Vegetable oil is an important commodity; however, the majority of commercially available vegetable oils have a fairly short shelf life, which limits their usefulness for long term food storage, disaster relief, space travel, food aid programs, and military rations. Vegetable oils with high oleic acid and reduced linolenic acid contents, especially with added antioxidant combinations, were previously found to have significantly longer oil stability index (OSI) values than traditional vegetable oils. This study used accelerated shelf life testing to estimate the ambient shelf life of high oleic sunflower oil (HOSUN) and high oleic canola oil (HOCAN), each containing 1,000 ppm ascorbyl palmitate, 200 ppm tertiary butyl hydroquinone, and 200 ppm mixed tocopherols. Oils were stored in the dark in low density polyethylene (LDPE), or polyethylene terephthalate (PET) bottles at 30, 40, 50, and 60°C. Control samples were stored in the dark in glass bottles at -50°C. Testing included peroxide values, qualitative headspace volatile analysis, descriptive sensory analysis, and consumer sensory acceptance. The estimated shelf life was calculated from the change in overall acceptance score over time using the Q10 method. The stabilized HOCAN in PET bottles was estimated to have a shelf life at ambient temperature of 6.8 years, while oil stored in LDPE bottles had an estimated shelf life of only 2.7 years. The estimated shelf life of HOSUN at room temperature in PET is 2.6 years and in LDPE is 0.88 years.

L’un des défis majeurs dans le domaine des polymères est la substitution des molécules pétro-sourcées en vue de l’élaboration de monomères, polymères et d'additifs pour polymères. Le travail de cette thèse s’axe sur la valorisation de molécules bio-sourcées et plus particulièrement, du cardanol et de dérivés d'huiles végétales. Le champ d’application des polymères étant large, nous avons choisi de nous centrer sur trois grandes problématiques.Dans un premier temps, nous nous sommes intéressés à la plastification du PVC qui, actuellement, est majoritairement réalisée par des phtalates, famille d’esters pétro-sourcés vivement suspectés d’être des perturbateurs endocriniens. Des additifs de substitution ont ainsi été synthétisés par une chimie simple à partir du cardanol et d’esters gras. Des stabilités thermiques et des propriétés plastifiantes très satisfaisantes ont été obtenues. Enfin, des tests de toxicité et d’écotoxicité ont démontré l’absence d'impact perturbateur sur la sécrétion d'hormones sexuelles et la non toxicité vis-à-vis de l'environnement de ces plastifiants bio-sourcés.Dans un second temps, nous avons revisité la chimie des résines phénoplastes habituellement préparées à partir du phénol et du formaldéhyde, deux molécules classées CMR. Nous avons adapté cette chimie robuste à un phénol bio-sourcé, le cardanol, et à un aldéhyde bio-sourcé, le nonanal, pour obtenir des résines phénoliques souples. Cette propriété recherchée est le résultat d’une plastification interne des chaines lipidiques pendantes au sein du réseau polymère. Par cet exemple, l’intérêt des dérivés d’huiles végétales pour l’élaboration de matériaux souples a été démontré. Un compromis entre la souplesse des résines phénoliques et leurs résistances chimique et thermique a été atteint.Enfin, nous nous sommes tournés vers l’élaboration de polyuréthanes réticulés à partir d’un ester gras, d’un diester gras et d’un triglycéride porteurs de fonctions alpha-hydroxycétone (collaboration avec l’équipe CASYEN de l’ICBMS). L’apport de la fonction alpha-cétone sur la réactivité du polyol vis-à-vis du réactif isocyanate n’est que modeste par rapport à des dérivés présentant un groupement alcool isolé sur la chaine (huile de ricin) et alcool associé à une autre fonction alcool (triglycéride 1,2-diol). Néanmoins, la présence d’interactions intramoléculaires provenant des groupements cétone a permis d’exacerber la stabilité thermique des matériaux PU et d’élaborer des PU réticulés souples par plastification interne comme dans le cas des résines phénoliques.Cette thèse a ainsi démontré l’apport des phénols lipidiques tels que le cardanol et des chaines grasses dans l’amélioration de la stabilité thermique et de la souplesse au sein de matériaux polymères. / One of the major challenges in the field of polymers is the substitution of oil-based molecules for the development of monomers, polymers and polymer additives. The topic of this thesis is focused on the valorization of bio-sourced molecules and particularly, cardanol and vegetable oil derivatives. Since the scope of polymers is broad, we have chosen to focus on the following three major issues.At first, we were interested in the plasticization of PVC, which is most often carried out by phthalates, a family of oil-based esters strongly suspected to be endocrine disruptors. Alternative additives were thus synthesized by simple chemical reactions from cardanol and fatty esters. Good thermal stabilities and satisfactory plasticizing properties were obtained. Finally, toxicity and ecotoxicity tests have demonstrated the absence of a disruptive impact on the secretion of sex hormones and the non-toxicity towards the environment of these bio-sourced plasticizers.In a second step, we were interested in the chemistry of phenolic resins usually prepared from phenol and formaldehyde, two molecules classified as CMR substances. Thus, a bio-sourced phenol, cardanol, and a bio-sourced aldehyde, nonanal, were reacted to reach flexible phenolic resins. This peculiar property is the result of internal plasticization of the pendant lipid chains within the polymer network. By this example, the interest of vegetable oil derivatives for the production of flexible materials was demonstrated. Finally, a compromise between the flexibility of phenolic resins and their chemical and thermal resistances was reached.Finally, we turned to the development of crosslinked polyurethanes from a fatty ester, a fatty diester and a triglyceride exhibiting alpha-hydroxyketone functions (collaboration with the CASYEN team of the ICBMS). The contribution of the alpha-ketone function on the reactivity of the related to the isocyanate reagent is only modest compared to isolated alcohol type derivatives (castor oil) and alcohol associated with another alcohol function ( triglyceride 1,2-diol). Nevertheless, the presence of intramolecular interactions from ketone groups made possible to enhance the thermal stability of the PU materials and to develop flexible crosslinked PUs by internal plasticization, as in the case of phenolic resins.This thesis brings out the advantages provided by the use of lipid phenols such as cardanol and fatty chains for the improvement of thermal stability and flexibility of polymer materials.

O transformador de potência é um importante equipamento utilizado no sistema elétrico de potência, responsável por transmitir energia elétrica ou potência elétrica de um circuito a outro e transformar tensões e correntes de um circuito elétrico. O transformador de potência tem ampla aplicação, podendo ser utilizado em subestações de usinas de geração, transmissão e distribuição. Neste sentido, mudanças recentes ocorridas no sistema elétrico brasileiro, causadas principalmente pelo aumento considerável de carga e pelo desenvolvimento tecnológico tem proporcionado a fabricação de um transformador com a aplicação de alta tecnologia, aumentando a confiabilidade deste equipamento e, em paralelo, a redução do seu custo global. Tradicionalmente, os transformadores são fabricados com um sistema de isolação que associa isolantes sólidos e celulose, ambos, imersos em óleo mineral isolante, constituição esta que define um limite à temperatura operacional contínua. No entanto, ao se substituir este sistema de isolação formado por papel celulose e óleo mineral isolante por um sistema de isolação semi- híbrida - aplicação de papel NOMEX e óleo vegetal isolante, a capacidade de carga do transformador pode ser aumentada por suportar maiores temperaturas. Desta forma, o envelhecimento do sistema de isolação poderá ser em longo prazo, significativamente reduzido. Esta técnica de aumentar os limites térmicos do transformador pode eliminar, essencialmente, as restrições térmicas associadas à isolação celulósica, provendo uma solução econômica para aperfeiçoar o uso de transformadores de potência, aumentando a sua confiabilidade operacional. Adicionalmente, à aplicação de sensores de fibra óptica, em substituição aos sensores de imagem térmica no monitoramento das temperaturas internas do transformador, se apresentam como importante opção na definição do equacionamento do comportamento do transformador sob o ponto de vista térmico. / The power transformer is important equipment used in electric power system, which is responsible for transmitting electricity or electric power from one circuit to another, transforms voltage and current in an electrical circuit. Moreover, it has wide application and can be used in substations of power plants, transmission and distribution. Recent changes in the electrical system caused mainly by the considerable increase in load and technological development provided by the manufacture of a transformer with the application of high technology, increasing the reliability of this equipment and, in parallel, reducing their overall cost. Traditionally, transformers are manufactured with a solid insulation system that combines solid insulation and cellulose, both immersed in oil, this constitution which limits the continuous operating temperature. However, when replacing this insulation system consisting of paper and cellulose insulating oil by a hybrid system consisting - application paper NOMEX and vegetable oil, the capacity of the transformer can be substantially increased. Thus, the aging of the insulation system may be at long term, significantly reduced. This technique of increasing the thermal limits of the equipment can essentially eliminate thermal constraints associated with conventional insulation, providing an economical solution for the optimization of power transformers, increasing their operational reliability. Additionally, the application of fiber-optic sensors, replacing the thermal imaging sensors to monitor the internal temperature of the transformer is presented as an important option in the definition of the equation of transformer behavior under the thermal point of view.

Made available in DSpace on 2017-07-25T19:30:01Z (GMT). No. of bitstreams: 1 ANDRESSAANDRADEESILVA.pdf: 600806 bytes, checksum: 32dffc5e0a618b7e0c7a7056f1218c40 (MD5) Previous issue date: 2011-08-31 / The influence of the application of fresh cow's milk to control powdery mildew (Erysiphe polygoni) in the bean crop in combination with fungicide and adjuvant. The experiment was conducted at the Farm School “Capão da Onça”, owned by the “Universidade Estadual de Ponta Grossa, in Ponta Grossa – Paraná. The experimental design was randomized blocks in factorial scheme 4 (milk doses: 0, 20, 35, 50 L ha-1) x 2 (presence or absence of fungicide azoxystrobin + cyproconazol) x 3 (no oil, mineral oil, vegetable oil) and four replications. The fungicide treatments azoxystrobin + cyproconazol (60 + 24 g ia ha-1) were applied at 24, 31, 41, 48 and 57 days after emergence (DAE). The assessments were started when the first symptoms of the disease appeared, at 45 DAE at the beginning of flowering, stage R5, with approximately 12 trefoil and then at intervals of seven days. Diagrammatic scale was used, analyzing 10 trefoil per plot, randomly selected of the central lines. The harvest was carried out in four rows of 2.5 m per plot to assess yield. The data of severity, area under the disease progress curve (AUDPC) and yield were subjected to analysis of variance and the means were significant when compared by the Tukey test at 5% probability. All treatments with milk proved to be superior to the control with no significant differences between the milk doses. Both in the presence and absence of fungicide, the AUDPC was lower compared with treatments without application of milk. The adjuvant vegetable oil had lower AUDPC values in the absence of milk. We observed the highest yields in the presence of fungicide with mineral oil adjuvant, considering the interaction between the fungicide and adjuvant factors. The use of milk to control powdery mildew in beans is economically and agriculturally viable, with no difference in disease control according to the dose of milk. / O objetivo do trabalho foi avaliar a influência da aplicação do leite de vaca in natura no controle do oídio (Erysiphe polygoni) na cultura do feijão (Phaseolus vulgaris). O presente experimento foi conduzido na Fazenda Escola Capão da Onça, pertencente à Universidade Estadual de Ponta Grossa, no município de Ponta Grossa – Paraná, o delineamento experimental utilizado foi de blocos casualizados, no esquema fatorial 4 (doses de leite: 0, 20, 35, 50 L ha-1) x 2 (presença ou ausência de fungicida azoxystrobin+cyproconazol) x 3 (sem óleo, óleo mineral, óleo vegetal) e quatro repetições. Os tratamentos com presença de fungicida azoxystrobin + cyproconazol (60 + 24 g i.a. ha-1) foram aplicados aos 24, 31, 41, 48 e 57 dias após a emergência (DAE). As avaliações foram iniciadas quando apareceram os primeiros sintomas da doença, aos 45 (DAE), no início da floração, estádio R5, com aproximadamente 12 trifólios e posteriormente em intervalos médios de 7 dias, analisou-se 10 trifólios por parcela, escolhidos aleatoriamente, nas linhas centrais das parcelas. Para avaliações de rendimento, foram colhidas quatro linhas de 2,5 m, por parcela. Os dados de severidade, área abaixo da curva de progresso da doença (AACPD) e rendimento foram submetidos à análise de variância e as médias quando significativas foram comparadas pelo teste de Tukey a 5% de probabilidade. Todos os tratamentos com leite mostraram-se superiores à testemunha e sem diferenças estatísticas entre si. Tanto na presença como na ausência de fungicida, a AACPD foi menor em comparação com os tratamentos sem aplicação de leite. O adjuvante óleo vegetal apresentou menores valores de AACPD, na ausência de leite. Observaram-se os maiores rendimentos na presença de fungicida com adjuvante óleo mineral, considerando a interação entre os fatores fungicida e adjuvante. A utilização do leite para controle do oídio do feijão é economicamente e agronomicamente viável, não havendo diferença no controle da doença conforme as doses de leite.

O transformador de potência é um importante equipamento utilizado no sistema elétrico de potência, responsável por transmitir energia elétrica ou potência elétrica de um circuito a outro e transformar tensões e correntes de um circuito elétrico. O transformador de potência tem ampla aplicação, podendo ser utilizado em subestações de usinas de geração, transmissão e distribuição. Neste sentido, mudanças recentes ocorridas no sistema elétrico brasileiro, causadas principalmente pelo aumento considerável de carga e pelo desenvolvimento tecnológico tem proporcionado a fabricação de um transformador com a aplicação de alta tecnologia, aumentando a confiabilidade deste equipamento e, em paralelo, a redução do seu custo global. Tradicionalmente, os transformadores são fabricados com um sistema de isolação que associa isolantes sólidos e celulose, ambos, imersos em óleo mineral isolante, constituição esta que define um limite à temperatura operacional contínua. No entanto, ao se substituir este sistema de isolação formado por papel celulose e óleo mineral isolante por um sistema de isolação semi- híbrida - aplicação de papel NOMEX e óleo vegetal isolante, a capacidade de carga do transformador pode ser aumentada por suportar maiores temperaturas. Desta forma, o envelhecimento do sistema de isolação poderá ser em longo prazo, significativamente reduzido. Esta técnica de aumentar os limites térmicos do transformador pode eliminar, essencialmente, as restrições térmicas associadas à isolação celulósica, provendo uma solução econômica para aperfeiçoar o uso de transformadores de potência, aumentando a sua confiabilidade operacional. Adicionalmente, à aplicação de sensores de fibra óptica, em substituição aos sensores de imagem térmica no monitoramento das temperaturas internas do transformador, se apresentam como importante opção na definição do equacionamento do comportamento do transformador sob o ponto de vista térmico. / The power transformer is important equipment used in electric power system, which is responsible for transmitting electricity or electric power from one circuit to another, transforms voltage and current in an electrical circuit. Moreover, it has wide application and can be used in substations of power plants, transmission and distribution. Recent changes in the electrical system caused mainly by the considerable increase in load and technological development provided by the manufacture of a transformer with the application of high technology, increasing the reliability of this equipment and, in parallel, reducing their overall cost. Traditionally, transformers are manufactured with a solid insulation system that combines solid insulation and cellulose, both immersed in oil, this constitution which limits the continuous operating temperature. However, when replacing this insulation system consisting of paper and cellulose insulating oil by a hybrid system consisting - application paper NOMEX and vegetable oil, the capacity of the transformer can be substantially increased. Thus, the aging of the insulation system may be at long term, significantly reduced. This technique of increasing the thermal limits of the equipment can essentially eliminate thermal constraints associated with conventional insulation, providing an economical solution for the optimization of power transformers, increasing their operational reliability. Additionally, the application of fiber-optic sensors, replacing the thermal imaging sensors to monitor the internal temperature of the transformer is presented as an important option in the definition of the equation of transformer behavior under the thermal point of view.

Les aldéhydes sont des produits chimiques importants dans la synthèse organique, en raison de leurs vastes applications dans les cosmétiques, les produits pharmaceutiques et les herbicides. De plus, ils peuvent être convertis en composés à valeur ajoutée tels que des tensioactifs, des polymères, etc. Classiquement, les aldéhydes sont produits par hydroformylation ou ozonolyse réductrice des alcènes. Cependant, les deux méthodes souffrent de l'utilisation de catalyseurs coûteux et de ligands sophistiqués (hydroformylation) ou de la nécessité d'un procédé à forte intensité énergétique (ozonolyse). En conséquence, le développement d'approches plus durables pour la production d'aldéhydes est hautement souhaitable.Dans ce contexte, nous avons développé deux méthodes pour produire des aldéhydes à partir de dérivés d’acides gras insaturés. La première voie consiste à préparer des a-hydroxycétones grasses à partir de 1,2-diols et les couper pour obtenir des aldéhydes avec de bons rendements. Dans cette voie, deux systèmes catalytiques (homogènes et hétérogènes à base de métaux) ont été développés pour oxyder les diols vicinaux en a-hydroxycétones correspondantes. La coupure de ces espèces a été effectuée par un procédé de rétro-benzoin utilisant des sels de thiazolium thermiquement stables et les aldéhydes ont été récupérés par distillation réactive. La seconde voie repose sur la décomposition des ß-hydroxy hydroperoxydes gras facilement préparés à partir d'oléate de méthyle époxydé. De plus, la décomposition de l'espèce peroxyde a été étudiée dans des conditions thermiques pour donner des aldéhydes. Enfin, la coupure des 1,2-dicétones gras et la valorisation des aldéhydes ont également été étudiés pour conduire aux esters correspondants pouvant être utilisés comme monomères / Aldehydes are important chemicals in organic synthesis, due to their vast applications in cosmetics, pharmaceuticals and herbicides. Moreover, they can be converted to value-added compounds such as surfactants, polymers, etc. Conventionally, aldehydes are produced through hydroformylation or reductive ozonolysis of alkenes. However, both methods suffer from the use of expensive catalyst and sophisticated ligands (hydroformylation) or the requirement of high energy intensive process (ozonolysis). As a result, the development of more sustainable approaches for the production of aldehydes is highly desirable.In this context, we have developed two methods to produce aldehydes from unsaturated fatty acid derivatives. The first route involves the preparation of fatty a-hydroxyketones from 1,2-diols and their cleavage to give aldehydes with good yields. In this route, two catalytic systems (metal-based homogeneous and heterogeneous) have been developed to oxidize vicinal diols to corresponding a-hydroxyketones. The cleavage of these species has been carried out through a retro-benzoin process using thermally stable thiazolium salts and the aldehydes were recovered by reactive distillation. The second route relies on the decomposition of fatty ß-hydroxy hydroperoxides that are easily prepared from epoxidized methyl oleate. Moreover, the decomposition of the peroxide species was studied under thermal conditions to give aldehydes. Finally, the cleavage of fatty 1,2-diketones and the valorization of aldehydes were also studied to give the corresponding esters that could be used as monomers

Ces dernières années, l’intérêt croissant porté aux considérations environnementales et à la sécurité des procédés pose la question de l’utilisation de solvants pétrochimiques nocifs non renouvelables tels que l’hexane, mais aussi de la quantité d’énergie investie dans le procédé de trituration des graines oléagineuses. L’objectif de cette thèse a donc consisté en la recherche et le développement de procédés d’éco-extraction d’huile végétale, issue de graines oléagineuses, grâce à des technologies innovantes (ultrasons et micro-ondes) et des solvants alternatifs plus respectueux de la santé et de l’environnement. La première partie de ce manuscrit propose en premier lieu l’optimisation du procédé d’extraction à l’hexane d’huile de colza à partir d’écailles de pression avec des ultrasons. Bien que ceux-ci aient un impact positif sur les rendements, le temps d’extraction et la consommation de solvant, l’utilisation de l’hexane reste problématique. Dans une deuxième partie, la substitution de l’hexane par des solvants alternatifs plus « verts » a donc été considérée. Une première approche expérimentale a été complétée par une approche prédictive grâce à l’utilisation d’outils d’aide à la décision : les paramètres de solubilité de Hansen et le modèle COSMO-RS. Cette démarche a conduit à la sélection d’un solvant, le 2-méthyltétrahydrofurane, pour la réalisation d’une étude complète allant de l’échelle laboratoire à l’échelle pilote. Dans une troisième et dernière partie, la combinaison de solvants alternatifs avec une technique innovante, les micro-ondes, pour l’extraction d’huile colza à partir d’écailles de pression a été envisagée. Cette étude a mis en évidence l’intérêt des micro-ondes dans le cas d’une sélectivité de chauffage entre la biomasse et le solvant. / In recent years, the growing interest in environmental considerations and process safety raises the issue of the use of non-renewable petrochemical harmful solvents such as hexane, but also the amount of energy invested in the process of oilseed crushing. The objective of this thesis has consisted in the research and development of green extraction processes of vegetable oil from oil seeds through innovative technologies (ultrasonic and microwave) and alternative solvents more respectful of health and environment. The first part of this manuscript describes the optimization with ultrasound of the extraction process, using hexane, of oil from rapeseed cake. Although ultrasound have a positive impact on extraction yield, extraction time and solvent consumption, the use of hexane remains questionable. In the second part, substituting hexane by "green" alternative solvents has been considered. A first experimental approach was supplemented by a predictive approach through the use of decision tools: Hansen solubility parameters and COSMO-RS model. This led to the selection of a solvent, 2-methyltetrahydrofuran, for conducting a comprehensive study from laboratory to pilot scale. In a third and final part, the combination of alternative solvents with an innovative technology, microwaves, for the extraction of oil from rapeseed cake was investigated. This study highlighted the benefit of microwaves in the case of a selective heating between biomass and solvent.

In the introduction this thesis brings a short summary of the energy, environmental and economical balance, related to the production and use of conventional fuels for diesel engines, and compares them with possibility of using recycled cooking vegetable oils as a fuel. The main part focuses on the laboratory analysis of major physical and chemical properties of this alternative fuel and on their comparison to diesel fuel, especially according to ČSN EN 590 norm. In conclusion there is a proposal of diesel vehicle modification to be propelled with waste vegetable oils.

This diploma thesis with resolution of technical and partially economical project of combustion exchanger of cogeneration unit for application of absorbing cooling. Considered types of exchangers are: combustions/water and combustions/steam. The other capitols include the description of cogeneration, trigeneration and other possible resolutions of intersections among mentioned systems; general overview of plant oils used as a fuel in energetics, particularly in compression engines in technology of combined production of electricity and heat.

No description available.