a new thoriated tungsten nozzle insert and has been tested with hydrogen-nitrogen mixtures simulating the decomposition products of ammonia and hydrazine. Arcjet power consumption ranged from 0.7 to 1.15 kW depending on low rate, input current, and mixture composition. At a nominal 1 kW power level the ammonia mixtures thrust efficiency was about 0.31 at specific impulse values ranging between 460 and 500 sec. Hydrazine mixtures gave similar thrust efficiencies at the same power level with specific impulse values between 395 and 430 sec. Large, spontaneous voltage mode changes were not observed once the thruster had passed a period of instability immediately following start up. This period of instability, and the startup at low pressure, were seen as major causes of constrictor damage during the tests.

Curran, F. M.↗

Low power dc arcjet operation with hydrogen/nitrogen propellant mixtures

The arcjet assembly from a flight model system was modified with a new thoriated tungsten nozzle insert and has been tested with hydrogen-nitrogen mixtures simulating the decomposition products of ammonia and hygrazine. Arcjet power consumption ranged from 0.7 to 1.15 kW depending on low rate, input current, and mixture composition. At a nominal 1 kW power level the ammonia mixtures thrust efficiency was about 0.31 at specific impulse values ranging between 460 and 500 sec. Hydrazine mixtures gave similar thrust efficiencies at the same power level with specific impulse values between 395 and 430 sec. Large, spontaneous voltage mode changes were not observed once the thruster had passed a period of instability immediately following start up. This period of instability, and the startup at low pressure, were seen as major causes of constrictor damage during the tests.

Curran, F. M.↗

Evidence for the involvement of carbonic anhydrase and urease in calcium carbonate formation in the gravity-sensing organ of Aplysia californica

To better understand the mechanisms that could modulate the formation of otoconia, calcium carbonate granules in the inner ear of vertebrate species, we examined statoconia formation in the gravity-sensing organ, the statocyst, of the gastropod mollusk Aplysia californica using an in vitro organ culture model. We determined the type of calcium carbonate present in the statoconia and investigated the role of carbonic anhydrase (CA) and urease in regulating statocyst pH as well as the role of protein synthesis and urease in statoconia production and homeostasis in vitro. The type of mineral present in statoconia was found to be aragonitic calcium carbonate. When the CA inhibitor, acetazolamide (AZ), was added to cultures of statocysts, the pH initially (30 min) increased and then decreased. The urease inhibitor, acetohydroxamic acid (AHA), decreased statocyst pH. Simultaneous addition of AZ and AHA caused a decrease in pH. Inhibition of urease activity also reduced total statoconia number, but had no effect on statoconia volume. Inhibition of protein synthesis reduced statoconia production and increased statoconia volume. In a previous study, inhibition of CA was shown to decrease statoconia production. Taken together, these data show that urease and CA play a role in regulating statocyst pH and the formation and maintenance of statoconia. CA produces carbonate ion for calcium carbonate formation and urease neutralizes the acid formed due to CA action, by production of ammonia.

Non-NASA Center↗

Radiation Chemistry in Ammonia-Water Ices

We studied the effects of 100 keV proton irradiation on films of ammonia-water mixtures between 20 and 120 K. Irradiation destroys ammonia, leading to the formation and trapping of H2, N2 NO, and N2O, the formation of cavities containing radiolytic gases, and ejection of molecules by sputtering. Using infrared spectroscopy, we show that at all temperatures the destruction of ammonia is substantial, but at higher temperatures (120 K), it is nearly complete (approximately 97% destroyed) after a fluence of 10(exp 16) ions per square centimeter. Using mass spectroscopy and microbalance gravimetry, we measure the sputtering yield of our sample and the main components of the sputtered flux. We find that the sputtering yield depends on fluence. At low temperatures, the yield is very low initially and increases quadratically with fluence, while at 120 K the yield is constant and higher initially. The increase in the sputtering yield with fluence is explained by the formation and trapping of the ammonia decay products, N2 and H2 which are seen to be ejected from the ice at all temperatures.

Loeffler, M. J.↗

Cooperative Research and Development Agreement between National Energy Technology Laboratory and Nuionic Technologies (Canada) Inc. [Abstract]

The National Energy Technology Laboratory (NETL) and NuIonic will collaborate in the development and commercial scaling of low-temperature and pressure ammonia synthesis using microwaves. Ammonia is one of the largest used chemicals in the world and is currently manufactured with a high temperature and pressure Haber-Bosch process. The current economical production scale of ammonia using Haber-Bosch (HB) synthesis is too large for the deployable scale of renewables (from 1 to 150 MW). Scaling down a HB process to 170,000 ton/year would increase production costs by a factor of 2-3. This collaboration will facilitate the deployment of a non-HB process for ammonia production that can directly interface and provide storage for intermittent renewable energy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Assessment of the polygeneration approach in wastewater treatment plants for enhanced energy efficiency and green hydrogen/ammonia production

Wastewater treatment plants (WWTPs) offer opportunities to optimize resource utilization and enhance energy efficiency. Here, this study provides a comprehensive analysis of using the polygeneration approach in WWTPs to reduce grid energy dependence, optimize energy distribution, and utilize surplus energy for hydrogen (H 2 ) and ammonia (NH 3 ) production. Several models were employed, including photovoltaic (PV) cells, parabolic trough collectors (PTCs), steam methane reforming, and polymer electrolyte membranes, to assess the feasibility of this approach. Three scenarios were evaluated and compared: Scenario 1 (Baseline) represents the current situation, Scenario 2 maximizes the Net Present Value (NPV), and Scenario 3 minimizes NH 3 production costs. Real data from As-Samra WWTP in Jordan was used to accurately assess the feasibility of each scenario. The results show that Scenario 2 offers the highest profitability and efficiency, with a NPV of 87.48 million USD and an annual NH 3 production of 15,417 tons, reducing both grid dependency and biogas fuel consumption. Both Scenarios 2 and 3 demonstrate the ability to meet thermal demands efficiently while generating significant revenue from NH 3 production. Scenario 3, in particular, achieves competitive H 2 and NH 3 production costs. Environmentally, Scenario 2 significantly reduces annual greenhouse gas emissions by 12.66 kilotons of CO 2eq , with near-zero carbon intensity for thermal energy due to solar reliance. In conclusion, the polygeneration approach offers a promising pathway for WWTPs to achieve greater sustainability, economic gains, and reduced environmental impact, providing valuable insights for decision-makers.

42 ENGINEERING↗

A Two-Stage Stochastic Programming Approach for the Design of Renewable Ammonia Supply Chain Networks

This work considers the incorporation of renewable ammonia manufacturing sites into existing ammonia supply chain networks while accounting for ammonia price uncertainty from existing producers. We propose a two-stage stochastic programming approach to determine the optimal investment decisions such that the ammonia demand is satisfied and the net present cost is minimized. We apply the proposed approach to a case study considering deploying in-state renewable ammonia manufacturing in Minnesota’s supply chain network. We find that accounting for price uncertainty leads to supply chains with more ammonia demand met via renewable production and thus lower costs from importing ammonia from existing producers. These results show that the in-state renewable production of ammonia can act as a hedge against the volatility of the conventional ammonia market.

Mitrai, Ilias (ORCID:0000000289896864)↗

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↗

High-throughput screening to predict highly active dual-atom catalysts for electrocatalytic reduction of nitrate to ammonia

Ammonia is an essential chemical owing to its importance in fertilizer production and other industrial applications. Electrocatalytic nitrate reduction to ammonia (NO 3 RR) holds great promise for low-temperature ammonia production while simultaneously addressing nitrate-based environmental concerns. To provide the mechanistic understanding needed to design an effective electrocatalyst, we systematically investigated the catalytic performance of metal-based dual-atom catalysts (DACs) anchored on two-dimensional (2D) expanded phthalocyanine (Pc) for NO 3 RR. We found that NO 3 RR can efficiently produce ammonia on Cr 2 -Pc, V 2 -Pc, Ti 2 -Pc, and Mn 2 -Pc surfaces with low limiting potentials of – 0.02, – 0.25, – 0.34, and – 0.41 V RHE , respectively. Moreover, using the free energy difference of *NO 3 - and *H as a descriptor, we found that the hydrogen evolution reaction is significantly suppressed on the DAC surface due to an ensemble effect in which the two metal atoms cooperate to selectively form ammonia. We performed high-throughput screening to develop an efficient metal-based DAC for NO 3 - reduction, followed by a mechanistic study to elucidate the NO3RR pathway on the DAC. Finally, this work provides design information for advancing sustainable ammonia synthesis under ambient conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The effects of arcjet operating condition and constrictor geometry on the plasma plume

Measurements of plasma number density and electron temperature were obtained in the plumes of lab arcjet thrusters using electrostatic probes of both spherical and cylindrical geometry. The two arcjet thrusters used had different constrictor and/or nozzle geometries and operated on mixtures of nitrogen, hydrogen, and ammonia to simulate the decomposition products of hydrazine and ammonia. An increase in the measured electron density was observed for both geometries with increasing arc power at a constant mass flow rate and with increasing mass flow rate at a constant arc current. For a given operating condition, the electron number density decreased exponentially off centerline and followed an inverse distance squared relationship along the thrust axis. Typical measured electron temperatures ranged from 0.1 to 0.2 eV.

Carney, Lynnette M.↗

The effects of arcjet thruster operating condition constrictor geometry on the plasma plume

Measurements of plasma number density and electron temperature were obtained in the plumes of lab arcjet thrusters using electrostatic probes of both spherical and cylindrical geometry. The two arcjet thrusters used had different constrictor and/or nozzle geometries and operated on mixtures of nitrogen, hydrogen, and ammonia to simulate the decomposition products of hydrazine and ammonia. An increase in the measured electron density was observed for both geometries with increasing arc power at a constant mass flow rate and with increasing mass flow rate at a constant arc current. For a given operating condition, the electron number density decreased exponentially off centerline and followed an inverse distance squared relationship along the thrust axis. Typical measured electron temperatures ranged from 0.1 to 0.2 eV.

Carney, Lynnette M.↗

Intermetallic Ni 3 Ga 1 Catalyst for Efficient Ammonia Reforming of Light Alkane

Ammonia reforming of light alkane is conventionally employed for HCN production where coproduct H 2 is burned for heating owing to the high reaction temperature (1200 °C) of such a highly endothermic process. Here, in this study, we show that a Ni 3 Ga 1 intermetallic compound (IMC) catalyst is highly efficient for such a reaction, realizing efficient conversion of C1–C3 alkanes at 575–750 °C. This makes it feasible for on-purpose CO x -free H 2 production assuming that ammonia, as an H 2 carrier, is ubiquitously available from renewable energy. At 650 °C and an alkane/ammonia ratio of 1/2, ethane and propane conversion of ~20% and methane conversion of 13% were obtained (with nearly 100% HCN selectivity for methane and ethane) over the unsupported Ni 3 Ga 1 IMC, which also shows high stability due to the absence of coke deposition. This breakthrough is achieved by employing a stoichiometric Ni 3 Ga 1 mixed oxalate solid solution as the precursor for the Ni 3 Ga 1 IMC.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The Sugar Model: Autocatalytic Activity of the Triose-Ammonia Reaction

Reaction of triose sugars with ammonia under anaerobic conditions yielded autocatalytic products. The autocatalytic behavior of the products was examined by measuring the effect of the crude triose-ammonia reaction product on the kinetics of a second identical triose-ammonia reaction. The reaction product showed autocatalytic activity by increasing both the rate of disappearance of triose and the rate formation of pyruvaldehyde, the product of triose dehydration. This synthetic process is considered a reasonable model of origin-of-life chemistry because it uses plausible prebiotic substrates, and resembles modern biosynthesis by employing the energized carbon groups of sugars to drive the synthesis of autocatalytic molecules.

Weber, Arthur L.↗

The abundance of ammonia in Comet P/Halley derived from ultraviolet spectrophotometry of NH by ASTRON and IUE

From an analysis of the spatial profiles of both the NH and OH UV emissions observed by the ASTRON satellite, the ratio of ammonia-to-water production rates in Comet Halley on April 9, 1986 is derived and found to lie in the range of 0.44-0.94 percent. In order to compare this result with those based on both ground-based and in situ observations made on other dates during the 1985-1986 apparition of the comet, the IUE observational data base for December 1985 and March-April 1986 is used to evaluate the ratio of NH to OH column density in the IUE field of view and thus constrain the long-term behavior of this ratio. The IUE data base indicates that, to within a factor of 2, the ammonia-to-water production rate ratio is the same for a small sample of moderately bright comets observed recently.

Feldman, P. D.↗

University of Minnesota, Twin Cities Final Scientific/Technical Report Small Scale Ammonia Synthesis Using Stranded Wind Energy

Ammonia absorber columns offer an alternative separation unit to replace condensation in the Haber-Bosch synthesis loop. Metal halide salts can selectively separate ammonia from the reactor outlet gas mixture and incorporate it into their crystal lattice with remarkably high thermodynamic capacity. While the salts’ working capacity can be limited and unstable when they are in their pure form, the capacity is stable and can be high when using a porous ceramic support. In this project, we found optimal conditions for sorbent fabrication, we demonstrated benchmark levels of uptake and release of ammonia, and we fabricated and demonstrated a prototype at a scale of 1 kg/day ammonia. This task allowed us to assess improvement in the techno-economic prospects for this new separation approach, making viable more distributed production of green ammonia from geographically dispersed renewable energy sources.

08 HYDROGEN↗

Reviewing flexibility in industrial electrification: Focusing on green ammonia and steel in the United States

The renewable energy transition in the power sector involves a paradigm shift for flexibility. Flexible demand is more attainable than before, while supply flexibility faces new constraints due to the increased share of variable renewable resources. Increased demand flexibility can allow less use of peaking power plants and avoid need for additional capacity. Industrial flexibility could be especially interesting in this regard, as industrial customers are larger on average than other customers and have typically provided the largest share of demand response in the United States. We consider industrial demand, studying characteristics of flexible industrial loads. We then examine the dynamics of change occurring around industrial load flexibility by focusing on two case studies: green ammonia and steel production via electric arc furnaces. Electric arc furnace steel production is an important component of current demand response programs, whereas green ammonia and green fuels offer new paradigms for flexibility. We analyze the structure and functions of the technological innovation systems of load flexibility in those two industries via interviews with twenty-two stakeholders. Here, we conclude that in the United States these technological innovation systems are not well-functioning for industry in general or for steel, but do seem to be present for green ammonia. Additionally, explicit connections between scope two greenhouse gas emissions (those from purchased energy) and flexibility are lacking, and likewise industry stakeholders do not appear to make a connection between decarbonization and load flexibility, thus flexible demand is not viewed as a tool in industrial decarbonization.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗