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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
11

Transesterificação química e enzimática de miscela etanólica de óleo de soja / Chemical and enzymatic transesterification of soybean oil ethanolic miscellae

Naiane Sangaletti 11 May 2012 (has links)
A matéria-prima na produção de biodiesel corresponde a mais que 70% do seu custo e o estudo de viabilidade tecnológica e econômica das diferentes matérias-primas se reveste de enorme importância. A extração do óleo de soja com solvente etanol resulta em duas miscelas, uma rica em óleo (miscela rica) e outra rica em etanol (miscela pobre). A miscela pobre pode ser reutilizada no processo de extração e a miscela rica pode ser utilizada diretamente sem a necessidade de dessolventização e de etapas de refino. A miscela rica em óleo foi esterificada por dois processos diferentes: químico e enzimático, com diferentes concentrações em razão molar (óleo:etanol), diferentes temperaturas e catalisadores básico (NaOH) ou enzimático (Novozym®435), buscando o maior rendimento em ésteres etilícos. O objetivo desse estudo foi avaliar o rendimento de ésteres etílicos aplicando enzimas imobilizadas Novozym®435 e um catalisador básico (NaOH) e analisar a viabilidade energética da produção de biodiesel a partir da transesterificação da miscela rica (óleo:etanol) em óleo de soja, sem necessidade de refino do óleo. Foi adotado o planejamento experimental e análise de superfícies de resposta para a seleção das melhores condições de processo, tendo como variáveis respostas o rendimento e a qualidade do biodiesel. Foram realizados ensaios de esterificação via enzimática e química. A reutilização da enzima foi estudada através da lavagem com diferentes solventes (etanol 96%, isopropanol e terc-butanol) e reações de transesterificação na presença do co-solvente terc-butanol. A produção de ésteres em miscelas permitiu a comparação dos custos entre o processo de catálise enzimática e catálise química com base na análise dos fluxos de materiais e energia. A miscela rica foi obtida após três banhos com miscela pobre e um último banho com etanol 99% (v/v), apresentando eficiência de 83% e um teor de óleo residual no farelo de 4,2%. Em sua composição, a miscela rica apresentou 90% em óleo de soja e até 7% de etanol. A transesterificação de miscela rica com catalisador NaOH foi otimizada e apresentou rendimento de ésteres etílicos (RE) 97,2% nas condições experimentais de: razão molar 1:12, concentração de catalisador 0,67% e temperatura de 30ºC. Na transesterificação enzimática, o rendimento máximo foi de 85% nas condições reacionais de razão molar 1:4,5, concentração de catalisador 9,5% e temperatura de 40ºC. A Novozym®435 não foi recuperada com sucessivas lavagens dos solventes. Entretanto, o terc-butanol como co-solvente aumentou o rendimento de ésteres para 94%. A análise dos fluxos de energia demonstrou que o a obtenção da matéria-prima (laminação e extração) foi a etapa que mais demandou energia. A produção de miscela rica em escala semi-piloto demandou mais energia que a de óleo refinado, porém, a etapa de transesterificação a partir de miscela rica, utilizando o catalisador químico, demandou menos energia comparada ao processo com catalisador enzimático e o convencional com metanol e etanol. A esterificação de miscela rica é energeticamente viável, entretanto, com um scale up adequado, a etapa de extração com etanol deve ser ajustada para viabilizar energeticamente a cadeia de produção de biodiesel por esta via alternativa. / The feedstock for biodiesel production represents more than 70% of the cost and technological and economic feasibility studies of different oil sources are of enormous importance. The extraction of soybean oil with ethanol solvent results in two miscella, one rich in oil (rich miscellae) and another rich in ethanol (poor miscellae). The poor miscellae can be reused in the extraction process and the rich miscellae can be used directly without dessolventizing and refining stages. The oil rich miscellae was esterified by two different processes: chemical and enzymatic, with different concentrations in the molar ratio (oil: ethanol), different temperatures and either basic catalyst (NaOH) or an enzyme (Novozym®435), searching for the highest production of ethyl esters. The study goal was to prove the feasibility of producing biodiesel from the transesterification of rich miscellae (oilethanol) in soybean oil, without oil refining and evaluating the performance of ethyl esters by applying immobilized enzymes Novozym®435 and a basic catalyst (NaOH). We adopted the experimental design and the surface response methodology for the best selection of process conditions, with the response variables the yield and the quality of biodiesel. Chemical and enzymatic esterification trials were conducted. The reuse of enzyme was studied by washing with different solvents (96% ethanol, isopropanol and tert-butanol) and the transesterification reaction in the presence of the co-solvent tert-butanol. The production of esters by enzymes in the miscellae allowed a comparison of the costs between the enzymatic and chemical catalysis process based on the energy flow analysis. The rich miscellae was obtained after three baths employing the poor miscellae and a last fourth bath with ethanol 99% (v/v), presenting efficiency of 83% and a residual meal oil content of 4.2%. In its composition, the rich miscellae showed 90% of soybean oil and up to 7% ethanol. The transesterification of the rich miscellae with NaOH catalyst was optimized and had a ethyl esters yield (RE) of 97.2% under the experimental conditions of: 1:12 molar ratio, catalyst concentration 0.67% and temperature 30° C. For the enzymatic transesterification, the maximum yield was 85% for the reaction conditions: molar ratio 1:4.5, catalyst concentration 9.5% and temperature 40° C. Novozym®435 was not recovered with successive washes of the solvents. However, the tertbutanol as a co-solvent increased the yield of esters to 94%. The energy flow analysis showed that obtaining the raw material (flaking and extraction) was the most energy demanding. The rich miscellae from the semi-pilot plant demanded more energy than the refined oil, however, the transesterification of the rich miscellae using chemical catalyst, required less energy compared to the enzymatic catalysis and the conventional process methanol and ethanol. The esterification of rich miscellae is feasible energetically, however, the extraction step with ethanol should be adjusted to enable energetically the chain of biodiesel production.
12

Anwendungen der Headspace-Festphasenmikroextraktion in der forensischen Analytik unter besonderer Berücksichtigung der Haaranalyse

Sporkert, Frank 07 December 2001 (has links)
In der vorliegenden Arbeit wurden Einsatzmöglichkeiten der Headspace-Festpahsenmikroextraktion (HS-SPME) in Kombination mit der GC-MS für forensische und toxikologische Fragestellungen, insbesondere in der Haaranalytik, untersucht. Für basenstabile Drogen- und Medikamentenwirkstoffe wurden Nachweismethoden nach alkalischer Hydrolyse der Haare mit Natriumhydroxid und anschließender HS-SPME entwickelt. Für das Lokalanaesthetikum Lidocain und für das Heroinsubstitutionsmittel Methadon wurden optimierte Verfahren auf Haarproben von Drogentodesfällen angewandt. Um die Einsatzmöglichkeiten der HS-SPME gerade für Wirkstoffmetaboliten zu erweitern, wurden drei Derivatisierungsmöglichkeiten überprüft: (i) Umsetzung von primären und sekundären Aminen im alkalischen Haarhydrolysat mit Alkylchloroformiaten zu Carbamaten ("in sample" Derivatisierung), (ii) "On Fiber" Derivatisierung primärer und sekundärer Amine nach erfolgter HS-SPME mit N-Methyl-bis-trifluoracetamid (MBTFA) sowie (iii) Reaktion von Monofluoressigsäure mit 1-Pyrenyldiazomethan (PDAM) an einer vorher mit dem Derivatisierungsreagenz benetzten SPME-Faser. Fettsäureethylester konnten nach einer Flüssigextraktion der Haare von Alkoholikern mit einem DMSO/n-Hexan-Gemisch extrahiert und nach optimierter HS-SPME nachgewiesen werden. Im Vergleich zu Haarproben von Abstinenzlern und Gelegenheitstrinkern ergaben sich deutliche Unterschiede in den Konzentrationen. Für die schnelle Bestimmung von Valproinsäure und Trichlorethanol wurde eine Quantifizierungsmethode aus Blut- und Urinproben erarbeitet. Die Anwendung der HS-SPME ermöglichte eine schnelle, einfache und lösungsmittelfreie Extraktion bei geringem Probenverbrauch. Sie führte zu sauberen Extrakten und für dieses Verfahren hohen absoluten Extraktionsausbeuten. Bessere Reproduzierbarkeiten, ein hoher Probendurchsatz und eine verlängerte Einsetzbarkeit der SPME-Faser wurden durch die Verwendung eines automatischen Probengebers erreicht. / In the presented thesis possible fields of applications of the headspace solid-phase microextraction (HS-SPME) in combination with gas chromatography-mass spectrometry (GC-MS) for forensic and toxicological problems were investigated with special focus on hair analysis. Detection methods after alkaline hydrolysis of hair with sodium hydroxid and following HS-SPME were developed for basic stable drugs. For the local anaesthetic lidocaine and for the heroine substitute methadone optimized methods were applied to hair of drug fatalities. In order to enhance the fields of application of the HS-SPME especially for drug metabolites three derivatization procedures were tested: (i) conversion of primary and secondary amines in the alkaline hair extract with alkylchloroformates to carbamates ("in sample" derivatization), (ii) "on fibre" derivatization of primary and secondary amines after HS-SPME with N-methyl-bis-trifluoroacetamide (MBTFA) and (iii) reaction of monofluoroacetic acid (compound 1080) with 1-pyrenyldiazomethane (PDAM) on a SPME-fibre previously occupied with the derivatization reagent. Fatty acid ethyl ester (FAEE) could detected after liquid extraction from hair of alcoholics with a mixture of DMSO/n-hexane and optimized HS-SPME. In comparison to hair samples of teetotalers and social drinkers significant differences in the concentrations of the FAEE were found. A quantification method were developed for the fast determination of valproic acid and trichloroethanol from blood and urine. The application of HS-SPME allows a fast, simple and solvent free extraction from a small sample amount. HS-SPME lead to clean extracts and high absolute extraction yields for this kind of extraction. Better reproducibilities, a high sample throughput and extended lifetime of the SPME-fibre were obtained using an automatic sampler.
13

Desempenho de motor Ciclo diesel em bancada dinamométrica utilizando Biodiesel etílico de soja / Performance of engine cycle diesel in dynamométer using mixtures diesel/biodiesel

Castellanelli, Márcio 27 July 2006 (has links)
Made available in DSpace on 2017-07-10T19:25:07Z (GMT). No. of bitstreams: 1 Marcio Castellanelli.pdf: 1580041 bytes, checksum: b88f98c62541a81dbb056e3bbb1905a3 (MD5) Previous issue date: 2006-07-27 / Ahead of the forecast of scarcity of the oil, the ethyl ester (biodiesel) if has presented as an excellent alternative fuel option for engines cycle diesel. The characteristics of biodiesel are similar of diesel in terms of viscosity and the calorific power, being able to be used without adaptations in the engines. For accomplishment of this work, a motor cycle was used diesel, of direct injection with four cylinders, without adaptations. The engine was connected to a dynamometer and systems of acquisition of data auxiliary for the register of the necessary data. The performances of torque, power and brake specific fuel consumption for the following mixtures had been evaluated: B2, B5, B10, B20, B50, B75 and B100. The best registered performance was given with the B20 mixture. / Diante da previsão de escassez do petróleo, o éster etílico (biodiesel) tem se apresentado como uma excelente opção de combustível alternativo para motores ciclo diesel. As características do biodiesel são semelhantes as do diesel em termos de viscosidade e poder calorífico, podendo ser utilizado sem adaptações nos motores. Para realização deste trabalho, utilizou-se um motor ciclo diesel, de injeção direta com quatro cilindros, sem adaptações. O motor foi acoplado a um dinamômetro e sistemas de aquisição de dados auxiliares para o registro dos dados necessários. Avaliaram-se os desempenhos de torque, potência e consumo específico de combustível para as seguintes misturas: B2, B5, B10, B20, B50, B75 e B100. O melhor desempenho registrado deu-se com a mistura B20.
14

Desempenho de motor Ciclo diesel em bancada dinamométrica utilizando Biodiesel etílico de soja / Performance of engine cycle diesel in dynamométer using mixtures diesel/biodiesel

Castellanelli, Márcio 27 July 2006 (has links)
Made available in DSpace on 2017-05-12T14:48:30Z (GMT). No. of bitstreams: 1 Marcio Castellanelli.pdf: 1580041 bytes, checksum: b88f98c62541a81dbb056e3bbb1905a3 (MD5) Previous issue date: 2006-07-27 / Ahead of the forecast of scarcity of the oil, the ethyl ester (biodiesel) if has presented as an excellent alternative fuel option for engines cycle diesel. The characteristics of biodiesel are similar of diesel in terms of viscosity and the calorific power, being able to be used without adaptations in the engines. For accomplishment of this work, a motor cycle was used diesel, of direct injection with four cylinders, without adaptations. The engine was connected to a dynamometer and systems of acquisition of data auxiliary for the register of the necessary data. The performances of torque, power and brake specific fuel consumption for the following mixtures had been evaluated: B2, B5, B10, B20, B50, B75 and B100. The best registered performance was given with the B20 mixture. / Diante da previsão de escassez do petróleo, o éster etílico (biodiesel) tem se apresentado como uma excelente opção de combustível alternativo para motores ciclo diesel. As características do biodiesel são semelhantes as do diesel em termos de viscosidade e poder calorífico, podendo ser utilizado sem adaptações nos motores. Para realização deste trabalho, utilizou-se um motor ciclo diesel, de injeção direta com quatro cilindros, sem adaptações. O motor foi acoplado a um dinamômetro e sistemas de aquisição de dados auxiliares para o registro dos dados necessários. Avaliaram-se os desempenhos de torque, potência e consumo específico de combustível para as seguintes misturas: B2, B5, B10, B20, B50, B75 e B100. O melhor desempenho registrado deu-se com a mistura B20.
15

Synthesis And Electrochromic Properties Of Conducting Polymers Of Succinic Acid Bis-(2-thiophen-3-yl-ethyl)ester And Their Use In Electrochromic Devices

Sacan, Lale 01 June 2006 (has links) (PDF)
ABSTRACT SYNTHESIS AND ELECTROCHROMIC PROPERTIES OF CONDUCTING POLYMERS OF SUCCINIC ACID BIS-(2-THIOPHEN-3-YL-ETHYL) ESTER AND THEIR USE IN ELECTROCHROMIC DEVICES Sa&ccedil / an, Lale M.Sc., Department of Chemistry Supervisor: Prof. Dr. Levent Toppare June 2006, 59 pages A new monomer / succinic acid bis-(2-thiophen-3-yl-ethyl)ester (SATE) was synthesized through the esterification reaction of 2-thiophen-3-yl-ethanol and succinyl chloride. The chemical structure of monomer was characterized via Nuclear Magnetic Resonance Spectroscopy (NMR) and Fourier Transform Infrared Spectroscopy (FTIR). Electrochemical behaviors of SATE alone and SATE in the presence of thiophene were studied by cyclic voltammetry (CV). The synthesis of homopolymer and copolymer were achieved via constant potential electrolysis. Both homopolymer (PSATE) and copolymer [P(SATE-co-Th)] were characterized by various techniques including cyclic voltammetry, FTIR, Scanning Electron Microscopy (SEM), Differential Scanning Calorimetry (DSC), Thermal Gravimetry Analysis (TGA) and UV-VIS Spectrophotometer. Conductivities of samples were measured by four probe technique. The electrochromic properties of the polymers were investigated via spectroelectrochemistry, colorimetry and switching studies. In addition, dual type electrochromic devices (ECDs) composed of PSATE, P(SATE-co-Th) and poly(3,4-ethylenedioxythiophene) (PEDOT) were constructed and evaluated. Spectroelectrochemistry, switching ability and stability of the devices were investigated by UV-Vis Spectrophotometer and Cyclic Voltammetry. They have shown to possess good switching times, reasonable contrasts, high stabilities and optical memories.
16

Synthesis Of Conducting Polymers Of Terepthalic Acid Bis-(2-thiophen-3-yl-ethyl)ester And Investigation Of Their Electrochromic Properties

Coskun, Yelda 01 June 2004 (has links) (PDF)
Terepthalic acid bis-(2-thiophen-3-yl-ethyl)ester (TATE) was synthesized through the reaction of 2-thiophen-3-yl-ethanol and terepthaloyl chloride. Electrochemical behavior of the TATE and TATE in the presence of thiophene were studied by cyclic voltammetry (CV). The chemical structure of monomer is characterized via Nuclear Magnetic Resonance Spectroscopy (NMR) and Fourier Transform Infrared Spectroscopy (FTIR). Homopolymer of TATE was synthesized by galvanostatic and potentiostatic methods, and copolymerization of TATE with thiophene was achieved via potentiostatic method. Both homopolymer (PTATE) and copolymer [P(TATE-co-Th)] were characterized by various techniques including cyclic voltammetry, FTIR, Scanning Electron Microscopy (SEM), Differential Scanning Calorimetry (DSC), Thermal Gravimetry Analysis (TGA) and UV-VIS Spectrophotometer. Conductivities of samples were measured by four probe technique. Electronic band gap of polymers measured as the onset of the &amp / #960 / -&amp / #960 / * transition using spectroelectrochemical analysis and colorimetry studies were investigated. Dual type polymer electrochromic devices (ECDs) based on PTATE, P(TATE-co-Th) and poly(3,4-ethylenedioxythiophene) (PEDOT) have been constructed. Spectroelectrochemistry, switching ability and stability of the devices were investigated by UV-Vis Spectrophotometer and Cyclic Voltammetry.
17

Controle da liberação do éster etílico de indometacina a partir de nanocápsulas poliméricas através da variação da concentração do monoestearato de sorbitano / Controlled release of indomethacin ethyl ester from polymeric nanocapsules with the variation of the concentratio of sorbitan monostearate

Jager, Eliézer January 2008 (has links)
O trabalho tem como objetivo determinar a influencia da concentração de monoestearato de sorbitano, componente do núcleo oleoso das nanocápsulas, na cinética de liberação do éster etílico de indometacina a partir de nanocápsulas de poli(ε-caprolactona) (PCL). Com este propósito o éster etílico de indometacina foi associado a cada sistema e sua hidrólise alcalina foi realizada para simular uma condição sink. A velocidade de consumo do éster etílico de indometacina foi menor conforme o aumento da concentração do monoestearato de sorbitano. O tempo de meia-vida do consumo do éster etílico de indometacina associado as nanocápsulas foi relacionado com a concentração do monoestearato de sorbitano, sendo maior, enquanto maior a concentração do monoestearato. O mecanismo de liberação foi determinado como sendo transporte anômalo. Foi observada uma relação linear direta entre o aumento da concentração do monoestearato de sorbitano e a concentração de partículas nas suspensões de nanocápsulas (R2=0,9711). Mistura de outras nanopartículas que não as nanocápsulas, foram observadas e caracterizadas. O fluxo difusional do éster a partir das nanocápsulas foi determinado e diminuiu significativamente com o aumento da concentração do monoestearato, devido a mudanças na viscosidade do núcleo das nanocápsulas com o aumento da concentração do monoestearato de sorbitano. Por fim, os resultados demonstraram que o principal fator que contribui para o retardo no tempo para o consumo do éster etílico de indometacina é a relação direta entre a concentração do monoestearato de sorbitano e a permeabilidade das nanocápsulas (R=0,9894). / The aim of this work was to evaluate the influence of the sorbitan monoestearate concentration, one of the components of the oil core of the nanocapsules, in the release kinetic of the indomethacin ethyl ester-loaded poli(ε-caprolactone) nanocapsules. In this way, the indomethacin ethyl ester was entrapped within each system and its alkaline hydrolysis was carried out to simulate a sink condition. The rate for the indomethacin ethyl ester consumption decreased with the increase in sorbitan monostearate concentrations. The indomethacin ethyl ester half-live was related to the sorbitan monostearate concentration, increasing as the sorbitan monostearate concentration increased. The drug release mechanism was determined as anomalous transport. Linear correlations were obtained between the increase in the sorbitan monostearate concentration and the particles concentration in the suspensions (R2 = 0.9711). Mixture of different nanoparticles that are not nanocapsules were observed by density gradient and characterized. The indomethacin ethyl ester fluxes from the nanocapsules were determined and presented a decrease of the flux as the sorbitan monostearate concentration increased. This result was related to changes in the oil core viscosity caused by the variation of the sorbitan monostearate concentration. Finally, the results demonstrated that the main factor that contributes for the delaying in the time for the indometahcin ethyl ester consumption was the direct relation between the sorbitan monostearate concentration and the apparent permeability of the nanocapsules (R2 = 0.9894).
18

Controle da liberação do éster etílico de indometacina a partir de nanocápsulas poliméricas através da variação da concentração do monoestearato de sorbitano / Controlled release of indomethacin ethyl ester from polymeric nanocapsules with the variation of the concentratio of sorbitan monostearate

Jager, Eliézer January 2008 (has links)
O trabalho tem como objetivo determinar a influencia da concentração de monoestearato de sorbitano, componente do núcleo oleoso das nanocápsulas, na cinética de liberação do éster etílico de indometacina a partir de nanocápsulas de poli(ε-caprolactona) (PCL). Com este propósito o éster etílico de indometacina foi associado a cada sistema e sua hidrólise alcalina foi realizada para simular uma condição sink. A velocidade de consumo do éster etílico de indometacina foi menor conforme o aumento da concentração do monoestearato de sorbitano. O tempo de meia-vida do consumo do éster etílico de indometacina associado as nanocápsulas foi relacionado com a concentração do monoestearato de sorbitano, sendo maior, enquanto maior a concentração do monoestearato. O mecanismo de liberação foi determinado como sendo transporte anômalo. Foi observada uma relação linear direta entre o aumento da concentração do monoestearato de sorbitano e a concentração de partículas nas suspensões de nanocápsulas (R2=0,9711). Mistura de outras nanopartículas que não as nanocápsulas, foram observadas e caracterizadas. O fluxo difusional do éster a partir das nanocápsulas foi determinado e diminuiu significativamente com o aumento da concentração do monoestearato, devido a mudanças na viscosidade do núcleo das nanocápsulas com o aumento da concentração do monoestearato de sorbitano. Por fim, os resultados demonstraram que o principal fator que contribui para o retardo no tempo para o consumo do éster etílico de indometacina é a relação direta entre a concentração do monoestearato de sorbitano e a permeabilidade das nanocápsulas (R=0,9894). / The aim of this work was to evaluate the influence of the sorbitan monoestearate concentration, one of the components of the oil core of the nanocapsules, in the release kinetic of the indomethacin ethyl ester-loaded poli(ε-caprolactone) nanocapsules. In this way, the indomethacin ethyl ester was entrapped within each system and its alkaline hydrolysis was carried out to simulate a sink condition. The rate for the indomethacin ethyl ester consumption decreased with the increase in sorbitan monostearate concentrations. The indomethacin ethyl ester half-live was related to the sorbitan monostearate concentration, increasing as the sorbitan monostearate concentration increased. The drug release mechanism was determined as anomalous transport. Linear correlations were obtained between the increase in the sorbitan monostearate concentration and the particles concentration in the suspensions (R2 = 0.9711). Mixture of different nanoparticles that are not nanocapsules were observed by density gradient and characterized. The indomethacin ethyl ester fluxes from the nanocapsules were determined and presented a decrease of the flux as the sorbitan monostearate concentration increased. This result was related to changes in the oil core viscosity caused by the variation of the sorbitan monostearate concentration. Finally, the results demonstrated that the main factor that contributes for the delaying in the time for the indometahcin ethyl ester consumption was the direct relation between the sorbitan monostearate concentration and the apparent permeability of the nanocapsules (R2 = 0.9894).
19

Controle da liberação do éster etílico de indometacina a partir de nanocápsulas poliméricas através da variação da concentração do monoestearato de sorbitano / Controlled release of indomethacin ethyl ester from polymeric nanocapsules with the variation of the concentratio of sorbitan monostearate

Jager, Eliézer January 2008 (has links)
O trabalho tem como objetivo determinar a influencia da concentração de monoestearato de sorbitano, componente do núcleo oleoso das nanocápsulas, na cinética de liberação do éster etílico de indometacina a partir de nanocápsulas de poli(ε-caprolactona) (PCL). Com este propósito o éster etílico de indometacina foi associado a cada sistema e sua hidrólise alcalina foi realizada para simular uma condição sink. A velocidade de consumo do éster etílico de indometacina foi menor conforme o aumento da concentração do monoestearato de sorbitano. O tempo de meia-vida do consumo do éster etílico de indometacina associado as nanocápsulas foi relacionado com a concentração do monoestearato de sorbitano, sendo maior, enquanto maior a concentração do monoestearato. O mecanismo de liberação foi determinado como sendo transporte anômalo. Foi observada uma relação linear direta entre o aumento da concentração do monoestearato de sorbitano e a concentração de partículas nas suspensões de nanocápsulas (R2=0,9711). Mistura de outras nanopartículas que não as nanocápsulas, foram observadas e caracterizadas. O fluxo difusional do éster a partir das nanocápsulas foi determinado e diminuiu significativamente com o aumento da concentração do monoestearato, devido a mudanças na viscosidade do núcleo das nanocápsulas com o aumento da concentração do monoestearato de sorbitano. Por fim, os resultados demonstraram que o principal fator que contribui para o retardo no tempo para o consumo do éster etílico de indometacina é a relação direta entre a concentração do monoestearato de sorbitano e a permeabilidade das nanocápsulas (R=0,9894). / The aim of this work was to evaluate the influence of the sorbitan monoestearate concentration, one of the components of the oil core of the nanocapsules, in the release kinetic of the indomethacin ethyl ester-loaded poli(ε-caprolactone) nanocapsules. In this way, the indomethacin ethyl ester was entrapped within each system and its alkaline hydrolysis was carried out to simulate a sink condition. The rate for the indomethacin ethyl ester consumption decreased with the increase in sorbitan monostearate concentrations. The indomethacin ethyl ester half-live was related to the sorbitan monostearate concentration, increasing as the sorbitan monostearate concentration increased. The drug release mechanism was determined as anomalous transport. Linear correlations were obtained between the increase in the sorbitan monostearate concentration and the particles concentration in the suspensions (R2 = 0.9711). Mixture of different nanoparticles that are not nanocapsules were observed by density gradient and characterized. The indomethacin ethyl ester fluxes from the nanocapsules were determined and presented a decrease of the flux as the sorbitan monostearate concentration increased. This result was related to changes in the oil core viscosity caused by the variation of the sorbitan monostearate concentration. Finally, the results demonstrated that the main factor that contributes for the delaying in the time for the indometahcin ethyl ester consumption was the direct relation between the sorbitan monostearate concentration and the apparent permeability of the nanocapsules (R2 = 0.9894).
20

ÉSTERES COMBUSTÍVEIS EM MOTOR DE CICLO DIESEL SOB CONDIÇÕES DE PRÉ-AQUECIMENTO E VARIAÇÃO NO AVANÇO DE INJEÇÃO / ESTERS FUELS IN DIESEL ENGINES UNDER PRE-HEATING CONDITIONS AND VARYING INJECTION TIMING

Machado, Paulo Romeu Moreira 23 April 2008 (has links)
The renewed interest in energy for biomass is supported by the need for different energy sources and the need to protect the environment. Recently, because of increases in crude oil prices, limited resources of fossil oil and environmental concerns there has been renewed focus on vegetable oils and animal fats to make a biodiesel fuel. What is known as biodiesel (methyl or ethyl esters) is a vegetable oil or animal fat chemically treated to replace traditional diesel fuel. Performance parameters and exhaust emissions of a diesel engine fuelled with sunflower and beef tallow ethyl esters and a blend of ethyl and methyl esters, subjected to pre-heating at two temperatures ranges, namely T55 (50 to 60ºC) and T75 (70 to 80ºC), in order to lower its viscosities, have been investigated. Tests were carried out at full load conditions in a four cylinders, four-stroke indirect injection diesel engine. Engine tests, short-term, were conducted at a range speed from 1900 to 4400 rpm. The injection timing was retarded from the manufacturer s recommended setting. The tests were carried out using the same engine and test procedures so that comparative assessments may be made. The tests data were used for evaluating the brake power, exhaust gas temperatures, specific fuel consumption and gaseous emissions. The analysis of the results determined that the level of pre-heating have influence on the performance for used esters. The tests performed at T55 showed the best values of torque (N.m), power (kW) and specific fuel consumption (g.kW-1.h-1) that the tests performed at T75. The bests experiments results were obtained with sunflower ethyl ester and the blend containing 50,0% sunflower ethyl ester and 50,0% beef tallow methyl ester, at -2º BTDC and T55 temperature range. The findings showed that, by using biodiesel, harmful emissions (CO, HC and NOx) can be reduced to some extent of B2 by adjusting the injection pump timing properly and pre-heating of fuel. / O renovado interesse por energia da biomassa é apoiado na necessidade de fontes alternativas de energia e de proteção ambiental. Recentemente, devido ao aumento dos preços do óleo cru, a limitação de seus recursos e as questões relacionadas ao ambiente, um renovado foco passou a existir sobre os óleos vegetais e gorduras animais para produção de um biodiesel combustível. O que é conhecido como biodiesel (éster metílico ou etílico) é um óleo vegetal ou gordura animal tratado quimicamente para substituir o combustível diesel tradicional. Parâmetros de desempenho e emissões de exaustão foram investigados para um motor diesel alimentado com ésteres etílicos de óleo de girassol e de sebo bovino e por uma mistura composta pelo éster etílico de óleo de girassol e pelo metílico de sebo bovino numa proporção volumétrica igual (50,0%+50,0%). Os ésteres estavam sujeitos ao pré-aquecimento segundo duas faixas de temperaturas, chamadas de T55 (50 a 60ºC) e T75 (70 a 80ºC), como forma de redução da viscosidade. Os testes foram conduzidos sob condição de carga máxima em um motor diesel de quatro cilindros, quatro tempos e de injeção indireta de combustível. Os ensaios de curta duração foram efetuados em uma faixa de rotações compreendida entre 1900 e 4400 rpm. O ponto de avanço de injeção foi atrasado em relação ao ponto original recomendado pelo fabricante. Os testes foram conduzidos utilizando o mesmo motor e os mesmos procedimentos de testes para permitir a comparação dos valores obtidos. Nos ensaios foram obtidos os valores de potência, torque, consumo específico de combustível e gases de exaustão. A análise dos resultados indica que o nível de pré-aquecimento tem influência sobre o desempenho dos ésteres utilizados. Os ensaios conduzidos à T55 mostraram melhores valores para torque (N.m), potência (kW) e consumo específico de combustível (g.kW-1.h-1) que os testes executados à T75. Os melhores resultados do experimento foram obtidos pelo éster etílico de girassol e pela mistura contendo 50,0% de éster etílico de girassol e 50% de éster metílico de sebo bovino, sob 2º (P2) de atraso no ponto de injeção e aquecidos na faixa de temperaturas de T55. Os resultados indicam que, pelo uso do biodiesel, as emissões prejudiciais (CO, HC e NOx) podem ser reduzidas aos mesmos níveis do B2 através do ajuste apropriado do ponto de avanço da injeção e o pré-aquecimento do combustível.

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