Depuis plusieurs années, la diminution des réserves de pétrole incite les différents pays à accroitre leur indépendance énergétique. De plus, diminuer l’impact environnemental de la voiture est devenu l’une des priorités de notre société. En ce sens, les normes Européennes anti-pollution sont devenues plus strictes, tandis que certains polluants sont pointés du doigt pour avoir un impact néfaste sur la santé et l’environnement. Pour répondre à cette double problématique, l’utilisation de biocarburants de type alcools dans les moteurs à allumage commandé est l’une des voies envisagées. Ce virage a déjà été entrepris à petite échelle par l’Union Européenne qui a tout d’abord autorisé l’ajout de 5%, puis de 10% d’éthanol dans l’essence. En plus de l’éthanol déjà commercialisé, le Biobutanol, biocarburant de seconde génération, apparait comme un candidat à fort potentiel pour une utilisation dans les moteurs à allumage commandé. L’objectif de ce travail de thèse est d’étudier le potentiel de l’utilisation de mélanges isooctane/butanol dans les moteurs à allumage commandé, en termes de performances et d’émissions polluantes. De plus, ces résultats sont comparés à ceux de mélanges isooctane/éthanol. Le dégagement de chaleur dans un moteur à allumage commandé est en partie piloté par la vitesse de combustion laminaire. Cette caractéristique a été étudiée de manière expérimentale et numérique pour différentes conditions initiales (pression et richesse) dans une enceinte à volume constant. Puis, une étude sur les premières étapes de la propagation de la combustion a été réalisée dans un moteur monocylindre à accès optique. Ces résultats en moteur ont été corrélés avec les informations laminaires. Enfin, les émissions de polluants réglementés et non-réglementés, ainsi que les performances ont été étudiées dans un moteur monocylindre à allumage commandé. Une baisse de la plupart de ces émissions a été observée avec l’ajout des deux alcools. / For the past few years, the oil stock decrease encourages the different countries to increase their energy independence. Moreover, reducing the environmental impact of transportation became one of the priorities of our society. In this way, European emissions standards are stricter while several pollutants have been identified to have a negative impact on health and the environment. To answer this double problem, the use of alcohols biofuels in spark-ignition engines is one the promising ways. The European Union have already taken a small step in that direction by allowing a maximum of 10% of ethanol into gasoline. As well as ethanol is already marketed, Biobutanol, a 2nd generation biofuel, appears as a serious candidate with a strong potential for a spark-ignition engines use. The objective of this dissertation is to study the potential of the iso-octane/butanol blends use in spark-ignition engines, in terms of performance and pollutants emissions. Moreover, these results are compared to isooctane/ethanol blends. The heat release in spark-ignition engine is piloted for a part by laminar burning velocity. This characteristic was studied experimentally and numerically for different initial conditions (pressure and equivalence ratio) in a constant volume bomb. Then, the early flame kernel growth was studied in a spark-ignition single cylinder engine equipped with optical accesses. Those results were correlated with the results on the laminar burning velocity. Finally, regulated and non-regulated pollutants emissions and engine performance were investigated in a spark-ignition single cylinder engine. A decrease of most pollutant emissions was observed with both alcohols addition.

Orientador: Renato Sprung / Tese doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-06T18:06:45Z (GMT). No. of bitstreams: 1 Villanueva_SandraBizarriaLopes_D.pdf: 2768871 bytes, checksum: ec40bbcbf8152a8c34f6d7fdd395af83 (MD5) Previous issue date: 2005 / Resumo: Materiais do tipo hidrotalcita foram sintetizados, calcinados e caracterizados, assim como utilizados na conversão catalítica de etanol. As sínteses foram realizadas com razões molares AI/(AI + Mg) iguais a 0,20; 0,25 e 0,33; em todos os casos os difratogramas de raios-X demonstraram que, efetivamente, fases de hidrotalcitas tinham sido obtidas. Esses materiais apresentaram áreas superficiais BET de cerca de 50 a 70 m2.g-l, à exceção da hidrotalcita sintetizada com agentes precipitantes contendo amônio, em que a área superficial foi de cerca de 7 m2g -I. A quimissorção de CO2 desses materiais revelou que hidrota1citas calcinadas são sólidos básicos e tal basicidade relaciona-se com o teor de magnésio substituído e também com a temperatura de ca1cinação. Os testes catalíticos foram realizados a temperaturas de 3000 C a 4000 C e verificou-se o aumento da taxa de reação com o incremento da temperatura. Os produtos de condensação éter etílico e nbutanol foram obtidos em maior proporção. Hidrotalcitas da série sódio apresentaram maior rendimento de n-butanol independentemente do teor de alumínio presente na amostra. Todas as amostras utilizadas apresentaram, a baixas conversões, quantidades significativas de n-butanol, o que pode indicar que, além da via de condensação aldólica, a formação desse produto também ocorre via condensação direta do etanol, ou seja, sem a dessorção para a fase gasosa da molécula de acetaldeído. Testes catalíticos comparativos realizados com óxido de magnésio e alumínio resultaram principalmente em acetaldeído e etileno, respectivamente. Traços de n-butanol foram identificados no óxido de magnésio quando testado a 4000 C, e éter etílico foi observado em maior quantidade no óxido de alumínio quando testado a 3000 C / Abstract: Hydrotalcites-like materiaIs were prepared, calcined and characterized as well as used in the catalytic reaction of ethanol. The synthesis were perfonned with AI/(AI + Mg) ratios of 0.20; 0.25 and 0.33; in all cases the x-ray showed hydrotalcites phases. These materiaIs resulted in BET areas of 50 at 70 m2.g-1, except for the hydrotalcite synthesized with NH3, that resulted in a BET area 00 m2g-1. The CO2 chemisorption on these materiaIs revealed that calcined hydrotalcites are basic catalysts and their basicity was related to the quantity of substituted magnesium and to the calcination temperature. The catalytic reactions were performed at 300, 350 and 4000 C; the reaction rate increasing with reaction temperature. The main reaction products identified were ether and n-butanol. The hydrotalcite synthesized with cation sodium presented the highest yield of n-butanoI independent of aluminum content present in the samples. The results of Iow conversions showed significant yield of n-butanoI, and this could indicate that the formation of that product occurs by aldoI condensation and aIso by straight condensation of ethanoI molecule, without acetaldehyde desorption to gas fase. Comparative catalytic tests performed with MgO and AI203 showed acetaldehyde and ethylene predominantly as reaction products. Traces of n-butanoI were identified with MgO when the reaction occurred at 4000 C, and ether was identified with AI203 when the reaction occurred at 3000 C / Doutorado / Desenvolvimento de Processos Químicos / Doutor em Engenharia Química

Déterminer la composition en triacylglycérols des huiles végétales est un défi important à relever aussi bien en biologie végétale que dans le domaine médical ou celui de l’industrie agro-alimentaire. La chromatographie en phase liquide à polarité inversée de phases en milieu non aqueux (NARP-LC) est la méthode la plus utilisée, avec cependant une utilisation récurrente de solvants chlorés. Le premier objectif de ce travail a été de proposer des conditions analytiques alternatives n’utilisant pas de solvants chlorés. Pour ce faire, nous avons établi le diagramme de force éluante sur phases stationnaires en C18 des phases mobiles binaires constituées d’acétonitrile comme solvant faible et de divers solvants forts (acétone, iso-propanol, acétate d’éthyle, butanol) à quatre températures différentes (25, 43, 63 et 85°C). La comparaison dans des conditions iso-éluantes de l’analyse de 9 huiles de graines contenant une large gamme de TAG nous a permis de montrer que le mélange MeCN/BuOH 74/26 à 25°C est le meilleur choix, en terme de sélectivité pour l’analyse des TAG. Ce qui répond à notre premier objectif. Dans un second temps, nous avons comparé le potentiel séparatif des phases stationnaires de nouvelle génération à petit diamètre de particules, partiellement ou totalement poreuses. L’optimisation des conditions chromatographiques nous a permis de décrire deux systèmes chromatographiques, très performants, en termes d’efficacité et de rapidité. Le premier permet la séparation de TAG contenant des acides gras polyinsaturés isomères de position en C18 : 3 et C18 : 2. L’identification de ces isomères particuliers a été réalisée grâce à la synthèse d’informations complémentaires, obtenues en GC/MS, LC/MS ainsi que l’utilisation de lois de rétention chromatographiques. En outre, ce travail nous a permis de proposer un tableau récapitulatif regroupant un très grand nombre de TAG, qui n’ont jamais été décrits à notre connaissance. Le second permet une analyse rapide de l’huile d’olive, en moins de 5 min, tout en respectant les consignes qualitatives imposées par l’organisme «Conseil Oléique International (COI)». Comparée aux méthodes officielles couramment utilisées, elle mérite d’être proposée comme méthode de référence pour le contrôle de qualité de l’appellation de ces huiles. / The determination of triacylglycerols in vegetable oils is an important challenge in plant biology, in the medical field, and in food industry. Nowadays, non-Aqueous Reversed Phase Liquid Chromatography (NARP-LC) using chlorinated solvents is commonly used for this purpose. The first objective of this work was to develop alternative analytical conditions that can avoid using chlorinated solvents. In a first step, by using C18 stationary phases, we have established the eluotropic solvent strength scale as a function of temperature of several binary mobile phases consisting of acetonitrile as weak solvent and various strong solvents including acetone, isopropanol, ethyl acetate, and butanol. The comparison of the results obtained under iso-eluotropic conditions for nine seed oils containing a wide range of TAG enabled us to show that the MeCN/BuOH (74/26, v/V) mixture operating at 25 °C are the best mobile phase conditions for TAG analysis, in terms of selectivity, thus avoiding the use of chlorinated solvents. In a second step, we compared the separation of TAGs on new generation of fully or partially porous stationary phase particles of small diameter. After optimizing the separating conditions, the obtained data allowed us to propose two highly efficient chromatographic systems. The first system enables the efficient separation of C18:3 and C18:2 positional isomers of C18 polyunsaturated fatty acids containing TAG. For the identification of these TAG isomers, it was necessary to combine the data obtained by GC-MS and LC -MS as well as the data obtained by the application of some chromatographic retention laws. Taken together, these results allowed us to provide a list containing a large number of TAG unknown to date. The second system allows rapid analysis of olive oil in less than 5 min. This system obeying the guidelines of the International Olive Council can be proposed as a candidate reference method for rapid quality control of olive oils.

Efterfrågan på energi ökar snabbt, och denna trend förväntas bestå. Det råder dock ingen tvekan om att världen för närvarande befinner sig i en energikris, som är en katastrof både ekonomiskt och miljömässigt. Följaktligen är sökandet efter alternativa energikällor för att ersätta fossila bränslen absolut nödvändigt. Biobränslen som härrör från biomassa ökar i popularitet på grund av deras höga tillgänglighet och förmåga att minska utsläppen av växthusgaser. Butylbutyrat är ett potentiellt substitut för diesel- och flygmotorbränsle, vilket gör det till en viktig energikälla för både land- och lufttransporter. I den här studien undersöks enzymatisk katalys för produktion av butylbutyrat genom förestring av butanol och smörsyra med hjälp av olika membran. Användningen av enzymer som katalysatorer erbjuder många fördelar jämfört med traditionella kemiska katalysatorer, såsom ökad selektivitet, mildare reaktionsförhållanden och miljövänliga processer. Estrarnas byggstenar, n-butanol och smörsyra, är viktiga kemikalier och kan produceras i biotekniska processer med hjälp av förnybara källor som lignocellulosabaserad biomassa, vilket bidrar till övergången från en petroleumbaserad till en hållbar energiförsörjning. Produktionen av butanol och smörsyra i bioreaktorer försvåras av de typiska hindren för biobränsleproduktion, såsom produkthämning, höga bearbetningskostnader i efterföljande led och låga utbyten. NanoLodge-projektet bygger på tre reaktorer, en för produktion av butanol och en för smörsyra, i två separata men sammankopplade kontinuerliga Clostridium fermenteringar, och ett tredje reaktionssystem för enzymatisk förestring. Alla tre processerna i en, med dedikerade membran som separerar de olika reaktiva systemen, förväntas öka utbytet och samtidigt skapa en mycket integrerad anläggning som kan skalas upp för storskalig drift. Med hjälp av Raman-spektroskopi, GC-FID, FTIR och SEM undersöktes och karakteriserades fem distinkta material och deras relativa membranförändringar, inklusive enzymet på det översta lagret. FTIR-resultaten indikerade att för några av dem var porerna effektivt fuktade med reaktanterna, och membranens hydrofobicitet ökades genom att applicera lämplig beläggning, som även innefattade enzymet. Även om varken syntes av butylbutyrat eller passage genom de olika skikten av membranen inträffade, visade Raman-spektroskopi och GC-FID att et av membranen var en möjlig kandidat för förestring. Dessutom kunde inte alla testade membran motstå reaktionsmediet eftersom SEM-bilder avslöjade att vissa områden av ytan och strukturen hade ändrats något. Mer studier behövs för att fastställa att det med lovande membranet och dess modifieringar, särskilt den hydrofoba naturen och det immobiliserade enzymet, är acceptabla för butylbutyratsyntes. Ytterligare forskning kan utforska processoptimering, enzymimmobiliseringstekniker och reningsmetoder nedströms för att förbättra den totala effektiviteten och ekonomiska bärkraften för denna enzymatiska förestringsprocess.

Orientadores: Eduardo Augusto Caldas Batista, Antonio José de Almeida Meirelles / Dissertação (mestrado) - Universidade Estadual de Campinas, Fauldade de Engenharia de Alimentos / Made available in DSpace on 2018-08-17T21:09:08Z (GMT). No. of bitstreams: 1 Fonseca_LucianaAparecidaAndradePreviato_M.pdf: 1748931 bytes, checksum: 613a144c2469dfa664248bafa33dc2ac (MD5) Previous issue date: 2011 / Resumo: Dados de equilíbrio são úteis para o projeto e otimização de processos que envolvem separação de fases, como destilação e extração. Os álcoois superiores são subprodutos do processo de destilação relacionados com o aroma de bebidas alcoólicas e que, quando purificados podem agir como solvente. Esse estudo tem por objetivo a obtenção de dados isobáricos de Equilíbrio Líquido-Vapor (ELV) para sistemas binários e ternários envolvendo álcoois superiores. Dados de Equilíbrio Líquido-Vapor foram medidos para os sistemas binários compostos por 2-propanol/2-metil-1-butanol a 560 e 760 mmHg e para os sistemas ternários compostos por 2-propanol/1-butanol/3-metil-1-butanol e 2-propanol/2-metil-1-propanol/2-metil-1butanol, ambos a 760 mmHg. As medidas experimentais foram realizadas em ebuliômetro Fischer (VLE 602) e as composições das fases foram determinadas por cromatografia gasosa. A consistência termodinâmica dos dados de ELV binário P-T-x-y foi avaliada pelo teste de área e teste de van Ness-Fredenslund e os resultados comprovaram a boa qualidade dos dados de ELV determinados nesse trabalho. Os parâmetros de interação binária dos modelos NRTL, Wilson e UNIQUAC foram ajustados aos dados experimentais dos sistemas binários utilizando-se o software comercial Aspen Plus 12.1. Os resultados mostram uma boa descrição do ELV por esses modelos. Esses parâmetros foram ainda utilizados para descrever ELV dos sistemas ternários. Esses últimos resultados mostram uma boa concordância entre os dados experimentais e os calculados / Abstract: Equilibrium data are useful for design and optimization of processes involving phase separation, such as distillation and extraction. The higher alcohols are byproducts of the distillation process related to the flavor of alcoholic beverages and that when purified can act as a solvent. This study aims to obtain isobaric Vapor-Liquid Equilibrium (VLE) data for binary and ternary systems involving higher alcohols. Vapor Liquid Equilibrium were measured for the binary system composed by 2-propanol/2-methyl-1-butanol at 560 and 760 mmHg and for the ternary systems composed by 2-propanol/1-butanol/3-methyl-1-butanol and 2-propanol/2-methyl-1-propanol/2-methyl-1butanol, both at 760 mmHg. The experimental measurements were performed in a Fischer ebulliometer (VLE 602) and the phase compositions were determined by gas chromatography. Thermodynamic consistency of the VLE binary data P-T-x-y was evaluate by area test and van Ness-Fredenslund test and the results proved the good quality of the VLE data determined in this work. The binary interaction parameters of the NRTL, Wilson and UNIQUAC models were fitted to the experimental binary VLE data in the commercial software Aspen Plus 12.1. The results show a good description of the VLE data. These parameters were used to describe the VLE data for the ternary systems and the results show a good agreement between experimental and calculated data / Mestrado / Engenharia de Alimentos / Mestre em Engenharia de Alimentos

Les travaux dont les résultats sont présentés dans ce manuscrit ont été menés dans le but de préparer des matériaux catalytiques à base de métaux nobles pour l'élimination de certains composés organiques volatils (COV). Différents catalyseurs à base de platine ont ainsi été préparés et leurs performances catalytiques évaluées pour l'oxydation de deux polluants : le n-butanol et l'acide acétique. Une première étude sur l'élimination oxydative et non-oxydative du n-butanol sur des catalyseurs à base de platine supportés sur alumine a été menée. Ce travail a porté essentiellement sur l'étude de l'effet des différents paramètres intervenant dans la réaction (oxygène, eau, métal). Le phénomène d'adsorption-désorption du polluant à la surface du catalyseur a également été étudié. S'inspirant des données de la littérature sur les propriétés redox particulières de la cérine, les travaux ont ensuite porté sur l'effet de l'ajout de CeO2 à des catalyseurs de type Pt/Al2O3 pour l'oxydation du n-butanol et de l'acide acétique. La modification des propriétés redox et acido-basiques ainsi que celle des performances catalytiques du matériau observées avec l'ajout de CeO2 a permis d'établir une corrélation entre activité catalytique en oxydation, capacité de stockage de l'oxygène et basicité. Cette corrélation a été confirmée dans la dernière étude menée sur des catalyseurs mis en forme de type monolithes enduits avec différents matériaux (Pt/Al2O3, Pt/CeO2, Pt/ZrO2, Pt/Al2O3-CeO2, Pt/Al2O3-ZrO2 et Pt/CeO2-ZrO2). / The results presented in this manuscript have aimed at preparing catalytic materials based on noble metals for the removal of volatile organic compounds (VOC). Thus, different platinum based catalysts have been prepared and their catalytic performances have been evaluated for n-butanol and acetic acid oxidation. A first study on oxidative and non-oxidative removal of n-butanol over alumina supported platinum based catalysts has been performed. This work focused on the study of the effect of the different parameters involved in the reaction (oxygen, water, metal). The adsorption-desorption phenomenon of the pollutant on the catalyst surface has also been studied.Inspired by the literature on the specific redox properties of ceria, the work was then focused on the effect of the addition of CeO2 to Pt/Al2O3 catalysts for n-butanol and acetic acid oxidation. The modification of the redox and acid-base properties as well as that of the catalytic performances of the material with the addition of CeO2 allowed to establish a relationship between catalytic oxidation activities, oxygen storage capacity and basicity. This correlation has been confirmed in the last study performed on the monolithic catalysts coated with different materials (Pt/Al2O3, Pt/CeO2, Pt/ZrO2, Pt/Al2O3-CeO2, Pt/Al2O3-ZrO2 and Pt/CeO2-ZrO2).

L'objectif de ce travail était d'étudier en profondeur la synthèse catalytique de lévulinates de butyle à partir de biomasse, d'abord en utilisant les isomères de butanol, puis les isomères de butène comme agents d'estérification. Généralement obtenus par estérification de l'acide lévulinique, les esters lévuliniques et notamment les lévulinates de butyle présentent des propriétés physiques et chimiques faisant d'eux de potentiels additifs de carburant, molécules plateformes, solvants ou encore additifs pour l'industrie alimentaire ou pharmaceutique. En convertissant sélectivement la cellulose en lévulinates de butyle, aucune étape de synthèse et de purification d'intermédiaires réactionnels n'a été nécessaire. Dans les isomères de butanol, la conversion de la cellulose en lévulinates avec H2SO4 a permis d'obtenir à 200°C respectivement 50 et 14% d'esters dans les alcools primaires et secondaire. L'utilisation de zircone sulfatée et de phosphotungstate de césium a abouti à la formation de 15% d'esters dans les alcools primaires, et de 3% dans l'alcool secondaire. L'utilisation d'oléfines comme substituant aux alcools fut étudiée en présence d'acide sulfurique. Avec le n-butène, l'estérification de l'acide lévulinique a donné 55% de lévulinate de sec-butyle à 100°C et en absence de solvant. A partir de cellulose, un rendement de 19% a été obtenu à 100°C dans l'iso-octane. Avec l'iso-butène, 50% de lévulinate de tert-butyle ont été obtenus à partir de l'acide lévulinique, sans solvant et à 25°C. En présence d'Amberlyst-15, 80% de rendement ont pu être obtenus, avec une réutilisation jusqu'à 6 fois du catalyseur sans désactivation notable / The objective of this work was to study in details the catalytic synthesis of butyl levulinates from biomass, first by using butanol isomers, then butene isomers as esterifying agents. Usually obtained by esterification of levulinic acid, levulinic esters including butyl levulinates possess physical and chemical properties making them potential fuel additives, platform molecules, solvents or additives for the food or pharmaceutical industry. By selectively converting cellulose into butyl levulinates, no step of synthesis and purification of reaction intermediates was necessary. In butanol isomers, the conversion of cellulose to levulinates with H2SO4 gave at 200°C, respectively 50 and 14 % of esters in the primary and secondary alcohols. The use of sulfated zirconia and cesium phosphotungstate led to 15% of esters from primary alcohols, and 3% from secondary alcohol. The use of olefins as alcohol substituents was studied in the presence of sulfuric acid. With n-butene, the esterification of levulinic acid gave 55% of sec-butyl levulinate at 100°C and in the absence of solvent. From cellulose, 19% yield was obtained at 100°C in iso-octane. With iso-butene, 50% of tert-butyl levulinate was obtained from levulinic acid, without solvent and at 25°C. In the presence of Amberlyst-15, 80% yield was obtained, with a reuse up to 6 times of the catalyst without significant deactivation

The global warming on earth has been obvious since the 1950’s. Fossil fuels have a big impact on the observed warming and it is time to replace them with more environmentally friendly fuels. Biobutanol has been proven to be a preferred substitute to fossil fuels. The yeast Saccharomyces cerevisiae is a potential butanol producer. A problem in the biobutanol production is that the product, butanol, is toxic to the producer. In this study four S. cerevisiae strains were investigated for 1- and 2-butanol tolerance with spot tests and growth measurements with different concentrations of 1- and 2-butanol.  One of the four strains, an ale yeast, showed a higher tolerance for 1- and 2-butanol. 2-butanol was overall more tolerated by the yeast. The gene expression for the genes TMC1, LPL1, FLR1 and RPN4 was also investigated at exposure of 3 % 2-butanol. RPN4 is important in the proteasome protein degradation, which is associated with butanol tolerance. TMC1, LPL1 and FLR1 are associated to RPN4, which make them potential genes coupled to butanol tolerance. The genes TMC1 and RPN4 showed an up-regulation when exposed to 3 % 2-butanol. In conclusion, 2-butanol is preferred as a biofuel produced by ale yeast and the ideal genes to use in genetic engineering to achieve a higher butanol tolerance is TMC1 and RPN4. These results contribute to the development of an effective production of biobutanol by S. cerevisiae.

[pt] Com o passar do tempo, a humanidade tem uma maior dependência na geração de energia, utilizada para promoção de conforto, transporte e outros. Com a finalidade de resolver este aumento de demanda, novas fontes eficientes, de preferência renováveis, estão sendo pesquisadas. O transporte é uma das atividades que tem maior dependência dos combustíveis fósseis, além de ser também um dos maiores geradores de gases de efeito estufa. É por isso, que em diversas partes do mundo, o homem pesquisa novas fontes de energia renováveis que possam ser substitutas dos atuais tradicionais usados no transporte. Sabe-se, que os motores Diesel são mais eficientes com relação aos motores Otto. Devido a este fato, há mais 30 anos pesquisam-se e desenvolvem-se sistemas de ignição por compressão, movidos com combustíveis renováveis, o qual permita a diminuição da dependência dos combustíveis fósseis e garanta a redução de gases de efeito estufa. O etanol é um candidato para substituir o oleo Diesel, mas tem que se levar em conta algumas alterações (aumento da relação de compressão, adição de melhoradores da autoignição, etc.) antes de ser utilizado nos motores Diesel. Com base nisto, a presente tese apresenta uma nova proposta, utilizar como melhorador da autoignição do etanol o n-butanol. Para tal propósito se desenvolveu diversos testes com diversas relações de compressão, percentuais em massa de aditivo na mistura de etanol e diversos avanços da injeção. Os testes foram realizados em uma máquina de compressão rápida (MCR) com misturas de etanol e polietilenoglicol 400 e 600, n-butanol, além dos testes refenciais com óleo Disel e ED95. Os resultados mostram que o n-butanol, com uma participação de 10 por cento na mistura, pode ser utilizado como melhorador da autoignição do etanol em sistemas de ignição por compressão. / [en] Over time, humanity has developed a greater reliance inpower generation, used to promoter comfort, transport and others. In order to address this increased demand new efficient sources are being searched, in preference, renewable sources. Transportation is one of the activities that have greater reliance on fossil fuels as well as being one of the largest generators of greenhouse gases. Therefore, in many parts of the world men are engaged in the search of new renewable energy sources that can substitute the current one used in transport. It is known that diesel engines are more efficient in comparison to the Otto engime. Due to this fact, for more than 30 years research has been conducted in order to develop ignition systems by compression, powered with renewable fuels, which reduces the dependence on fossil fuels and the emission of greenhouse gases. Ethanol is a viable candidate to replace diesel oil, but some improvements have to be accounted for before it s used in diesel engines, improvements such as the increase in compression ratio, adding auto-ignition improves, etc. Based on the facts presented, this thesis offers a new proposal, the use of n-butanol as an auto-ignition improver for ethanol. For this purpose several tests have been executed with various compression ratios, mass percentage of additive in the mixture off ethanol and many start of injections. The tests were performed in a rapid compression machine (RCM) with mixtures of ethanol and polyethylene glycol 400 and 600, and n-butanol inaddition to the reference test with diesel oil and ED95. The results show that n-butanol with a 10 per cent share of the mixture, can be used as an auto ignition improver for ethanol in compression ignition systems.

Understanding the composition of atmospheric organic particulate matter (OPM) is essential for predicting its effects on climate, air quality, and health. However, the polar oxygenated fraction (PO-OPM), which includes a significant mass contribution from carboxylic acids, is difficult to speciate and quantitatively determine by current analytical methods such as gas chromatography-mass spectrometry (GC-MS). The method of chemical derivatization and two-dimensional GC with time of flight MS (GC×GC/TOF-MS) was examined in this study for its efficacy in: 1) quantifying a high percentage of the total organic carbon (TOC) mass of a sample containing PO-OPM; 2) quantitatively determining PO-OPM components including carboxylic acids at atmospherically relevant concentrations; and 3) tentatively identifying PO-OPM components. Two derivatization reagent systems were used in this study: BF₃/butanol for the butylation of carboxylic acids, aldehydes, and acidic ketones, and BSTFA for the trimethylsilylation (TMS) of carboxylic acids and alcohols. Three α-pinene ozonolysis OPM filter samples and a set of background filter samples were collected by collaborators in a University of California, Riverside environmental chamber. Derivatization/GC×GC TOF-MS was used to tentatively identify some previously unidentified α-pinene ozonolysis products, and also to show the characteristics of all oxidation products determined. Derivatization efficiencies as measured were 40-70% for most butyl derivatives, and 50-58% for most trimethylsilyl derivatives. A thermal optical method was used to measure the TOC on each filter, and a value of the quantifiable TOC mass using a gas chromatograph was calculated for each sample using GC×GC separation and the mass-sensitive response of a flame ionization detector (FID). The TOC quantified using TMS and GC×GC-FID (TMS/TOCGC×GC FID) accounted for 15-23% of the TOC measured by the thermal-optical method. Using TMS and GC×GC/TOF-MS, 8.85% of the thermal optical TOC was measured and 48.2% of the TMS/TOCGC×GC-FID was semi-quantified using a surrogate standard. The carboxylic acids tentatively identified using TMS and GC×GC/TOF-MS accounted for 8.28% of the TOC measured by thermal optical means. GC×GC TOF-MS chromatograms of derivatized analytes showed reduced peak tailing due in part to the lesser interactions of the derivatized analytes with the stationary phase of the chromatography column as compared to the chromatograms of underivatized samples. The improved peak shape made possible the greater separation, quantification, and identification of high polarity analytes. Limits of detection using derivatization and GC×GC/TOF-MS were μL injected for a series of C2-C6 di-acids, cis-pinonic acid, and dodecanoic acid using both butylation and TMS. Derivatization with GC×GC/TOF-MS was therefore effective for determining polar oxygenated compounds at low concentrations, for determining specific oxidation products not previously identified in OPM, and also for characterizing the probable functional groups and structures of α-pinene ozonolysis products.