A contribution towards the performance and structural understanding of copper and nickel salts as ammonia stores

The ongoing depletion of fossil fuels and the severe consequences of the greenhouse effect make the development of alternative energy systems crucially important. While hydrogen is, in principle, a promising alternative, releasing nothing but energy and pure water. Hydrogen storage is complicated and no completely viable technique has been proposed so far. This work is concerned with the study of one potential alternative to pure hydrogen: ammonia, and more specifically its storage in solids. Ammonia, NH3, can be regarded as a chemical hydrogen carrier with the advantages of strongly reduced flammability and explosiveness as compared to hydrogen. Furthermore, ammine metal salts presented here as promising ammonia stores easily store up to 50 wt.-% ammonia, giving them a volumetric energy density comparable to natural gas. The model system NiX2–NH3 ( X = Cl, Br, I) is studied thoroughly with respect to ammine salt formation, thermal decomposition, air stability and structural effects. The system CuX2–NH3 ( X = Cl, Br) has an adverse thermal decomposition behaviour, making it impractical for use as an ammonia store. This system is, however, most interesting from a structural point of view and some work concerning the study of the structural behaviour of this system is presented. Finally, close chemical relatives to the metal ammine halides, the metal ammine nitrates are studied. They exhibit interesting anion arrangements, which is an impressive showcase for the combination of diffraction and spectroscopic information. The characterisation techniques in this thesis range from powder diffraction over single crystal diffraction, spectroscopy, computational modelling, thermal analyses to gravimetric uptake experiments. Further highlights are the structure solutions and refinements from powder data of (NH4)2[NiCl4(H2O)(NH3)] and Ni(NH3)2(NO3)2, the combination of crystallographic and chemical information for the elucidation of the (NH4)2[NiCl4(H2O)(NH3)] formation reaction and the growth of single crystals under ammonia flow, a technique allowing the first documented successful growth and single crystal diffraction measurement for [Cu(NH3)6]Cl2.

Performance of Plate Type Heat Exchanger as Ammonia Condenser

In this study, I experimentally analyzed the performance of a commercial semi-welded plate type heat exchanger (PHE) for use with ammonia systems. I determined performance parameters such as overall heat transfer coefficient, capacity, and pressure drop of the semi-welded PHE. This was analyzed by varying different parameters which demonstrated changes in overall heat transfer coefficient, capacity, and pressure drop. Both water and ammonia flow rates to the semi-welded PHE were varied independently, and analyzed in order to understand how changes in flow rates affected performance. Inlet water temperature was also varied, in order to understand how raising condenser water inlet temperature would affect performance. Finally, pressure drop was monitored to better understand the performance limitations of the semi-welded PHE. Testing of the semi-welded will give insight as to the performance of the semi-welded PHE in a potential ocean thermal energy conversion system, and whether the semi-welded PHE is a viable choice for use as an ammonia condenser.

Stress in pacu exposed to ammonia in water

The present study evaluated stress indicators in pacu exposed to ammonia in water under the following conditions: without NH4Cl (0.00 g/L); with 0.0078 g NH4Cl/L; and with 0.078 g NH4Cl/L (pH 8.3 and 27 ºC). After the salt dilution the water flow was interrupted and reestablished in 24 hours. Sampling occurred prior to the addition of NH4Cl (control) and after 12, 24 and 48 hours. Glycaemia increased only in fish with the highest salt concentration when compared with group control, regardless of time, and at 24 hours, regardless of treatment. Plasma ammonia, highest in fish exposed to the highest NH4Cl concentration, decreased progressively up to 48 hours. Plasma chloride only decreased in fish not exposed to salt when compared with control and osmolality increased after 24 hours. Hematocrit (Ht), number and volume of erythrocytes and hemoglobin did not change when NH4Cl was added; Ht decrease was reported after 12 hours, but it was not followed by the other blood parameters. The results show tolerance of the pacu to ammonia in the environment.

Ammonia effects on proton conductivity properties of coordination polymers

Crystalline metal phosphonates are referred to as a type of structurally versatile coordination polymers [1]. Many of them contain guest molecules (H2O, heterocyclics, etc.), acidic sites and, furthermore, their structure can be also amenable for post‐synthesis modifications in order to enhance desired properties [2]. In the present work, we examine the relationships between crystal structure and proton conductivity for several metal phosphonates derive from multifunctional ligands, such as 5-(dihydroxyphosphoryl)isophthalic acid (PiPhtA) [3] and 2-hydroxyphosphonoacetic acid (H3HPAA). Crystalline divalent metal derivatives show a great structural diversity, from 1D to 3D open-frameworks, possessing hydrogen-bonded water molecules and acid groups. These solids present a proton conductivity range between 7.2·10-6 and 1.3·10−3 S·cm-1. Upon exposure to ammonia vapor, from an aqueous solution, solid state transformations are observed accompanied of enhance proton conductivities. The stability of these solids under different environment conditions (temperature and relative humidities) as well as the influence of the ammonia adsorption on the proton conduction properties of the resulting solids will be discussed.

Study of ammonia borane and its derivatives: Influence of nanoconfinements and pressures

Recently, ammonia borane has increasingly attracted researchers’ attention because of its merging applications, such as organic synthesis, boron nitride compounds synthesis, and hydrogen storage. This dissertation presents the results from several studies related to ammonia borane. ^ The pressure-induced tetragonal to orthorhombic phase transition in ammonia borane was studied in a diamond anvil cell using in situ Raman spectroscopy. We found a positive Clapeyron-slope for this phase transformation in the experiment, which implies that the phase transition from tetragonal to orthorhombic is exothermic. The result of this study indicates that the rehydrogenation of the high pressure orthorhombic phase is expected to be easier than that of the ambient pressure tetragonal phase due to its lower enthalpy. ^ The high pressure behavior of ammonia borane after thermal decomposition was studied by in situ Raman spectroscopy at high pressures up to 10 GPa. The sample of ammonia borane was first decomposed at ∼140 degree Celcius and ∼0.7 GPa and then compessed step wise in an isolated sample chamber of a diamond anvil cell for Raman spectroscopy measurement. We did not observe the characteristic shift of Raman mode under high pressure due to dihydrogen bonding, indicating that the dihydrogen bonding disappears in the decomposed ammonia borane. Although no chemical rehydrogenation was detected in this study, the decomposed ammonia borane could store extra hydrogen by physical absorption. ^ The effect of nanoconfinement on ammonia borane at high pressures and different temperatures was studied. Ammonia borane was mixed with a type of mesoporous silica, SBA-15, and restricted within a small space of nanometer scale. The nano-scale ammonia borane was decomposed at ∼125 degree Celcius in a diamond anvil cell and rehydrogenated after applying high pressures up to ∼13 GPa at room temperature. The successful rehydrogenation of decomposed nano-scale ammonia borane gives guidance to further investigations on hydrogen storage. ^ In addition, the high pressure behavior of lithium amidoborane, one derivative of ammonia borane, was studied at different temperatures. Lithium amidoborane (LAB) was decomposed and recompressed in a diamond anvil cell. After applying high pressures on the decomposed lithium amidoborane, its recovery peaks were discovered by Raman spectroscopy. This result suggests that the decomposition of LAB is reversible at high pressures.^

High Pressure and Low Temperature Study of Ammonia Borane and Lithium Amidoborane

Hydrogen has been considered as a potentially efficient and environmentally friendly alternative energy solution. However, one of the most important scientific and technical challenges that the “hydrogen economy” faces is the development of safe and economically viable on-board hydrogen storage for fuel cell applications, especially to the transportation sector. Ammonia borane (BH3NH3), a solid state hydrogen storage material, possesses exceptionally high hydrogen content (19.6 wt%).However, a fairly high temperature is required to release all the hydrogen atoms, along with the emission of toxic borazine. Recently research interests are focusing on the improvement of H2 discharge from ammonia borane (AB) including lowering the dehydrogenation temperature and enhancing hydrogen release rate using different techniques. Till now the detailed information about the bonding characteristics of AB is not sufficient to understand details about its phases and structures. Elemental substitution of ammonia borane produces metal amidoboranes. Introduction of metal atoms to the ammonia borane structure may alter the bonding characteristics. Lithium amidoborane is synthesized by ball milling of ammonia borane and lithium hydride. High pressure study of molecular crystal provides unique insight into the intermolecular bonding forces and phase stability. During this dissertation, Raman spectroscopic study of lithium amidoborane has been carried out at high pressure in a diamond anvil cell. It has been identified that there is no dihydrogen bond in the lithium amidoborane structure, whereas dihydrogen bond is the characteristic bond of the parent compound ammonia borane. It has also been identified that the B-H bond becomes weaker, whereas B-N and N-H bonds become stronger than those in the parent compound ammonia borane. At high pressure up to 15 GPa, Raman spectroscopic study indicates two phase transformations of lithium amidoborane, whereas synchrotron X-ray diffraction data indicates only one phase transformation of this material. Pressure and temperature has a significant effect on the structural stability of ammonia borane. This dissertation explored the phase transformation behavior of ammonia borane at high pressure and low temperature using in situ Raman spectroscopy. The P-T phase boundary between the tetragonal (I4mm) and orthorhombic (Pmn21) phases of ammonia borane has been determined. The transition has a positive Clapeyron slope which indicates the transition is of exothermic in nature. Influence of nanoconfinemment on the I4mm to Pmn21 phase transition of ammonia borane was also investigated. Mesoporus silica scaffolds SBA-15 with pore size of ~8 nm and MCM-41 with pore size of 2.1-2.7 nm, were used to nanoconfine ammonia borane. During cooling down, the I4mm to Pmn21 phase transition was not observed in MCM-41 nanoconfined ammonia borane, whereas the SBA-15 nanocondfined ammonia borane shows the phase transition at ~195 K. Four new phases of ammonia borane were also identified at high pressure up to 15 GPa and low temperature down to 90 K.

Ammonia volatilization from different beef cattle production systems with tropical pastures during the seasons.

2016

Assessing the impact of ammonia content in VFA-rich streams on the PHA-storing MMC acclimatization and the PHA production stage

The use of environmentally friendly products increased the interest in renewable resources as alternatives to petrochemical products. Polyhydroxyalkanoates (PHAs) are examples of such promising products, as they are biodegradable polymers with numerous potential applications. PHA production approach consists of using an open mixed microbial culture (MMC) and inexpensive feedstocks (waste or industry byproducts feedstock). The PHA process generally comprises three stages: (1) acidogenic fermentation (AF) stage (conversion of organic carbon into fermentation products); (2) culture selection stage (enrichment in PHA-storing organisms by applying Feast and Famine regime); and (3) PHA production stage (PHA accumulation up to the culture’s maximum capacity). AF of protein-rich residues results in ammonia-rich fermented streams, which can be presented as a challenge for the PHA production stage. The presence of ammonia during this stage may induce organisms to grow instead of producing PHAs. For this reason, the assessment of the effect of a high content of ammonia on PHA production it is the utmost importance. The main goal of the current project is to select a MMC enriched in PHA-accumulating organisms in conditions of high ammonia content and to evaluate the effects of ammonia presence during PHA accumulation. The culture was selected applying the Feast & Famine strategy, and fed, firstly, using a synthetic mixture of VFAs and later using a fermented stream obtained from the fermentation of protein-rich raw materials. The selected culture could accumulate up to 24% PHA per VSS with the synthetic mixture of VFAs and up to 29% for the real fermented stream. The PHA accumulation resulted in different production in the presence and absence of ammonia. Regarding to the synthetic feed, 59%wt. PHA (VSS basis) in the absence of ammonia, and 55%wt. (VSS basis) in the presence, were obtained. For the real feed, the PHA content was about 40%wt. (VSS basis) in both reactors.

Electrochemical Oxidation Of Landfill Leachate In A Flow Reactor: Optimization Using Response Surface Methodology.

Response surface methodology based on Box-Behnken (BBD) design was successfully applied to the optimization in the operating conditions of the electrochemical oxidation of sanitary landfill leachate aimed for making this method feasible for scale up. Landfill leachate was treated in continuous batch-recirculation system, where a dimensional stable anode (DSA(©)) coated with Ti/TiO2 and RuO2 film oxide were used. The effects of three variables, current density (milliampere per square centimeter), time of treatment (minutes), and supporting electrolyte dosage (moles per liter) upon the total organic carbon removal were evaluated. Optimized conditions were obtained for the highest desirability at 244.11 mA/cm(2), 41.78 min, and 0.07 mol/L of NaCl and 242.84 mA/cm(2), 37.07 min, and 0.07 mol/L of Na2SO4. Under the optimal conditions, 54.99 % of chemical oxygen demand (COD) and 71.07 ammonia nitrogen (NH3-N) removal was achieved with NaCl and 45.50 of COD and 62.13 NH3-N with Na2SO4. A new kinetic model predicted obtained from the relation between BBD and the kinetic model was suggested.

Um novo índice de qualidade das águas para proteção da vida aquática aplicado ao Rio Atibaia, região de Campinas/Paulínia-SP

In this paper a water quality index is developed to subsidize management actions in the Atibaia River for upon protection of aquatic organisms. This index is composed of two measurable environmental parameters normaly, ammonia and dissolved oxygen, the latter representing the contribution of organic matter. Concentrations of these two variables were normalized on a scale from 0 to 100 and translated into statements of quality (excellent, good, regular, bad and very bad). The index was applied to three monitoring points in the Atibaia River and compared to other indices used by the State of São Paulo Environmental Agency (CETESB). The results showed that the degradation in this watershed follows the urban population density. The developed index is more restricted than the other ones routinely used to infer water quality.

A síntese da amônia: alguns aspectos históricos

The ammonia synthesis from its elements plays an important role in the survival of humankind. A short historical development of discoveries of the nitrogen cycle, the nitrogen sources for agriculture and the ammonia synthesis (in laboratory and industry) are presented. Some brief aspects of nitrogen chemistry are described. Short biographies of Fritz Haber and Carl Bosch, the main persons in this epopee, are also presented.

Ambiência aérea em alojamento de frangos de corte: poeira e gases

Air quality in animal production environment has been refereed as an interesting point for studies in environmental control systems with the focus both to the animal health which live in total confinement, as to the workers. The objective of this research was to determine the variation on the aerial environmental quality in two types of broiler housing: conventional (Gc) and tunnel type (Gt). The total dust values in both houses offered adequate rearing conditions to the birds; however, regarding the inhale dust in the air was above the limits recommended for humans. Carbon monoxide concentration in the heating phase during the evaluated period was above the 10 ppm maximum recommended, and it was higher during the cold season in Gt house (30 ppm) when compared to the Gc house (18 ppm). Ammonia concentration peaks in the air were above the 20 ppm recommended from the 20th day of production in both houses and in daily average, for a period higher in Gt (4h30) when compared to Gt (2h45). Only traces of nitrate oxide and methane were found while carbonic dioxide gas concentration evaluated during daytime met the limits allowed for both birds and labor.

Estimativa de bem-estar de frango de corte em função da concentração de amônia e grau de luminosidade no galpão de produção

Brazil is an important poultry meat export country, and large parts of its destination are countries with specific rearing restrictions related to broiler s welfare. One of the aerial pollutants mostly found in high concentrations in closed poultry housing environment is ammonia. There are evidences that broilers welfare may be compromised by the continuous exposition to this pollutant in rearing housing. This research aimed to estimate broilers welfare reared under specific thermal environmental attributes and bird s density, as function of the ammonia concentration and light intensity inside the housing environment using the Fuzzy Theory. Results showed that the best welfare value (0.89 in the scale: 0-1) approximately 90% of the ideal was found in the conditions that associated the ideal thermal environment, with bird s density between 13-15 birds m-2, with values of the ammonia concentration in the environment below 5 ppm, and light intensity near 1 lx. Using the predictive method it was possible to estimate broilers welfare with relation to the ammonia concentration and light intensity in the housing.

Efeitos de dietas com níveis crescentes de milho no metabolismo ruminal de energia e proteína em bubalinos

Avaliaram-se os efeitos de dietas com níveis crescentes de milho em grão moído (0, 22, 37 e 49% na MS) em substituição ao feno de coast-cross mantendo-se diferentes relações proteína:carboidratos não-fibrosos (PB:CNF = 1,01; 0,39; 0,33 e 0,27) sobre o metabolismo ruminal de búfalos. Utilizaram-se quatro búfalos fistulados no rúmen, mantidos em delineamento quadrado latino 4 × 4, para a coleta de amostras do líquido ruminal, colhidas em cada período experimental (de 28 dias) nos tempos 0, 2, 4 e 8 horas após a alimentação. Em geral, os bubalinos apresentaram boa capacidade tamponante no rúmen, com pH médio alto (6,70) e aumento da ingestão de milho em grão moído. O acréscimo nos níveis de milho na dieta promoveu aumento da produção de ácido butírico. Somente a dieta com 49% de milho promoveu melhor fermentação ruminal, com menor propoção de ácidos acético:propiônico. A relação PB:CNF de 1,01 indica deficiência de energia da dieta disponível para microrganismos no rúmen ao longo do dia, enquanto dietas com PB:CNF entre 0,39 e 0,27 promovem fermentações ruminais semelhantes, o que indica sincronismo na utilização de nitrogênio e energia pelos microrganismos no rúmen nessas condições.