Дисертації з теми "Blended oil"

Microbiological oil solutions of provitamin A (β-carotene) as a dietary supplement are not widely used due to their low oxidation stability. The aim of research is determination of the effect of sesame antioxidants on the oxidative stability of provitamin A in oil solutions. The peroxide number of vegeTable oils is determined by the standard method by the titrimetric method. The value of the period of induction of oil oxidation is determined graphically from the growth curves of peroxide numbers. The content of tocopherols in oils is determined by spectrophotometric method. The content of sesamol and sesamoline in oils is determined by the colorimetric method. The oxidative stability of oils is determined using the accelerated "active oxygen" method. To plan the experiment and process the data, mathematical methods are applied using the software Microsoft Office Excel 2003. The oxidation stability of blended oils (a mixture of sesame, high oleic, sunflower and corn refined oils) and its components is investigated. Blended oil has a lower oxidative stability than sesame oil, but higher than corn and high oleic sunflower. The oxidative stability of the blend is enhanced by the antioxidant content of sesamol and sesamoline. The content of the above antioxidants, as well as the amount of tocopherols, is studied in blended oils. The oxidation stability of the obtained solution of provitamin A in blended oils is investigated. The period of induction of oxidation of blended oils with the addition of 0.2 % β-carotene increases by 1.3 times compared with the period of induction of the original blended oil. Blended long-life oil is recommended to be used to stabilize fat-soluble biologically active compounds.

In this study the performance, emission and economic evaluation of using the clove stem oil (CSO)–diesel blended fuels as alternative fuels for diesel engine have been carried out. Experiments were performed to evaluate the impact of the CSO–diesel blended fuels on the engine performance and emissions. The societal life cycle cost (LCC) was chosen as an important indicator for comparing alternative fuel operating modes. The LCC using the pure diesel fuel, 25% CSO and 50% CSO–diesel blended fuels in diesel engine are analysed. These costs include the vehicle first cost, fuel cost and exhaust emissions cost. A complete macroeconomic assessment of the effect of introducing the CSO–diesel blended fuels to the diesel engine is not included in the study. Engine tests show that performance parameters of the CSO–diesel blended fuels do not differ greatly from those of the pure diesel fuel. Slight power losses, combined with an increase in fuel consumption, were experienced with the CSO–diesel blended fuels. This is due to the low heating value of the CSO–diesel blended fuels. Emissions of CO and HC are low for the CSO–diesel blended fuels. NOx emissions were increased remarkably when the engine was fuelled with the 50% CSO–diesel blended fuel operation mode. A remarkable reduction in the exhaust smoke emissions can be achieved when operating on the CSO–diesel blended fuels. Based on the LCC analysis, the CSO–diesel blended fuels would not be competitive with the pure diesel fuel, even though the environmental impact of emission is valued monetarily. This is due to the high price of the CSO.

Дисертація на здобуття наукового ступеня кандидата технічних наук за спеціальністю 05.18.06 – технологія жирів, ефірних масел і парфумерно-косметичних продуктів. – Національний технічний університет "Харківський політехнічний інститут" Міністерства освіти і науки України, Харків, 2017. Дисертація присвячена науковому обґрунтуванню та розробці технології майонезних соусів підвищеної біологічної цінності. Обгрунтовано склад купажованої жирової основи для виробництва майонезних соусів підвищеної біологічної цінності. Запропоновано і обгрунтовано вибір рослинної сировини для введення в рецептуру емульсійної продукції підвищеної біологічної цінності. Встановлено кількісні залежності вмісту поліфенолів в порошку шкірки винограду двох сортів від взаємного впливу температури і часу зберігання. Обґрунтовано раціональні температурні параметри і концентрація оцтової кислоти для переводу протопектинів порошку виноградної шкірки в розчинний стан і зміни структурно-механічних властивостей майонезних соусів з додаванням даного виду рослинної сировини. Обґрунтовано і розроблено комплексний загусник некрохмальної природи для виробництва емульсійної продукції підвищеної біологічної цінності. Визначено кількісні залежності ефективної в'язкості емульсії від концентрації складових загусника. Визначено кількісні залежності смакових якостей емульсії від концентрації складових комплексного підкислювача з мінімальним вмістом оцтової кислоти і максимально можливим вмістом цитринової та яблучної кислот для створення характерного ненав'язливого кислого присмаку. Знайдено технологічне рішення щодо зниження показників мікробіологічного та окиснювального псування при зберіганні майонезних соусів без додавання штучних антиоксидантів і консервантів. Запропоновано структурну схему виробництва майонезних соусів підвищеної біологічної цінності.
Dissertation for a candidate degree of technical sciences (Ph.D.) by speciality 05.18.06 – fats, essential oils and parfume-cosmetic products technology. National Technical University "Kharkov Polytechnic Institute" Ministry of Education and Science of Ukraine, Kharkov, 2017. The dissertation is devoted to the scientific substantiation and development of the mayonnaise sauces with enhanced biological value technology. Was substantiated the composition of blended oil for the production mayonnaise sauces with enhanced biological value. It was proposed and proved choice of vegetable raw materials for the compounding of emulsion production with enhanced biological value. Established quantitative dependences of the content of polyphenols in grapes skin powder of two varieties from mutual influence of temperature and storage time. Were substantiated the rational parameters of temperature and concentration of acetic acid for transferring from protopectin of grape skin powder to soluble form and changes in the structural and mechanical properties of the mayonnaise sauce with the addition of this species of plant raw materials. Substantiated and developed a сomplex thickener of non-starch nature for the production emulsion products with enhanced biological value. Was defined the quantitative dependence of the effective viscosity and stability of the emulsion from the thickener components concentration. Was defined the quantitative dependences of tastes of an emulsion on concentration of components of a complex acidifier with the minimum content of an acetic acid and the greatest possible content of citric and malic acids for creation of the reference unobtrusive sour smack. Was detected the technology decision for decrease of indexes of microbiological and oxidative spoilage at storage mayonnaise sauces without addition of syntetic antioxidants and preservatives. Was proposed the structural diagram of the production of mayonnaise sauces with enhanced biological value.

Дисертація на здобуття наукового ступеня кандидата технічних наук за спеціальністю 05.18.06 – технологія жирів, ефірних масел і парфумерно-косметичних продуктів. – Національний технічний університет "Харківський політехнічний інститут" Міністерства освіти і науки України, Харків, 2017. Дисертація присвячена науковому обґрунтуванню та розробці технології майонезних соусів підвищеної біологічної цінності. Обгрунтовано склад купажованої жирової основи для виробництва майонезних соусів підвищеної біологічної цінності. Запропоновано і обгрунтовано вибір рослинної сировини для введення в рецептуру емульсійної продукції підвищеної біологічної цінності. Встановлено кількісні залежності вмісту поліфенолів в порошку шкірки винограду двох сортів від взаємного впливу температури і часу зберігання. Обґрунтовано раціональні температурні параметри і концентрація оцтової кислоти для переводу протопектинів порошку виноградної шкірки в розчинний стан і зміни структурно-механічних властивостей майонезних соусів з додаванням даного виду рослинної сировини. Обґрунтовано і розроблено комплексний загусник некрохмальної природи для виробництва емульсійної продукції підвищеної біологічної цінності. Визначено кількісні залежності ефективної в'язкості емульсії від концентрації складових загусника. Визначено кількісні залежності смакових якостей емульсії від концентрації складових комплексного підкислювача з мінімальним вмістом оцтової кислоти і максимально можливим вмістом цитринової та яблучної кислот для створення характерного ненав'язливого кислого присмаку. Знайдено технологічне рішення щодо зниження показників мікробіологічного та окиснювального псування при зберіганні майонезних соусів без додавання штучних антиоксидантів і консервантів. Запропоновано структурну схему виробництва майонезних соусів підвищеної біологічної цінності.
Dissertation for a candidate degree of technical sciences (Ph.D.) by speciality 05.18.06 – fats, essential oils and parfume-cosmetic products technology. National Technical University "Kharkov Polytechnic Institute" Ministry of Education and Science of Ukraine, Kharkov, 2017. The dissertation is devoted to the scientific substantiation and development of the mayonnaise sauces with enhanced biological value technology. Was substantiated the composition of blended oil for the production mayonnaise sauces with enhanced biological value. It was proposed and proved choice of vegetable raw materials for the compounding of emulsion production with enhanced biological value. Established quantitative dependences of the content of polyphenols in grapes skin powder of two varieties from mutual influence of temperature and storage time. Were substantiated the rational parameters of temperature and concentration of acetic acid for transferring from protopectin of grape skin powder to soluble form and changes in the structural and mechanical properties of the mayonnaise sauce with the addition of this species of plant raw materials. Substantiated and developed a сomplex thickener of non-starch nature for the production emulsion products with enhanced biological value. Was defined the quantitative dependence of the effective viscosity and stability of the emulsion from the thickener components concentration. Was defined the quantitative dependences of tastes of an emulsion on concentration of components of a complex acidifier with the minimum content of an acetic acid and the greatest possible content of citric and malic acids for creation of the reference unobtrusive sour smack. Was detected the technology decision for decrease of indexes of microbiological and oxidative spoilage at storage mayonnaise sauces without addition of syntetic antioxidants and preservatives. Was proposed the structural diagram of the production of mayonnaise sauces with enhanced biological value.

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.

Thesis (MTech (Mechanical Engineering))--Cape Peninsula University of Technology, 2016.
The high cost of fossil fuels and the fact that the world has arguably reached its peak oil production, has driven the need to seek alternative fuel sources. The main objective of the current study is to determine the performance of a laboratory-mounted diesel engine when fuelled with varying laboratory prepared biofuel and biodiesel and whether the advancement of the injection timing parameters will improve the engine power output and improve the smoke effect of these different fuel blends. The laboratory prepared biofuels used in this project range from 100% bio-fuel (BF100) to 50%, 30% and 10% biodiesel blends (BF50, BF30 and BF10, respectively). It should be noted that these blends are not commercially available, since they were blended in the laboratory specifically for these tests. The overall results of the study show that there is a distinct opportunity for using certain bio-fuel blends in specific applications as the power outputs are no more than one quarter less than that of base diesel. Concomitantly, the smoke opacity in all of the blends is lower than that of base diesel, which is a significant benefit in terms of their overall air emissions.

The purpose with this study is to compare four different models to VaR in terms of accuracy, namely Historical Simulation (HS), Simple Moving Average (SMA), Exponentially Weighted Moving Average (EWMA) and Exponentially Weighted Historical Simulation (EWHS). These VaR models will be applied to one underlying asset which is the Brent Blend Oil using these confidence levels 95 %, 99 % and 99, 9 %. Concerning the return of the asset the models under two different assumptions namely student t-distribution and normal distribution will be studied

Blends of lubricant base stocks are commonly employed to produce lubricants with optimised performance. However, the influence of blending on lubricant behaviour within high pressure, mechanical contacts, particularly the film forming capacity and friction, have largely gone unstudied. This thesis examines both of these aspects for a range of base fluids and their blends. Film thickness generation and fluid friction are reviewed in the context of elastohydrodynamic (EHD) lubrication. Various models addressing the origin and mechanism of liquid viscosity are reviewed. The derivation of viscosity as a thermodynamic property is also reviewed and its relevance to the current study is discussed. Consideration is also given to two commonly accepted yet contrasting models of EHD traction, resulting in one being adopted for this research. The relationship of molecular structure to film generation is examined experimentally by studying a number of single component fluids with widely varying chemical structures. It is shown that pressure-viscosity coefficients derived from film thickness are strongly related to the respective chemical “family” of the lubricant. EHD friction (traction) measurements are also made and analysed in order to establish a reliable method for comparing the influence of fluid composition on traction. The method, based on a well regarded fluid model, allows accurate description of full fluid traction by means of the Eyring stress and pressure-viscosity coefficient in the central EHD contact. Binary blends of well-defined base fluids are studied. It is found that the pressure- viscosity coefficient, as derived by the aforementioned methods, varies nonlinearly with the composition and tends toward the lower value of the individual components, at times attaining values lower than either of the individual components.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior
Extensos estudos sobre o biodiesel comprovam suas inúmeras vantagens, entretanto os diferentes tipos de biodieseis obtidos por diferentes matérias-primas podem resultar em desvantagens e pode produzir um biodiesel inadequado para o uso. Assim, o objetivo deste estudo é avaliar biodieseis produzidos de diferentes óleos usados de frituras (OUF), que são uma escolha econômica, devido seu baixo custo, bem como avaliar os efeitos de blendas de biodiesel de óleo de fritura/inajá sobre as propriedades do biodiesel. O óleo de inajá é uma fonte promissora para a produção de biodiesel, pois a amêndoa apresenta um elevado percentual de óleo. Os biodieseis metílicos foram produzidos por transesterificação usando catalisador alcalino, seu perfil em ácidos graxos, teores de glicerina livre, mono-, di- e triglicerídeos foram analisados por cromatográfica a gás equipada com detector por ionização por chama (CG-DIC). Todas as propriedades dos biodieseis foram determinadas de acordo com os métodos padrões da ANP. Foram coletados onze diferentes óleos usados de fritura, os resultados por CG-DIC apresentaram pequena variação nos seus perfis em ácidos graxos. Dez OUF apresentaram como componentes majoritários, o linoleato de metila e oleato de metila, respectivamente. Apenas um OUF apresentou como majoritários o oleato de metila e palmitato de metila. Apesar da similaridade no perfil em ácidos graxos dos OUF, há uma grande variação nas propriedades dos seus biodieseis, que não puderam ser em sua totalidade justificadas pela composição em ácidos graxos. Este fato sugere que os componentes derivados da degradação térmica, podem influenciar nas propriedades do biodiesel. Entretanto a estabilidade a oxidação pode ser correlacionada com o perfil em ácidos graxos, assim somente a amostra com superior conteúdo de saturados, apresentou uma superior estabilidade oxidativa. As blendas de biodiesel de óleo de fritura/inajá apresentaram diferentes perfis de ácidos graxos. O biodiesel de inajá apresenta como majoritários, o laureato de metila e miristato de metila respectivamente. Assim, as blendas resultaram em uma redução de ésteres insaturados e no aumento de ésteres de cadeia curta saturados. Apenas as propriedades do biodiesel da blenda de 50% v/v dos dois biodieseis, foram analisadas. Esta blenda apresentou melhores resultados para as propriedades do biodiesel em comparação ao biodiesel de óleo de inajá puro, uma maior estabilidade oxidativa e menor índice de acidez em relação ao biodiesel de OUF, entretanto apresentou baixo ponto de fulgor. Este estudo mostrou que presença de compostos de degradação térmica nos óleos de fritura pode afetar as propriedades do biodiesel. Entretanto os óleos de fritura coletados em Boa vista apresentaram uma boa qualidade, resultando em um biodiesel dentro do limite estabelecido pela ANP. O biodiesel do óleo de inajá apresentou várias propriedades fora do estabelecido pela ANP, tornando-se inviável seu uso como biodiesel. As blendas dos dois biodieseis são promissoras, quanto à correção das propriedades do biodiesel em relação aos biodieseis puros.

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The large consumption of fossil fuels that still today predominates the world's energy supply is one of the great villains in greenhouse gases emissions (GHG), that are largely responsible for global warming. The oil reserves tend to depletion, and the growing demand of energy needed to feed the technological advances, the search for solutions to minimize emissions of pollutants and waste recovery, discarded improperly by man, became an opportunity to add value and produce energy from raw materials, that cause major environmental impacts. The biodiesel from waste frying oil has been shown to be effective alternative in renewable energy production, as well as having large potential energy, generates by-products that may be incorporated in the processing of raw materials, adding final value. This work evaluated the use of blends of diesel oil with oil and biodiesel from waste frying, in fixed and varying proportions of 10% for each treatment, B0 being the absence of biodiesel and B100 being entirely, as an alternative renewable fuel in burners for heating of pools. The conduct of the experiment occurred in the thermal pool block physiotherapy State University of Western Paraná (UNIOESTE), during the month of August 2014, in the Cascavel campus, using entirely randomized design. The fuels were evaluated for their behavior at room temperature and passing through a heating process, which on average was 50,63 °C, before to combustion in the burner. We evaluated data: percentage of water and impurities, viscosity, density, calorific value, emission of CO2, O2, and the exhaust temperature in the produced blends. Were also collected input and output temperature information in the boiler, flow water, flow and fuel temperature, to determine the specific consumption and efficiency. There was a reduction in thermal efficiency of the system, as increased the percentage of biodiesel contained in mixtures, operating at room temperature. However, with the pre-heating, we obtained a significant improvement. KEYWORDS:
O grande consumo de combustíveis fósseis que ainda hoje predomina na oferta de energia mundial é um dos grandes vilões nas emissões de gases de efeito estufa (GEE), que são os grandes responsáveis pelo aquecimento global. As reservas de petróleo tendem ao esgotamento, e com a crescente demanda de energia necessária para suprir os avanços tecnológicos, a busca por soluções para minimizar as emissões de poluentes e o aproveitamento de resíduos, descartados de forma indevida pelo homem, tornou-se uma oportunidade de agregar valores e produzir energia a partir de matérias-primas, que causam grandes impactos ambientais. O biodiesel de óleo residual de fritura tem se mostrado como alternativa eficaz na produção de energia renovável, pois além de possuir alto potencial energético, gera subprodutos que podem ser incorporados no processamento da matéria-prima, agregando valor final. Este trabalho buscou avaliar a utilização de blendas de óleo diesel com óleo e biodiesel de resíduos de fritura, em proporções fixas e variadas em 10% para cada tratamento, sendo B0 a ausência de biodiesel e B100, sua totalidade, como alternativa de combustível renovável em queimadores para aquecimento de piscinas. A condução do experimento ocorreu na piscina térmica do bloco de fisioterapia da Universidade Estadual do Oeste do Paraná (UNIOESTE), durante o mês de agosto de 2014, no campus de Cascavel, utilizando delineamento experimental inteiramente casualizado. Os combustíveis foram avaliados quanto ao seu comportamento à temperatura ambiente e passando por um processo de aquecimento, que em média foi de 50,63 ºC, antes da combustão no queimador. Foram avaliados dados de: percentual de água e impurezas, viscosidade, densidade, poder calorífico, emissão de gases CO2, O2, e a temperatura de escape nas blendas produzidas. Também foram coletadas informações da temperatura de entrada e saída da caldeira, vazão de água, fluxo e temperatura do combustível, para determinação do consumo específico e eficiência. Verificou-se uma redução na eficiência térmica do sistema, à medida que aumentou o percentual de biodiesel contido nas misturas, operando na temperatura ambiente. Porém, com o pré-aquecimento, obteve-se uma melhora significativa. PALAVRAS-

As traditional sources of energy become depleted, significant research interest has gone into conversion of biomass into renewable fuels. Biomass-derived synthesis gas typically contains concentrations of approximately 30 to 600 ppm H2S in stream. H2S is a catalyst poison which adversely affects downstream processing of hydrogen for gas to liquid plants. The water-gas shift reaction is an integral part of converting CO and steam to H2 and CO2. Currently, all known water-gas shift catalysts deactivate in sulfur concentrations typical of biomass-derived synthesis gas. Novel catalysts are needed to remain active in the presence of sulfur concentrations in order to boost efficiency and mitigate costs. Previous studies have shown molybdenum to be active in concentrations of sulfur greater than 300 ppm. Cobalt has been shown to be active as a spinel in concentrations of sulfur less than 240 ppm. Ceria has received attention as a WGS catalyst due to its oxygen donating properties. These elements were synthesized via Pechini's method into various blends of spinel metal oxide solutions. Initial activity testing at lower steam to gas ratios produced near equilibrium conversions for a Ce-Co spinel which remained active in 500 ppm H2S over a temperature range of 350 °C to 400 °C. The catalysts became poisoned and deactivated in higher concentrations of sulfur. Addition of molybdenum to the Ce-Co base had little effect on sulfur tolerance, but it did lead to a reduction in selectivity for methanation. Surface area increased due to adsorbed H2S, and X-Ray Diffraction confirmed that bulk sulfiding did not occur. Incorporation of Ce and Co into a Fe spinel hindered conversion at lower temperatures and deactivated in higher levels of sulfur.

Thesis (PhD)--Stellenbosch University, 2012.
ENGLISH ABSTRACT: World crude oil demand and production is set to increase in the long term and is projected to increase from 82 barrels per day in 2007 to an estimated 104 million barrels per day in 2030 according to the International Energy Agency. The environmental challenges posed by the current and projected increased future fuel use, with specific reference to air, aquatic and terrestrial impact, are driving producers and legislators to change fuel specifications and consequently fuel properties to be less harmful to the environment. Traditionally transportation fuels are produced through crude oil refining but in South Africa more than one third of the liquid fuels are produced synthetically through catalytic conversion of gassified coal via the Fischer-Tropsch process by Sasol. Diesel from syncrude is referred to as synthetic diesel and the refiner must blend various hydrocarbon streams, effectively tailoring the diesel to its final composition. Biodiesel from renewable sources like vegetable oils is considered environmentally more acceptable than petrodiesel because of its high biodegradability in the environment, lower sulphur and aromatic hydrocarbon content as well as lowered particulate content in the exhaust emissions. The present research was aimed at evaluating whether the composition of diesels derived from different feed stocks, that included coal, natural gas, crude oil and soybean oil, would influence its biodegradability and ecotoxicity. Acute aquatic tests that included freshwater fish, crustaceans, algae and marine bacteria were used to determine the acute toxicity of diesels. In addition, quantitative structure activity relationship models were used to estimate the biodegradation and ecotoxicity properties of the diesels in an attempt to develop a cost effective tool to determine those properties. The results indicated that the 2-D GC technique quantitatively and qualitatively identified the hydrocarbon constituents in the diesels. The relevance of using the 2-D GC technique was in identifying and quantifying the hydrocarbon breakdown products and being used in a mass balance to confirm the potential biological breakdown processes of the materials used in the present study. The differences in theoretical oxygen demand (ThOD) of the different experimental diesel blends using various blending materials and biodiesel, emphasised and confirmed the importance of calculating the ThOD for the respective blending materials when measuring the biodegradation rates. Furthermore, the biodegradation hierarchy of Pitter and Chudoba (1990) in order of decreasing biodegradability: alkanes > branched alkanes > cyclo-alkanes > aromatic hydrocarbons, could be expanded to include FAME: FAME > alkanes > branched alkanes > cyclo-alkanes > aromatic hydrocarbons. The biochemical pathways identified for the biodegradation of all the diesels was enzyme-enhanced β-oxidation. The present research also indicated that biodiesel addition to crude-derived diesels to increase the density to within the current required specifications for diesels cannot be a reality in SA because of the underdeveloped biodiesel industry. To increase the density by using biodiesel to within the specification for GTL diesel, more than 27% biodiesel would be required, which is currently is not achievable from an economic perspective as well as governmental national strategy perspective. The addition of biodiesel as lubricity enhancer seems more plausible, because less than 5% would be required for petrodiesels. The results on the ecotoxicity of the diesels and diesel blends demonstrated a general lack of acute toxic effect, especially for the fish and crustaceans used during the present study. Although algal and bacterial tests showed an effect at most of the WAF loading rates, none were high enough to enable the calculation of a median effect loading rate (EL50). QSAR‟s, like EPI Suite, together with prediction models, like the Fisk Ecotoxicity Estimation Model, can be used to screen for ecotoxicity and biodegradability of hydrocarbons found in Petrodiesels. It was less applicable for the prediction of biodiesel constituents. The use of different cut-off values for the constituents of biodiesel could be developed in future research. The use of this combination enabled the present research into the potential toxicity of hydrocarbon mixtures to be conducted, especially since tests on individual constituents are impractical. QSAR‟s may provide a relatively cost-effective way to screen for potential environmental acceptability of such mixtures. The contributors to the toxicity of mixtures of hydrocarbons found in diesels were evaluated and it appears that paraffins contribute more to the overall toxicity than previously thought and aromatics less. By putting well-defined policies and incentives in place, a robust biodiesel industry could be created that will enable SA to contribute to the mitigation of the threat of climate change, to become less dependent on foreign oil and to develop rural agriculture. The key to energy security is not one solution to South Africa‟s energy needs, but a multifaceted approach to the complex subject of sustainable energy security. The end of the hydrocarbon era of energy is not in sight, at least for the near future, but soon even hydrocarbon energy in the form of coal and crude oil will have to be re-evaluated as SA‟s major energy resource for economic and energy security. In SA the potential of developing natural gas resources through fracking, nuclear, solar, wind, biological and even wastes to energy processes as well as better energy efficiency, in a balanced and diverse energy portfolio, could pave the way toward energy security in the long run.
AFRIKAANSE OPSOMMING: Ru-olie aanvraag en produksie wêreldwyd is besig om toe te neem en die Internasionale Energie Agentskap projekteer dat wêreld ru-olie verbruik sal toeneem van 82 vate per dag in 2007 tot „n beraamde 104 vate per dag in 2030. Die omgewings uitdagings wat huidige en toekomstige toename in brandstof verbruik, spesifiek die impak op lug gehalte, water- en grond, mag hê, is dryfvere vir produseerders en reguleerders om brandstof spesifikasies te verander om minder omgewings impak te veroorsaak. Brandstof vir vervoer doeleindes word oor die algemeen van ru-olie gemaak, maar in Suid Afrika word ongeveer „n derde van die vloeibare brandtof gemaak deur middel van gekatiliseerde omskakeling van vergasde steenkool via die Fischer-Tropsch proses by Sasol. Diesel wat uit sintetiese ru-olie gemaak is, is sinteties en die raffineerder moet verskillende koolwaterstof strome meng om „n finale produk te lewer. Biodiesel wat uit hernubare hulpbronne soos plant-olies en diervet gemaak word, kan oorweeg word vir die vervaardiging van meer omgewings aanvaarbare brandstof met laer swael en aromatiese koolwaterstof inhoud en ook minder partikel inhoud in die uitlaatgas. Die huidige navorsing het beoog om te evalueer of die samestelling van diesels wat vervaardig is uit verskillende hulpbronne, wat steenkool, aardgas, ru-olie en sojaboon olie ingesluit het, die biodegradeerbaarheid en ekotoksisiteit kan beïnvloed. Akute akwatiese toetse wat varswater vis, krustaseë, alge en marine bakterieë ingesluit het, was aangewend om die akute toksisiteit van die diesels te bepaal. Kwantitatiewe struktuur aktiwiteit verwantskaps modelle is ook gebruik om die biodegradeerbaarheid en ekotoksisiteits eienskappe van die diesels te beraam om vas te stel of 'n bekostigbare alternatief beskikbaar is om daardie eienskappe te bepaal. Die resultate het aangedui dat die 2D GC tegniek kwantitatief en kwalitatief gebruik kan word om die koolwaterstowwe in die diesels te identifiseer. Die benutting van die 2D GC tegnieke is egter om die koolwaterstof afbraak produkte te identifiseer en ook om die massa balans gedurende die biodegradering te bevestig. Die verskil in teoretiese suurstof aanvraag van die verskillende diesels het die belangrikheid daarvan blemtoon en bevestig om die teoretiese suurstof aanvraag korrek te bereken en sodoende die biodegradasie korrek te bepaal. Verder kan die biodegradasie hierargie van Pitter en Chudoba (1990) volgens afnemende biodegradasie: alkane > vertakte alkane > siklo-alkane > aromatiese koolwaterstowwe, uitgebrei word om vetsuur-metielesters in te sluit: vetsuur-metielesters > alkane > vertakte alkane > siklo-alkane > aromatiese koolwaterstowwe. Die biochemiese roetes wat geïdentifiseer is vir die biodegradasie van die diesels, was ensiem-verbeterde β-oksidasie. Die huidige navorsing het ook aangedui dat biodiesel toevoeging tot ru-olie vervaardigde diesel om die digtheid te verhoog to binne huidige spesifikasies is nog nie lewensvatbaar in Suid Afrika nie as gevolg van die onderontwikkelde biodiesel industrie. Om die digtheid te verhoog met biodiesel tot binne spesifikasie verg meer as 27% biodiesel en is huidiglik nie haalbaar vanuit 'n ekonomiese persketief en ook nie vanuit 'n regerings nasionale strategie perspektief nie. Die toevoeging van biodiesel as lubrisiteits vervetering blyk meer van toepassing te wees aangesien minder as 5% biodiesel toevoeging benodig sou wees. Die resultate van die ekotoksisiteits toetse het 'n algemene gebrek aan akute toksisiteits effek aangedui, veral vir vis en skaaldiere wat in die huidige studie gebruik is. Howel alge en bakteriële toetse daarop gedui het dat 'n toksiese effek wel aanwesig was, was dit gering en kon die median effektiewe ladings koers (EL50) nie bepaal word nie. QSARs, soos Epi Suite, tesame met voospellings modelle, soos die Fisk Ecotoxicity Estimation Model, kan gebruik word om ekotoksisiteit en biodegradeerbaarheid van koolwaterstowwe in petrodiesels te beraam, alhoewel dit minder van toepassing was op biodiesel. Die gebruik van ander afsny waardes spesifiek vir biodiesel kan oorweeg word in toekomstige navorsing. Die molecules wat bygedra het tot die toksisiteit van die koolwaterstof mengsels was geëvalueeren daar is gevind dat die paraffiniese molekules meer begedra het tot die totale toksisiteit en die aromate minder. Deur goed gedefinieerde beleid en aansporings meganismes inplek te sit, kan 'n biodiesel industrie in SA geskep word wat SA sal help om by te dra tot die bekamping van klimaats vendering en sodoende minder afhanklik te wees van buitelandse olie en ook landbou in SA te bevorder. Die sluetel tot energie sekuriteit is nie een oplossing vir SA se energie aanvraag nie, maar eerder 'n veelsydige benadering tot die komplekse onderwerp van volhoubare energie sekuriteit. Die einde van koolwaterstof energie is nog nie in sig nie, ten miste nie in die nabye toekoms nie, maar binnekort sal selfs koolwaterstof energie in die vorm van steenkool en ru-olie heroorweeg moet word as SA se hoof energie hulpbronne vir ekonomiese en energie sekuriteit. In SA moet die potensiaal van natuurlike gas ontginning deur middel van hidrauliese breking, kernkrag, wind energie, biologiese energie en selfs afval tot energie prosesse bestudeer word, so-ook beter energie doeltreffendheid om sodoende 'n gebalansweerde energie portefuelje te skep wat die weg sal baan na energie sekuriteit op die lang termyn.

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In Brazil, rural communities away from the big centers, away from transmission and distribution electric grid, doesn´t have electric power hindering local economic progress. So, an alternative to a solution of the problem is a source of energy through fuels a base of vegetable oil, local raw material, renewable and of less environmental impact, justifying this work. The production service and the performance and emissions of a diesel generator set operating with fuels a vegetable oil base of soybean, linseed and crambe. The fuels were tested from a 5kVA generator set, without mechanical adaptation and connected to a electrical charges bank manufactured to dissipate the generated electric energy. Biofuels were obtained from the mixture of conventional diesel oil with soybean oil, linseed and crambe at incremental levels of 10%, 30%, 50% and 70% of vegetable oil in the composition of the fuel mixture and submitted to physicochemical viscosity analysis and density. In the evaluation of the performance of the generator was measured voltage (V), electric current (A), frequency of electric current (Hz), electrical power (W), wight (g), generator set noise (dB) and measured the exhaust gas concentration. The results of the studies show us that mixtures of conventional diesel (B8) with vegetable oil of soybean, linseed and crambe, in concentrations of up to 30%, presented with an effective technical alternative for a partial replacement of conventional diesel in the production of electric power, with reduction in emission levels and maintenance of the performance of the generator set.
No Brasil, comunidades rurais afastadas dos grandes centros, distantes das redes de transmissão e distribuição de energia, carecem de energia elétrica dificultando o progresso econômico local. Assim, uma alternativa para a solução do problema é a própria geração de energia através de combustíveis a base de óleo vegetal, matéria prima local, renovável e de menor impacto ambiental, justificando este trabalho. Avaliou-se o desempenho e emissões de um conjunto motor gerador diesel operando com combustíveis a base de óleo vegetal de soja, linhaça e crambe. Os combustíveis foram ensaiados a partir de um conjunto motor gerador de 5kVA, sem adaptação mecânica e ligado a um banco de cargas resistivas fabricado para dissipação da energia elétrica gerada. Os biocombustíveis foram obtidos da mistura do óleo diesel convencional com óleo de soja, linhaça e crambe em níveis incrementais de 10%, 30%, 50% e 70% de óleo vegetal na composição da mistura combustível e submetidos a análise físico-química de viscosidade e densidade. Na avaliação de desempenho do conjunto motor gerador foram realizadas medições de tensão (V), corrente elétrica (A), frequência da corrente elétrica (Hz), potência elétrica (W), consumo mássico (g), ruído do conjunto motor gerador (dB) e realizado a medição da concentração dos gases de exaustão. Os resultados dos estudos realizados apontam que misturas do diesel convencional (B8) com óleo vegetal de soja, linhaça e crambe, em concentrações de até 30%, apresentam-se como uma alternativa técnica eficaz na substituição parcial do diesel convencional na produção de energia elétrica, com redução nos níveis de emissões e manutenção de desempenho do conjunto motor gerador.

Application of thermogravimetric analysis to the renewable energy sources is a novel study and it has been becoming attractive by the researchers in recent years. In this thesis, thermal and kinetic properties of biodiesel as new energy source, diesel and canola oil have been analyzed by using very popular thermogravimetric analysis methods which are
Differential Scanning Calorimetry (DSC) and Thermogravimetry (TGA/DTG). The main aim of the study is to observe the combustion and pyrolysis behaviour of methanol route biodiesel and diesel blends at different blending rates. Additionally, combustion and pyrolysis behaviour of canola oil, the origin of biodiesel have been analysed to observe the transesterification reaction effect on biodiesel. Therefore, biodiesel, diesel, canola oil and blends of diesel and biodiesel at different percentages are exposed to isothermal heating under nitrogen and air atmosphere with a constant heating rate of 5, 10 and 15

This research sought to demonstrate the potential of biodiesel and softwood derived Fast Pyrolysis Oil (FPO) blends as an alternative low-carbon drop-in diesel fuel. FPO was supplied from an in-house fluidized bed reactor as well as a commercial source. Separate FPO-biodiesel blends from both FPO sources were prepared using initial volumetric ratios of 80:20 and 60:40 (biodiesel:FPO, by volume). Upon blending each performed volumetric ratio, mixing and a 24 hour settling period, two layers formed and the top, biodiesel-rich layers containing about 5 and 10 vol % FPO were decanted and characterized on the basis of a thermogravimetric analysis, viscosity, acid number, water content, elemental analysis, and heating value. Significant decreases in viscosity, acidity, and water content from the original FPO validated blending as means of extracting compounds suitable for use as fuels from pyrolytic liquids in biodiesel. A single cylinder, direct injection diesel engine was used to analyze the combustion performance of the FPO fuel blends against neat diesel and biodiesel. Fuel performance was characterized on the basis of a thermodynamic analysis and corresponding exhaust measurements for CO₂, CO, unburned hydrocarbons, particulate matter, and NOx. Two thermodynamic measurement campaigns were performed in order to provide insight into FPO fuel performance across various engine conditions. In addition to the thermodynamic measurements, in-cylinder high-speed photography was implemented to support the interpretation of thermodynamic combustion data. Engine testing revealed similar indicated efficiencies for biodiesel and diesel at all considered engine-operating modes, while blend fuels showed indicated efficiencies between 75 and 95% of diesel values. FPO fuels exhibited increased ignition delays and shorter combustion durations with greater FPO blend concentrations, though this could be partially compensated for using a pilot injection strategy. The longer ignition delays of the blend fuels resulted in overly lean regions of the cylinder, which produced largely premixed combustion events contributing to brake specific CO and uHC emissions up to 1.5 and 3.5 greater than diesel, respectively. Specific PM emissions were 41-62% lower for blend fuels than diesel. Both blends of in-house FPO showed similar PM emission performance, however at higher concentrations than low blend commercial fuel.
Applied Science, Faculty of
Graduate

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A exploração de petróleos nas diversas bacias sedimentares dá origem a óleos com composições químicas variáveis no qual exibe grandes diferenças de em suas propriedades físico-químicas, podendo estas características individuais serem mantidas mesmo após a formação das misturas (Blends). O conhecimento da composição do petróleo é uma necessidade imprescindível numa refinaria para o ajuste das condições do processo, pois definem a quantidade e a qualidades das diversas frações que podem ser obtidas. Neste contexto, métodos de espectroscopia no infravermelho médio, com reflectância total atenuada (FTIR-ATR) podem ser uma alternativa eficaz para fornecer metodologias analíticas rápidas, práticas, não destrutiva e de fácil amostragem para monitorar a composição do petróleo. Desta forma, é proposta deste trabalho estudar e desenvolver modelos de calibração multivariados, capazes de determinar a composição de blends de petróleo, formado por óleos de quatro Campos produtores, utilizando como descritores as absorções obtidas por medidas de FTIR-ATR. A metodologia é baseada na modelagem por mínimos quadrados parciais por intervalos (iPLS) e sinergismos de intervalos (siPLS), avaliados pelos erros gerados na previsão de novas amostras. Os resultados são promissores e indicam que os modelos se ajustam melhor a óleos com menor densidade. A absorção da molécula de água no infravermelho faz com que a água emulsionada seja um interferente no processo de modelagem. Os melhores resultados foram apresentados pelo algoritmo siPLS com erros de previsão entre 1,5 a 1,6 % e valores de correção em torno de 0,99 para óleos dos dois Campos com menor densidade. A partir dos resultados obtidos é possível elaborar um modelo estatístico para ser utilizado no processo de mistura de petróleos com objetivo de prever ou determinar a real composição do Blend
The exploitation of oil in various sedimentary basins gives rise to oils with variable chemical compositions in which displays great differences in their physical-chemistry properties, these individual characteristics can be maintained even after the blend. The composition of the oil is an indispensable necessity in a refinery for the adjustment of process conditions, because they define the amount of various fractions that can be obtained. In this context, methods of spectroscopy mid-infrared with attenuated total reflectance (FTIR-ATR) can be an effective alternative analytical methodologies to provide rapid, practical, not destructive sampling and easy to monitor the composition of oil. This way, this work is proposed to determine the composition of blends of oil, formed by four fields of oil producers by FTIR-ATR measurements. The modeling methodology is based on partial least squares interval (iPLS) and synergisms intervals (siPLS) assessed the errors generated in prediction of new samples. The results are promising indicating that the models best fits the oils with lower density. The absorption of water molecule in IR causes the emulsified water is interfering in a process modeling. The best results were presented by the algorithm with errors siPLS forecast of 1.5 to 1.6% and offset values around 0.99% for oils two fields with lower density. From the results, we develop a statistical model to be used in the mixing process oil in order to predict or determine the actual composition of Blend

Orientador: Maria Alvina Krähenbühl
Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química
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Resumo: A busca por combustíveis alternativos vem ganhando destaque nas últimas décadas. A substituição de combustíveis fósseis tem sido impulsionada por fatores ambientais, econômicos e sociais, uma vez que toda a sociedade depende de seu uso. Neste contexto, uma alternativa que tem se destacado é o do biodiesel. O biodiesel representa uma alternativa renovável, biodegradável, não inflamável e de baixa toxicidade para o diesel. Os parâmetros de solubilidade tridimensional definidos por Hansen são baseados em forças de dispersão entre as unidades estruturais, interações entre os grupos polares e de ligação de hidrogênio. Estes parâmetros de solubilidade são propriedades importantes de várias substâncias e ferramentas muito úteis para a seleção de seus solventes ou a previsão de seu comportamento em diferentes aplicações. A sua concepção e avaliação baseia-se na regra básica de "similaridade" para solubilidade. Neste trabalho foram determinados os parâmetros de solubilidade de Hansen (?D, ?P e ?H) e raio da esfera de solubilidade do soluto (R0) para os óleos de soja, fritura, palma, coco e mamona; para os biodieseis provenientes desses óleos, diesel e blendas biodiesel-diesel (B10 e B20), usando 45 solventes e misturas de solventes. Os valores dos parâmetros de solubilidade obtidos para os óleos de soja e fritura foram idênticos e similares àqueles obtidos para os óleos de coco e palma. O óleo de mamona apresentou maiores valores ?P e ?H, devido à presença de uma hidroxila em sua estrutura carbônica. O mesmo comportamento foi observado para os biodieseis, ou seja, biodieseis de soja e fritura, com parâmetros de solubilidade idênticos, e similares aos biodieseis de palma e coco; o biodiesel de mamona exibindo valores de ?P e ?H mais elevados entre os biocombustíveis produzidos. Os parâmetros de solubilidade de Hansen de quatro biocombustíveis (soja, palma, coco e mamona) foram obtidos a partir dos valores da média dos parâmetros de solubilidade dos ésteres graxos metílicos, proveniente de cada óleo vegetal, utilizando os métodos de contribuição de grupos. Posteriormente, as solubilidades dos biocombustíveis foram preditas usando abordagens de van Krevelen, Greenhalgh e Bagley. O óleo diesel apresentou menores valores de ?D, ?P e ?H se comparado com os valores obtidos para os biodieseis. Os valores dos parâmetros de solubilidade do diesel, B10 e B20 foram semelhantes, aumentando os valores de acordo com a quantidade (em volume) de biodiesel adicionado ao combustível diesel
Abstract: The search for alternative fuels has been gaining attention in recent decades. The replacement of fossil fuels has been driven by environmental, economic and social factors, since the whole of society is dependent on their usage. In this context, one alternative that has been highlighted is that of biodiesel. Biodiesel represents a renewable, biodegradable, non-inflammable and low toxicity alternative to diesel. The three dimensional solubility parameters defined by Hansen are based on dispersion forces between structural units, interaction between polar groups and hydrogen bonding. These solubility parameters are important properties of the various substances and very useful tools in the selection of their solvents or the prediction of their behavior in different applications. Their design and evaluation are based on the basic rule of "similarity" for solubility. In this work the Hansen solubility parameters (?D, ?P and ?H) and the radii of the solubility spheres of the solutes (R0) were determined for soybean, frying, palm, coconut and castor oils, for the biodiesels obtained from these oils and diesel and the biodiesel-diesel blends (B10 and B20), using 45 solvents and solvent mixtures. The values obtained for the solubility parameters of the soybean and frying oils were identical and similar to those obtained for the coconut and palm oils. Castor oil showed higher ?P and ?H values due to the presence of a hydroxyl in its carbon structure. The same behavior was observed for the biodiesels, i.e. identical solubility parameters for the soybean and frying biodiesels which were similar to the palm and coconut biodiesels, the castor biodiesel showing the highest values for ?P and ?H of the biofuels produced. The Hansen solubility parameters for four biofuels (soybean, palm, coconut and castor) were obtained from the values of the average solubility parameter for the fatty acid methyl esters derived from any vegetable oil, using the group contribution methods. Subsequently, the values for the solubility of the biofuels were predicted using the van Krevelen, Greenhalgh, and Bagley approaches. Diesel presented lower values for ?D, ?P and ?H when compared to the values obtained for the biodiesels. The values of the solubility parameters of diesel, B10 and B20 were similar, the values increasing according to the amount (by volume) of biodiesel added to the diesel fuel
Doutorado
Desenvolvimento de Processos Químicos
Doutor em Engenharia Química

This research was designed to assess the effects of alternate lipid diets on chinook salmon, Oncorhynchus tshawytscha, where canola oil (CO) was used as a vegetable lipid alternative to marine lipid. Diets supplemented with anchovy oil (AO) or CO blended with AO so that CO composed to a maximum of 41% dietary lipid content were fed to juvenile salmon twice daily. The salmon grew to a maximum of 86 grams over the study with no significant effect of diet treatment on fish growth. Similar results were obtained for an array of whole body physiological parameters including feed efficiency, hematocrit, percent muscle water and plasma Na+ and CI- concentrations. Examination of whole body fatty acid composition reflected the respective dietary lipid composition. Salmon were kept in freshwater during the majority of the study and-were periodically challenged to 24 hour seawater transfers. Gill physiology was assessed in response to the transfer and in relation to dietary treatment. Gill Na+/K+-ATPase, a dominant ATP- consuming enzyme present in chloride cells of the fish gill, was used as an indicator of salinity tolerance. Na+/K+-ATPase activity was measured and found not to be significantly different across dietary groups kept in freshwater or between salinity challenged groups. In the gill, two differentially expressed Na+/K+-ATPase isoforms, ala and alb were determined to differ in response to increased environmental salinity. Na+/K+-ATPase αla mRNA expression demonstrated sensitivity to seawater exposure and was down-regulated, while alb mRNA expression increased in response to salinity transfer. At the end of the freshwater phase of the study, salmon were transferred to full strength seawater. At this time, Na+/K+-ATPase physiology was assessed for dietary effects. Na+/K+-ATPase activity did not differ between salmon fed diets based on AO or the maximum amount of CO blended with AO . In response to increasing levels of CO in the diet, Na+/K+-ATPase αla mRNA levels did not change in fish exposed to freshwater or seawater. However, as CO content increased in the diet, Na+/K+-ATPase αlb mRNA decreased in a linear manner. Fish fed a diet containing only marine lipid had higher Na+/K+-ATPase αlb mRNA levels than those of fish ingesting the diet with the higher CO content. These data suggest that cellular fatty acids may play a role in Na+/K+- ATPase αlb expression in salmon held in freshwater. To determine the effect of time and diet on the osmoregulatory capacity o f these fish, Na+/K+-ATPase activity and isoform expression were analyzed using the fish fed with the two most extreme differences in fatty acid composition over 97 days. Na+/K+-ATPase αlb mRNA was found to be more highly expressed in fish fed a marine oil-based diet relative to those fish fed the diet with higher CO content during specific times during development. However, these molecular differences were not translated into detectable physiological differences among juvenile salmon. It is concluded that CO is a viable alternative to marine oils for juvenile chinook salmon provided essential fatty acid requirements of the salmon are met through inclusion of some marine oil.
Science, Faculty of
Zoology, Department of
Graduate

This work presents the use of analytical techniques, conventional and advanced for the chemical characterization of four samples of blends crude oils from the PETROBRAS station, Oiteirinhos II (Carmópolis-SE). These samples, which have different exploration characteristics, were identified as CEOL 1, CEOL 2, CEOL 3 and CEOL 4. After the collection in the field and subsequently separation of water residue through centrifugation at 2500 rpm, the blends were characterized by density, asphaltenes content, fractionation SARA (saturates, aromatics, resins and asphaltenes) and by the application of micropyrolisys off-line. The advanced characterization to elucidate the chemical relationship between the samples were made using the Thermogravimetry (TGA), Infrared Spectroscopy (IR), Spectroscopy in Ultraviolet (UV), Matrix Assisted Laser Desorption Ionization - Time of Flight - Mass Spectrometry (MALDI-TOF-MS), Gas Chromatography Mass Spectrometry (GC/MS), Gas Chromatography with Flame Ionization Detector (GC-FID) and Comprehensive Two-Dimensional Gas Chromatography (GC x GC). The blends CEOL 3 presented the highest density (0.9737 g mL-1), confirming the results of MALDI-TOF-MS, that shows predominantly high molecular mass compounds in the composition. The SARA fractionation indicates the Saturated fraction as the largest fraction in all oils (> 50%). The analysis of TGA explained similar bands of mass loss in all blends and their asphaltenes. The characterization by IR showed bands related to the hydrocarbon composition and the UV showed the presence of mono, di and tri aromatics structures in the blends as well in their respective asphaltenes. The chromatographic analysis (GC/MS, GC-FID and GC x GC) showed that all blends have a paraffinic profile, with the predominance of n-alkanes of low molecular weight (n-C10 to n-C40) and characteristics of oxide depositional environment (Pr/Ph>1) and lacustrine origin (CPI>1). The analysis by GC/MS showed that the distribution area relating to the free n-alkanes in the CEOL 3 blends is approximately 30% lower than the other samples, and that after the micropyrolysis process these areas become approximately the same. For biomarkers, GC/MS was possible to identify the majority presence of tri- and tetracyclic terpanes (m/z 191) and regular steranes (m/z 217) as the major constituents of the blends, pointing also to the release of occluded biomarkers in asphaltenic structures after the micropyrolysis process. The identification and subsequent correlation between biomarkers indicated that the blends crude oils studied have partial biodegradation characteristics, with a blend of mature and immature oils from terrigenous and/or algal organic matter.
Este trabalho apresenta o emprego de diversas técnicas analíticas, convencionais e avançadas, para a caracterização química de quatro blendas de óleos brutos provenientes da estação da Petrobras de Oiteirinhos II (Carmópolis-SE). Estas amostras, que apresentam diferentes características de exploração, foram identificadas como CEOL 1, CEOL 2, CEOL 3 e CEOL 4. Após a coleta em campo e posterior separação dos resíduos de água por centrifugação a 2500 rpm, as blendas foram caracterizados a partir da determinação da densidade, do teor de asfaltenos, fracionamento SARA (Saturados, Aromáticos, Resinas e Asfaltenos) e aplicação da micropirólise off-line. A caracterização avançada, aplicada para elucidar a relação química entre as amostras, foram realizadas utilizando as técnicas de Termogravimetria (TGA), Espectroscopia no Infravermelho (IV), Espectroscopia no Ultravioleta (UV), Espectrometria de Massa por Tempo de voo com Desorção-Ionização a Laser Assistida por Matriz (MALDI-TOF-MS), Cromatografia Gasosa acoplada a Espectrometria de Massas (CG/EM), Cromatografia Gasosa com Detector de Ionização de Chama (CG-DIC) e Cromatografia Gasosa Bidimensional Abrangente (CG x CG). A blenda CEOL 3 apresentou a maior densidade (0,9737 g mL-1) corroborando com os resultados de MALDI-TOF-MS, mostrando a predominância de compostos de alta massa molecular em sua composição. O fracionamento SARA aponta a fração de Saturados como a maior fração em todos as blendas (>50%). A análise de TGA expôs faixas de perdas de massas semelhantes em todas as amostras e seus asfaltenos. A caracterização por IV apresentou estiramentos referentes à composição de hidrocarbonetos e o UV a presença de estruturas mono, di e tri aromáticos tanto nas blendas como em seus respectivos asfaltenos. As análises cromatográficas (CG/EM, CG-DIC e CG x CG) mostraram que todos as blendas possuem um perfil parafínico, com predominância de n-alcanos de baixo peso molecular (n-C10 a n-C40) com características de ambiente deposicional óxido (Pr/Ft>1) de origem lacustre (CPI>1). A análise por CG/EM mostrou ainda que a distribuição em área referente a n-alcanos livres presentes na blenda CEOL 3 é cerca de 30% menor do que as outras amostras, e que após o processo de micropirólise essas áreas passam a ser aproximadamente iguais. Para biomarcadores, por CG/EM foi possível identificar a presença majoritária de terpanos tri e tetracíclicos (m/z 191) e esteranos regulares (m/z 217), como constituintes majoritários das blendas em estudo, apontando ainda, a liberação de biomarcadores ocluídos nas estruturas asfaltênicas após o processo de micropirólise. A identificação e posterior correlação entre os biomarcadores indicaram que as blendas de óleos brutos possuem características de biodegradação parcial, com uma mistura de muito e pouco evoluídos termicamente, provenientes de matéria orgânicas terrígenas e/ou algas.

Um problema importante na produção de filmes ativos utilizando agentes ativos lipofílicos é a dificuldade de dispersão desses agentes na solução formadora de filme (SFF). As nanoemulsões podem ser uma alternativa para dispersar esses compostos na matriz biopolimérica. Os objetivos gerais desta pesquisa foram: 1) Desenvolver nanoemulsões óleo-em-água (O/A), com três agentes ativos na fase óleo, sendo dois antimicrobianos - cinamaldeído e óleo essencial de alho - e um antioxidante - alfa-tocoferol, e caracterizar essas nanoemulsões, inclusive sua estabilidade; e 2) Desenvolver, caracterizar e aplicar filmes ativos à base de gelatina-quitosana (G-Q), ativados com nanoemulsões O/A preparadas nas condições ótimas de processo: N1: α-tocoferol/cinamaldeído; N2: α-tocoferol/óleo essencial de alho; N3: α-tocoferol/cinamaldeído e óleo essencial de alho; e N4: óleo de canola. As nanoemulsões O/A foram preparadas usando um microfluidizador e Tween 20 e Span 60 como emulsificantes, caracterizadas e incorporadas na SFF. Os filmes foram produzidos pela técnica de Casting incorporando 0 ou 5 g agente ativo nanoemulsificado/100 g biopolímero e usando glicerol como plastificante. Os filmes foram caracterizados em termos de propriedades físicas, mecânicas, de permeabilidade ao vapor de água e isotermas de sorção, ópticas, microestruturais, e atividades antimicrobiana e antioxidante. Além disso, um estudo de migração dos agentes ativos em simuladores de alimentos foi realizado. A mortadela fatiada foi embalada em bandejas de poliestireno usando filmes como separador de fatias. Posteriormente, foi avaliada a aceitação sensorial da mortadela e sua vida útil com base em análises físico-químicas e microbiológicas. Os resultados mostraram emulsões O/A com tamanho de gota nanométrico, distribuição monomodal, potencial ζ >-30 mV, alta estabilidade física e eficiência de encapsulação e propriedades ativas. Por outro lado, os filmes ativos não apresentaram diferenças significativas (p>0,05) quanto à espessura, umidade, permeabilidade ao vapor de água e propriedades térmicas. A solubilidade em água, ângulo de contato, transmissão de luz, rigidez e resistência à tração e o brilho dos filmes foram reduzidos (p<0,05), enquanto a deformação na ruptura, opacidade, grau de inchamento, cor e rugosidade da superfície aumentaram consideravelmente (p<0,05) em razão da incorporação das nanoemulsões. Os modelos matemáticos de BET, GAB, Peleg e Oswin descreveram o comportamento de absorção de vapor de água dos filmes. As análises de DSC, FTIR e de difração de raios-X sugeriram compatibilidade entre a gelatina e a quitosana. Uma boa distribuição das nanogotas de óleo que encapsulavam os agentes ativos na matriz biopolimérica foi confirmada pelas análises de MEV e MFA. As nanoemulsões e os filmes ativos foram efetivos contra a Pseudomonas aeruginosa e Listeria monocytogenes e apresentaram atividade antioxidante frente aos radicais DPPH•, ABTS•+ e o reagente FRAP. As cinéticas de migração dos agentes ativos apresentaram comportamento Fickiano, com valores de coeficientes de difusão efetiva (D) entre 10-14 e 10-15 m2/s. Por outro lado, as fatias de mortadela embaladas sem filme foram as mais aceitas sensorialmente. Porém, o filme ativo utilizado ofereceu a maior ação antimicrobiana contra a L. monocytogenes e P. aeruginosa, inicialmente inoculadas na mortadela, além do maior efeito protetor contra bactérias deteriorantes, assim como inibiu a oxidação lipídica por mais tempo (5 dias) durante o estudo de vida útil. Em geral, este estudo evidenciou que os filmes à base de G-Q carregados com agentes ativos nanoemulsificados pode ter potencial como material de embalagem para melhorar a vida útil de alimentos.
A major problem in the production of active films using lipophilic active agents is their poor dispersion in the film-forming solution (FFS). Nanoemulsions may be an alternative to disperse these compounds within the biopolymeric matrix. The main aims of this research were: 1) to develop oil-in-water (O/W) nanoemulsions incorporated with three active agents in the oil phase, two antimicrobials - cinnamaldehyde and garlic essential oil - and one antioxidant - α-tocopherol and characterize those nanoemulsions, even their stability, and 2) Develop, characterize and applicate gelatin-chitosan (G-Ch) based films activated with O/W nanoemulsions prepared under optimal conditions: N1: α-tocopherol/cinnamaldehyde; N2: α-tocopherol/garlic essential oil; N3: α-tocopherol/cinnamaldehyde and garlic essential oil; and N4: canola oil. The O/W nanoemulsions were prepared using a microfluidizer and Tween 20 and Span 60 as emulsifiers, characterized, and then loaded into the FFS. The films were produced by the casting method incorporating 0 or 5 g of nanoemulsified active agent/100 g biopolymer, using glycerol as a plasticizer, and subsequently characterized in terms of their physical, mechanical, water vapor permeability, water sorption, optical, microstructural, antimicrobial and antioxidant properties. In addition, a study of active agent migration into food simulants was performed. The sliced mortadella was packed in polystyrene trays using films as a slice separator. After, a sensorial acceptance evaluation and shelf life study, based on physicochemical and microbiological analyses, were performed for the mortadella sausage. The results showed O/A emulsions with nanometric droplet size, monomodal distribution, ζ potential greater than -30 mV, high physical stability, high encapsulation efficiency, and active properties. On the other hand, the active films presented no significant differences (p>0.05) in terms of thickness, moisture content, water vapor permeability, and thermal properties. The solubility in water, contact angle, light transmission, tensile strength, and brightness of films were reduced (p<0.05), whilst the deformation at break, opacity, degree of swelling, color, and surface roughness considerably increased (p<0.05), due to the incorporation of nanoemulsions. The mathematical models of BET, GAB, Peleg and Oswin described the water vapor absorption behavior of the films. The DSC, FTIR, and x-ray analyses suggested compatibility between the gelatin and chitosan. A good distribution of the oil nanodroplets encapsulating the active agents within the matrix was confirmed by AFM and SEM analyses. The active nanoemulsions and films were effective against Pseudomonas aeruginosa and Listeria monocytogenes, and showed antioxidant activity against the DPPH• and ABTS•+ free radicals, as well as the FRAP reagent. The kinetic migration of the active agents presented a Fickian behavior with values of effective diffusion coefficients (D) between 10-14 and 10-15 m2/s. On the other hand, the mortadella slices packed without films were the most sensorially accepted. However, the active films used offered the greatest effectiveness against L. monocytogenes and P. aeruginosa initially inoculated in the mortadella sausage, and highest protective effect against spoilage bacteria, as well as inhibiting lipid oxidation for longer time (5 days) during the shelf life study. Overall, this study offered clear evidence that G-Ch based films, loaded with nanoemulsified active agents, can have potential as packaging material for enhancing the shelf life of food.

Desde 2008 o óleo diesel comercializado no território nacional tem recebido a adição crescente de biodiesel, além da redução gradativa nos teores de enxofre, que é uma tendência mundial de minimizar o impacto gerado pela queima de combustíveis fósseis. Aspectos relacionados com a qualidade final das misturas diesel com biodiesel, desde a produção até o armazenamento, tem recebido especial atenção. O objetivo desse trabalho foi avaliar a suscetibilidade à contaminação microbiana, durante o armazenamento simulado, do óleo diesel puro e mistura B10 com diferentes teores de enxofre: ULSD (S10), LSD (S50), HSD (S500) e UHSD (S1800). Os resultados dessa pesquisa mostraram que Pseudallescheria boydii apresentou maior habilidade de crescer na mistura B10 que Paecilomyces variotii. As análises de degradação, por espectroscopia no infravermelho, revelaram que os combustíveis avaliados possuem distintas características moleculares de acordo com os teores de enxofre. Os dados de RMN H-1 mostraram que o diesel com maior teor de enxofre (UHSD) apresentou reduzido teor de ramificações e compostos aromáticos comparado ao diesel com menor teor de enxofre (ULSD). O sequenciamento de alto rendimento (Illumina) do rDNA 16 e 18S mostrou que os Filos mais abundantes presentes no inóculo misto ao longo do tempo foram: Proteobacteria, Firmicutes, Bacteroidetes, Actinobacteria, Ascomycota e Basidiomycota. Os prováveis metabólitos identificados por UPLC/Q-ToF - MS, na fase aquosa, foram os ácidos: mirístico, palmítico, esteárico, oleico, linoleico e α-linolênico com abundância relativa de 2-10 vezes superior aos controles, indicando degradação de origem microbiana. Entre os 10 parâmetros avaliados de estabilidade química, somente a estabilidade oxidativa apresentou desconformidade com o Regulamento Técnico ANP e os níveis de contaminação microbiana, ao final de 90 dias, foram considerados aceitáveis. O conjunto de dados sugere que a redução de compostos sulfurados no diesel não induz suscetibilidade à contaminação microbiana, porém fatores como a origem da matéria prima, processo de refino e adição de biodiesel devem ser considerados. Os resultados desses estudos auxiliam na melhor compreensão dos microrganismos e metabólitos envolvidos nos processos de biocorrosão e biodeterioração do diesel e suas misturas visando a qualidade final do combustível.
Since 2008, the diesel fuel sold in the country has received the increasing addition of biodiesel, in addition to the gradual reduction in sulfur content, which is a global trend to minimize the impact generated by burning fossil fuels. Aspects related to the final quality of diesel and biodiesel blends, from production to storage, has received special attention. The aim of this study was to evaluate the susceptibility to microbial contamination during simulated storage, in pure diesel and blend B10 with different sulfur contents: ULSD (S10), LSD (S50), HSD (S500) and UHSD (S1800). The results of this research showed that Pseudallescheria boydii had greater ability to grow in the blend B10 than Paecilomyces variotii. The degradation analysis, infrared spectroscopy, showed that these fuels have different molecular characteristics according to their sulfur content. The data H1 NMR showed that the diesel with higher sulfur content (UHSD) showed a low level of branching and aromatic compounds compared to diesel fuel with lower sulfur content (ULSD). The high throughput sequencing (Illumina) of 16S and 18S rDNA showed the Phyla most abundant present in the mixed inoculum over time were: Proteobacteria, Firmicutes, Bacteroidetes, Actinobacteria, Ascomycota and Basidiomycota. Putative metabolites identified by UPLC / Q-ToF-MS in the water phase were: myristic, palmitic, stearic, oleic, linoleic and α-linolenic acids with relative abundance of 2-10 times higher than controls indicating degradation of microbial origin. Among the 10 evaluated parameters for chemical stability, only oxidative stability showed nonconformity with the ANP Technical Regulation and microbial contamination levels at the end of 90 days were considered acceptable. The data set suggest that the reduction of sulfur compounds in diesel fuel are not induced microbial susceptibility contamination, but factors such as the origin of the raw material, refining process and adding biodiesel to be considered. The results of these studies help to better understand the microorganisms and metabolites involved in the biocorrosion and biodeterioration processes of diesel and their blends aiming at the final quality of the fuel.

This study aims at analysing how African oil benchmarks within the OPEC Reference Basket relative to the WTI and Brent benchmarks which are considered as global pricing benchmarks for the period starting from 1997-2008. The Nigerian Bonny Light and Algerian Saharan blend were the two benchmarks used for this study. A time series analysis was applied to the weekly price data series set and with the aid of a breakpoint unit root test and Cusum of Squared test to determine if there was a change in the persistence of the spread of each African benchmark relative to the global benchmarks. The results for from the unit root test indicated the presence of a structural break in the price spread in 2004 for the Bonny Light benchmark and in 2005 for the Saharan blend relative to both global benchmarks. The Cusum Squared test for the four benchmark pairings indicated a change in persistence of the price spreads. The null hypothesis was rejected for the alternative hypothesis of the price spread process having a relatively high persistence value after a while. The Cusum Test results showed a change in persistence for both African benchmarks relative to the WTI benchmark and no change in persistence relative to the Brent benchmark. The results of from the Time series analysis indicated the competitive nature of African benchmarks relative to global benchmarks and this could benefit exporting countries by virtue of setting up derivative markets. The derivative markets would allow for the trade of benchmark spreads, futures contracts, options and other financial instruments for African oil producers.

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Capes
Apesar de serem muito eficientes, os catalisadores homogêneos utilizados na obtenção de biodiesel apresentam problemas no processo de separação da glicerina, biodiesel e catalisador. Dentre os catalisadores heterogêneos estudados, tem-se verificado a aplicação de Carvão Ativado como suporte catalítico. Porém, não há relatos na literatura acerca da utilização de Carvão Ativado Pilarizado como catalisador no processo de transesterificação. O óleo de mamona apresenta-se com potencialidade na produção de biodiesel, porém sua densidade e viscosidade são muito altas. Uma alternativa encontrada tem sido a utilização de “blends”. Este trabalho teve como objetivo obter biodiesel a partir de “blend” de óleos vegetais (óleo de mamona e óleo de algodão) por meio de catálise heterogênea utilizando carvão ativado pilarizado como catalisador. Os CA’s de TM tiveram rendimentos acima de 25% em todos os tratamentos. Foi constatado caráter ácido dos CA’s, entre 4,0 e 5,0, sendo confirmado com a análise de ácido de Boehm. Na determinação de área BET foram encontrados resultados entre 31,16 mm2/g (T7) e 310,94 mm2/g (T8). Os CA’s apresentaram estrutura hexagonal com formação de túbulos, algumas amostras com canais mais definidos, sulcos celulósicos fibrosos e poros de diferentes tamanhos. No CAP houve diminuição da área superficial e volume dos poros, uma vez que estes se encontram preenchidos pelos pilares de alumínio. A utilização dos blends ajustaram algumas características dos óleos, destacando a diminuição na viscosidade. Para os testes catalíticos foi utilizado o blend F3. A conversão do blend em Ésteres Metílicos de Ácidos Graxos (FAME) variou de 67,04% (T1) e 89,92% (T8). Foi observado que as variáveis de Temperatura e Rotação apresentaram influência significativa na conversão do Blend em Biodiesel. De acordo com os resultados, pode-se concluir que o Carvão Ativado Pilarizado (CAP) mostrou-se eficiente quanto à produção de biodiesel em sistema aberto.
Although they are very efficient, the homogeneous catalysts used to obtain biodiesel present problems in the separation process of glycerine, biodiesel and catalyst. Among the heterogeneous catalysts studied, the application of activated carbon as catalytic support has been verified. However, there are no reports in the literature about the use of Pilarized Activated Charcoal as a catalyst in the transesterification process. Castor oil presents with potential in biodiesel production, but its density and viscosity are very high. An alternative found has been the use of blends. The objective of this work was to obtain biodiesel from vegetable oils blend (castor oil and cottonseed oil) by means of heterogeneous catalysis using activated charcoal pillarized as catalyst. The CAs of TM had yields above 25% in all treatments. It was verified acidic character of CAs, between 4.0 and 5.0, and was confirmed with the analysis of Boehm acid. In the determination of BET area results were found between 31.16 mm2/g (T7) and 310.94 mm2/g (T8). The CA's presented a hexagonal structure with formation of tubules, some samples with more defined channels, fibrous cellulosic grooves and pores of different sizes. In the PAC there was a decrease in the surface area and volume of the pores, since they are filled by the aluminum abutments. The use of the blends adjusted some characteristics of the oils, highlighting the decrease in viscosity. For the catalytic tests the blend F3 was used. The blend conversion to Fatty Acid Methyl Esters (FAME) ranged from 67.04% (T1) and 89.92% (T8). It was observed that the variables of Temperature and Rotation presented a significant influence on the conversion of Blend to Biodiesel. According to the results, it can be concluded that Pilarized Activated Carbon (CAP) was efficient in the production of biodiesel in the open system.

O consumidor está se tornando mais consciente da relação entre alimentação e doenças, o que tem impulsionado as pesquisas na área de alimentos funcionais e seus efeitos no organismo. As gorduras são um importante componente da dieta humana, porém a dieta ocidental apresenta um desequilíbrio quanto ao tipo de gordura consumida. As gorduras saturadas são consumidas em grande quantidade, o que pode provocar doenças cardiovasculares, que atualmente constituem a principal causa de morte no Brasil. O consumo de manteiga, cujo componente mais abundante é a gordura do leite, vem caindo muito pois a gordura do leite é altamente saturada, mas tem sabor muito agradável e é muito apreciada pelo consumidor. Além disso, a margarina surgiu como um substituto que apresenta melhor espalhabilidade à temperatura de refrigeração. Assim, os objetivos do trabalho são: desenvolver uma base gordurosa que utilize a gordura do leite, mantenha as qualidades inerentes da manteiga, mas que apresente maior espalhabilidade e contenha maiores teores de ácidos graxos w-6. Para isso, foi adicionado à gordura do leite o óleo de milho, que apresenta alto teor de ácidos graxos poliinsaturados, e as misturas foram submetidas à interesterificação química. Foram avaliadas as interações que ocorreram nestas misturas binárias antes e depois da reação. As misturas foram analisadas quanto a acidez, composição em ácidos graxos e triacilgliceróis, índices de iodo e saponificação, ponto de amolecimento, consistência, conteúdo de gordura sólida, curvas de solidificação, cinética de cristalização, estrutura cristalina e dimensão fractal. Foi utilizado como catalisador da reação química o metóxido de sódio, em proporção de 0,5%. A reação foi realizada à temperatura de 65 a 70ºC por uma hora. Foram obtidos lipídeos estruturados contendo teores de até 22% de ácidos graxos poliinsaturados w-6 pela adição de até 40% óleo de milho à gordura do leite, que originalmente possuía apenas cerca de 2%. Os coeficientes obtidos para as propriedades de consistência e conteúdo de gordura sólida relativos às interações entre as gorduras foram sempre negativos, demonstrando efeito antagônico, característico de interações monotéticas entre as gorduras. A mistura contendo 70% de gordura do leite e 30% de óleo de milho apresentou plasticidade própria de um spread, propriedade que foi melhorada com a reação de interesterificação. A adição de óleo de milho não provocou mudanças substanciais na estrutura da rede cristalina da gordura do leite, apenas diminuiu a quantidade de gordura cristalizada.
Consumer is becoming increasingly aware of the dependence of human health on proper nutrition, what has impelled researches in the field of functional foods and its effects on human metabolism. Fats are an important component of the diet, but ocidental diet can not be considered balanced as for the type of fat consumed. Saturated fats are consumed in great amounts, what can lead to cardiovascular diseases, the main death cause in Brazil. The consumption of butter, which principal component is milkfat, has been declining due to milkfat’s high degree of saturation, although it has a very pleasant flavor and is very appreciated by consumer. Besides, margarine appeared as a substitute that presents more spreadability at refrigeration temperature. The objective of this study was to develop a blend based on milkfat, that keeps the inherent qualities of butter but presents better spreadability and higher contents of w-6 fatty acids. Milkfat was blended with corn oil, a vegetable oil that contains high levels of polyunsaturated fatty acids, and the blends were submitted to chemical interesterification. The interactions between the two fats before and after interesterification were evaluated. The blends were analyzed as for free fatty acids, fatty acid and triacylglycerol composition, iodine and saponification values, softening point, consistency, solid fat content, crystallization kinetics, crystalline structure, and fractal dimension. Sodium methoxide (0,5% w/w) was used as catalyst for chemical interesterification. The reaction was undertaken at 65-70ºC for one hour. Structured lipids containing up to 22% of polyunsaturated fatty acids were obtained with the addition of up to 40% of corn oil to milkfat, which originally had only about 2%. The coefficients related to the interactions between the two fats were always negative for consistency and solid fat content, revealing an antagonistic effect, characteristic of monotectic interactions between fats. The blend containing 70% of milkfat and 30% of corn oil presented good plasticity for a spread. This property was improved by interesterification. The addition of corn oil did not cause substantial changes on the crystalline structure of milkfat, but only decreased the content of crystallized fat.

Conselho Nacional de Desenvolvimento CientÃfico e TecnolÃgico
As propriedades fÃsico-quÃmicas do Ãster EtÃlico do Ãleo de Mamona (EEOM) foram estimadas a partir de modelos teÃricos e anÃlises experimentais. Por nÃo ser um combustÃvel comercial, o EEOM foi manufaturado por meio de um processo de fabricaÃÃo denominado (Transesterification Double Step Process) TDPS. AtravÃs do mÃtodo de contribuiÃÃo de grupos, as propriedades crÃticas e o ponto de ebuliÃÃo normal foram estimados. Utilizando os valores das propriedades crÃticas e correlaÃÃes matemÃticas, estimaram-se a tensÃo superficial, a entalpia de vaporizaÃÃo, a pressÃo de vapor, a condutividade tÃrmica, a viscosidade e a densidade. A anÃlise experimental do EEOM foi conduzida utilizando tÃcnicas tradicionalmente associadas à pesquisa de densidade e viscosidade de combustÃveis. Na anÃlise experimental de viscosidade utilizou-se um viscosÃmetro copo Ford. TambÃm foram analisadas experimentalmente as misturas ternÃrias do EEOM, etanol e diesel comercial em diversas fraÃÃes volumÃtricas. A anÃlise das misturas ternÃrias vem como uma alternativa para amenizar os valores de viscosidade e densidade do EEOM no combustÃvel de uso final, estimando os valores de fraÃÃes volumÃtricas que podem atender as normas brasileiras e europeias. Os resultados das propriedades fÃsico-quÃmicas servirÃo como base para rotinas computacionais de simulaÃÃo aplicadas ao estudo de emissÃes de poluentes e formaÃÃo do jato combustÃvel para o EEOM.
The physicochemical properties of the Ethyl Ester of Castor Oil (EECO) were estimated from theoretical models and experimental analysis. As it is not a comercial fuel, the EECO has been manufactured by a special fabrication process denominated (Transesterification Double Step Process) TDPS. Through the group contribution method, critical properties and normal boiling point were estimated. Using the values of the critical properties and mathematical correlations, were surface tension, enthalpy vaporization, vapor pressure, thermal conductivity, viscosity and density estimated. The experimental analysis of EEOM was conducted using techniques traditionally associated with research of density and viscosity of fuel. In the experimental analysis of viscosity it was used a Ford cup viscometer. As an alternative to alleviate the values of viscosity and density of the fuel EECO in ultimate use, as well as analyzed mixtures EECO, ethanol and diesel trade in various volume fractions, estimating the values that can meet the Brazilian and European standards. The results of the physical and chemical properties will serve as a basis for computer simulation routines applied to the study of emissions and formation of jet fuel for EECO.

碩士
國立臺灣大學
農業化學研究所
99
The aim of this study is to develop an analytical approach for discriminating sesame oil blended with soybean oil or canola oil. Firstly we established a promising HPLC-ELSD chromatographic condition for the detection of triacylglycerol (TAG) species of oil samples. TAG species of all oil samples were then determined under the conditions. Based on the composition of TAG species of oil samples, three unique peaks assigned as LLnL, OLnL and PLnL which did not appear on the chromatogram of any sesame oil samples represented that the characteristic components of soybean oil could be employed as judging the adulteration of sesame oil with soybean oil. Similarly, the unique components, OLnL and OLnO of canola oil could be used for judging the adulteration of sesame oil with canola oil. Additionally, a statistical method, namely discriminant analysis of principal components (DAPC), using TAG species of oil sample as parameters was employed for qualitative analysis of sesame oil blended with soybean oil or canola oil. The results showed that this statistical method was feasible and promising to judge the adulteration of sesame oils with soybean oils or canola oils.

碩士
國立中興大學
食品暨應用生物科技學系所
105
Owning to the demand of market, blended sesame oil and sesame flavor oil are blended products derived from sesame oil. The ingredients of these products are sesame oil blended with different levels of soybean oil in general. In this study, the antioxidant activity, physiologically active substance, oxidation stability, and fatty acid composition of the blended products were discussed. The gas chromatograph analyses showed that the fatty acid compositions of sesame oil and soybean oil were both similar to each other. Referring to the DPPH radical scavenging activity, ferric reducing antioxidant power, Trolox equivalent antioxidant capacity (TECA), and the levels of sesamin, and sesamolin, sesame oil were found to be have obviously higher values than those of the other oil products blended with soybean oil. In addition, IC50 value indicated that sesame flavor oil performed better in ferric reducing antioxidant power. The p-anisidine values, which represented the oxidation level of sesame oil, blended sesame oil, sesame flavor oil, and soybean oil, were 7.51, 6.19, 5.08, and 3.23, respectively. Our results demonstrated that sesame oil had a higher oxidation level than the other oil samples.

碩士
輔仁大學
食品科學系碩士班
104
Hypercholesterolemia is one of the major risk factors of both cerebrovascular and cardiovascular diseases. Diets with unsaturated fatty acids can decrease blood lipid. Camellia oil is similar to olive oil rich in monounsaturated fatty acids, while soybean oil is rich in linoleic acids and linolenic acids, both of which are vital in maintaining normal physiological function. The objectives of this study were to study the effect of several vegetable oils (camellia oil, soybean oil, palm oil) and blended oil composed of soybean oil and camellia oil on blood lipids reduction and antioxidative activity. A total of 40 five to six week-old male hamsters were used, administered with diet AIN-93G for one week, and then divided into five groups, including control, with the oil contents of control diet and high fat diet (HF) being 5% and 14% with 0.2 % cholesterol ,respectively. After six weeks feeding, hamsters were sacrificed and analyzed. Results showed that hamsters fed with high fat diet can raise serum triglycerides (TG), total cholesterol (TC) and aspartate aminotransferase (AST), but the alanine aminotransferase (ALT) remained unaffected. Diets with unsaturated fatty acids could reduce significantly (p < 0.05) both serum total cholesterol and low-density lipoprotein cholesterol (LDL), along with lower ratio of LDL-C/HDL-C, but increased significantly (p < 0.05) liver total cholesterol. Camellia oil and blended oil failed to reduce HDL-C, whereas soybean oil showed a reversed trend. The higher the degree of oil unsaturation, the lower the activities of fatty acid synthase (FAS), glucose 6- phosphate dehydrogenase (G-6-PDH) and malic enzyme (ME) for soybean oil and blended oil, as well as the level of liver triglyceride. Also, the higher the degree of oil unsaturation, the higher the level of serum TBARs and the lower the antioxidative activity of liver for soybean oil. However, the liver TBARs remained unaffected. Taken together, both camellia oil and blended oil were more efficient in reducing serum lipids in hamsters and TBARs in serum. Soybean oil could inhibit activity of lipogenesis-associated enzyme, and reduce liver lipid. Nevertheless, soybean oil could also reduce liver antioxidative activity.

碩士
國立臺北科技大學
車輛工程系所
94
The brake specific fuel consumption (BSFC) and NOx have been increased by using the pure rapeseed oil methyl ester (ROME), but it can reduce the concentration of smoke and HC effectively without influence on the engine performance. The fuel system, lubrication system, and the piston rings have been caused harmful affections in diesel engine easily for the long-term use of pure ROME. In order to solve these problems, this study blends the different proportion of ROME with premium diesel (PD) to investigate the effect on engine performance, BSFC, exhaust gas emissions and combustion characteristics. Experimental results demonstrated that the blending fuel of 20% ROME with PD (ROME20) and the blending fuel of 50% ROME with PD (ROME50) can maintain equally the engine performance as compared with using the pure ROME. Furthermore, with the blending proportion increased or decreased, the BSFC and the exhaust gas emission can be changed.

We hypothesized that beef patties formulated with the addition of a beef fat, plant oil and rosemary extract (antioxidant) blend would increase unsaturated fatty acid content and maintain desirable sensory attributes as compared to 10 and 20% fat control beef patties. Treatment patties were formulated by combining beef trimmings (6% fat) with a lipid blend mixture (4% or 14% addition, respectively) containing 57% beef tallow, 0.3% rosemary extract and 43% of either high oleic safflower oil (SO), olive oil (OO), or corn oil (CO) to achieve a total fat content of 10 or 20%. Treatment patties were similar to control patties for lipid oxidation at 0 and 3 d of refrigerated (2oC) storage and up to 56 d of frozen (-10oC) storage. Cooked lipid blend patties at 10 or 20% fat content were similar to or higher, respectively, than control patties for juiciness and were no different for other sensory attributes evaluated. At 10 and 20% fat levels, oleic acid (18:1) in cooked SO patties (46.1 and 50.3%, respectively) and OO patties (43.8 and 48.1%, respectively) was higher than the control (37.3 and 37.6%, respectively). Unsaturated to saturated fatty acid ratios at the 10 and 20% fat levels were higher in SO (1.37 and 1.60, respectively) and CO (1.40 and 1.48, respectively) patties than the control (0.97 and 0.94, respectively). The incorporation of nutritionally enhanced lipid blends increased unsaturated fatty acid content and maintained desirable sensory attributes of beef patties while suppressing lipid oxidation.

碩士
國立臺北科技大學
車輛工程系所
95
The oil-bearing rate and heat value for rapeseed oil methyl ester are higher than soybean oil methyl ester and rapeseed methyl ester. Biodiesel that has high oil-bearing rate can cost down as well as high heat value can decrease BSFC. Therefore, Sunflower oil methyl ester is a very worthy of being popularized biodiesel. But for a long term used at diesel engine, engine parts, lubrication and fuel system may cause destruction due to soluable orgnic friction and accumulation of soaps included in biodiesel. Therefore, to use pure biodiesel on diesel engine directly is not proper. So sunflower oil methyl ester used in this study is blended with fossil premium diesel. After engine performance experiment, the experimental results demonstrated that BSFC and the concentration of NOx for 20% sunflower methyl ester blended with premium diesel (SOME20) and 50% sunflower methyl ester blended with premium diesel (SOME50) as compared with pure sunflower oil methyl ester are decreased 7.92%, 8.12% and 4.12%, 4.23%, respectively. But the concentration of Smoke and HC emission is increased 89.52%, 16.75% and 37.75%, 9.58%, respectively. Therefore, the higher proportion of sunflower oil methyl ester blended fuel is used, the more BSFC and the concentration of NOx emission are increased. On the other hand, the more concentrations of Smoke and HC emission are decreased.

碩士
國立臺北科技大學
車輛工程系所
95
Using pure corn oil methyl ester on diesel engine not only maintains engine performance but also reduces the concentration of Smoke more than 50 percent. But for a long term used, functions of the piston ring is destroyed easily, oil and diesel filter as well as injection nozzle may cause plug, even the metal parts rusted due to biodiesel has soluable orgnic friction, accumulation of soaps and impurity included. So biodiesel blended with fossil premium diesel for prolonging diesel engine life time is necessary. In this study, B20 and B50 corn oil methyl ester blended fuels are blended by corn oil methyl ester with fossil premium diesel. After diesel engine performance experiment, experimental results demonstrated that BSFC and the concentration of NOx emission for B20 and B50 are lower than B100 about 8.45%, 7.57% and 3.61%, 5.12%, respectively. For the concentrations of Smoke and HC emission, either increase about 72.57%, 12.62% and 49.11%, 6.69%, respectively. Therefore, the higher proportion of corn oil methyl ester blended fuel is used, the more BSFC and the concentration of Nox emission are increased. On the other hand, the more concentrations of Smoke and HC emission are decreased.

博士
國立臺灣大學
環境工程學研究所
100
In this study, the effects of system parameters on the transesterification yield (YF) of biodiesel from tung (Vernicia fordii) and blended oils with CH3OH and KOH, and on key properties of biodiesel such as acid value (AV), iodine value (IV), kinematic viscosity (KV), density and cold filter plugging point (CFPP) were investigated. The background experimental conditions were as follws. The blended oil is consisted of 20, 50 and 30 wt.% of tung, canola and palm oils, respectively. The molar ratio of methanol to oil (M/O) and KOH catalyst concentration (MC) are 6:1 and 1 wt.%, respectively. Temperature (TR), ultrasonic frequency (fUS) and ultrasonic power (PWUS) were kept at 20 to 30 oC, 20 kHz and 270 W, respectively. The sample volume (VL) was 390 mL. The ultrasonic irradiation time (tUS) was set in the range of 1-30 min. The results showed that YF reaches high value of 87-91% for tung-oil biodiesel as tUS ≥ 5 min, while of about 92-94% for blended-oil biodiesel as tUS ≥ 1 min. At tUS = 10 min, the properties of biodiesel produced from tung oil are with AV of 0.11 mg KOH/g, IV of 159.36 g I2/100 g, KV of 9.17 mm2/s, density of 905 kg/m3 and CFPP of -16 oC, while those from blended oil are with AV of 0.11 mg KOH/g, IV of 120.35 g I2/100 g, KV of 5.54 mm2/s, density of 887 kg/m3 and CFPP of -5 oC. Comparing these values with the ASTM-D6751 standards with AV < 0.5 mg KOH/g, KV = 1.9-6 mm2/s and density = 860-900 kg/m3 points out that the tung oil should be blended with other oils in order to produce biodiesel satisfying the biodiesel standards. Moreover, the results indicated that a certain enough time, say 5 min, is needed to provide sufficient cavity heating and mixing via ultrasonic wave ensuring good properties of biodiesel produced. The KV of biodiesel using blended oil decreases from 6.26 mm2/s at tUS = 1 min to 5.54 mm2/s at tUS = 5 min, thus meeting the ASTM-D6751 value of 1.9-6.0 mm2/s. Effective performances of biodiesels produced from tung oil and blended oil consisting 20, 50 and 30 wt.% of tung, canola and palm oils employing ultrasonic irradiation also were elucidated. The YF and KV, which are essential key indices to tung-oil derived biodiesel, were measured. Appropriate conditions of TR, MC, tUS, settling time (tS) and M/O were identified. The background conditions were PWUS = 270 W, TR = 25 oC, M/O = 6, MC = 1 wt.%, tUS = 5 min and tS = 10 min. The YF increases while the KV beneficially decreases with increasing TR to 60 oC. As MC increases to 2 wt.%, the YF reaches plateau value of 98% for both tung-oil derived biodiesels without and with blending with further reduction of KV. High YF is achieved at short tUS of 5 min using MC of 2 wt.%. Steady sate is approached at tS = 30 min. At MC = 2 wt.%, tUS = 5 min, tS = 30 min and M/O = 6, the YF and KV respectively are 98.33% and 4.26 mm2/s at TR = 25 oC, while are 99.68% and 4.08 mm2/s at TR = 60 oC for the blended-oil biodiesel. Thus, the suitable conditions for the effective production of tung-oil derived biodiesels applying ultrasound irradiation are at: TR = 60 oC, MC = 2 wt.%, M/O = 6, tUS = 5 min and tS = 30 min. However, for the sake of energy-saving, the transesterification condition using TR of 25 oC may be employed, causing only slight reduction of YF of about 1.35% while increase of KV of about 0.18%. The properties of AV, IV and density of the blended-oil biodiesel produced at 25 oC are 0.06 mg KOH/g, 103.52 g I2/100 g and 885 kg/m3, respectively, satisfied with the standards of ASTM-D6751 and EN 14214. The corresponding CFPP of -5 oC, which is lower than 0 oC, also meets the standard of CNS 15072. The beneficial use of tung oil in pre-blended oil for the production of biodiesel was further studied at various blending compositions of tung, canola and palm oils (CBT, CBC and CBP). The effects of MC, CBT, PWUS and VL on the YF and the properties of AV, IV, KV, density and CFPP were investigated. The pre-blending of tung oil with palm oil greatly decreases the CFPP of palm-oil biodiesel, whereas the presence of canola and palm oils with tung oil reduces the IV and KV of tung-oil biodiesel. An MC of 2 wt.% was found to be appropriate. For PWUS/VL = 0.92-2.08 W/mL, CBT can be as high as 60 wt.% with 30 wt.% CBC and 10 wt.% CBP to produce biodiesel with high YF and satisfactory qualities of the said properties. The information obtained in this study is useful for the proper use of tung oil in conjunction with other edible oils for the production of biodiesel with satisfactory qualities and the rational design and operation of ultrasonically catalytic transesterification process.

博士
國立虎尾科技大學
動力機械工程系機械與機電工程博士班
106
In this study, the bio-oils produced by fast pyrolysis and slow pyrolysis were used to investigate the combustion characteristics of droplets of bio-oil blended with butanol fuels The proportion of the bio-oil blended with butanol was 0 vol.% (pure bio-oil), 50 vol.%, 70 vol.%, 90 vol.% and 100 vol.% (pure butanol), respectively. Using a suspended droplet heating device at the same temperature 723K.When the droplets were burned, the droplet combustion behaviors of the bio-oil blended with different butanol ratios were analyzed by high-speed photography synchronous schlieren and chemiluminescence. The surface temperature of the droplets were measured by the infrared thermal imaging camera. The characteristics of fuels were analyzed by using thermo-gravimetric analyzer (TGA) coupled with a fourier-transform infrared spectrometers (FTIR) and the gas chromatography mass spectrometry (GC-MS). The composition of the bio-oil was affected by the pyrolysis characteristics of cellulose, hemicellulose and lignin in the biomass. Therefore, the bio-oil contained more aliphatic compounds, leading to produce aromatic compounds when bio-oil burned. When bio-oil blended with butanol, the polycyclic aromatic hydrocarbons of the soot precursors decreased, the viscosity of mixed bio-oils decreased, and the heat value of mixed bio-oils increased. The weight change of the pure bio-oil in the TGA was observed. The fast pyrolysis bio-oil contained more water and light components (C2-C8) evaporating in low boiling point (<434K). However, the slow pyrolysis bio-oil contained more heavy components (C16-C21) which had relatively high boiling points (>573K). Since the bio-oil belonged to a high concentration of oxygen-containing organic matter, the residues of bio-oil was produced by a polymerization reaction. The residues were continuously heated at a high temperature to generate exothermic reaction. The main functional groups in the thermal evaporation process could be divided into two parts. The first part was O-H, C-H, C=C, and C-O functional groups of the substances produced during the endothermic reaction when the light compounds pyrolysised at low temperature; the second part was the products, CO2 and CO, produced during the exothermic reaction when heavy compounds polymerized and combustion at high temperature. In the thermal decomposition kinetics, high-mixed butanol (10 % bio-oil/90 % butanol, PF10B90) had activation energy (60.61 KJ/mol) from 303K to 412K and activation energy (8.83 KJ/mol) from 723K to 756K, indicating that the release of volatile substances could be improved. The activation energy of the volatile stage in the Bio-oil Blended with Butanol Fuels gradually increased and the activation energy in the combustion stage gradually decreased, which significantly improved the combustion performance of the mixed bio-oils. Fast pyrolysis bio-oil and slow pyrolysis bio-oil both had bubble growth or micro-expansion. Because the slow pyrolysis bio-oil was low volatile, it caused the longer evaporation time of the droplets. The high viscosity inhibits the diffusion of the volatile components to the surface because the surface tension was increased and the mass diffusion of the liquid phase to the gas phase on the surface of the droplet was suppressed. When a high proportion of butanol was mixed, the density of the liquid was lowered. The diffusion rate of the low-density fuel from the high concentration zone to the flame zone was increased, so that the burning time was decreased. In addition, the surface temperature rise time was gradually decreased due to the change of liquid density and the gas diffusion coefficient, which affected the heating time of the droplet surface. The C2* chemiluminescence of the combusted bio-oil droplets surrounded in the flame downstream zone of the droplet, indicated that most of the fuel was reacted here. The radiation intensity of the C2* chemiluminescence was increased, especially in the flame wake zone. This reaction may be the intermediate product and the soot burned. When the butanol blended in bio-oil, the radiation intensity of the C2* chemiluminescence gradually decreased, which indicated that the soot formation was reduced. On the other hand, The Gr number of the bio-oil with butanol increased significantly, because the butanol volatility enhanced the Stefan flux. In this study, higher mixed butanol ratios and producing higher Gr numbers both helped to reduce the formation of the soot tail.

碩士
國立臺北科技大學
車輛工程系所
94
High productivity and low cost biodiesels for the palm oil is especially suitable for diesel engine. But the palm oil has the characteristics of bad fluidity in atmospheric temperature; it has to do the transesterification reaction to be palm oil methyl ester (POME). Therefore, it can be used in the region above 15℃, such as the seasons of summer and autumn in our country. The fuel system, lubrication system and the piston ring have been caused harmful affections in diesel engines for the long-term use of pure POME. In order to improve the poor fluidity of POME fuel, this study blends the different proportion of POME with premium diesel (PD) to investigate the effect on engine performance, brake specific fuel consumption (BSFC), exhaust gas emissions and combustion characteristics in diesel engines. Experimental results demonstrated that the blending fuel of 20% POME with PD (POME20) and the blending fuel of 50% POME with PD can effectively reduce BSFC and the concentration of NOx. However, the concentrations of smoke and HC have been slightly increased as compared with pure POME under full load condition at the highest engine speed.

碩士
國立臺北科技大學
車輛工程系所
94
One of the most attractive alternative biodiesels for diesel engines is palm kernel oil methyl ester (PKME), because it has the higher productivity and the lower cost than the other biodiesels. Moreover, PKME is burned easily due to the short chain carbon molecules, so the concentration of smoke can be improved effectively for diesel engines. The lubrication system, fuel system, and the mechanical parts have been caused harmful affections in diesel engines easily for the long-term use of pure biodiesels. Therefore, this study blends the different proportion of PKME with premium diesel to investigate the effect on engine performance, brake specific fuel consumption (BSFC), exhaust gas emissions and combustion characteristics in diesel engines. Experimental results demonstrated that the blending fuel of 50% PKME with premium diesel (PKME50) can reduce the BSFC and the exhaust gas emissions. However, the engine performance is slightly lower as compared with using PD. The blending fuel of 20% PKME with PD (PKME20) can improve the BSFC and the exhaust gas emission without influence on the engine performance.

碩士
國立臺北科技大學
車輛工程系所
94
The waste fried oil methyl ester (WOME) can improve the concentration of smoke and HC, especially in the concentration of smoke reduction, but the brake specific fuel consumption (BSFC) to compare of premium diesel (PD) has increased. In addition, it has harmful affections on fuel system, lubrication system as well as the piston ring in diesel engines for a long-term use. Therefore, the blending different proportion of WOME with PD can be clarified how much proportion of WOME should be reduced in this study. Experimental results demonstrated that the BSFC and the concentration of exhaust gas emissions has obviously improved in the blending fuel of 50% WOME with PD (WOME50), but the engine performance has reduced. Using the blending fuel of 20% WOME with PD not only reduce the use of amount of WOME, but also the BSFC, exhaust gas emission and combustion characteristics can be improved more reasonable without influence on engine performance.

碩士
國立臺北科技大學
車輛工程系所
96
Edible fried oil, generally named waste fried oil, has been paid a very high attention for the source of biodiesel material in recent years. Due to it not only has the fat of animal and vegetable but also includes the characteristics of high iodine value, acid valence, and the amount of glycerin etc. Moreover, engine life time is affected by these characteristics and its impurities which make the parts of diesel engine and fuel system filth heaped, blocked and corroded easily. So increasing cost on distilled waste fried oil methyl ester can be ameliorated problems. The blended fuels of distilled waste fried oil methyl ester(DWOME) and the waste fried oil methyl ester(WOME) are respectively used in this study. After engine performance experiment, the experimental results demonstrated that BSFC, the concentration of each exhaust gas emissions and EGT for DWOME is worse than WOME, but in order to prolong diesel engine life time, using distilled waste fried oil methyl ester is better choice.

碩士
國立臺北科技大學
車輛工程系所
97
Oil content and heat values of peanut oil methyl ester biodiesel is higher than soybean oil and rapeseed methyl ester biodiesel, therefore, high oil content can cut down the production cost and high values can reduce the fuel consumption, it is the kind of most worth promoting biodiesel. Because of general biodiesel contain dissolved organic matter and the relationship between the saponified matter and other substances on the long-term used in diesel engines will result in engine parts, lubrication and fuel system damage and should not be pure biodiesel directly to the engine. In this study, peanut oil methyl ester biodiesel mix used in the petrochemical super diesel by engine performance test result shows that the engine performance is not affected situation, mixing ratio 20% of PEME20 and mixing ratio 50% of PEME50 for peanut oil methyl ester Health biodiesel blended fuel than pure peanut oil methyl ester biodiesel, it can reduce the fuel consumption rate of 8.2% and 5.67%, NOx emission concentration for 11.05% and 4.42%, but the concentration in the smoke increased by 58.29% and 30.44%, HC emissions for 19.39% and 11.65%. The results indicated that added the peanut oil methyl ester biodiesel mixing ratio is higher, the fuel oil consumption rate and NOx emission concentrations were more and more increasing, otherwise, emission concentration for smoke and HC were more and more reducing.

碩士
國立臺北科技大學
車輛工程系碩士班
91
The study uses blended fuel by adding light naphtha in soybean oil without transesterification. The blended fuel might replace petroleum diesel for increasing the using time limit of petroleum diesel and decreasing vehicle exhaust gas emission and pollution. The experiment proceeded by operating a DI diesel engine of one cylinder. The result of this study indicated the more ratio of light naphtha adding in soybean oil, the more improving in fuel consumption and exhaust gas density value. And although fuel consumption of blended fuel is higher than premium diesel (PD), the less exhaust gas density is emitted. This is because the short period of ignition delay period and the slowly premixed combustion phase. If fuel injection or injection pressure can be adjusted in the future trials, it could be improved more in fuel consumption.

碩士
國立屏東科技大學
環境工程與科學系所
105
This study focuses on the effects on the emissions of persistent organic pollutants (POPs), including polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs), and polybrominated diphenyl ethers (PBDEs) by using multi-components waste cooking oil-based biodiesel blends. The base fuel was traditional diesel (abbreviated as D), while the additives included various fractions of butanol (B), 5% water-containing butanol (B’), acetone (A), 5% water-containing butanol (A’), isopropyl alcohol (I), and waste cooking oil-based biodiesel (W). The fuel blends, B30, B'30, A3, A'3, B30A3, and B'30A'3, were tested at 1.5 and 3.0 kW engine output power to analyze all the aforementioned POPs collected in the engine exhaust. The emission concentrations of four POPs were in the order PBDEs ≫ PBDD/Fs > PCBs > PCDD/Fs, despite using different blending fuels at both engine loads. PBDE had the highest level among the POPs, being equal to 2–3 times to the others. On the other hand, the order of emitted toxicity followed PCDD/Fs > PCBs ≈ PBDD/Fs, while the toxicity of PCDD/F emissions were about 10 times higher than those of PCBs and PBDD/Fs. Among the dioxin compounds, the emissions of PCDDs represented 46–73% (57% in average) and 50–72% (59% in average) of total PCDD/F mass and toxicity concentrations, respectively, and were significantly higher than those of PCDFs. Specifically, the highly chlorinated PCDD/Fs (OCDD, OCDF, 1,2,3,4,6,7,8-HpCDD, and 1,2,3,4,6,7,8-HpCDF) contributed 83% of total PCDD/Fs mass concentration. However, the low-chlorinated PCDD/F congeners played important roles in the toxicity emissions; 2,3,7,8-TeCDD and 1,2,3,7,8-PeCDD dominated the B30A3 and B'30A'3 emissions and 1,2,3,7,8-PeCDD and 2,3,4,7,8-PeCDF were dominant by using the other fuels. The Non-o-PCB contributed almost all toxicity (~100%) of 14 dioxin-like-PCBs, even though its contribution in mass was only 9–32% (16% in average) among the congeners. Specifically, PCB-118, -105 and -77 had the three higher mass contents among the PCB congeners, while PCB-126 dominated 90% of PCB toxicity emissions. A similar case was found in PBDFs, which exhibited ~100% toxicity of PBDD/Fs. Additionally, the mass emissions of PBDEs were mostly provided by deca-BDEs (47.0–90.5%, 82.4% in average), while nona-BDEs and tri- to octa-BDEs were only contributed 10% and 8%, respectively. The reductions of POPs were observed by using various diesel blends in comparison to using W20. The mass reduction amounts (%) of four POPs were in the order PCDD/Fs > PCBs ≈ PBDD/Fs > PBDEs, and the order of toxicity reductions was PCDD/Fs > PCBs > PBDD/Fs. For PCDD/Fs, the mass and toxicity levels of 17 congeners were reduced by using various additives, when the OCDD and OCDF mass emissions showed the most significant improvement. The highest reduction in toxicity was found for 2,3,7,8-TeCDD at 1.5 kW and for 1,2,3,7,8-PeCDD at 3.0 kW. For dioxin-like PCBs, the greatest decreases of mass and toxicities were both observed from PCB-126 (82.1% in mass and 80.0% in toxicity). Consequently, the additive of butanol and acetone, including pure and hydrous mixtures, could further effectively reduce the POP emissions from W20.