Auswahl der wissenschaftlichen Literatur zum Thema „Ammonia separation“

SUMMARYTreatments which lowered the rate of ammonia volatilization from surface-applied cattle slurry were evaluated in three field experiments during 1989/90 at the Agricultural Research Institute of Northern Ireland. The relative effects of separation, dilution with water before application and washing with a water spray after application, on ammonia volatilization rates were compared over 4 days using ventilated enclosures. As the loss rate of ammonia during the first 4 days after application was highly correlated with the loss rate over the first 4 hours after application, the loss rate in the first 4 hours was used as a rapid method to assess the efficacy of various combinations of separation, dilution and acidification. Ammonia volatilization loss rates from treatment combinations were compared to the loss rate from whole slurry.A 50% decrease in ammonia volatilization was achieved by separation through a 0·4 mm mesh, separation through a 10·0 mm mesh plus dilution with 86% by volume of water, or separation through a 2·0 mm mesh plus washing with 53% by volume of water.A 75% decrease in ammonia volatilization was achieved by acidification to pH 6·5, or combinations of separation and dilution, namely separation through a 0·4 mm mesh plus 50% dilution or separation through a 5·0 mm mesh plus 100% dilution.A 90% decrease in ammonia volatilization was achieved by acidification to pH 6·0, dilution by 50% plus acidification to pH 6·5, or separation through a 0·4 mm mesh plus acidification to pH 6·5.The effects of separation and acidification on ammonia volatilization were cumulative. There was a highly significant inverse linear relationship between ammonia volatilization rate and volume of nitric acid used. Adding 10 M nitric acid at 1·4% by volume lowered volatilization by 75% of that from whole slurry and increased the nitrogen content of the slurry by 2 g N/l, making it a more balanced NPK fertilizer for cut swards. Because the variable value of cattle slurry is due to loss of nitrogen as ammonia and smothering of the sward with slurry solids, a combination of separation or dilution to lower sward contamination and acidification with nitric acid to lower volatilization may be the best practical option for improving cattle slurry as a fertilizer for cut grass.

Electrochemical processes are considered promising technologies for ammonia recovery from wastewater. In electrochemical processes, cation exchange membrane (CEM), which is applied to separate compartments, plays a crucial role in the separation of ammonium nitrogen from wastewater. Here we provide a comprehensive review on the application of CEM in electrochemical systems for ammonia recovery from wastewater. Four kinds of electrochemical systems, including bioelectrochemical systems, electrochemical stripping, membrane electrosorption, and electrodialysis, are introduced. Then we discuss the role CEM plays in these processes for ammonia recovery from wastewater. In addition, we highlight the key performance metrics related to ammonia recovery and properties of CEM membrane. The limitations and key challenges of using CEM for ammonia recovery are also identified and discussed.

Anaerobic digestion can adapt to free ammonia to a certain extent. During the anaerobic digestion of slaughterhouse waste, however, an ammonia concentration of up to 15 g N l−1 can be reached in the sludge liquid and this will even inhibit adapted sludge. To lower this concentration, a fraction of the digester liquid must therefore be continuously separated from the digested sludge and the free ammonia stripped before the liquid is recycled to the digester. A mesophilic laboratory digester was successfully operated with an ammonium concentration of 4–5 g l−1 and a pH of 8.0–8.4. After free ammonia stripping, the excess liquid was treated in a laboratory SBR for nitrogen and phosphorus removal before being added to the receiving water. The effluent had no toxic effect on daphnia and algae.

In the process of recycling chemical product in coking object, ammonia and tar were indispensable both metallurgy and agriculture, so the control of separation process for tar-ammonia was one of the most important control problems. Due to the density difference between the tar and ammonia was greater, easier to separate, the control method based on PID was used in field at present. But the control effect of traditional PID was not good because of environment change and fluctuation in material composition. Separation process for tar-ammonia was analyzed firstly, in view of the shortcoming of traditional PID control algorithm, single neuron PID control algorithm based on variable scale method was adopted through using optimization method. Detailed algorithm steps were designed and applied to tar-ammonia separation system. Simulation results show that by comparison with traditional PID algorithm, the algorithm have the following advantages: faster learning speed, shorter adjusted time and good convergence performance.

Mineral carbonation routes have been extensively studied for almost two decades at Åbo Akademi University, focusing on the extraction of magnesium from magnesium silicates using ammonium sulfate (AS) and/or ammonium bisulfate (ABS) flux salt followed by carbonation. There is, however, a need for proper recovery and recirculation of chemicals involved. This study focused on the separation of AS, ABS and aqueous ammonia using different setups of bipolar membrane electrodialysis using both synthetic and rock-derived solutions. Bipolar membranes offer the possibility to split water, which in turn makes it possible to regenerate chemicals like acids and bases needed in mineral carbonation without excess gas formation. Tests were run in batch, continuous, and recirculating mode, and exergy (electricity) input during the tests was calculated. The results show that separation of ions was achieved, even if the solutions obtained were still too weak for use in the downstream process to control pH. Energy demand for separating 1 kg of NH4+ varied in the range 1.7, 3.4, 302 and 340 MJ/kg NH4+, depending on setup chosen. More work must hence be done in order to make the separation more efficient, such as narrowing the cell width.

The effective separation of ammonia from the synthesis loop in ammonia synthesis plants is an important step in its manufacture. This work presents the use of nanocomposite MFI zeolite membranes prepared by a pore-plugging method for this separation process. Performance of a zeolite membrane is highly dependent on the operating conditions. Therefore, the influences of differential pressure, temperature, sweep gas flow, feed gas flow and gas composition are studied experimentally. Transport of NH3 in this membrane is by surface diffusion in the intracrystalline (zeolite) pores in parallel with capillary condensation in the intercrystalline (non-zeolite) pores. The separation of NH3 from a mixture with H2 and N2 is by preferential adsorption of NH3, which hinders the permeation of weakly adsorbed H2 and N2. Differential pressure has only relatively small effects in the pressure range 300kPa – 1550kPa. Increase in sweep flow rate has little effect on NH3 gas permeance, but H2 and N2 permeances increase thereby decreasing the selectivities. Increase in feed flowrate also has little effect on NH3 permeance. However, the N2 and H2 permeances increase and there is a subsequent decrease in selectivities. Membrane performance was found to be highly dependent on temperature. NH3 permeance in the mixture increases linearly with temperature. NH3 selectivity was found to increase with temperature up to 353K after which it starts to decrease due to N2 and H2 permeances increasing with temperatures beyond 353K (αNH3/N2 = 46 and αNH3/H2 = 15) and is therefore the optimum temperature for separation. A potential barrier model is developed to describe the hindering effect of NH3 on H2 and N2 permeance. The model fails to predict correctly H2 and N2 permeances in the ternary mixture using pure gas (H2 and N2) permeances. Binary mixture permeation H2/N2 studies showed that there are diffusion effects (single file diffusion) that have not been taken into account in the potential barrier model. When permeances of the individual components in the binary mixture are used in the model instead of the pure gas permeances, there is an improved agreement between experimental and predicted results.

ENGLISH ABSTRACT: Leaching of nickel laterite was conducted with a solution of ammonia and ammonium carbonate in a closed vessel. The vessel used in this study was designed to leach and perform solid-liquid separation at the same time. For solid-liquid separation, stainless steel sintered metal filter media were used. The sintered metal filter medium was selected for its high strength to withstand pressure, chemical resistance to caustic solution and back flushing properties. Optimum leaching conditions were determined by varying temperature, ammonia concentration, ammonium carbonate concentration and oxygen pressure. After leaching and filtration, the pH of the leach liquor was measured and samples were analyzed for dissolved metals (Ni, Fe and Co) using atomic absorption spectrophotometry. The most significant variable effect on leaching of nickel was the ammonia concentration. The maximum dissolution of nickel from the unroasted ore was 11.90% at 4 M NH3, 100oC, 2 M (NH4)2CO3 and 2 bar O2 pressure. Optimization from the leaching data was done using response profiling and desirability in Statistica software. Optimum leaching conditions were determined to be 3 M NH3, 2 M (NH4)2CO2, 100oC and 2 bar O2 pressure. The mineralogy of the ore before and after leaching was studied to understand why nickel extraction from unroasted ore was poor. XRF analysis of solids after leaching showed that iron, silicon, and magnesium remained the same. The only metal which showed significant decrease from solids was nickel. XRD analysis of solids after and before leaching showed that most mineral phases present in the ore are not affected by the leaching solution. SEM with EDS detection was used to determine nickel distribution within the ore. The results showed that nickel is mostly associated with iron. The iron is surrounded by magnesium and silicon. Silicate minerals do not react with ammonia and ammonium carbonate solution. From filtration experiments, the filtration differential pressure had no significant effect on the filtration rate. An average filtration rate of 0.29±0.07 ml/min.cm2 was obtained. The filtration rate from these experiments was very low. The main reason was due to quick pore clogging of sintered metals. Pore clogging was found to be mainly on the surface of the filter medium. Laterites have been found to have low permeability due a lot of clay present in the ore. Rheological studies on this ore showed that the ore has shear thickening behavior. However, a very clear filtrate was obtained. After each leach and filtration experiment, the sintered metals was unblocked by back flushing with water and air. Back flushing was successful because all 18 experiments were carried out using the same sintered filter medium. The effect of roasting the ore prior to leaching was investigated using optimum conditions obtained when leaching the unroasted ore. There was a slight improvement in nickel extraction when the ore was roasted. The average percentage extraction of nickel from 3 experimental runs was 19.25%±0.19 at 100oC, 3M NH3, 2M (NH4)2CO3, and 5 bar oxygen pressure. Some part of nickel in the ore was unextractable due to association of nickel with recrystallized silicate minerals in the reduced ore. Roasting improved permeability of the ore. The filtration rate improved significantly after roasting the ore. The average filtration rate was 2.60±0.05 ml/min.cm2. Dissolution kinetics of the unroasted and roasted saprolitic laterite were investigated with regard to the effects of temperature, ammonia concentration, ammonium carbonate concentration, and oxygen pressure. For the unroasted ore, it was found that dissolution rate and degree of nickel extraction increases with increasing temperature. Increase in ammonia concentration improves the degree of nickel extraction. Nevertheless, nickel extraction does not depend entirely on ammonia concentration because even when ammonia concentration is high and ammonium carbonate concentration is zero nickel extraction is low. An increase in ammonium carbonate concentration also increases the degree of nickel extraction. Ammonium carbonate is critical for the extraction, since ammonium ions in the solution prevent hydrolysis of the nickel ammine complex. Oxygen did not have a significant effect on the degree of nickel extraction. The leaching of nickel laterite was found to be a two stage leaching process. In the first stage, the dissolution of nickel is faster but after 15 minutes, the reaction rate is reduced. The reaction rate is reduced by inert minerals which host nickel. These minerals contain iron magnesium and silicon. The fast dissolution of nickel in the first stage represents leaching of free nickel in the ore. The data for the second stage of leaching was analyzed by the shrinking core model, and the results suggested that the dissolution rate is controlled by mixture kinetics (ash layer diffusion and surface reaction control). The activation energy for the dissolution reaction was calculated as 56.5 KJ/mol. The reaction order with respect to ammonia and ammonium carbonate were determined to be 0.3 and 0.26 respectively. For the roasted ore, the highest degree of nickel extraction was obtained at 60oC, 3M NH3, 2M (NH4)2CO3, and 5 bar oxygen pressure. The percentage extraction under these conditions was 28.7%. Temperature did not have a significant effect on the leaching rate. An increase in NH3 and (NH4)2CO3 increased the final extraction of nickel but did not have any effect on leaching rate in the first stage of leaching. In the absence of ammonium carbonate, nickel extraction is almost zero. The experimental data did not give linear fit to the shrinking core models investigated for the unroasted ore. The reason for this could be due to the sampling time interval which was too far apart, or the leaching behavior of roasted nickel is complicated and cannot explained by shrinking core model alone. Leaching experiments demonstrate that for a high degree metal extraction and improved reaction kinetics with ammonia and ammonium carbonate, the solution temperature should be high (>100oC) for the unroasted ore. In order to leach at high temperature with ammonia and ammonium carbonate a closed vessel is required to prevent reagent loses. The reaction kinetics showed that the reaction is controlled mostly by ash layer diffusion; this indicates that a low degree of nickel extraction in the unroasted saprolitic laterite is due to inert minerals (ash layer) which host nickel within the ore. In order to obtain a high degree of nickel extraction, the ore needs to be roasted under reducing conditions. Roasting conditions need to be carefully controlled to ensure high dissolution of nickel. In fact optimum roasting conditions which will give maximum dissolution of nickel, must be determined before working with the bulk of the ore.
AFRIKAANSE OPSOMMING: Logingstoetse van saprolitiese lateriet met 'n oplossing van ammonia en ammonium karbonaat is gedoen in 'n druk houer. Die logingsvat vir hierdie studie is ontwikkel om die loging sowel as die vloeistof – vastestof skeiding te doen. Gesinterde metaal filter medium was gebruik vir die vloeistof – vastestof skeiding aangesien dit die volgende eienskappe vertoon; die vermoë om druk te weerstaan, die chemiese weerstand teen bytsoda oplossing, asook voordelige terugspoel eienskappe. Optimum loogkondisies is bepaal deur die temperatuur, ammoniak konsentrasie, ammonium karbonaat konsentrasie, en suurstof druk te varieer. Na loging en filtrasie is die pH van die loogvloeistof gemeet en monsters is deur atoom absorpsie spektrofotometrie geanaliseer vir opgeloste metale (Ni, Fe en Co). Die veranderlike wat die grootste effek op die loging van nikkel gehad het was die ammoniak konsentrasie. Die maksimum herwinning van nikkel van uit ongeroosterde erts was 11.9 % by 4 M NH3, 100 oC, 2 M (NH4)2CO3 en 2 bar O2 druk. Optimisering van die loogdata is gedoen deur die respons profiel te analiseer met Statistica sagteware. Optimum loogkondisies was bepaal as 3 M NH3, 2 M (NH4)2CO2, 100 oC en 2 bar O2 druk. Die mineralogie van die erts voor en na loging is bestudeer om te bepaal waarom die nikel opbrengs van ongeroosterde erts so laag was. XRF analise van die vastestof na loging het gewys dat yster, silikon en magnesium nie deur loging affekteer is nie. Slegs nikkel het 'n merkwaardige afname getoon. XRD analsiese van die vastestof voor en na loging wys dat die meeste mineraal fases teenwoordig in die erts nie deur die loogoplossing affekteer is nie. SEM met EDS deteksie is gebruik om die nikkel verspreiding in die erts te bepaal. Die resultate wys dat nikkel meestal met yster assosieer. Die yster is omring deur magnesium en silikon. Silikaat minerale reageer nie met ammoniak en ammonium karbonaat oplossing nie. In filtrasie eksperimente is daar gevind dat die filtrasie differensiële druk geen noemenswaardige effek op die filtrasie tempo gehad het nie. Die gemiddelde filtrasietempo was 0.29+0.07 ml/min.cm2. Die filtrasie tempo van hierdie eksperimente was baie laag, hoofsaaklik as gevolg van blokkasie van porieë van die sinter metaal filter medium. Dit is gevind dat blokkasie van porieë hoofsaaklik op die oppervlak van die filter medium plaasvind. Lateriedes toon 'n lae deurlaatbaarheid as gevolg van die erts se hoë klei inhoud. Rheologiese studies op hierdie erts wys dat die erts skuif verdikking (“shear thickening”) gedrag vertoon. 'n Baie helder filtraat is egter verkry. Die gesinterde metale is na elke loog en filtrasie eksperiment skoongemaak deur terugspoeling met water en lug. Hierdie procedure was suksesvol, aangesien al 18 eksperimente met dieselfde filter medium uitgevoer is. Die effek van erts roostering voor loging is ondersoek by die optimum kondisies wat verkry was vir die loging van ongeroosterde erts. Nikkel ekstraksie het effens verbeter met geroosterde erts. Die gemiddelde persentasie ekstraksie van nikkel van drie eksperimentele lopies was 19.25 % + 0.19 by 100 oC, 3 M NH3, 2 M (NH4)2CO3, en 5 bar suurstofdruk. 'n Gedeelte van die nikkel in die erts was onherwinbaar as gevolg van die assosiasie van nikkel met her-gekristaliseerde sillikaat-minerale in die gereduseerde erts. Die porositeit van die erts is verbeter deur dit te rooster. Die filtrasie tempo het merkwaardig verbeter nadat die erts gerooster is. Die gemiddelde filtrasie tempo was 2.6+0.05 ml/min.cm2. Kinetika vir die oplossing van ongeroosterde en geroosterde saprolitiese lateriet is ondersoek, met in ag geneem die effekte van temperatuur, ammonia konsentrasie, ammonium karbonaat konsentrasie en suurstofdruk. Vir ongeroosterde erts is gevind dat die oplossingstempo en graad van nikkel ekstraksie toeneem met toenemende temperatuur. Toename in ammoniak konsentrasie lei tot 'n toename in nikkel ekstraksie, maar nikkel ekstraksie is nie alleenlik afhanklik van ammoniak nie. 'n Toename in ammonium karbonaat konsentrasie lei ook tot 'n toename in nikkel ekstraksie. Ammonium karbonaat is krities vir die ekstraksie, aangesien ammonium ione in die oplossing die hidrolise van die nikkel-amien kompleks verhoed. Suurstof het nie 'n merkwaardige effek op die totale nikkel ekstraksie gehad nie. Vir die bepaling van reaksie kinetika is 100˚C gebruik as die logingstemperatuur. Die loging van saprolitiese nikkel lateriet vind in twee stadia plaas. In die eerste fase is die oplossing van nikkel vinnig, maar na 15 minute neem die reaksietempo af. Die reaksietempo word verlaag deur inerte minerale wat teenwoordig is in die nikkel erts. Hierdie minerale bevat yster, magnesium en silikon. Die vinnige oplossing van nikkel in die eerste fase verteenwoordig die loging van vry nikkel in die erts. Die data vir die tweede stadium is geanaliseer deur die krimpende kern model, en die resultate dui aan dat die oplossingstempo deur 'n gemengde meganisme beheer word (as laag diffusie en oppervlak reaksie beheer). Die aktiveringsengergie vir die oplossingsreaksie was bereken as 56.5 kJ/mol. Die reaksieorde ten opsigte van ammoniak en ammonium karbonaat is onderskeidelik bepaal as 0.3 en 0.26. Die hoogste graad van nikkel ekstraksie vir die geroosterde erts is verkry by 60oC, 3 M NH3, 2 M (NH4)2CO3, en 5 bar O2 druk. Die persentasie ekstraksie by hierdie kondisies was 28.7 %. Temperatuur het nie 'n merkwaardige effek op loogtempo gehad nie. 'n Toename in NH3 en (NH4)2CO3 het die graad van nikkel ekstraksie laat toeneem, maar het nie enige effek op die loogtempo gehad nie. In die afwesigheid van ammonium karbonaat het byna geen nikkel ekstraksie plaasgevind nie. Die eksperimentele data het nie 'n lineêre passing vir die krimpende kern model soos vir die ongeroosterde erts ondersoek gegee nie. Die rede hiervoor is dat die monsternemings interval te groot was, of dat die logings karakteristiek van geroosterde nikel gekompliseerd is en nie alleen deur die krimpende kern model voorspel kan word nie. Logings eksperimente wys dat die temperatuur hoog moet wees (> 100 oC) om 'n hoë graad van nikkel ekstraksie te verkry met die ongeroosterde erts. 'n Geslote reaktor word benodig om by 'n hoë temperatuur met ammoniak en ammonium karbonaat te loog om reagens verliese te verhoed. Die reaksie kinetika word grootliks deur aslaag diffusie beheer. Hieruit kan gesien word dat 'n lae graad van nikkel ekstraksie uit die ongeroosterde saprolitiese lateriet die gevolg is van nie-reaktiewe minerale (aslaag) waarin die nikkel binne die erts bevat word. Om 'n hoë graad van nikkel ekstraksie te verkry moet die erts onder reduserende kondisies gerooster word. Rooster kondisies moet versigtig beheer word om hoë oplossing van nikkel te verseker. Optimum rooster kondisies om maksimum nikkel oplossing te verkry, moet bepaal word voordat daar met groter hoeveelhede erts gewerk kan word.

This diploma thesis deals with the solution of ammonia separation from waste raw materials of agricultural production. It focuses on determining the efficiency of desorption from an experimental stripping device depending on the measurement temperature. Ammonia water solutions and liquid digestate samples from technical practice were used to verify the functionality of the equipment. Increasing separation efficiency with increasing temperature has been demonstrated. The device was gradually improved during the measurement for a better profitability of the separation process. The results of the experiments are discussed concerning the theoretical assumptions and compared with other methods of ammonia separation.

A proposta deste trabalho é estudar a tecnologia para a remoção de amônia do lixiviado através do processo físico-químico de arraste com ar e a sua caracterização por processos de fracionamento com membranas de MF e UF. Foram analisados no processo de arraste de ar os parâmetros pH, vazão de ar e tempo de operação. Foi verificada a remoção de nitrogênio amoniacal de 93,5% em um tempo de operação de 6 horas, com ajuste de pH igual a 11 e vazão de ar 100 L/h. Após a remoção do nitrogênio amoniacal, os lixiviados foram submetidos a processo de fracionamento com membranas de microfiltração (MF) e ultrafiltração (UF), sendo investigadas a remoção de amônia, a condutividade, DQO, COD, cloreto e pH. Obtiveram-se resultados praticamente constantes à medida que o lixiviado permeou nas membranas de MF e UF. Ademais, empregaram-se testes de toxicidade e ensaios de tratabilidade biológica com amostras de lixiviado bruto, lixiviado tratado (baixa concentração de amônia) e lixiviados fracionados com membranas de MF e UF. Nos ensaios de tratabilidade biológica os resultados mostraram que não houve uma remoção significativa de matéria orgânica e nos testes de toxicidade com organismos Danio rerio, embora tenha ocorrido uma redução na toxicidade na sequência dos experimentos, foi constatado que o lixiviado bruto, lixiviado tratado com remoção de amônia e fracionados com membranas de MF e UF mantiveram elevada toxicidade.
The proposal of present work is to study the technology for removing ammonia from leachate by physico-chemical process of air stripping and its characterization after fractionation processes with MF and UF membranes. Were analyzed the process of entrainment of air pH, air flow rate and operating time. Moreover, there was the removal of ammonia nitrogen from 93.5% in a running time of 6 hours, with pH adjustment equal to 11 and air flow rate 100 L / h. Soon after the first treatment the leachate were characterized in the process of fractionation with membranes (MF and UF) and were investigated the remotion of ammonia, conductivity, COD, COD, chloride and pH. Getting results were nearly constant as the leachate permeated the membranes of MF and UF. Moreover, were employed for toxicity tests and biological treatability tests on samples of raw leachate, leachate treatment group (low ammonia concentration) and leachates fractionated with the MF and UF membranes. In tests of biological treatability results showed no significant removal of organic matter and toxicity tests with organisms Danio rerio, besides the occurrence of a reduction in toxicity, it was found that the raw leachate, leachate treated with removal of ammonia and fractionated with the MF and UF membranes maintained high values of toxicity.

Municipal wastewater contains a significant amount of nutrients such as phosphorus (P) and nitrogen (N). Therefore have the interest of recovering these nutrients at wastewater treatment plants (WWTP) increased. Nutrient recovery would generate revenue for the WWTP, as it is possible to sell the products as fertiliser. Today, there are several techniques on the market to recover P as magnesium ammonium phosphate (MAP) and N as ammonium sulphate (AMS). Urine is the fraction contributing with the highest concentration of nutrients. Techniques to separate urine from the rest of the wastewater have been developed. These techniques enable the possibility to recover nutrients from the urine fraction separately; this is beneficial since the nutrient concentration would be higher. The purpose with this study was to examine the possibility for increased nutrient recovery at centralised WWTPs through urine separation.   Different techniques for nutrient recovery were compared by their recovery efficiency, chemical demand, and hydraulic retention time (HRT). A WWTP with enhanced biological P removal was modelled with Danish Hydraulic Institute’s (DHI) software WEST. Eight scenarios, with different percentage of the population equivalents using urine separation techniques, were simulated. The P recovery was calculated from phosphate (PO4) in the hydrolysed excess sludge and the separated urine. The N recovery was calculated from the ammonium (NH4) in the supernatant from the anaerobe digester. The theoretical biogas production was also calculated, from the modelled sludge.    The comparison of P recovery techniques showed no substantial differences in their recovery efficiency, chemical demand, and HRT. The comparison of N recovery techniques showed three techniques with a higher efficiency than the other methods. Ekobalans Fenix AB, CMI Europe Environment, and Organics developed these techniques. To determine which method to use, requests for proposal from different providers are recommended. As the urine separation increased, the influent P and N load decreased. When the urine separation increased and the operational parameters were kept constant, the effluent concentration of P and N decreased. The ratio of total Kjeldahl nitrogen (TKN) and total nitrogen (TN) however increased as the urine separation increased. The total MAP production calculated from the modelled hydrolysis showed that the production increased as the urine separation increased. On the other hand, the total MAP production from calculated hydrolysis showed a decrease in production as the urine separation increased. The difference in these results could be because of the performance of the modelled hydrolysis was better with a smaller nutrient load, resulting in a larger release of PO4 as the urine separation increased. The total AMS production increased as the urine separation increased. This, due to the increase of the TKN:TN ratio. The biogas production was not substantially affected by the increased urine separation.

Several commercially available reverse osmosis (RO) membranes were characterized with aqueous solutions of ammonium sulfate, potassium triphosphate, and mixtures of these two salts at different feed concentrations, compositions and pressures. The objective of this study was to investigate the rejection of these solutes, in particular the ammonium ion (NH4+), by different RO membranes. The aqueous solutions were assumed to come from an anaerobic digester via a process, currently under investigation by CHFour Biogas Inc., to maintain low concentrations of ammonia in the digester in order to maximize the biogas production. The ammonium ions present in the liquid produced from the process are then concentrated using membrane separation. The concentrated ammonium solution would be a valuable fertilizer that could be used by agriculture. The membranes were characterized with three models: the solution-diffusion model, the Kedem-Katchalsky model, also known as the irreversible thermodynamics model, and the Donnan Steric Pore Model (DSPM). The solution-diffusion and irreversible thermodynamics models were found to be inadequate for proper membrane characterization and the use of the DSPM model yielded membrane properties in good agreement with those found in already existing literature. The pore radius of investigated membranes ranged from 0.39 to 0.51 nm. The effect of pH on membrane surface charge was also studied, with the conclusion that increases in pH led to increasingly negative surface charges. This affected the transport of individual ions through the membrane due to preferential passage of the counter-ions. The effects of applied pressure on the stoichiometric nature of salt rejections were also studied. The minimal observed rejection from the range of experiments carried out using ammonium sulfate was 93%Non-stoichiometric rejections of ions were also observed in the experiments with single and multiple solutes. Furthermore, the rejection of ammonium ions in the presence of other ions (K+, SO42-, PO43-) increased as feed concentration increased, which was a result of the synergistic effects of feed pH and ionic interactions. The minimum NH4+ rejection in the presence of other ions was 95.4%, which suitability using RO membranes for concentration of ammonium from dilute aqueous solutions.

Concentrating quaternary (positive) charge at polymer surfaces is important for applications including layer-by-layer polyelectrolyte deposition and antimicrobial coatings. Prior techniques to introduce quaternary charge to the surface involve grafting of quaternary ammonium moieties to a substrate or using polyurethanes with modified hard segments however there are impracticalities involved with these techniques. In the case of the materials discussed, the quaternary charge is introduced via polyurethane based polymer surface modifiers (PSMs) with quaternized soft segments. The particular advantage to this method is that it utilizes the intrinsic phase separation between the hard and soft segments of polyurethanes. This phase separation results in the surface concentration of the soft segments. Another advantage is that unlike grafting, where modification has to take place after device fabrication, these PSMs can be incorporated with the matrix material during device fabrication. The soft segments of these quaternized polyurethanes are produced via ring opening copolymerization of oxetane monomers which possess either a trifluoroethoxy (3FOx) side chains or a quaternary ammonium side chain (C12). These soft segments are subsequently reacted with 4,4’-(methylene bis (p-cyclohexyl isocyanate)), HMDI and butanediol (BD) to form the PSM. It was initially intended to increase the concentration of quaternary ammonium charge by increasing PSM soft segment molecular weight. Unexpectedly, produced blends with surface microscale phase separation. This observation prompted further investigation of the effect of PSM soft segment molecular weight on phase separation in PSM-base polyurethane blends and the subsequent effects of this phase separation on the biocidal activity. Analysis of the surface morphology via tapping mode atomic force microscopy (TMAFM) and scanning electron microscopy (SEM) revealed varying complexities in surface morphology as a function of the PSM soft segment molecular weight and initial annealing temperature. Many of these features include what are described as nanodots (100-300 nm), micropits (0.5-2 um) and micropeaks (1-10 um). It was also observed that surface morphology continued to coarsen with time and that the larger features were typically observed in blends containing PSMs with low molecular weight soft segments. This appearance of surface morphological feature correlates with decreased biocidal activity of the PSM blends, that is, the PSM blends exhibit little to no activity upon development of phase separated features. A model has been developed for phase separation and concomitant reduction of surface quaternary charge. This model points the way to future work that will stabilize surface charge and provide durability of surface modification.

The isolation of individual enantiomers of drugs is an important subject of interest in the pharmaceutical and medical fields, because stereochemistry can have a significant effect on the biological activity of the drug. Therefore, it is important to develop enantiomeric separation methods for the determination of the optical purity of drugs, since the undesired enantiomer is regarded as one of the impurities. The available single isomer anionic cyclodextrins (CD) can resolve the enantiomers of only a few weakly acidic analytes. To rectify this problem, the chloride salts of heptakis(6-deoxy-6-morpholinio)-cyclomaltoheptaose (HMBCD), and mono(6- deoxy-6-N,N,N r,N r,N r-pentamethylethylenediammonio)-cyclomaltoheptaose (PEMEDA-BCD), the first members of the permanently charged, single-isomer cationic cyclodextrin family, have been synthesized. The purity of process intermediates and final products was determined by HPLC-ELSD and indirect UV-detection capillary electrophoresis. Structural identity was verified by 1D and 2D NMR and massBoth cationic CD derivatives have been used for the separation of the enantiomers of strong acid, weak acid, weak base, ampholytic, and neutral analytes by capillary electrophoresis. Because the charge state of these cationic chiral resolving agents is independent of the pH of the buffer, separation could be performed in both low and high pH buffers without compromising the charge density of the resolving agent. Contrary to expectation, the multiply charged HMBCD showed poor complexation with the newly synthesized strong electrolyte test analytes. The weak binding between the analytes and HMBCD resulted in separation of enantiomers of only three strong electrolyte analytes. Strong complexation was observed between PEMEDA-BCD and the anionic and nonionic analytes in both low and high pH buffers, though complexation was stronger in the high pH buffer. Due to strong complexation between the anions and PEMEDA-BCD, only low concentrations of the resolving agent were required to effect good enantiomer resolutions. spectrometry.

Thesis (M.S.)--University of Missouri-Columbia, 2007.
The entire dissertation/thesis text is included in the research.pdf file; the official abstract appears in the short.pdf file (which also appears in the research.pdf); a non-technical general description, or public abstract, appears in the public.pdf file. Title from title screen of research.pdf file (viewed on April 15, 2008) Vita. Includes bibliographical references.

Several overviews of flow chemistry appeared recently. Katherine S. Elvira and Andrew J. deMello of ETH Zürich wrote (Nature Chem. 2013, 5, 905) on micro­fluidic reactor technology. D. Tyler McQuade of Florida State University and the Max Planck Institute Mühlenberg reviewed (J. Org. Chem. 2013, 78, 6384) applications and equipment. Jun-ichi Yoshida of Kyoto University focused (Chem. Commun. 2013, 49, 9896) on transformations that cannot be effected under batch condi­tions. Detlev Belder of the Universität Leipzig reported (Chem. Commun. 2013, 49, 11644) flow reactions coupled to subsequent micropreparative separations. Leroy Cronin of the University of Glasgow described (Chem. Sci. 2013, 4, 3099) combin­ing 3D printing of an apparatus and liquid handling for convenient chemical synthe­sis and purification. Many of the reactions of organic synthesis have now been adapted to flow con­ditions. We will highlight those transformations that incorporate particularly useful features. One of those is convenient handling of gaseous reagents. C. Oliver Kappe of the Karl-Franzens-University Graz generated (Angew. Chem. Int. Ed. 2013, 52, 10241) diimide in situ to reduce 1 to 2. David J. Cole-Hamilton immobilized (Angew. Chem. Int. Ed. 2013, 52, 9805) Ru DuPHOS on a heteropoly acid support, allowing the flow hydrogenation of neat 3 to 4 in high ee. Steven V. Ley of the University of Cambridge added (Org. Process Res. Dev. 2013, 17, 1183) ammonia to 5 to give the thiourea 6. Alain Favre-Réguillon of the Conservatoire National des Arts et Métiers used (Org. Lett. 2013, 15, 5978) oxygen to directly oxidize the aldehyde 7 to the car­boxylic acid 8. Professor Kappe showed (J. Org. Chem. 2013, 78, 10567) that supercritical ace­tonitrile directly converted an acid 9 to the nitrile 10. Hisao Yoshida of Nagoya University added (Chem. Commun. 2013, 49, 3793) acetonitrile to nitrobenzene 11 to give the para isomer 12 with high regioselectively. Kristin E. Price of Pfizer Groton coupled (Org. Lett. 2013, 15, 4342) 13 to 14 to give 15 with very low loading of the Pd catalyst. Andrew Livingston of Imperial College demonstrated (Org. Process Res. Dev. 2013, 17, 967) the utility of nanofiltration under flow conditions to minimize Pd levels in a Heck product.

The German chemist Friedrich Wöhler is generally credited with the first laboratory synthesis of a known organic compound (urea) from inorganic materials. He accomplished this by the simple heating of an inorganic salt, ammonium cyanate (NH4OCN). “I must tell you,” he wrote to his mentor Jöns Jakob Berzelius in 1828, “that I can prepare urea without requiring a kidney of an animal, either man or dog.” While this report may seem relatively minor given the structural simplicity of urea, its impact was revolutionary. For the first time, the preparation and isolation of an organic compound had been achieved in the absence of the elemental “vital force” of living systems previously believed to be required for the construction of all such compounds. This milestone of 19th century organic chemistry was later followed by many others, including Kolbe’s synthesis of acetic acid in 1847 and Fischer’s synthesis of glucose in 1890. With the support of evolving methods for compound separation, purification, and spectroscopic analysis, rapid advances in the sophistication of organic synthesis followed throughout the 20th century, developing in tandem with an ever-deepening understanding of the underlying organic processes associated with living systems. While it is certainly true that syntheses of many structurally complex unnatural compounds of theoretical interest are also among the most remarkable achievements in synthetic strategy, tactical execution, and perseverance, the realm of natural products remains the dominant source for the most challenging and potentially beneficial targets available for such synthetic efforts. Figure 8.1 shows a small selection of some natural (and unnatural) products which have been produced via synthesis over the years, from Wöhler’s time to the present. Note the increasing levels of structural sophistication and stereochemical complexity that have eventually been mastered by practitioners of organic synthesis. In our own time, the traditional boundaries between organic and biological chemistry are disappearing in ways that are likely to transform the design and synthesis of organic molecules, from the construction of synthetic biologicals designed to act as biomarkers, biosensors, or drug delivery agents, to the development of molecular motors, self-replicating macromolecular systems, and even synthetic life forms.

In various novel thermodynamic cycles which utilize waste heat and geothermal resources, the Kalina cycle is the most significant improvement in thermal power plant design and it has been considered as an ambitious competitor against the Organic Rankine Cycle. However, the kalina cycle faces the complicated separate process and the design of separators still depends on the experience empirical formulae. Therefore, the vertical gravity separator used for separating ammonia-water mixture plays a vital important role in this system. The separator should keep high separation performance and enable the system to operate with stability. In this paper, we propose the initial structure design of a vertical gravity separator according to the separation theories. Based on the initial structure design of separator, conventional separator has been improved by changing the structure and operational parameters, including the ammonia concentration, inlet velocity, diameter, angle and height of inlet, and that has been numerically simulated by the means of CFX in computational fluid dynamics. In-depth estimating the separating performance of vertical gravity separator, different structural and operational parameters of vertical gravity separator are simulated and discussed. The separation performance and the distribution of ammonia-water mixture are estimated including flow field, trajectories of motion of particles, pressure drop, separation efficiency and so on. The results can be expected to be of great technical interest as basis for the design of vertical gravity separators.

The goal of the present manuscript is the investigation of two novel systems for partial CO2 capture from the exhausts of fossil fuelled powerplants. These systems should be relatively cheap and easily applicable to existing powerplants with minor modification, in order to make them accessible by a large range of users and favour a significant diffusion of partial CO2 sequestration. Two basic processes were proposed: 1. Absorption with a liquid solution of water and NH3; 2. Absorber/desorber system with a liquid solution of water and phosphates. In the first one, the exhausts react into an absorber column with a liquid sorbent, which is a solution of water and ammonia. The process sequestrates the CO2 in carbammate and bicarbonate and the final product are salt of ammonia, i.e. ammonium carboamate (NH4HCO3) and ammonium bicarbonate (NH4NH2COO). The outgoing streams of this process are the exhaust gas with a reduced content of CO2 and a secondary product formed by salts of ammonium, which have an interesting market potential as fertilizers. The obtained CO2 reduction level was more than 40%, while the amount of secondary products is high enough to get it marketable. In the second process, the exhausts passing through an absorber column react with a liquid sorbent, which is a solution of water and sodium (or potassium) phosphate. The process sequestrates the CO2 in bicarbonate ions by means of the ions phosphate and the outlet stream is a solution of water and phosphate and carbonate ions. This stream is collected in a desorbing column, where the phosphate ions are almost completely regenerated. The CO2 reduction level is always higher than 20% and it can also reach very high values, depending on the parameters of process.

Cogeneration can improve the energy utilization efficiency significantly. In this paper, a new ammonia-water system is proposed for the cogeneration of refrigeration and power. The plant operates in a parallel combined cycle mode with an ammonia-water Rankine cycle and an ammonia refrigeration cycle, interconnected by absorption, separation and heat transfer processes. The performance was evaluated by both energy and exergy efficiencies. The influences of the key parameters, which include the rectifier operation pressure, reflux ratio and reboiler temperature, the basic working solution concentration, the cooling water temperature and the Rankine cycle turbine inlet parameters on the cycle performance, were investigated. It is found that the cycle has a good thermal performance, with energy and exergy efficiencies of 25% and 50.9%, respectively, for the base-case studied (having a maximum cycle temperature of 450°C). Comparison with the conventional separate generation of power and refrigeration having the same outputs, shows that the energy consumption of the cogeneration cycle is lower by 21.6%.

A significant barrier to the use of fuel cells for portable and small stationary applications is the lack of a supply of pure hydrogen with high specific energy. Anhydrous ammonia is an attractive fuel because it has very high intrinsic specific energy, requires no water for decomposition, and has established distribution channels throughout the world. A compact membrane reactor hydrogen generation system using anhydrous ammonia as a fuel has been developed which produces greater than 99.95% purity hydrogen at a rate sufficient to power a 100 We PEM fuel cell. Ammonia concentrations in the resultant hydrogen product are non-detectable. Hydrogen recovery through the membrane is as high as 80% and the membrane reactor thermal efficiency (LHV) is 70%. The primary features of this system are a catalytic reactor, a hydrogen separation membrane integrated into the reaction chamber, and a catalytic combustion module to provide heat for the ammonia decomposition reaction and subsequent conversion of trace ammonia reject. The membrane reactor is planar in configuration and allows for a simple, single unit design to provide pure hydrogen for fuel cell applications. The total system can provide specific energies of greater than 500 Wh/kg for a 72 hour run making it an attractive solution of portable and long unattended run time applications.

Separation of the flow of seeds and fertilizers during sowing of barley and the subsequent processing of the sowing with ammonia made it possible to increase the number of shoots and the weight of plants by a factor of three, while reducing the consumption of mineral fertilizers.