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A dissertation submitted to the Faculty of Engineering and the Built Environment, University of the Witwatersrand, Johannesburg, in fulfilment of the requirements for the degree of Master of Science in Engineering. Johannesburg 2016 / Stringent worldwide emissions legislation, the drive to lower carbon emissions, together with the ever increasing demand to preserve the environment has led to a considerable demand for cleaner and more efficient coal combustion technologies. A primary technology for the reduction of emissions of oxides of nitrogen (NOx) is the installation of low NOx coal combustion burners. Extensive research into various burner characteristics and, in particular, the aerodynamic characteristics required to improve combustion performance of low NOx coal burners has been extensively undertaken and is ongoing. In this work the aerodynamic behaviour of a full-scale, aerodynamically staged, single low-NOx coal burner was numerically investigated. The objective of the study was to develop a single low NOx burner CFD model in Ansys Fluent, to better characterize and understand the flame shape in terms of the temperature profile achieved. CFD serve as an additional tool to assist with plant optimization, design proposals and occurrence investigations. To have confidence in the single burner coal combustion CFD model, the results of the model were compared to data obtained from an existing operational low NOx burner on site during a pre-defined load condition. To further improve on the theoretical CFD combustion model, drop tube furnace (DTF) experiments have been done to calculate the single rate Arrhenius kinetic parameters (pre-exponential factor and activation energy) for coal devolatilization and char combustion of the specific South African coal used. The combustion CFD simulations showed with a lower than design air flow through the burner, a reduced amount of swirl was achieved. This reduced amount of swirl produces a jet like flame and influences the way in which the combustion species are brought together. Under these operating conditions the flame distance from the burner mouth was predicted to be 1.2 (m). A very promising result was obtained through CFD and compared well with the in-flame temperature measurement obtained through the burner centre-line of approximately 1.4 (m). In an attempt to improve the aerodynamic profile of the burner under the same operating conditions the swirl angle on the tertiary air (TA) inlet was increased. The increased swirl on the TA inlet of the burner showed an improvement on the aerodynamic profile and had a significant impact on the temperature distribution within the flame. The increased swirl resulted in an improved flame distance of approximately 0.5 (m) from the burner mouth. The effect of increased swirl on the temperature profile of the flame displayed the aerodynamic dependence of the low NOx burner on combustion performance. / MT2017

A dissertation submitted to the Faculty of Science, University of the Witwatersrand, Johannesburg, in fulfilment of the requirements for the degree of Master of Science June 2015 / Lephalale is the home of Matimba, one of Eskom’s coal-fired power stations. Matimba is the biggest power station with a dry cooling system in the world. There are other industries (including coal mines) currently in operation in close proximity to the station. This industrial area is expected to grow as more industrial activities are planned for the following years. These activities will aggravate the levels of air pollution and possibly result in it being a “hot spot” for air pollution. The impact of air quality on health is covered by the National Ambient Air Quality Standards (NAAQS), but the impact of air quality on the terrestrial and aquatic ecosystem is not known. Therefore, this study focuses on the deposition of nitrogen oxides (NOx) (as nitrogen dioxide (NO2)) and sulphur dioxide (SO2) within Lephalale in the Waterberg-Bojanala Priority Area. Additionally, inter-annual variability of NOx and SO2 ambient concentrations and back trajectories of air masses were analysed. The study obtained ambient air quality data and meteorological data from Eskom for the period 2008–2012, while additional meteorological data were obtained from the Agricultural Research Council (ARC) and the South African Weather Service (SAWS). An inferential model was used to estimate the dry deposition flux of SO2 and NOx (as NO2), and the Hybrid Single Particle Langrangian Integrated Trajectory (Hysplit) Model was used to cluster back trajectories of air masses. The results of the seasonal dry deposition velocities of SO2 (0.17 to 0.23 cm/s) and NOx (0.10 to 0.15 cm/s) (as NO2) were higher in summer and lower in winter. They were also within the magnitude of the deposition velocities found in previous studies in the Highveld. The high deposition velocities in summer were attributed to photosynthetically active vegetation, turbulence and solar radiation. However, seasonal dry deposition fluxes of SO2 and NOx were higher in winter across the years. The higher flux values in winter were attributed to higher ambient concentrations of the trace gases. Additionally, the annual dry deposition flux of SO2 ranged between 0.43 and 0.67 kg S ha-1 yr-1, while NOx (as NO2) ranged between 0.84 and 1.05 kg N ha-1 yr-1 over the period studied. The annual deposition flux values found in the current study are lower than those found in previous studies in the Highveld. This difference could be because of the lower ambient concentrations of SO2 and NOx observed in this study. There is an inter-annual variability of the ambient concentrations of SO2 and NOx during the period 2008–2012. However, the difference is not large or statistically significant. The dominant direction of the back trajectories of air masses is east and southeast across all seasons for the entire period of 2008–2012. This lack of seasonal pattern in back trajectories and source regions cannot explain the seasonal changes in ambient concentrations (SO2 and NOx). Hence, climatic factors (e.g. change in weather) or seasonal changes in combustion source intensity must be responsible.

M. Tech. Mechanical engineering. / Acid deposition is caused by the emission of acidic gases, for example, nitrogen oxides and sulfur dioxide. Nitrogen oxide emissions can be controlled by the proper selection of equipment and operating conditions. Sulfur dioxide on the other hand, can be cleaned by means of procombustion, combustion or post-combustion techniques; the latter being the most effective. The objective of this study is to find suitable additives which will augment the reactivity of lime towards FGD (flue gas desulfurization), while at the same time being easily available at a low price. Zeolite based sorbents yielded the highest reactivity, and all additives, except iron waste, had pozzolanic materials as their main reactive compounds.

<p>Diss. (sammanfattning) Umeå : Umeå universitet, 1993, härtill 7 uppsatser.</p> / digitalisering@umu

Στην παρούσα εργασία μελετάται η αντίδραση αναγωγής των οξειδίων του αζώτου με προπυλένιο σε ισχυρά οξειδωτικές συνθήκες με χρήση καταλυτών Rh υποστηριγμένων σε τροποποιημένους φορείς TiO2 με ιόντα διαφορετικού σθένους (W6+ ή Ca2+) από το μητρικό κατιόν (Ti4+). Η τροποποίηση του φορέα επιτεύχθηκε με την διάχυση των ενισχυτικών κατιόντων στο κρυσταλλικό πλέγμα του TiO2 σε υψηλές θερμοκρασίες. Στους φορείς που παρασκευάστηκαν πραγματοποιήθηκαν μετρήσεις ειδικής επιφάνειας (ΒΕΤ), κρυσταλλικής δομής (XRD), ειδικής αγωγιμότητας (AC-Impedance) καθώς και μετρήσεις επιφανειακής οξύτητας (TPD-MS). Σε γενικές γραμμές η ενίσχυση του φορέα TiO2 έχει σαν αποτέλεσμα την διατήρηση της ειδικής επιφάνειας, την αύξηση της επιφανειακής οξύτητας, και την αλλαγή της ειδικής αγωγιμότητας σε σχέση με τον μη ενισχυμένο φορέα. Οι υποστηριγμένοι καταλύτες Rh παρασκευάστηκαν με την μέθοδο του υγρού εμποτισμού από νιτρική πρόδρομη ένωση. Οι καταλύτες που παρασκευάστηκαν χαρακτηρίστηκαν ως προς την διασπορά της ενεργού φάσης καθώς και του μέσου μεγέθους των κρυσταλλιτών του μετάλλου με χημορόφηση H2. Η σύγκριση των καταλυτών με βάση την ενεργότητα τους για την αναγωγή του ΝΟ καθώς και την εκλεκτικότητά τους σε Ν2, έδειξε δύο διαφορετικές δράσεις της ενίσχυσης. Ενίσχυση με ιόντα W6+, οδηγεί σε αύξηση της ενεργότητας με παράλληλη ελαφρά αύξηση της εκλεκτικότητας σε Ν2. Η ενίσχυση του καταλύτη με ιόντα Ca2+ οδηγεί σε αύξηση της ενεργότητας για την αναγωγή του ΝΟ με παράλληλη όμως, σημαντική μείωση της εκλεκτικότητας σε Ν2. Η συμπεριφορά αυτή ερμηνεύτηκε με βάση το θεωρητικό υπόβαθρο που περιγράφει τις τροποποιήσεις των ηλεκτρονιακών ιδιοτήτων του φορέα και είναι γνωστό ως φαινομένου DIMSI. Η βελτίωση των καταλυτικών ιδιοτήτων που παρουσιάζουν οι ενισχυμένοι καταλύτες έδωσε το ερέθισμα για την μελέτη του μηχανισμού της αντίδρασης για την αναγωγή του ΝΟ με προπυλένιο στους καταλύτες αυτούς καθώς και τις διαφορές που παρουσιάζουν σε σχέση με τον μη-ενισχυμένο καταλύτη. Η μελέτη του μηχανισμού πραγματοποιήθηκε με χρήση των τεχνικών υπέρυθρης φασματοσκοπίας (FTΙR) και φασματοσκοπίας μάζας (Mass Spectroscopy). Σε γενικές γραμμές τα αποτελέσματα δείχνουν ότι το ΝΟ ροφάται μοριακά σε κέντρα Rh. Παρουσία ανηγμένων κέντρων το ΝΟ διασπάται προς ατομικά ροφημένα είδη Ν και Ο. Ανα-συνδυασμένη εκρόφηση των ειδών Ν οδηγούν στον σχηματισμό Ν2 στην αέρια φάση, ενώ παραγωγή του Ν2Ο σχετίζεται με την δημιουργία του συμπλόκου είδους Rh(NO)2. Η αναγέννηση των ενεργών κέντρων επιτυγχάνεται με την μερική οξείδωση του προπυλενίου σε οξειδωμένα κέντρα Rh αρχικά προς ακρολεϊνη. Περαιτέρω οξείδωση της ακρολεϊνης οδηγεί στον σχηματισμό θραυσμάτων COO- και CHx με τον ενδιάμεσο σχηματισμό ειδών του τύπου του ακρυλικού οξέος. / In the present study, the catalytic reduction of NO with propylene in the presence of excess oxygen was examined, over Rh catalysts supported on doped TiO2 carriers with tungsten or calcium cations. Doped TiO2 carriers were prepared employing the solid state diffusion technique at elevated temperatures. Characterization of doped carriers consisted of specific surface (BET) area and crystalline mode (XRD) measurements as well as measurements of the specific conductivity (AC-Impedance) and surface acidity (TPD-MS). In general, doping TiO2 results in an increase of the surface acidity, in alterations of specific conductivity and in the preservation of the specific surface in a manner, which depends on dopant concentration and calcinations temperature. Supported Rh catalysts were prepared following the wet impregnation method using Rh(NO3)3 as the precursor metal compound. Characterization of the prepared catalysts consisted of dispersion and mean metal crystalline size measurements, employing hydrogen chemisorption at ambient temperature. Comparison of the doped catalysts, as far as the activity toward NO reduction and the selectivity to N2 is concerned, shows two different behaviors. Doping with W6+ cations results in higher NO reduction activity with a slightly increase of selectivity toward dinitrogen formation. Doping with Ca2+ leads to higher catalytic activity for the reduction of NO, while the selectivity was found to decrease upon increasing calcium content. The above observations are explained by the theory of dopant induced metal support interactions (DIMSI). The mechanistic pathways of the above mentioned reaction over Rh/TiO2 catalysts were studied employing infrared (IR) and mass spectroscopy (MS). The results showed, that NO is molecularly absorbed on the Rh. In the presence of reduced Rh sites NO dissociation occurs, resulting in N and O adspecies. Recombination of N species results in the production of dinitrogen in the gas phase. N2O formation is correlated with the presence of the dinitrosyl complex species on the catalytic surface. Reaction of the latter with NO from the gas phase leads to N2O production. Regeneration of oxidized Rh sites is achieved via oxidation of propylene to acrolein. Further oxidation of the latter leads to the formation of carboxylates.

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Viena didžiausių problemų, atsirandančių dėl oro taršos miestų ore, yra tarša, sukelta fotocheminių oksidantų, tarp jų, ir priežemio ozono. Darbo tikslas: nustatyti priežemio ozono koncentracijos sklaidą Kauno mieste ir jos ryšį su meteorologinėmis sąlygomis. Tyrimai buvo vykdomi 2006 - 2009 metais. Darbo objektas - Kauno miestas. Visoje miesto teritorijoje priežemio ozono koncentracija buvo matuota 10 skirtingų matavimo vietų. Ozono koncentracijai nustatyti buvo naudotas „Aeroqual 300 Series” ozono matuoklis. Priežemio ozono koncentracija buvo matuota vidudienį nuo 12 iki 14 ir vakare nuo 17 iki 19 valandos. Kiekvienoje vietoje buvo atlikta nuo 4 - 6 matavimų, kiekvieno sezono metu. Tyrimų metu nustatyta, kad priežemio ozono koncentracijos pasiskirstymas kiekvieno sezono metu yra skirtingas. Didžiausia vidutinė sezoninė priežemio ozono koncentracija buvo nustatyta pavasario - vasaros sezonų metu (72 g/m3), o mažiausia žiemos sezono metu (7 g/m3). 2009 m. pavasario sezono metu Vileikos g., prie GMF nustatyta didžiausia vienkartinė priežemio ozono koncentracija (128 g/m3). Buvo vertintas priežemio ozono koncentracijos ryšys su meteorologinėmis sąlygomis ir azoto oksidų (NOx) koncentracija. Gauti rezultatai parodė, statistiškai reikšmingą teigiamą ryšį tarp ozono koncentracijos ir temperatūros (r = 0,73; p = 0,00) ir NO2 koncentracijos (r = 0,48; p = 0,03). Tai rodo, kad didėjant temperatūrai ir NO2 koncentracijai, didėja ir priežemio ozono koncentracija. Tarp priežemio... [toliau žr. visą tekstą] / One of the major problems resulting from air pollution of the urban area, is the pollution caused by photochemical oxidants, among their, ground level ozone. The aim of this work was to assess distribution of ground level ozone concentration in Kaunas and its relationship to meteorological situation. Measurements was carried out in 2006 - 2009. Object of work has been selected Kaunas city. Throughout the city area ground level ozone concentration was measured by a sampling scheme for the 10 different measurement points. For determinate of ground level ozone concentration, we used ozone quality monitor „Aeroqual 300 Series“. Ground level ozone concentration was measured at midday from 12 to 14 and in the evening from 17 to 19 hours. Each site was carried out from 4 - 6 measurements. Study rezults revealed, that ground level ozone concentration distribution of each season is different. The maximum average ozone concentration was found in spring - summer season (72 g/m3), and the lowest in winter season (7 g/m3). The higher ground level ozone concentration episode (128 g/m3) was stated in spring season in 2009 year. Relationship between ground level ozone concentration and meteorological situations and nitrogen oxides (NOx) concentration was evaluated. The results showed statistically significant positive relationship between ozone concentration and temperature (r = 0,73; p = 0,00) and NO2 concentration (r = 0,48; p = 0,03). Between ground level ozone concentration and wind... [to full text]

This thesis engages a comparison of the development of atmospheric deposition of nitrogen and phosphorus in different regions of the Czech Republic. The work explains the formation of atmospheric deposition and related terms such as the source of pollution, emissions, air pollution and nitrogen oxides. There are stated types of atmospheric deposition, sampling procedure and the process of determining the size of atmospheric deposition. This work describes the methods that were used in the calculations and evaluations. It also deals with the selection of suitable measuring stations for processing the development of atmospheric nitrogen deposition. The atmospheric deposition of phosphorus were not measured in the territory of the Czech Republic in the period from 2000 to 2010. The aim of this work is to find trends in time series of concentrations of NOx and statistical evaluation of the development of atmospheric nitrogen deposition. For these chapters were selected concentration of nitrogen oxides in the regional towns of the Czech Republic. In the chapter of spatial analyzes of the concentration of nitrogen oxides is selected Ústecký kraj, mainly due to the fact that this area is characterized by significantly high atmospheric deposition of nitrogen and total air pollution. A therm the Black Triangle is often used for this location.

L’objet de cette thèse est l’étude de la séparation membranaire de l’air appliquée à la réduction desémissions d’oxyde d’azote (NOx) des moteurs Diesel. Il a en effet été démontré précédemment quel’utilisation d’air dopé en azote pour la combustion Diesel entrainait une diminution des émissions deNOx. Les travaux présentés ici ont consisté à produire des outils de modélisation d’un module deséparation membranaire des gaz de type fibres creuses et à valider expérimentalement ces outils.Deux approches de modélisation ont été retenues, une approche génie chimique a conduit à unmodèle monodimensionnel applicable en régime stationnaire ; une approche dynamique des fluidesa permis de développer un modèle bidimensionnel valable en régime transitoire. Le premier modèlea été utilisé pour le dimensionnement de modules, le second pour simuler les performances deséparation de ces modules. Par ailleurs, l’influence du taux de dopage en azote de l’air sur la quantitéde NOx émis a été numériquement étudiée à l’aide d’un outil commercial. Enfin, la possibilitéd’implanter un tel module sur un moteur Diesel de série et les paramètres limitants ont été étudiés àl’aide d’un code commercial et d’un modèle développé par Renault. / The purpose of this work is the study of the air membrane separation applied to the reduction ofnitrogen oxides (NOx) emissions of Diesel engines. As a matter of fact, previous works proved thatusing nitrogen-doped air in Diesel combustion led to lower NOx emissions. The study presentedherein consisted in developing a set of modeling tools simulating a gas separation hollow fibersmembrane module and in experimentally validating these tools. A chemical engineering approachresulted in a monodimensional model suitable for stationary regime; a flow dynamic approach led toa bidimensional model dedicated to transitory regime. The first model was used to design modulessize, the second one to simulate separation performances of these modules. Beside, the impact ofnitrogen doping on NOx emissions was numerically studied with a commercial software. Finally, thefeasibility of the introduction of such a module in a mass-produced Diesel engine was investigatedwith a model developed at Renault on a commercial software.