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At least 415 records · Page 23

Ammonia Remediation in Hanford WTP Liquid Secondary Waste

The Hanford Site Effluent Treatment Facility (ETF) treats aqueous waste streams; some of these waste streams have high concentrations of ammonium ion. When the WTP begins operation the ETF LSW is slated to be stabilized by grouting prior to disposal. During stabilization of such waste by grouting the pH would rise considerably, leading to the evolution of ammonia gas. Such an ammonia release would require engineering controls to assure worker and environmental safety. The primary objective of this work was to perform a parametric study of the efficacy of ammonia destruction from solution using sodium nitrite addition under varying conditions that expands upon previous work.

54 ENVIRONMENTAL SCIENCES↗

Metal nitride materials for solar-thermal ammonia production [Slides]

Solar Thermal Ammonia Production has the potential to synthesize ammonia in a green, renewable process that can greatly reduce the carbon footprint left by the conventional Haber-Bosch reaction. Co 3 Mo 3 N has been identified as a potential candidate for ammonia production. It is synthesized via oxide precursor synthesis followed by nitridation under 10% H 2 /N 2 . The synthesis method can be extended to other candidate nitrides. The Co 3 Mo 3 N → Co 6 Mo 6 N reduction is demonstrated on TGA with rapid kinetics. The formation of NH 3 is qualitatively observed, but not quantitatively determined. The material retains crystal structure, but no secondary phases are observed in XRD. Partial re-nitridation back to CMN331 of ~35% of max nitridation is observed. Reaction parameters in TGA differ from experimental conditions in the literature. Experiments at Georgia Tech better mimic re-nitridation conditions with more sensitive, quantitative analytical techniques (GC-MS). The ASU NH 3 synthesis/re-nitridation reactor is under development and will permit experiments (reduction/re-nitridation) under precisely controlled T, pH 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Solar-Thermal Ammonia Production Via a Nitride Looping Cycle [Slides]

Solar Thermal Ammonia Production has the potential to synthesize ammonia in a green, renewable process that can greatly reduce the carbon footprint left by conventional Haber-Bosch reaction. Ternary nitrides in the family A 3 B x N (A=Co, Ni, Fe; B=Mo; x=2,3) have been identified as a potential candidate for NH 3 production. Experiments with Co 3 Mo 3 N in Ammonia Synthesis Reactor demonstrate cyclable NH 3 production from bulk nitride under pure H 2 . Production rates were fairly flat in all the reduction steps with no evident dependence on the consumed solid-state nitrogen, as would be expected from catalytic Mars-van Krevelen mechanism. Material can be re-nitridized under pure N 2 . Bulk nitrogen per reduction step average between 25 – 40% of the total solid-state nitrogen. Selectivity to NH 3 stabilized at 55 – 60% per cycle. Production rates (NH 3 and N 2 ) become apparent above 600 °C at P(H 2 ) = 0.5 – 2 bar. Optimal point of operation to keep selectivity high without compromising NH 3 rates currently estimated at 650 °C and 1.5 - 2 bar. The next steps are to optimize production rates, examine effect of N 2 addition in NH 3 synthesis reaction, and test additional ternary nitrides.

14 SOLAR ENERGY↗

Development of 250 kW Ammonia and Hydrogen Industrial Burner Test Facility at the National Energy Technology Laboratory

In an effort to investigate the viability of ammonia and hydrogen as fuels in the industrial heating sector, the Department of Energy’s National Energy Technology Laboratory is developing a 250 kW burner test facility. The pursuit of a decarbonized industrial heating sector requires innovative approaches to convert existing assets to alternative fuels while maintaining adequate radiative heat transfer and limiting NOx. This new capability will leverage NETL’s experience and prior investments in ammonia and hydrogen combustion, to advance atmospheric pressure industrial combustion systems for industries such as cement kilns and glass factories. The intention in coming years is to collaborate with burner manufacturers and heavy industry partners to study, develop, and validate strategies for converting existing hardware from carbon-based fuels to next-generation clean ammonia and hydrogen technologies.

May, Kristyn Johnson↗

Intensification and Integration of Hydrogen and Ammonia Production

In this project the Colorado School of Mines developed a more efficient method for on-site and on-demand generation of high purity hydrogen from ammonia for hydrogen fueling stations. Used primarily as a fertilizer, ammonia is the world’s highest volume commodity chemical. Having 17.6% hydrogen by mass, it also shows potential as a hydrogen carrier and carbon-free fuel. The team developed new technology to generate fuel cell quality hydrogen from ammonia using a catalytic membrane reactor (CMR). In addition, during the project we pivoted to use this CMR technology for the production of NH3/H2 mixtures for use in clean combustion applications. We demonstrated that these mixtures may serve as a drop-in replacement for conventional hydrocarbons such as natural gas. This project entails development of new catalysts, new membranes, and their innovative integration. This project helped generate >$4M in follow on funding at Mines, and resulted in the formation of a clean tech startup, Blaze Energy Technologies, which has licensed IP developed in this project and is working to commercialize this technology.

08 HYDROGEN↗

Bioinorganic Chemistry of Nitrification: Structure and Function of Ammonia Monooxygenase (Final Technical Report)

The overarching goal of this project was to elucidate biochemical mechanisms that ubiquitous microorganisms use to enable primary metabolism based on nitrification, the multi-electron oxidation of ammonia (NH 3 ) to nitrite (NO 2 – ). This chemistry enables life to substitute carbon based fuel with nitrogen. Understanding the underlying chemistry was pursued to help inform the use of ammonia as an alternative fuel source compared to petroleum, capitalizing on the widespread infrastructure for production and distribution of this substance in the US. This project specifically focused on characterizing ammonia monooxygenase, an integral membrane copper protein that initiates nitrification via the aerobic oxidation of NH 3 to hydroxylamine (NH 2 OH).

09 BIOMASS FUELS↗

Effects of Extractive Ammonia Pretreatment on the Ultrastructure and Glycan Composition of Corn Stover

Lignocellulosic biomass is highly recalcitrant and requires a pretreatment step to improve the enzyme accessibility and fermentable sugar yields during enzymatic hydrolysis. Our previous studies demonstrated the rearrangement of the hydrogen bond network within CIII, makes it “amorphous-like” and facilitates easier glucan chain extraction by enzyme. Also, these changes increase the number of solvent-exposed glucan chain hydrogen bonds with water ~50% lowering the surface-bound cellulase by 60–70%. Also, major chemical modifications to lignin occur via ammonolysis of ester-linked ferulate and coumarate linkage. These apparent ultrastructural changes help the enhancement of cellulase activity resulting in higher production of fermentable sugars during enzyme hydrolysis of EA pretreated corn stover relative to Ammonia Fiber Expansion (AFEX) pretreatment. To understand ultra-structural modifications that occur during EA pretreatment, Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) were used to examine untreated and EA-pretreated corn stover in an effort to visualize changes in the biomass resulting from the pretreatment. In addition, Immunofluorescence Microscopy was applied to both untreated and pretreated plant cell walls using glycan-directed monoclonal antibodies to reveal possible changes in the spatial distributions of wall glycan epitopes resulting from EA pretreatment. This evaluation was complemented with glycome profiling to determine the glycan epitope compositions of EA-pretreated cell walls relative to untreated and AFEX pretreated corn stover, where lignin and carbohydrates are not extracted. Distinct differences could be observed in the case of xyloglucan, unsubstituted and substituted pectin- and pectic-arabinogalactan-epitope levels in the plant cell wall after EA pretreatment compared with untreated and AFEX-pretreated walls. Liquid ammonia induced de-lignification of cell wall has helped to clearly identify the glucans that are intact after pretreatment. These studies support some of our hypothesis that liquid ammonia cleaves lignin–carbohydrate ester linkages, partially solubilizing lignin and its associated carbohydrates. Specifically, the imaging studies clearly show that some of the cell wall components are extracted as a separate liquid stream during the EA process, thereby creating porous, interconnected tunnel-like networks in the plant cell walls thereby providing better access of carbohydrate polymers to enzymes and thereby increasing the sugar yield from the EA-pretreated biomass.

09 BIOMASS FUELS↗

Unexpectedly acidic nanoparticles formed in dimethylamine-ammonia-sulfuric-acid nucleation experiments at CLOUD

New particle formation driven by acid–base chemistry was initiated in the CLOUD chamber at CERN by introducing atmospherically relevant levels of gas-phase sulfuric acid and dimethylamine (DMA). Ammonia was also present in the chamber as a gas-phase contaminant from earlier experiments. The composition of particles with volume median diameters (VMDs) as small as 10 nm was measured by the Thermal Desorption Chemical Ionization Mass Spectrometer (TDCIMS). Particulate ammonium-to-dimethylaminium ratios were higher than the gas-phase ammonia-to-DMA ratios, suggesting preferential uptake of ammonia over DMA for the collected 10–30 nm VMD particles. This behavior is not consistent with present nanoparticle physicochemical models, which predict a higher dimethylaminium fraction when NH 3 and DMA are present at similar gas-phase concentrations. Despite the presence in the gas phase of at least 100 times higher base concentrations than sulfuric acid, the recently formed particles always had measured base : acid ratios lower than 1 : 1. The lowest base fractions were found in particles below 15 nm VMD, with a strong size-dependent composition gradient. The reasons for the very acidic composition remain uncertain, but a plausible explanation is that the particles did not reach thermodynamic equilibrium with respect to the bases due to rapid heterogeneous conversion of SO 2 to sulfate. Furthermore, these results indicate that sulfuric acid does not require stabilization by ammonium or dimethylaminium as acid–base pairs in particles as small as 10 nm.

54 ENVIRONMENTAL SCIENCES↗

The catalytic removal of ammonia and nitrogen oxides from spacecabin atmospheres

Investigations were made on methods for the removal of ammonia and to a lesser extent nitrogen oxides in low concentrations from air. The catalytic oxidation of ammonia was studied over a temperature range of 250 F to 600 F and a concentration range 20 ppm to 500 ppm. Of the catalysts studied, 0.5 percent ruthenium supported on alumina was found to be superior. This material is active at temperatures as low as 250 F and was found to produce much less nitrous oxide than the other two active catalysts, platinum on alumina and Hopcalite. A quantitative design model was developed which will permit the performance of an oxidizer to be calculated. The ruthenium was found to be relatively insensitive to low concentrations of water and to oxygen concentration between 21 percent and 100 percent. Hydrogen sulfide was found to be a poison when injected in relatively large quantities. The adsorption of ammonia by copper sulfate treated silica gel was investigated at temperatures of 72 F and 100 F. A quantitative model was developed for predicting adsorption bed behavior.

Gully, A. J.↗

Ammonia photolysis on Jupiter.

Ammonia photolysis under simulated Jovian conditions indicates that the photochemical reaction would rapidly convert all the ammonia of Jupiter to nitrogen even in a large excess of hydrogen. It is suggested that ammonia is observed because the planet's atmosphere is deep and hot and/or because electrical discharge phenomena are important.

Nicodem, D. E.↗

Pyrolysis of organic compounds in the presence of ammonia The Viking Mars lander site alteration experiment

The influence of ammonia on the pyrolysis pattern of selected organic substances sorbed on an inorganic phase was investigated. The thermal degradation products were identified by gas chromatography-mass spectrometry. The feasibility of this technique was tested on a meteoritic sample. All substances examined react with ammonia at the pyrolysis temperature of 500 C, the major products being nitriles and heterocyclic compounds in which nitrogen was incorporated. Based on these results, a model for the non-equilibrium production of organic compounds on Jupiter is discussed. The investigation was performed in connection with the Viking lander molecular analysis. The results obtained indicate that the concentrations of ammonia in the retrorocket fuel exhaust would have been probably too small to produce significant changes in the Martian soil organic compounds if any were found.

Holzer, G.↗

Reactivity of stratospheric aerosols to small amounts of ammonia in the laboratory environment

Trace ammonia in laboratory air reacts easily with sulfuric acid aerosol samples to form crystalline ammonium sulfate. Argon atmospheres, however, protect sampling surfaces from ammonia contamination. It is found that atmospheric aerosols treated in this way contain only sulfuric acid. After an hour exposed to laboratory air, these same samples convert to ammonium sulfate. Aerosol particles have been collected, using argon control, to determine if the absence of crystalline sulfate is common. But so far there is no evidence that aerosols are neutralized by ammonia in the stratosphere.

Hayes, D.↗

Stability of ammonia in the primitive terrestrial atmosphere

The rate at which ammonia would have been destroyed in the earth's atmosphere under assumed NH3 mixing ratio conditions of 10 to the -8th to 0.0001 is calculated by a one-dimensional photochemical model, and the destruction rates are compared with possible biotic and abiotic ammonia sources. It is found that, while the mixing ratio of 10 to the -8th needed for the evolution of life could have been maintained by abiotic sources, the value of 0.00001 needed for the production of significant greenhouse warming could not have been sustained abiotically. The increase of atmospheric ammonia due to biological activities during the Archean is also considered lower than the level required for the generation of measurable thermal effects.

Kasting, J. F.↗

The Jovian ammonia abundance from interferometric observations of limb darkening at 3.4 mm

The relative abundances of the various atomic and molecular constituents in the Jovian atmosphere are important data for studies of the origin of the solar system. The determination of the ammonia abundance presents a number of difficulties. However, difficulties related to a use of the microwave sensing technique can be largely overcome by measuring the brightness distribution across the disk. In particular, information about the atmosphere can be obtained from the degree of limb darkening, which requires only a relative brightness measurement as opposed to an absolute measurement. Valdes and Welch (1978) have used the considered approach in a study of Jupiter at 1.3 cm. In the present investigation a more general relation between the amount of limb darkening in the broad 1.25-cm inversion band of ammonia and the ammonia abundance is derived. The model is applied to new measurements of Jupiter's limb darkening at 3.4 mm.

Valdes, F.↗

Sources of atmospheric ammonia

The information available on factors that influence emissions from the principal societal sources of ammonia to the atmosphere, namely combustion processes, volatilization of farm animal wastes, and volatilization of fertilizers, is reviewed. Emission factors are established for each major source of atmospheric ammonia. The factors are then multiplied by appropriate source characterization descriptors to obtain calculated fluxes of ammonia to the atmosphere on a state-by-state basis for the United States.

Harriss, R. C.↗

Production of ammonia-depleted surface layers on the Saturnian satellites by ion sputtering

On the basis of laboratory-derived data on the ion erosion of water and ammonia ices, it is suggested that the surfaces of the Saturnian satellites Enceladus, Tethys, Dione, and Rhea could have become enriched with water ice over a reasonable geological time period owing to the preferential erosion of the ammonia by magnetosphere ion bombardment. This mechanism serves as an alternative explanation to other processes invoked for the absence of ammonia spectral features in these satellites.

Lanzerotti, L. J.↗

New interstellar masers in nonmetastable ammonia

The first astronomical detections of several ammonia inversion transitions involving nonmetastable levels with energies as high as 1090 K above the ground state are reported. The (J, K) = (9, 6) inversion transition shows maser-like emission in the directions of W51, NGC 7538, W49, and DR 21(OH). The NH3 (6, 3) line exhibits similar characteristics in W51 but is seen in absorption in NGC 7538. These are the first definite detections of ammonia masers in space. The intensities and narrow line widths (0.5-1.5 km/s) for the emission features are in contrast to the previously detected broad, weak, nonmetastable lines attributed to thermal emission in these sources. Temporal variability appears to be evident in the (9, 6) emission in W49 over a 4 month period. The highly excited (J, K) = (9, 6) and (6, 3) ammonia lines are found in regions containig compact H II regions and strongly infrared sources with associated H2O and OH masers; i.e., in regions of active star formation.

Madden, S. C.↗

The ammonia-water phase diagram and its implications for icy satellites

A Holzapfel-type diamond anvil cell is used to determine the NH3 - H2O phase diagram in the region from 0 to 33 mole percent NH3, 240 to 370 K, and 0 to 5 GPa. The following phases were identified: liquid; water ices Ih, III, V, VI, VII, and VIII; ammonia monohydrate, NH3.H2O; and ammonia dihydrate NH3.2H2O. Ammonia dihydrate becomes prominent at moderate pressures (less than 1 GPa), with planetologically significant implications, including the possibility of layering in Titan's magma ocean.

Johnson, M. L.↗