Magister Philosophiae - MPhil / Due to an increasing demand for energy, alternative renewable energy sources are investigated globally. However fossil fuels are still one of the main energy sources. The combustion of these fuels produces by-products such as SOx, NOx and CO2, which have detrimental effects on the environment and human health. Therefore, effective methods are needed to minimize the pollution and affects that these by-products cause. Catalysts are commonly employed to convert these by-products to less harmful and/or resalable products. Ceria and ceria based materials are good candidates for the removal and conversion of SOx and NOx. Ceria and ceria related materials are most effective as catalysts when they are in the nano-form with good crystallinity and nanoparticles that are uniform. The growth of nanoparticles is preceded by a nucleation process which can occur by solid-state restructuring of a gel or precipitation from a saturated solution. The precipitation method was selected to synthesize Ceria nanoparticles. Synthesis conditions such as temperature, solution type and ageing time and their effect on the physical and chemical forms of the Ceria particles were investigated. The morphology and structural properties were investigated using Scanning Electron Microscopy, X-ray diffraction and Transmission Electron Microscopy. X-ray Photoelectron Spectroscopy was used to investigate the chemical properties. It was found that low temperatures, low base volume and a solvent with a small dielectric constant favor the formation of small crystallites with a relatively large concentration of defects. These defects are desirable since they enhance the catalytic activity of ceria.

Thesis. 1977. Ph.D.--Massachusetts Institute of Technology. Dept. of Chemical Engineering. / M̲i̲c̲ṟo̲f̲i̲c̲ẖe̲ c̲o̲p̲y̲ a̲v̲a̲i̲ḻa̲ḇḻe̲ i̲ṉ A̲ṟc̲ẖi̲v̲e̲s̲ a̲ṉḏ S̲c̲i̲e̲ṉc̲e̲.̲ / Vita. / Bibliography : leaves 378-385. / by John A. Wilkens. / Ph.D.

Red mud is a waste product of alumina production and has an adverse effect on environment. About 90 million tonnes of red mud are produced annually throughout the world and little is recycled for useful applications. The world nickel reserves consist of approximately 30% sulphide ores and 70% oxide ores. Despite the relative abundance of oxide ores, 55% of nickel and nickel alloys produced today are derived from sulphide ores. However, with the production of nickel and its alloys from low-grade oxide ores becoming increasingly important, a major concern is high sulphur level in the resultant alloy. For this reason, desulphurization of the ferronickel becomes an important consideration. In the present study, experiments were conducted to determine if red mud could be used as a major ingredient of custom designed fluxes for the desulphurization of ferronickel alloy. Factors investigated included desulphurization rates, contact angle measurements and flux-refractory interactions.

Red mud is a waste product of alumina production and has an adverse effect on environment. About 90 million tonnes of red mud are produced annually throughout the world and little is recycled for useful applications. The world nickel reserves consist of approximately 30% sulphide ores and 70% oxide ores. Despite the relative abundance of oxide ores, 55% of nickel and nickel alloys produced today are derived from sulphide ores. However, with the production of nickel and its alloys from low-grade oxide ores becoming increasingly important, a major concern is high sulphur level in the resultant alloy. For this reason, desulphurization of the ferronickel becomes an important consideration. In the present study, experiments were conducted to determine if red mud could be used as a major ingredient of custom designed fluxes for the desulphurization of ferronickel alloy. Factors investigated included desulphurization rates, contact angle measurements and flux-refractory interactions.

<p>Reaction kinetics of copper sulphide matte (Cu₂S) with an oxidizing slag was investigated. Silica-saturated fayalite (2FeO.SiO₂) slag was synthesized by melting powder mixtures of iron, silica and hematite with respective ratios of 1:2:3.6 at high temperatures. Experiments were performed in an inert atmosphere using a high-temperature furnace equipped with X-ray fluoroscopy and pressure transducer. The effect of temperature (1400 – 1475 °C) and matte droplet size (0.5 – 2 g) on desulphurization rate was evaluated. Chemical titration was performed on quenched slag samples synthesized at different temperatures in order to determine the amounts of Fe²⁺ and Fe³⁺ in the slags. Slag/matte samples quenched from high temperatures were extensively analyzed by means of optical microscope as well as scanning electron microscope (SEM), the latter equipped with an energy dispersive X-ray spectrometer (EDS). EDS analysis of the quenched samples showed that some areas of pure Cu were formed inside the matte droplets. It indicated that desulphurization reaction indeed has taken place and copper was formed as the product. In addition, EDS showed that some Fe-rich areas were formed inside the matte droplets. Gas halo formation around the droplets was confirmed by X-ray fluoroscopy observations. Additionally, it was seen that dome-like bubbles formed during high-temperature experiments on top of the matte droplets with mass equal to 0.75-gram or larger. In contrast to Fe-C metal droplets in contact with oxidizing slags, no droplet swelling was detected in this study. Reaction kinetics investigations showed that initial desulphurization rate increased with increasing temperature and matte droplet size. In fact, it was shown that rate increased linearly with matte droplet surface area. Finally, mass transfer in the slag phase and mass transfer in the gas halo formed around the droplet were found to be the rate-controlling mechanisms prior to and after gas halo formation, respectively.</p> / Master of Applied Science (MASc)

The aim of the present work was to get an overview of the steel cleanness in tool steel. Plant trial studies of three steel grades were done with different focuses. Firstly the change of the inclusion characteristics during the vacuum degassing in the ladle was looked upon. The top slag composition was altered and sampling was made before and after vacuum degassing and the results showed that the top slag composition has an effect on the inclusion composition. Thermodynamic calculations indicated that the oxygen activity for the steel/inclusion was twice as large as that of the steel/top slag before vacuum degassing. However, after vacuum degassing the oxygen activity values were close. In order to study the inclusion characteristics during vacuum degassing the process was interrupted at five pre-determined time points for sampling. During vacuum the number of the smaller inclusions was decreased. However, for the larger inclusions (&gt;11.2µm) the number of inclusions had increased. Throughout the degassing process the inclusion composition was found to approach the top slag composition and at the end of the process only one type of inclusion composition was found. The removal of hydrogen, nitrogen and sulphur was studied. Samples were taken before and after vacuum degassing. It was found that the removal kinetics of hydrogen and nitrogen can be described with first-order reactions. When 10 minutes of vacuum degassing have passed, the removal of hydrogen and nitrogen is more or less finished for the studied steel grades. Two steel grades with similar process route and with only a few differences in steel composition were studied. The sum of FeO and MnO was found to be a clear indicator for when reoxidation had taken place. The results from oxygen activity calculations indicate that calculations of oxygen activities with multivalence slag species such as Fe and Cr requires measurements for validations to ensure that reliable results are obtained. / Syftet med denna studie var att få en överblick av verktygsståls renhet. Studier på tre olika stålsorter utfördes. Inneslutningsbilden under vakuumbehandling undersöktes. Resultaten är baserade på industriförsök likväl som termodynamiska beräkningar. Försöken gjordes på två olika stålsorter där toppslaggens sammansättning varierades och stål- och slaggprover tog ut före och efter vakuumbehandling. Proverna analyserades för att bestämma den kemiska sammansättningen på stål och slagg, men inneslutningsbilden undersöktes också. Med hjälp av termodynamiska beräkningar beräknades syreaktiviteten för jämvikterna stål/inneslutning och stål/toppslag. Beräkningarna jämfördes sinsemellan samt med uppmätt syreaktivitet från stålsmältan. Resultaten visar att toppslaggens sammansättning har en påverkan på inneslutningarnas sammansättning. Specifikt så fanns att när CaO-halten i toppslaggen ökar syns en ökning av CaO i inneslutningssammansättningen. De termodynamiska beräkningarna visar att syreaktiviten för jämvikten stål/inneslutning är dubbelt så stor som den för jämvikten stål/topplagg före vakuumbehandling. Dock är syreaktiviteterna för de olika jämvikterna lika efter vakuumbehandlingen. För att studera hur inneslutningsbilden utvecklas under vakuumbehandling avbröts vakuumbehandlingen vid fem förutbestämda tidpunkter. Vid varje avbrott av vakuumbehandlingen togs stål- och slaggprover som analyserades för att bestämma totalsyre, inneslutningsmängd och inneslutningssammansättning. Före vakuumbehandlingen var antalet inneslutningar stort, medan antalet små inneslutningar minskade under vakuumbehandlingen. Däremot konstaterades att antalet stora inneslutningarna (&gt;11.2μm) ökade under avgasningen. Vad beträffar inneslutningssammansättningen syntes en variation i analys före vakuumbehandlingen som sedan förändrades till att likna toppslaggens sammansättning under vakuumbehandlingstiden. I slutet av processen märktes endast en typ av inneslutningssammansättning i stålsmältan. Vad som också noterades var att efter ungefär 10 minuter av vakuumbehandling så hade inneslutningsantalet nått sitt minimumvärde. För att erhålla rent stål är väte-, kväve- och svavelreningen också av stor vikt under vakuumbehandlingen. Dessa tre element studerades genom att prover togs vid olika tillfällen i processen; före, under (vid fem olika förutbestämda tidpunkter) och efter vakuumbehandling. De kemiska sammansättningarna för stål- och slaggproverna användes för att beräkna väte-, kväve- och svavelreningarna. Beräkningarna visade att för väte och kväve så kan kinetiken beskrivas med en förstagradsekvation. Specifikt så gäller detta för stålsorten i studien, samt under förutsättningen att svavelhalten är lägre än 0,003 vikts-%. Dessutom så visade resultaten att väte- och kvävereningen är i stort sett klar för den studerade stålsorten efter 10 minuters vakuumbehandling. När det gäller svavel så kan en förstagradsekvation inte användas vid beräkningarna Istället uppvisar svavel en tendens att följa jämviktshalten av svavel genom hela avgasningsprocessen. Genom att kontrollera processen finns stora möjligheter att erhålla en bra renhet på stålet. Två stålsorter studerades i denna specifika studie, där de hade en liknande processväg samt endast ix några små skillnader i stålanalysen. Stål- och slaggprover samlades in och analyserades. Summan av FeO och MnO visade sig vara en klar indikation på när reoxidation har skett, men mängden "carry-over" slagg från ljusbågsugnen kunde inte predikteras med hjälp av någon specifik indikator. Dessutom så beräknades syreaktiviten och beräkningarna jämfördes sedan med uppmätt syre i stålet. Resultaten indikerar att beräkningar av syreaktivitet med toppslagger som innehåller multivalenselement, såsom Fe och Cr, kräver valideringar med mätningar för att trovärdiga predikteringar ska erhållas. / <p>QC 20160523</p>

Thesis (Sc.D.)--Massachusetts Institute of Technology, Dept. of Chemical Engineering, 1979. / MICROFICHE COPY AVAILABLE IN ARCHIVES AND SCIENCE. / Vita. / Bibliography: leaves 594-611. / Sc.D.

Effective distribution of hydrogen in refinery hydrogen networks is a major concern for refiners tackling the stringent specifications on maximum sulphur levels in middle distillates and the increasing global demand of diesel fuel. A major challenge is the implementation of a shift from conventional to ultra-deep methods of desulphurisation. Meanwhile, the capacity of secondary conversion processes such as fluid catalytic cracking (FCC) and hydrocracking in refineries has steadily increased in converting the bottom of the barrel into high-value lighter products resulting in increased levels of hydroprocessing, which exerts a higher demand on refinery hydrogen systems. Previous methodologies on hydrogen network optimization have been developed mainly based on the assumption of fixed hydroprocessing performance with constant hydrogen consumption and light hydrocarbon yields, in order to reduce the complexity of the optimisation problem. Consequently, critical interactions among feed and catalyst properties, hydroprocessor operating conditions, product quality and yields, and hydrogen consumption are usually neglected. This research work involves three major aspects: 1. Development of semi-empirical nonlinear lumped hydrodesulphurisation (HDS) and hydrocracker models that are robust and sufficiently detailed to capture the behaviour of the process with changes in feed characteristics and operating conditions. The formation of light hydrocarbons during HDS reactions have been accounted for. Hydrocracker conversion models and five/six-lumped product yield models for vacuum gas oil (VGO) and vacuum residue (VR) feedstocks have been developed from a combination of first principles and empirical methods based on several process parameters. The proposed models are validated with different feedstocks and shows good agreement with industrial data. 2. Integration of HDS and hydrocracker performance models into refinery hydrogen network models to explore existing interactions between processes and the hydrogen network, and their combined effect on the overall network objective. 3. Optimization of the overall superstructure under different operating scenarios to facilitate the efficient distribution and utilization of hydrogen and the maximization of clean high-value products. The integrated superstructure network model is developed and optimized within the General Algebraic Modelling System (GAMS). The model is representative of the dynamic interactions between hydrodesulphurisation and hydrocracking processes in the refinery hydrogen network as demonstrated by the reproducibility of industrial refinery data. Thus, this work presents a holistic and realistic implementation of refinery hydrogen management technique.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / A necessidade de redução da emissão de poluentes, visando diminuir os sérios problemas de poluição atmosférica enfrentados atualmente, é hoje uma das principais preocupações mundiais, provocando o surgimento de leis mais rígidas, que restringem o teor de enxofre na gasolina e no diesel. Assim, o desenvolvimento de tecnologias mais eficazes na remoção de enxofre nestes combustíveis tem recebido atenção crescente. Estas tecnologias incluem a extração física com solvente, a adsorção seletiva, processos de redução/oxidação microbiológicos e a dessulfurização oxidativa (ODS). A dessulfurização oxidativa converte os compostos de enxofre em sulfonas que podem ser facilmente separadas por processos físicos. Portanto, a ODS apresenta grande potencial para tornar-se um processo complementar a processo de hidrodessulfurização tradicional na produção de combustíveis altamente dessulfurizados. Neste contexto, este trabalho visou o estudo do desempenho de catalisadores de V2O5 suportados em alumina, sílica e sílica-alumina frente à reação de ODS do dibenzotiofeno em presença do peróxido de hidrogênio, como oxidante, e da acetonitrila, como solvente polar aprótico. Os catalisadores foram preparados por impregnação ao ponto úmido e caracterizados por difração de raios-X (DRX), análise textural, redução à temperatura programada (TPR-H2), dessorção de amônia à temperatura programa (TPD-NH3) e espectroscopia Raman. O efeito de parâmetros reacionais como quantidade de solvente, relação O/S e concentração de catalisador foram investigados, utilizando a alumina como suporte, visando estabelecer as condições reacionais que levassem a maiores valores de conversão do dibenzotiofeno (DBT). Uma vez estabelecidas estas condições, foi analisado o efeito do teor de V2O5 presente no catalisador e, posteriormente, o efeito do suporte catalítico. Os resultados obtidos mostraram a 70 C razão molar H2O2/Sde 16,6, razão carga/solvente igual a 1:1 e 100 mg do catalisador 15 % V2O5/SiO2, a conversão obtida foi de 95% / The need to reduce the gaseous emissions which causes serious environmental problems is a worldwide concern nowadays. Therefore, stricter laws aiming at to reduce the sulfur content in gasoline and diesel are being adopted in different countries, among them Brazil. Thus, the development of more efficient technologies to remove sulfur in these fuels has received increasing attention. These technologies include the physical extraction with a solvent, selective adsorption, microbiological reduction/oxidation processes and oxidative desulphurization (ODS). The oxidative desulfurization (ODS) converts sulfur compounds into sulfones that can be easily separated by physical processes. Therefore, the ODS has a great potential to become a process complementary to traditional hydrodesulfurization in the production of highly desulfurized fuels. In this context, this work studied the performance of V2O5 catalysts supported on alumina, silica and silica-alumina toward ODS reaction of dibenzothiophene in the presence of hydrogen peroxide as the oxidant, and acetonitrile as polar aprotic solvent. The catalysts were prepared by incipient wetness impregnation and characterized by X-ray diffraction (XRD), textural analysis, temperature programmed reduction (TPR-H2), temperature programmed desorption (TPD-NH3) and Raman spectroscopy. The effect of experimental parameters such as amount of solvent, O/S ratio and catalyst concentration were investigated, using alumina as a support, aiming at establishing the conditions that could lead to the higher conversion of dibenzothiophene (DBT). Once established these conditions, the effect of V2O5 content was investigated and then the effect of catalytic support. The results showed that at 70 C, H2O2/S molar ratio of 16.6, solvent/diesel ratio equal to 1: 1 and 100 mg of 15% V2O5/SiO2 catalyst, the conversion obtained was 95%

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