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<p> The hydrogenolysis reactions of a series of small paraffinic hydrocarbons (propane, n-butane, isobutane, isopentane, and neopentane) were examined using a continuous stirred-tank catalytic reactor. The catalyst was 0.5 weight percent ruthenium scipported on γ-alumina.</p> <p> The reaction orders with respect to hydrocarbon and hydrogen and the activation energies were determined for the reaction of each hydrocarbon. The order of reactivity was also examined.</p> <p> The product distributions from each hydrocarbon were measured over a wide range of conversion (5 to 80%) and several temperatures. Reaction networks proposing reversible adsorption-desorption of the hydrocarbons and irreversible rupture of the carbon-carbon bonds in the surface species were applied to these data.</p> <p> Some conclusions were made concerning the mechanism of hydrogenolysis and the rate-limiting step.</p> / Thesis / Doctor of Philosophy (PhD)

Nynas AB is a company that refines oil  for different applications such as insulating oils  for the electrical industry and base oils for both the lubricant and chemical industry. Different types of base oils are produced for the lubricant industry in order to provide required properties such as good viscosity, solvency, volatility, etc. But sometimes, the oils produced in the refineries (known as “straight cut” oils) do not have the all properties required by a customer, and a way for achieving those properties is to blend different straight cut base oils. To save money and time, empirical correlations are used to facilitate the prediction of the properties of those blends.Those correlations are adapted to products from a single site produced from certain crude oils. The company has recently decided to introduce a new stream of products with different characteristics, which means that the new properties of the products and blends can not be predicted by using the existing empirical correlations. The objective of this project was to analyze blends containing these new products and find the new correlations. The names of the oils are classified information and were renamed in the report and also number of the tables with result in appendices has been reduced to protect Nynas AB.  The correlations were surprisingly good for most of the blends. The differences between the values obtained by the blending program (which was calculating the properties) and the experimental values were very small. But the calculated values for properties such as flash point and pour point, were quite different from the experimental ones for some of the samples. Finally, there was one type of blends, between the Naphthenic oil 2 (N 2) and Paraffinic oil B (P (B)), were it was not possible to get any results with the blending program, because the viscosities at 40 °C of those oils (N 2 and P(B)) were too similar. As mentioned before, the property that was most difficult to predict was the pour point, specially for blends containing paraffinic oil blend with a naphtenic oil. However, suggestions were made based on the experimental values of how to get correlations based on. Anyhow, empirical correlations were developed based on the experimental data.

Commercial aviation has demonstrated its ability to be a key driver of global socio-economic growth to this date. This growth, resulting from an ever increasing need for air-travel, has been observed to be environmentally unsustainable. Any technological enhancements to the upcoming fleet of aircraft or operational improvements have been overshadowed by this very demand for air-travel. Any further investigation into innovative concepts and optimisation approaches bring in trade-off difficulties due to limitations in current technology. This creates a constraint on design space exploration. The need to mitigate civil aviation’s environmental impact has necessitated this sector to expand its frontier and seek radical technologies. Among a range of other technologies, advanced biofuels for civil jet engines have been claimed to be one of the most promising solutions. “Techno-economic Environmental Risk Analysis (TERA) of Advanced Biofuels for Civil Aviation” is a study that contributes to knowledge through conception plus application of quantitative/ qualitative approaches to assess the technical viability, financial feasibility and environmental competence of 2nd and 3rd generation biojet fuels, through their application into the existing scenario of civil aviation, against that of the fossil-derived conventional jet fuel (Conv.Jet fuel). TERA of advanced biofuels aims to accomplish the aforementioned through a holistic, multi-disciplinary study entailing life cycle studies, carbon-foot printing, sustainability analysis, fuel chemistry, virtual studies comprising combustion thermodynamic, engine/aircraft performance and emission prediction, economic studies entailing biofuel price prediction and business case analysis as opposed to earlier studies. TERA of Advanced biofuels study entails development of elaborate life cycle models, ALCEmB (Assessment of Life Cycle Emissions of Biofuels) and ALCCoB (Assessment of Life Cycle Cost of Biofuels) to predict life cycle emissions and costs, respectively, of the advanced biofuels from the point of raw material generation to the point of finished product consumption (a “cradle-grave” approach). A virtual experiment, to assess the impact of the “performance” properties of the advanced biofuels on a representative twin-shaft turbofan/airframe combination, relative to that of Conv.Jet fuel, was also undertaken through numerical modelling and simulation.Evaluation through ALCEmB revealed that Camelina-SPK, Microalgae-SPK and Jatropha-SPK delivered 70%, 58% and 64% savings in life cycle emission, relative to Conv.Jet fuel. The Net Energy Ratio (NER) analysis indicates that current technology for the biofuel processing is energy efficient and technically feasible. An elaborate post-combustion gas property evaluation infers that the Bio-SPKs exhibit improved thermodynamic behaviour. This thermodynamic effect has a positive impact on mission-level fuel consumption which reflected as fuel savings in the range of 3 - 3.8% and, therefore, emission savings of 5.8-6.3% in CO2 and 7.1-8.3% in LTO NOx, relative to that of Jet-A1. An economic feasibility analysis which entails prediction of hypothetical biofuel price prediction and its impact on direct operating cost (DOC) of an aircraft which infers that Bio-SPKs, over a user-defined medium-range mission profile, costs an additional 95-100% in terms of aircraft DOC, relative to that operated with conventional Jet-fuel, within short (2020) and medium (2020). However, the advanced biofuels are able to exhibit financial competence from 2020 onwards, relative to that of Conv.Jet fuel. However, the Bio-SPKs exhibit this economic feasibility only against a backdrop of persistent Conv.Jet fuel price volatility and severe environmental taxation between the analysis periods (2020-2075).

Characterization of jet fuels obtained from sources other than crude oil is a modern area of research that is developing continuously to replace available petroleum-based fuels with ‘drop-in’ alternative fuels. Therefore, reliable composition-property relations are developed to correlate the hydrocarbon compositions of formulated synthetic fuels with their properties to be certified for aviation commercial use. Intensive studies have been initiated at Texas A&M University Qatar in collaboration with industry and academia to study synthetic jet fuels derived from natural gas. These studies are being implemented at its Fuel Characterization Lab where the most advanced testing equipment is used and strict Quality Management and safety systems are followed. This study is divided into two tracks. The first track is focused on conducting experimental investigations using in-house formulated synthetic jet fuels derived from natural gas via Gas-to-Liquid technology and Fischer-Tropsch chemistry. Throughout this research work, these fuels will be referred to as Synthetic Paraffinic Kerosene (SPK). These experimental investigations activities are composed of three phases: the first phase focuses on the influence of SPK building blocks (paraffinic hydrocarbons) on fuels’ properties, the second phase concerns evaluating the role of aromatics and cyclo-paraffins on properties, and the third phase studies the influence of mixing SPK with conventional Jet A-1 derived from crude oil. All of the aforementioned experimental investigations are aimed at building an experimental data bank to assist the efforts of the formulation of new generations of SPKs that meet aviation industry standards. On the other hand, the second track is directed towards the development of mathematical correlations for four properties of high importance to SPK certification. These correlations aim at optimizing fuel composition whereby major physical/chemical properties of ASTM D1655 are met at the lowest cost of composed fuel. The primary findings of this study showed that GTL derived SPK paraffinic constituents can improve certain properties while affecting others negatively, and emphasizing the necessity of aromatics in improving specific properties. Further studies compensating the absence of aromatics and sulfur through blended Jet A-1 revealed a practical solution through jet fuels optimization based on cost and technical effective manners.

[pt] Neste trabalho é desenvolvido um modelo constitutivo para representar o comportamento reológico complexo apresentado pelos petróleos parafinicos, na faixa de temperaturas em que estes tendem a se solidificar, em virtude do aprisionamento da fase líquida na rede cristalina formada pela parafina que daí da solução. São considerados os efeitos de memória térmica do óleo e, numa etapa posterior, os efeitos das taxas de cisalhamento através de um modelo de potencia generalizado. Inicialmente são realizados medidas em um viscosímetro cone-placa, em que as amostras são submetidas a diferentes histórias de resfriamento e taxas de cisalhamento. O modelo é baseado nestes dados experimentais obtidos. Para verificação dos resultados previstos pelo modelo, um circuito de testes é construído, com seções de 6 m de comprimento e diâmetros de meio, três quartos e 1. A concordância dos valores previstos pelo modelo com os dados experimentais é apenas qualitativa e estima-se que a diferença entre estes valores possa ser atribuída, entre outros fatores, ao cisalhamento excessivo causado por sucessivas passagens do óleo pela bomba e outros acidentes de tubulação. / [en] In the present work a constitutive model is developped in order to reproduce the rheological behaviour of waxy crude oils near and below their pour points, as wax starts to leave the liquid phase dependency of such behaviour on the previous thermak history of the oil and, later, the effects of shear rate are included by fitting it to a generalized Power Law model. The accuracy is verified on a test loop specially built to hand such oils and, although the predicted values are not in total agreement with measured ones, the qualitative behavior is well reproduced and further efforts should take place in order to get a test loop where the shearing effect, due mainly to the pump, will not interfere that much.

Este trabalho trata de um estudo experimental das respostas de desgaste e de atrito encontradas em um sistema deslizante lubrificado. Para tanto, foram realizados ensaios de deslizamento em um equipamento para ensaios de desgaste, adotando-se o dispositivo pino-contra-disco, para ensaios com movimento relativo rotativo contínuo entre as amostras, e o dispositivo pino-contra-placa, para ensaios com movimento relativo alternado, ou oscilatório, entre as amostras. Os materiais metálicos ensaiados foram pinos de aço AISI 52100 e contra-corpos de aço AISI 8640. O óleo lubrificante foi o mineral de base parafínico, IV 100. Foram variadas as condições de aditivação e de contaminação do óleo lubrificante e foram utilizados dois níveis de carregamento mecânico, determinada pela relação velocidade/carga. O desgaste foi estudado por microscopia óptica e eletrônica de varredura, medição da área afetada pelo desgaste, perfilometria das superfícies desgastadas e análise de óleo. O atrito e o potencial de contato foram monitorados ao longo dos ensaios. Os resultados obtidos mostraram que o desgaste dos corpos metálicos foi sensível ao carregamento mecânico, à aditivação e à contaminação do óleo. Diferenças foram notadas nas morfologias superficiais entre os resultados de desgaste dos ensaios rotativos e oscilatórios. / This work concerns with experimental study of wear and friction responses of lubricated sliding system. Sliding tests were carried out using pin-on-disk wear testing machine for tests with continuous rotating movement, and the pin-on-plate device, for reciprocating tests between specimens. The metallic test coupons were AISI 52100 steel pins and AISI 8640 steel counter-faces. The used lubricant was paraffinic mineral oil, VI 100. The presence of additives and contamination in the lubricant oil were investigated under two mechanical loading levels, determined by the velocity/load relation. The wear was studied by means of optic and scanning electronic microscopes, perfilometry and dimensional analysis of the worn surfaces and oil analysis. The friction and the contact potential were monitored through out the sliding tests. The results showed that the wear of the metallic materials was susceptible to the mechanical loading, the additive and the contamination existence in the oil. It was observed differences among the wear results of the rotating and the reciprocating tests in terms of surface morphologies.

Este trabalho trata de um estudo experimental das respostas de desgaste e de atrito encontradas em um sistema deslizante lubrificado. Para tanto, foram realizados ensaios de deslizamento em um equipamento para ensaios de desgaste, adotando-se o dispositivo pino-contra-disco, para ensaios com movimento relativo rotativo contínuo entre as amostras, e o dispositivo pino-contra-placa, para ensaios com movimento relativo alternado, ou oscilatório, entre as amostras. Os materiais metálicos ensaiados foram pinos de aço AISI 52100 e contra-corpos de aço AISI 8640. O óleo lubrificante foi o mineral de base parafínico, IV 100. Foram variadas as condições de aditivação e de contaminação do óleo lubrificante e foram utilizados dois níveis de carregamento mecânico, determinada pela relação velocidade/carga. O desgaste foi estudado por microscopia óptica e eletrônica de varredura, medição da área afetada pelo desgaste, perfilometria das superfícies desgastadas e análise de óleo. O atrito e o potencial de contato foram monitorados ao longo dos ensaios. Os resultados obtidos mostraram que o desgaste dos corpos metálicos foi sensível ao carregamento mecânico, à aditivação e à contaminação do óleo. Diferenças foram notadas nas morfologias superficiais entre os resultados de desgaste dos ensaios rotativos e oscilatórios. / This work concerns with experimental study of wear and friction responses of lubricated sliding system. Sliding tests were carried out using pin-on-disk wear testing machine for tests with continuous rotating movement, and the pin-on-plate device, for reciprocating tests between specimens. The metallic test coupons were AISI 52100 steel pins and AISI 8640 steel counter-faces. The used lubricant was paraffinic mineral oil, VI 100. The presence of additives and contamination in the lubricant oil were investigated under two mechanical loading levels, determined by the velocity/load relation. The wear was studied by means of optic and scanning electronic microscopes, perfilometry and dimensional analysis of the worn surfaces and oil analysis. The friction and the contact potential were monitored through out the sliding tests. The results showed that the wear of the metallic materials was susceptible to the mechanical loading, the additive and the contamination existence in the oil. It was observed differences among the wear results of the rotating and the reciprocating tests in terms of surface morphologies.

Made available in DSpace on 2015-05-14T13:21:08Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 2470601 bytes, checksum: bbe63c6c08f3ff229939be1fa3d736d8 (MD5) Previous issue date: 2011-11-16 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / The aim of this study is the preparation and characterization of the Pd/C catalyst for the stearic acid decarboxylation in order to obtain paraffinic biodiesel. The precursors used in the coal preparation were the coconut endocarp and the Manila palm sheath. These coals were chemically activated and by microwave hydrothermal treatment with HNO3 solution. Its characterization showed that the microwave activation induced a decrease in catalysts microporous structure. The porous structure of each coal was determined by N2 adsorption at 77 K. The isotherm data were by BET, Langmuir, t-plot and BJH methods. The ZCP values and the ash content were determined. The identification and quantification of chemical groups on the activated coals surface used the Boehm method and infrared spectroscopy, which showed formation of carboxylic groups for all samples. The coals originated from the coconut endocarp (CAE AC and CAE MW), activated by both methods, had higher SMIC than the coals from the palm sheath (CAB and CAB AC MW). The CAB coals are more mesoporous, while the CAE coals have a more relevant microporous structure. The Pd/C catalysts were prepared by dry impregnation and by alcohol reduction. The catalysts characterization was performed using the SEM-FE, H2 chemisorption, N2 adsorption/desorption of at 77 K and FTIR. The metallic phase deposition favored a decrease in total surface area. The catalysts synthesized by dry impregnation showed larger micropore areas. The SEM-FE showed that in the catalysts prepared by alcohol reduction the metal deposition occurred preferentially at the surface, where as it in the catalysts prepared by dry impregnation, probably occurred within the pores. The Pd/C catalysts used in the catalytic decarboxylation reaction of stearic acid, at 350°C in H2 atmosphere showed conversions and high selectivity for heptadecane. The catalysts derived from coal CAE showed higher selectivity in relation to the formation of the desired product, the heptadecane. We observed a trend of higher conversions for the catalysts synthesized by dry impregnation. Some catalysts showed deactivation after three hours of reaction. / A proposta deste trabalho é estudar a preparação e caracterização do catalisador Pd/C para a descarboxilação do ácido esteárico, a fim de obter biodiesel parafínico. Os precursores utilizados na preparação dos carvões foram o endocarpo do coco da baía e a bainha da palmeira de manila. Estes carvões foram ativados quimicamente e por microondas com solução de HNO3. A estrutura porosa de cada carvão foi determinada por adsorção de N2 a 77 K. Os dados das isotermas foram tratados pelas metodologias de BET, Langmuir, t-plot e BJH. Sua caracterização permitiu concluir que a ativação por microondas induziu uma diminuição da estrutura microporosa dos catalisadores. Foram determinados os valores de PCZ e teor de cinzas. Na identificação e quantificação dos grupos químicos da superfície dos carvões utilizou-se o método de Boehm e espectroscopia de infravermelho, que evidenciaram a formação de grupos carboxílicos para todas as amostras ativadas. Os carvões originados do endocarpo do coco ativados quimicamente e por microondas (CAE AC e CAE MW) apresentaram SMIC mais elevadas do que os carvões provenientes da bainha da palmeira (CAB AC e CAB MW). Os carvões CAB são mais mesoporosos, enquanto os CAE possuem estrutura microporosa mais relevante. Todos os carvões ativados apresentaram PCZ ácido. A ativação do CAE por microondas favoreceu o aumento da estrutura mesoporosa, com significativa diminuição da microporosa. Os catalisadores Pd/C foram preparados por impregnação seca e por redução por álcool. A caracterização destes catalisadores foi feita através do FE-SEM, quimissorção de H2, adsorção/dessorção de N2 a 77 K e FTIR. A deposição da fase metálica favoreceu uma diminuição da área superficial total. Os catalisadores sintetizados por impregnação seca apresentaram maiores áreas de microporos. O FE-SEM mostrou que nos catalisadores preparados por redução por álcool a deposição do metal ocorreu preferencialmente na superfície, enquanto nos preparados por impregnação seca, possivelmente ocorreu dentro dos poros. Os catalisadores Pd/C utilizados na reação de descarboxilação catalítica do ácido esteárico a 350 ºC, em atmosfera de H2 apresentaram elevada atividade catalítica e seletividade para o heptadecano. Os catalisadores derivados do carvão CAE mostraram seletividade superior em relação à formação do produto desejado, o heptadecano. Foi observada uma tendência de conversões maiores para os catalisadores sintetizados por impregnação seca. Alguns catalisadores apresentaram desativação após três horas de reação.

Fuktbevarare är de produkter som oftast skrivs och rekommenderas av dermatologer, och den vanligaste typen av fuktgivare är lotioner och krämer. Dessa produkter är emulsioner, vilka ofta innehåller medicinsk vit olja (MWO) på grund av deras skyddande egenskaper samt enastående hudkompabilitet. Traditionellt så har de MWO som används varit parafinska. Då naftenoljor ofta har visat sig ha bättre emulsions stabilitet, har detta examensarbete ämnat attjämföra emulsions stabiliteten för Nynas ABs nya MWO, N-MWO, med en parafinsk motsvarighet, P-MWO. Jämförelsen av de två oljorna genomfördes genom att variera följande faktorer: olje- och emulgator typ, koncentration av emulgator samt både med och utan parfym. De två emulgator system som användes bestod av Promulgen D (en kommersiell produkt från Lubrizol) samt kombinationen av Tween 80 och Span 20. Bättre emulsionsstabilitet och mindre droppstorlek och fördelning utficks då högre koncentration Promulgen D användes. En högre koncentration av Tween 80 och Span 20 gav dock inte samma gynnsamma effekt. Resultaten från samtliga tester påvisade att emulsions stabiliteten inte påverkades utav parfym. Det som istället gav störst påverkan var typ av emulgator. De prover som innehöll P-MWO samt Tween 80 och Span 20 fasseparerade. Detta berodde dock troligen mer på att P-MWO inte var kompatibel med dessa emulgatorer eftersom oljetypen inte påverkade emulsionsstabiliteten när Promulgen D användes som emulgator. / Moisturizers are the most prescribed products in dermatology, and the most common type of moisturizer delivery systems are lotions and creams. These are emulsions and often contain medical white oil (MWO) due to their protective properties and excellent skin compatibility. The MWO used in cosmetics have traditionally been paraffinic. However, as naphthenic oils often have been proven to create better emulsion stability, this thesis aimed to compare Nynas AB's new MWO, N-MWO, with a paraffinic oil, P-MWO, with similar properties regarding their emulsion stability. The two oils were compared by analyzing their emulsion stability using a rheometer and a Mastersizer 3000 while varying the following factors: type of oil, type of emulsifier, emulsifier concentration, and with and without perfume. The two emulsifying systems used were the commercial product Promulgen D from Lubrizol and the combination of Tween 80 and Span 20. Better emulsion stability and smaller droplet size distribution were obtained when a higher content of Promulgen D was added. However, a higher concentration of Tween 80 and Span 20 did not have the same favorable effect. The results showed that the addition of perfume had no effect, while the type of emulsifier influenced the emulsion stability the most. The samples made from Supela 240 and Tween 80 and Span 20 phase separated. This was more likely due to P-MWOs incompatibility with these emulsifiers as oil type did not influence the emulsion stability when Promulgen D was used as an emulsifier.