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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.
141

Catalytic Material Design: Impact of Synthesis Conditions on the Pore Architecture and Catalytic Performance of Micro-Mesoporous Silica Supported Catalysts

Kane, Ashwin 05 October 2022 (has links)
No description available.
142

Corrélation composition chimique-structure-propriétés de réductibilité / mobilité de l’oxygène / catalyse d’oxydation au sein d’oxydes à base de cérium, zirconium et de praséodyme / Correlation between chemical composition-structure-properties of reducibility and oxygen mobility with the oxidation of automotive pollutants by (Ce, Zr, Pr) mixed oxides

Frizon, Vincent 05 March 2018 (has links)
Ces travaux de thèse ont pour vocation d'étudier des oxydes mixtes Ce1-x-yZrxPryO2-z afin de corréler composition chimique-structure avec les propriétés de réductibilité/mobilité ionique de l'oxygène associées aux performances catalytiques pour l'oxydation du CO et du propane, en conditions essence et Diesel. La connaissance de la quantité de terres rares au degré d'oxydation +4 a été déterminante. Notamment, plus le taux de Pr4+ est important, plus le composé est réductible et plus la mobilité de l'oxygène s'accroît. L'évaluation du coefficient de diffusion de l'oxygène D* a montré que sa valeur devenait élevée, rivalisant ainsi avec les meilleurs conducteurs ioniques de l'oxygène à basse température. Les échanges isotopiques de l'oxygène permettent de montrer que la vitesse d'échange croît quand le taux de Pr augmente. L'étude de la combustion du propane sur ces oxydes a montré qu'une bonne mobilité de l'oxygène permettait d'améliorer les performances catalytiques. Ainsi, l'oxyde de composition Ce0,45Zr0,1Pr0,45O2-x (CZP45) présente les meilleures propriétés pré-citées et l'activité catalytique la plus élevée. L'oxyde CZP45 a donc été imprégné de Pd afin d'être comparé à deux catalyseurs utilisés industriellement et à iso-teneur en Pd, dispersée sur ?-Al2O3 (Diesel) et Ce0,5Zr0,5O2-x (essence). En régime Diesel, Pd-CZP45, après une étape initiale de réduction, présente une meilleure activité catalytique à basse température que Pd-?-Al2O3 pour l'oxydation du propane. Nous avons expliqué ces excellentes performances par la présence de clusters de Pd2+/Pd° finement dispersés sur l'oxyde (CZP45) et par la capacité du catalyseur à adsorber et conduire l'oxygène / This work describes characterizations of Ce1-x-yZrxPryO2-z mixed oxides to link their chemical composition-structure with their reducibility/oxygen mobility. These latter properties were correlated with their catalytic activity for the oxidation of CO and propane, both in stoichiometric (gasoline) and lean-burn (Diesel) conditions. The determination of the quantity of rare earth at the +4 oxidation degree, especially for Pr4+, has been of paramount importance. Actually, the higher the Pr4+ rate, the more reducible is the oxide and the better is the oxygen mobility. The evaluation of the diffusion coefficient of the oxygen D* highlighted high values, similar to those of the best reported oxygen ionic conductors at low temperature. Isotopic exchanges showed that the oxygen exchange rate increases with the Pr loading in the oxide. The catalytic activity for propane combustion of these oxides increases with their oxygen mobility. Finally, CZP45 (Ce0,45Zr0,1Pr0,45O2-x) exhibits the best pre-quoted properties as well as the highest catalytic activity. Therefore, CZP45 has been impregnated with Pd. The activity of Pd-CZP45 catalyst was compared with two industrially catalysts containing the same Pd content supported either on ?-Al2O3 (Diesel) or Ce0,5Zr0,5O2-x (gasoline). In Diesel conditions, Pd-CZP45 shows a better low-temperature catalytic activity than Pd-?-Al2O3 for propane oxidation after an initial step of reduction. We have attributed these remarkable performances to the presence of Pd2+/Pd° clusters finely dispersed on the oxide CZP45 and to its ability to adsorb and conduct oxygen
143

The Impact of Hydrocarbon and Carbon Oxide Impuritiesin the Hydrogen Feed of a PEM Fuel Cell

Kortsdottir, Katrin January 2016 (has links)
The proton exchange membrane fuel cell generates electricity from hydrogen and oxygen (from air) through electrocatalytic reactions in an electrochemical cell. The Pt/C catalyst, commonly used in PEM fuel cells, is very sensitive to impurities that can interact with the active catalyst sites and limit fuel cell performance. Unfortunately, most hydrogen is currently produced from fossil sources, and inevitably contains impurities. The subject of this thesis is the effect of hydrogen impurities on the operation of a PEM fuel cell using a Pt/C anode. The impurities studied are carbon monoxide (CO), carbon dioxide (CO2), and selected hydrocarbons. Particular focus is given to the interaction between the impurities studied and the anode catalyst. The main method used in the study involved performing cyclic voltammetry and mass spectrometry, simultaneously. Other electrochemical techniques are also employed. The results show that all the impurities studied adsorb to some extent on the Pt/C catalyst surface, and require potentials comparable to that of CO oxidation, i.e., about 0.6V, or higher to be removed by oxidation to CO2. For complete oxidation of propene, and toluene, potentials of above 0.8, and 1.0V, respectively, are required. The unsaturated hydrocarbons can be desorbed to some extent by reduction, but oxidation is required for complete removal. Adsorption of ethene, propene, and CO2 is dependent on the presence of adsorbed or gaseous hydrogen. Hydrogen inhibits ethene and propene adsorption, but facilitates CO2 adsorption. Adsorption of methane and propane is very limited and high concentrations of methane cause dilution effects only. The adlayer formed on the Pt/C anode catalyst in the presence of CO2, or moderate amounts of hydrocarbons, is found to be insffuciently complete to notably interfere with the hydrogen oxidation reaction. Higher concentrations of toluene do, however, limit the reaction. / Polymerelektrolytbränslecellen genererar elektricitet fran vätgas och syrgas (fran luft) genom elektrokatalytiska reaktioner i en elektrokemisk cell. Den platina-baserade katalysator som oftast används i dessa bränsleceller är känslig mot föroreningar, då dessa kan interagera med katalysatorns aktiva yta, och därmed begränsna bränslecellens prestanda. Tyvärr produceras dagens vätgas huvudsakligen fran fossila källor och innehåller därför oundvikligen föroreningar. Denna avhandling behandlar hur olika vätgasföroreningar påverkar katalysatorns aktivitet och bränslecellens drift. De föroreningar som studeras är kolmonoxid (CO) och koldioxid (CO2), samt ett antal mindre kolväten. Störst fokus ligger på hur dessa föroreningar interagerar med anodens Pt/C katalysator. Den metod som huvudsakligen används är cyklisk voltammetri kombinerat med masspektrometri, men flera elektrokemiska metoder har använts. Resultaten visar att alla undersökta föroreningar adsorberar på Pt/C katalysatorns yta i större eller mindre utstreckning. For att avlägsna det adsoberade skiktet genom oxidation till CO2 krävs potentialer jämförbara med CO oxidation, dvs ca 0,6V, eller högre. Fullständig oxidation av propen eller toluen kräver potentialer högre än 0,8V respektive 1,0V. De omättade kolvätena kan delvis avlägsnas genom reduktion, men fullständig avlägsning kräver oxidation. Närvaron av väte, i gasform eller adsorberat pa katalysatorn, hämmar adsorptionen av eten och propen, men främjar CO2 adsorption. Metan och propan adsorberar i mycket begränsad utstreckning på Pt/C katalysatorns yta. De prestandaförluster som uppstår av höga koncentrationer av metan förklaras av utspädning av vätgasen. Det adsorberade skiktet som bildas när Pt/C katalysatorn exponeras för CO2 eller måttliga koncentrationer av studerade kolväten, är inte tillräckligt heltäckande for att märkbart påverka vätgasreduktionen. Däremot kan höga koncentrationer av toluen begränsa reaktionen. / <p>QC 20161010</p>
144

Vanadiumdotierte Metalloxide und -oxofluoride als Katalysatoren in selektiven Oxidationsreaktionen

Scheurell, Kerstin 17 January 2006 (has links)
In der vorliegenden Arbeit wurden unter Anwendung unterschiedlicher Präparationstechniken vanadiumdotierte Metalloxide bzw. –oxofluoride synthetisiert, umfassend charakterisiert und in katalytischen, selektiven Oxidationsreaktionen (ODH von Propan und Methanoloxidation) getestet. Die Festkörper- und oberflächenchemischen Eigenschaften wurden generell mittels CHN-Analyse, ICP-OES, XRD, Raman-, FTIR-, MAS-NMR- und ESR-Spektroskopie, Py-PAS, TPD und Tieftemperatur-Stickstoffadsorption untersucht. Ergänzend kamen an ausgewählten Proben der temperaturprogrammierte Sauerstoffisotopenaustausch und Adsorptionsuntersuchungen von Methanol zum Einsatz. Als katalytische Testreaktionen dienten die oxidative Dehydrierung von Propan und die selektive Methanoloxidation. Unabhängig von der angewendeten Synthesemethode zeigte sich, dass die Festkörpereigenschaften sowohl durch den Vanadiumgehalt, als auch wesentlich durch die Art des Wirtsgitters beeinflusst werden. Es konnte nachgewiesen werden, dass eine hohe Sauerstoffaustauschaktivität und das Vorhandensein Brønsted-saurer Zentren auf den Katalysatoroberflächen die Aktivierung der Edukte in den hier untersuchten katalytischen Reaktionen begünstigen. In Bezug auf die Selektivität zu den Zielprodukten Propen bzw. Formaldehyd sind diese Eigenschaften allerdings nachteilig, da an derartigen Zentren immer die Produkte der Totaloxidation (CO und CO2) gebildet werden. Besonders bemerkenswert ist das Verhalten der vanadiumdotierten Aluminiumoxofluoride. Diese Phasen wurden mit einer neuen Methode synthetisiert und enthalten fast ausschließlich Lewis-saure Zentren. Die Matrix wird zudem maßgeblich durch die Fluoridionen bestimmt, sodass die Sauerstoffmobilität und –austauschaktivität sehr gering sind. Dadurch reagieren sie, trotz einer relativ hohen katalytischen Aktivität, außerordentlich selektiv in den hier untersuchten selektiven Oxidationsreaktionen. / In this thesis, vanadium containing metal oxides and oxyfluorides were prepared, thoroughly characterised and tested as catalysts in selective oxidation reactions. Bulk and surface properties of all samples were studied by means of CHN-analysis, ICP-OES, XRD, Raman-, FTIR-, MAS-NMR- und ESR-spectroscopy, Py-PAS, TPD and BET-adsorption. Moreover, the oxygen isotope exchange behaviour and the methanol adsorption properties of selected samples were analysed in order to correlate the surface properties with the catalytic behaviour of the materials. Irrespective of the preparation technique applied, the properties of the solids strongly depend on the host lattice as well as on the vanadium content. It has been clearly revealed that a high oxygen exchange activity and the presence of Brønsted acid sites on the catalyst surface promote the activation of the educts in selective oxidation reactions. The enhanced activity, however, is generally accompanied by a low selectivity towards the desired products propylene and formaldehyde, respectively. The low selectivity is caused by the high concentration of catalytically active sites leading to the formation of carbon oxides as total oxidation products of propane and methanol. A very promising catalytic behaviour was observed with vanadium-doped aluminium oxyfluorides. The oxyfluorides were prepared by a new method and contain almost exclusively Lewis-acid sites. The matrix is mainly determined by the fluoride anions resulting in a reduced oxygen mobility and exchange activity. Hence, the vanadium-doped aluminium oxyfluorides exhibit a relatively high catalytic activity accompanied by an excellent selectivity in the oxidation reaction of propane and methanol.
145

Síntese de catalisadores baseados em vanádio suportado em aluminas de transição modificadas por metais alcalinos e avaliação catalítica na reação de desidrogenação oxidativa do propano / Synthesis of vanadium-based catalysts supported on transition alumina modified with alkali metals and catalytic evaluation for oxidative dehydrogenation of propane reaction

Crivelaro, Vinicius Martin 21 October 2016 (has links)
Em ultimas décadas, a conversão de alcanos leves em suas correspondentes olefinas tem sido objeto de intensas pesquisas, impulsionadas inclusive pelo aumento crescente da demanda do propileno como um importante produto petroquímico. A desidrogenação oxidativa (ODH) do propano representa uma via alternativa promissor para a produção de propeno, ao apresentar-se como uma reação exotérmica e não limitada termodinamicamente. Diferentes óxidos suportados ou mistos têm sido desenvolvidos com a finalidade de aumentar a atividade e seletividade em relação as olefinas. Metais alcalinos são importantes agentes promotores que proporcionam uma melhor seletividade as olefinas devido a redução da acidez e aumento da basicidade da superfície do catalisador. A proposta deste presente trabalho foi desenvolver metodologias de síntese de catalisadores de oxido de vanádio suportado em aluminas de diferentes fases cristalinas e dopados com sódio ou potássio a fim de avalia-los em testes catalíticos de desidrogenação oxidativa do propano. Para tanto, foram utilizadas as seguintes técnicas de caracterização: volumetria N2, difratometria de raios X (DRX) e redução a temperatura programada (RTP). As características acidas e/ou básicas dos suportes e catalisadores foram avaliadas pelas reações de decomposição de isopropanol. / In recent decades, the conversion of light alkanes to their corresponding olefins has been the subject of intense research, mainly driven by the increasing demand of propylene as an important petrochemical product. Oxidative dehydrogenation (ODH) propane is a promising alternative way to propylene production, which it is presented as an exothermic reaction and not limited thermodynamically. Different supported or mixed oxides have been developed in order to increase the activity and selectivity to olefins. Alkali metals are important promoters, which provide improved selectivity to olefins due to reduction of acidity and increasing basicity of the catalyst surface. The purpose of the present study was to develop synthesis methods of vanadium oxide catalysts supported on alumina of the different crystalline phases and doped with sodium or potassium in order to evaluate them in catalytic tests of propane oxidative dehydrogenation. For in such a way, the following characterization techniques were used: N2 volumetry, X-ray diffractometry (XRD) and temperature programmed reduction (TPR). The properties acid and/or basic of supports and catalysts were evaluated by the isopropanol decomposition reaction.
146

Estudo experimental da ebulição de hidrocarbonetos em tubo de multi mini canais

Silva, Priscila Forgiarini da 06 November 2017 (has links)
Submitted by JOSIANE SANTOS DE OLIVEIRA (josianeso) on 2017-12-13T12:59:28Z No. of bitstreams: 1 Priscila Forgiarini da Silva_.pdf: 2273220 bytes, checksum: 4943272627a06de991d941e1c6bfd457 (MD5) / Made available in DSpace on 2017-12-13T12:59:28Z (GMT). No. of bitstreams: 1 Priscila Forgiarini da Silva_.pdf: 2273220 bytes, checksum: 4943272627a06de991d941e1c6bfd457 (MD5) Previous issue date: 2017-11-06 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / PROSUP - Programa de Suporte à Pós-Gradução de Instituições de Ensino Particulares / Este trabalho apresenta um estudo experimental da transferência de calor e queda de pressão na ebulição do isobutano, R600a, e do propano, R290, em um tubo composto por sete mini canais paralelos, cujo diâmetro hidráulico é de 1,47 mm. Os testes em ebulição foram realizados com uma temperatura de saturação de 20 ºC, para ambos os fluidos refrigerantes e pressão de saturação de 300 kPa, para o R600a e de 840 kPa para o R290, com velocidades mássicas entre 35 e 170 kg/(m²s) e fluxos de calor na seção de testes entre 5,3 e 21 kW/m². De acordo com os testes realizados verificou-se que o coeficiente de transferência de calor, para ambos os fluidos refrigerantes, aumenta conforme o incremento do fluxo de calor e velocidade mássica. O coeficiente de transferência de calor atingiu valores entre 1 a 18 kW/(m²K) para o R290 e de 1 a 9 kW/(m²K) para o R600a. A queda de pressão aumentou com o incremento da velocidade mássica e título de vapor em todos os testes, enquanto que o fluxo de calor apresentou influência na queda de pressão apenas nas maiores velocidades mássicas. Observou-se que a queda de pressão por aceleração apresenta a menor parcela, enquanto que, a queda de pressão por atrito apresenta a maior parcela. Na comparação entre o R290 e o R600a, verificou-se que o isobutano apresenta maior queda de pressão. Também foram analisados os padrões de escoamento, sendo observados os padrões de bolhas isoladas, pistonado, agitado, anular ondulado e anular, sendo que o padrão de bolhas isoladas foi observado somente para o R290, e o padrão anular mostrou-se presente para títulos superiores a 0,4. / This work presents an experimental study of heat transfer and pressure drop in boiling of isobutane, R600a, and propane, R290, in a tube composed of seven parallel mini channels, whose hydraulic diameter is 1.47 mm. Boiling tests were performed with a saturation temperature of 20 ºC for both refrigerants and saturation pressure of 300 kPa for R600a and 840 kPa for R290, with mass velocities between 35 and 170 kg/(m²s) and heat flux in the test section between 5.3 and 21 kW/m². According to the tests performed it was verified that the heat transfer coefficient for both refrigerant fluids increases as the heat flux and mass velocity increase. The heat transfer coefficient reached values between 1-18 kW/(m²K) for the R290 and 1-9 kW/(m²K) for the R600a. The pressure drop increased with increasing mass velocity and vapor quality in all tests, while the heat flux showed influence on the pressure drop only at higher mass velocities. It was observed that the pressure drop by acceleration presents the smallest portion, while the friction presents the largest portion. In the comparison between R290 and R600a, it was found that isobutane showed a higher pressure drop. Flow patterns were also analyzed, with isolated bubble, piston, agitated, annular and annular bubble patterns being observed, and the isolated bubble pattern was observed only for R290, and the annular pattern was present for quality higher than 0.4.
147

Síntese de catalisadores baseados em vanádio suportado em aluminas de transição modificadas por metais alcalinos e avaliação catalítica na reação de desidrogenação oxidativa do propano / Synthesis of vanadium-based catalysts supported on transition alumina modified with alkali metals and catalytic evaluation for oxidative dehydrogenation of propane reaction

Vinicius Martin Crivelaro 21 October 2016 (has links)
Em ultimas décadas, a conversão de alcanos leves em suas correspondentes olefinas tem sido objeto de intensas pesquisas, impulsionadas inclusive pelo aumento crescente da demanda do propileno como um importante produto petroquímico. A desidrogenação oxidativa (ODH) do propano representa uma via alternativa promissor para a produção de propeno, ao apresentar-se como uma reação exotérmica e não limitada termodinamicamente. Diferentes óxidos suportados ou mistos têm sido desenvolvidos com a finalidade de aumentar a atividade e seletividade em relação as olefinas. Metais alcalinos são importantes agentes promotores que proporcionam uma melhor seletividade as olefinas devido a redução da acidez e aumento da basicidade da superfície do catalisador. A proposta deste presente trabalho foi desenvolver metodologias de síntese de catalisadores de oxido de vanádio suportado em aluminas de diferentes fases cristalinas e dopados com sódio ou potássio a fim de avalia-los em testes catalíticos de desidrogenação oxidativa do propano. Para tanto, foram utilizadas as seguintes técnicas de caracterização: volumetria N2, difratometria de raios X (DRX) e redução a temperatura programada (RTP). As características acidas e/ou básicas dos suportes e catalisadores foram avaliadas pelas reações de decomposição de isopropanol. / In recent decades, the conversion of light alkanes to their corresponding olefins has been the subject of intense research, mainly driven by the increasing demand of propylene as an important petrochemical product. Oxidative dehydrogenation (ODH) propane is a promising alternative way to propylene production, which it is presented as an exothermic reaction and not limited thermodynamically. Different supported or mixed oxides have been developed in order to increase the activity and selectivity to olefins. Alkali metals are important promoters, which provide improved selectivity to olefins due to reduction of acidity and increasing basicity of the catalyst surface. The purpose of the present study was to develop synthesis methods of vanadium oxide catalysts supported on alumina of the different crystalline phases and doped with sodium or potassium in order to evaluate them in catalytic tests of propane oxidative dehydrogenation. For in such a way, the following characterization techniques were used: N2 volumetry, X-ray diffractometry (XRD) and temperature programmed reduction (TPR). The properties acid and/or basic of supports and catalysts were evaluated by the isopropanol decomposition reaction.
148

Modélisation globale de l'infiltration chimique en phase vapeur (CVI) et étude de la chimie du dépôt de pyrocarbone en CVD/CVI

Reuge, Nicolas 08 July 2002 (has links) (PDF)
Ce mémoire est consacré à la modélisation de l'infiltration chimique en phase vapeur (CVI), procédé utilisé pour la fabrication des composites thermostructuraux et en particulier les carbone-carbone (C/C). Il s'articule autour de deux axes : le premier concerne la mise au point d'un outil de simulation globale du procédé, c'est-à-dire à l'échelle d'un four, et le second la détermination d'un modèle chimique apte à décrire de manière réaliste le dépôt de pyrocarbone et suffisamment simple pour être utilisé dans une simulation globale. La modélisation globale inclut une description mathématique détaillée des phénomènes de transfert de masse (convection et diffusion multicomposant) et de chaleur, des réactions chimiques homogènes et hétérogènes, et des relations d'interface entre les milieux libre (le four) et poreux (la préforme). Un outil de simulation globale a ensuite été développé avec une résolution en couplage faible (milieu libre / milieu poreux). Les potentialités de cette approche quantitative sont mises en valeur à travers une étude de modélisation de la CVI du carbure de silicium, avec variation des paramètres débit de gaz réactif et diamètre de réacteur. Un modèle chimique du dépôt de pyrocarbone à partir du précurseur propane, comprenant deux espèces légères moyennes conduisant au pyrocarbone laminaire lisse et une espèce moyenne plus lourde (HAP) conduisant au pyrocarbone laminaire rugueux, est ensuite proposé. Il reproduit les résultats expérimentaux de dépôt CVD. Pour l'identifier également en CVI, des milieux poreux modèles constitués d'un empilement quasi-compact de filaments ont été élaborés, densifiés et caractérisés. Il a été nécessaire d'affiner le modèle chimique pour que le calcul reproduise ces résultats expérimentaux de CVI. Enfin, la comparaison entre les résultats d'expériences de CVD et CVI acquises dans diverses conditions et le cadre de modélisation a permis de mieux interpréter ceux-ci. Ainsi, l'existence d'un nouveau mode de dépôt de pyrocarbone fortement anisotrope a été confirmée.
149

Further development of Sand Bed Burner / Vidareutveckling av Sandbäddsbrännare

Jansson, Adam January 2014 (has links)
To determine whether a weapon system meets the requirements set for insensitivity, the system is getting exposed for special tests. One of these tests shows how the system reacts when it ends up in a fire. This test is called the "Fast Cook-Off (FCO) Test", called FCO-test, and performed with a Sand Bed Burner (SBB). According to primary testing provision, the fuel for this test is used of jet fuel such as Jet A-1. A project at Bofors Test Center (BTC) is in progress to use an alternative fuel of Liquefied Petroleum Gas (LPG). This fuel is very advantageous compared to jet fuel in terms of environmental impact, work environment and testing costs. The aim of this thesis is to improve the existing test equipment considering fire over the entire surface and solve the problems with dropped gas flow and freezing of gas bottles. SBB works in the sense that the new petrol LPG streams into the SBB and expands in the free space below the sand bed before the gas will diffuse through the bed of sand and the fire engulfs the object. LPG is a condensable gas that requires oxygen. LPG exceed from liquid to gas phase and needs a large lateral surface to take up more energy which results in better evaporationto the phase transfer. Reaction products from complete combustion of LPG are only water vapor and carbon dioxide, the same as in your exhaled air. To solve these problems it was needed to change P11 composite bottles to P45 steel bottles to get a longer evaporation and larger lateral surface. Four flow inlets instead were used of one into SBB for a better stream in the free space under the sand bed. Propane regulators used to get a lower and more constant flow to avoid freezing. Compressed airconnected tothe SBB to geta mix between oxygen and LPG. The result shows in higherheat radiation efficiency even though the flow was settled down to 1/3 with the new propane regulators. In test 2 the value was 37 kW/m2 and in test 7 it was around 57 kW/m2. Because of a smaller flow and bigger steel bottles the freezing disappeared. Smaller grain of sand together with four inlets and compressed air gave a more complete combustion.
150

Extração do óleo de sementes de crambe (Crambe abyssinica) empregando propano subcrítico: caracterização do óleo e farelo / Extraction of crambe (Crambe abyssinica) seed oil using propane subcritical: characterization of oil and bran

Santos, Kátia Andressa 21 February 2014 (has links)
Made available in DSpace on 2017-07-10T18:08:04Z (GMT). No. of bitstreams: 1 Katia Andressa Santos.pdf: 1963088 bytes, checksum: b32ddfe59cde547120036db9bad8218c (MD5) Previous issue date: 2014-02-21 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Crambe (Crambe abyssinica) is an oilseed with high content of oil rich in erucic acid, a fatty acid with industrial application. In the extraction of vegetable oils are traditionally employed methods such as pressing and/or organic solvents, which are known to have several inconvenient. Within this context, this work aims to evaluate the use of propane in subcritical conditions in obtaining crambe oil, comparing the yields and characteristics of the oil obtained by this technique to oil produced by the conventional method with organic solvents hexane and dichloromethane. A 22 factorial design was employed to evaluate the effects of temperature and pressure on the yield of extraction with subcritical propane being used in experiments at temperatures between 40 and 80 oC and pressures between 80 and 160 bar, with a fixed solvent flow rate of 1.6 x10 -3 kg min- 1 and the total extraction time of 80 minutes. Mathematical modeling of the kinetics of subcritical extraction was also performed using the model of Sovová. Crambe oil was characterized as the total fatty acids, free glycerol compounds and levels of tocopherols profile. Also, calorimetric analyzes were performed to determine the oxidative stability of the oil and its melting point. In seeds and bran were determined their chemical composition and contents of phenolic compounds. The results confirmed the high fat seeds of crambe, and obtained yields of 51 and 48% in extractions with dichloromethane and hexane, respectively. In subcritical propane extraction, temperature was the only variable that had an effect on the response, with the highest yield (32.8%) obtained in the condition of 80 °C and 160 bar. The different experimental conditions revealed no significant differences in total, at a significance level of 5% fatty acid profile, and these consist mainly of monounsaturated fatty acids, such as erucic acid (56.72 to 59.38%). In the free fraction glycerol, free fatty acids content below 2% and among the phytosterols, &#946;-sitosterol beyond and campesterol was possible to identify and quantify the brassicasterol, characteristic of the family to which belongs the crambe. Regarding tocopherols, crambe oil extracted with subcritical propane showed high levels of these compounds, especially &#947; -tocopherol, which directly focused on the oxidative stability. The bran extraction residue, was found to be a source of protein and potential antioxidants, such as phenolic. As for the mathematical modeling, the model Sovová satisfactorily represented the experimental data in all conditions employed. / O crambe (Crambe abyssinica) é uma oleaginosa com elevado teor de óleo rico em ácido erúcico, um ácido graxo de grande aplicação industrial. Na extração de óleos vegetais, tradicionalmente são empregados métodos como a prensagem e/ou a utilização de solventes orgânicos, que são conhecidos por apresentarem diversos inconvenientes. Dentro deste contexto, o presente trabalho visa avaliar a aplicação do propano em condições subcríticas na obtenção de óleo de crambe, comparando os rendimentos e características do óleo obtido por esta técnica ao óleo extraído pelo método convencional com os solventes orgânicos hexano e diclorometano. Um planejamento experimental 22 foi empregado para avaliar os efeitos da temperatura e pressão no rendimento da extração com propano subcrítico, sendo utilizadas nos experimentos temperaturas entre 40 e 80 oC e pressões entre 80 e 160 bar, com vazão fixa de solvente de 1,6x10-3 kg min-1 e tempo total de extração de 80 minutos. Também foi realizada a modelagem matemática da cinética de extração subcrítica empregando o modelo de Sovová. O óleo de crambe foi caracterizado quanto ao perfil de ácidos graxos totais, compostos livres de glicerol e teores de tocoferóis. Ainda, análises calorimétricas foram realizadas para determinar a estabilidade oxidativa do óleo e seu ponto de fusão. Nas sementes e farelos foram determinados sua composição centesimal e teores de compostos fenólicos. Os resultados comprovaram o elevado teor lipídico das sementes de crambe, sendo obtidos rendimentos de 51 e 48% nas extrações com diclorometano e hexano, respectivamente. Na extração com propano subcrítico, a temperatura foi a única variável que apresentou efeito sobre a resposta, sendo o maior rendimento (32,8%) obtido na condição de 80 oC e 160 bar. As condições experimentais não revelaram diferenças significativas quanto ao perfil de ácidos graxos totais, ao nível de significância de 5%, e estes são constituídos majoritariamente por ácidos graxos monoinsaturados, como o ácido erúcico (56,72 a 59,38%). Na fração não ligada ao glicerol, os ácidos graxos livres apresentaram teores abaixo de 2% e, dentre os fitosteróis, além do &#946;-sitosterol e campesterol, foi possível identificar e quantificar o brassicasterol, característico da família à qual o crambe pertence. Quanto aos tocoferóis, o óleo de crambe extraído com propano subcrítico apresentou teores elevados destes compostos, principalmente de &#947;-tocoferol, o que incidiu diretamente na sua estabilidade oxidativa. O farelo, resíduo da extração, além de potencial proteico revelou ser fonte de compostos antioxidantes, como os fenólicos. Em relação à modelagem matemática, o modelo de Sovová representou satisfatoriamente os dados experimentais em todas as condições empregadas.

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