Luktämnen i omgivningen kan utgöra distraktorer som försämrar den kognitiva prestationen. Detta gör luktens påverkan till en viktig arbetsmiljöfråga. De flesta vänjer sig vid lukter i omgivningen – de habituerar. Men ibland sker inte denna tillvänjning. Syftet var att undersöka ifall det finns ett samband mellan skillnad i habituering till ett luktämne och arbetsminne och inhibering. En grupp av 40 individer i åldrarna 19 till 64 exponerades för n-butanol under 45 minuter. Deltagarna gjorde upprepade skattningar av luktämnets intensitet och delades in i grupperna: icke-habituerare och habituerare. Före och under exponeringen utförde deltagarna 3-back, ämnat att mäta arbetsminne, och Stroop, ämnat att mäta inhibering. Gruppen icke-habituerare tenderade att prestera sämre på 3-back både före och under exponeringen. Oförmåga till habituering kan vara ett beteendeuttryck för sämre arbetsminneskapacitet och eventuellt andra sårbarhetsfaktorer. Dessa faktorer bör undersökas vidare. / Odorants in the environment can serve as distractors that impair cognitive performance. The impact of odors constitute an important occupational health issue. Most people get used to smells in the environment – they habituate. But occasionally habituation does not occur. The aim was to investigate whether there is a correlation between difference in habituation to an odorant and working memory and inhibition. A group of 40 individuals between the ages of 19 to 64, were exposed to n-butanol for 45 minutes. Participants made repeated ratings of intensity of the odorant. Two groups were created based on non-habituation and habituation. Before and during the exposure, the participants performed 3-back, used to measure working memory, and Stroop, used to measure inhibition. The group who did not habituate showed a tendency to perform worse on 3-back, before and during exposure. Inability to habituate may be a behavioral expression of poorer working memory capacity, and possibly other vulnerability factors. These factors should be further investigated.

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).

[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.

The present work studies the use of a two-zone computer model to simulate the operation of an internal combustion engine with spark ignition fueled with alcohol fuels and gasohol. To fit the model to the experimental data, a parameter estimation technique was used and the heat transfer correlation that could better fit the tested fuels and engine was determined. The tested fuels were: hydrous ethanol, wet ethanol (from 10% to 40% of water, by volume), n-butanol, n-butanol/ethanol blend and gasohol. In addition to the experimental tests with the engine, tests with a packed distillation column under batch process were made in order to determine the energy efficiency involved between production and use as a fuel for hydrous ethanol and wet ethanol fuels. The results showed that the two-zone model was able to predict satisfactorily the behavior of all tested fuels, accurately obtaining the engine performance parameters. In terms of energy efficiency, wet ethanol fuels have advantage over hydrous ethanol fuel, especially in the case of 30% of water by volume, where energy efficiency reaches its maximum value, considering the distillation and engine combustion processes. The n-butanol fuel was capable of act as a surrogate for both hydrous ethanol and gasohol with efficiency, leading the engine to have good performance in the tested operational conditions and appearing, due to this, as an interesting alternative of renewable fuel to be inserted in the Brazilian energy matrix. / O presente trabalho investiga o uso de um modelo computacional de duas zonas para simular o funcionamento de um motor de combustão interna com ignição por centelha abastecido com álcoois combustíveis e gasolina. Para o ajuste do modelo fez-se uso de técnica de estimação de parâmetros e determinação da correlação de transferência de calor capaz de melhor se ajustar aos combustíveis e ao motor testados. Os combustíveis utilizados foram: etanol hidratado, etanol super-hidratado (de 10% a 40% de água, em volume), n-butanol, misturas de n-butanol e etanol e gasolina e etanol. Além dos testes experimentais com motor, testes de bancada com uma coluna de destilação recheada em regime descontínuo foram realizados a fim de determinar a eficiência energética do processo de produção e queima de etanol hidratado e super-hidratado. Os resultados obtidos mostraram que o modelo de duas zonas é capaz de prever de maneira satisfatória o comportamento de todos os combustíveis testados, com determinação precisa de parâmetros de desempenho do motor. Em termos de eficiência energética, o etanol super-hidratado tem vantagem em relação ao etanol hidratado combustível, em especial quando com 30% de água em volume, onde a eficiência energética é máxima, considerados os processos de destilação e queima no motor. O n-butanol combustível usado mostrou-se capaz de substituir eficientemente tanto o etanol hidratado como a gasolina brasileira, levando o motor a ter boa performance nas condições operacionais testadas e aparecendo, dessa forma, como interessante alternativa de combustível renovável a ser inserida na matriz energética brasileira.

Cette étude a été menée en collaboration entre une équipe universitaire UBO, un organisme de recherche appliqué à la gestion de pollutions chimiques accidentelles liées au transport maritime (Cedre) et d'entreprises industrielles. La collecte de données physico-chimiques sur quatre produits est organisée autour d'une double démarche : identification des facteurs encore non pris en compte dans les protocoles de gestion d'accidents et mise au clair des grandes lois régissant des phénomènes déjà identifiés comme importants. Ainsi peuvent être présentées en toute limpidité des équations raisonnables mais simples, utilisables dans des logiciels d'aide à la décision. Dans ce cadre sont traitées les limites de solubilité, avec l'influence de la salinité et de la température. Cet ouvrage contient donc une collection de données (solubilités, tensions superficielles et interfaciales, masses volumiques, stabilité chimique, vitesses d'évaporation), mais surtout met en évidence l'importance des tensions interfaciales dans la gestion des étalements et contribue à clarifier l'influence de la salinité et de la température sur les solubilités dans les conditions marines.

Les Hydroxyapatites (HAp) sont des matériaux basiques dont les propriétés catalytiques atypiques, notamment leur très bonne sélectivité pour la transformation de l'éthanol en n-butanol, sont encore mal rationnalisées. La modulation de leur paramètres de synthèse ainsi leur aptitude à la substitution nous ont permis de jouer sur leur versatilité en termes de composition, stœchiométrie et morphologie en vue d'établir des relations structure-propriétés acido-basiques. De fait, au niveau macroscopique, la stœchiométrie -exprimée par le rapport Ca/P de cœur- et la morphologie de ces matériaux sont les deux facteurs déterminant pour le contrôle de la basicité des HAp. S'il reste à expliciter la différence de composition entre le cœur et la surface, dans tous les cas, qu'il s'agisse de sous stœchiométrie ou d'un mélange avec d'autres phases phosphates de calcium, dépourvues d'OH, la diminution de la teneur en hydroxyles va de pair avec une diminution de la réactivité basique. Cela oriente vers un rôle central de ces espèces au niveau moléculaire. Pour identifier la nature des sites superficiels impliqués en catalyse, une méthodologie visant à discriminer les signatures spectroscopiques IR et RMN des espèces OH et POH de cœur et de surface a été développée, notamment via des marquages isotopiques. L'implication de ces espèces superficielles a ensuite été suivie par adsorption de molécule sonde acides, CO2, acétylène, propyne (interaction paire acide base) et basiques, CO, pyridine. Si le CO2 conduit à une carbonatation de surface mais en aussi du cœur du matériau, les contributions OH et PO-H de surface interagissent avec les molécules protiques. Par contre, les cations ne sont pas systématiquement accessibles aux sondes et les PO4 de la HAp ne présentent pas d'interaction avec des molécules protique. Ces résultats nous conduisent à proposer l'implication d'une paire OH/PO-H atypique qui, en combinaison avec une importante mobilité des protons de ces matériaux, pourrait justifier en partie l'aptitude inhabituelle des HAp à former sélectivement du n-butanol dans la réaction de Guerbet.

This study investigated the equilibrium sorption capacities and rates of sorption of some alcohols on Na- and/or H- form of ZSM-35 at different temperatures by gravimetric method using an electrobalance. The alcohols studied were methanol, ethanol, propan-1-ol, propan-2-ol, n-butanol. The ZSM-35 sample used in sorption experiments resulted from a study for synthesis of high silica ZSM-35 zeolite. This ZSM-35 sample was called as NaZSM-35. The influence of ion-exchange on the sorption capacity and kinetics was investigated by converting NaZSM-35 into H-form by the ion exchange method. In this method, a sufficient amount of ZSM-35 sample (200-250 mg) was mixed with 25 ml of 1 N NH4Cl solution for 24 hours at room temperature. This procedure was repeated until no Na+ was detected by a Flame Photometer. After the ion exchange was completed , the sample was washed with deionized water, filtered, dried and recalcined for the removal of the ammonia and this sample was denoted as HZSM-35. The highest sorption capacity (cm3/g) was observed for methanol on HZSM-35 / 0.1656 cm3/g and the lowest sorption capacity was observed for propan-2-ol at NaZSM-35 / 0.003 cm3/g. Sorption of methanol and ethanol were very rapid. The sorption capacities of other three alcohols / propan-1-ol, propan-2-ol and n-butanol, were lower and they had slower rates of sorption. HZSM-35 had greater limiting sorption capacity than NaZSM-35 for propan-1-ol, propan-2-ol and n-butanol at all temperatures.

Abstract Limited oil resources, environmental concerns and legislation promoting renewable energy and restricting carbon dioxide emissions have increased biofuel production in recent years. Other alternatives besides bioethanol and biodiesel are also needed to fulfil the continuously increasing transportation fuel demand. Production processes should be material, energy and resource efficient and sustainable, i.e. causing as low negative economic, environmental and social impacts as possible. There are still some limitations and development areas to be solved before feasible industrial biofuels and biochemicals production processes are obtained. The production of biobutanol and bioethanol was studied in this work. Production processes, challenges and improvement requirements were considered especially in the case of the Acetone-Butanol-Ethanol (ABE) fermentation process. In addition, the sustainability assessment of biofuels production was discussed and an indicator-based approach to sustainability evaluation for different raw materials was used. Pervaporation as a product removal and purification method was experimentally studied. Two different applications were tested: a hydrophobic composite membrane with polydimethyl siloxane and polyacrylonitrile layers was used for the separation of acetone, n-butanol and ethanol from dilute aqueous solutions on a laboratory scale, and a hydrophilic polyvinyl alcohol membrane was applied for the dehydration of bioethanol at a pilot-scale. Results indicated that pervaporation can be used as a separation technique in biofuels production processes. New knowledge obtained during the research also promotes the efficient and sustainable production of biofuels and biochemicals and the development of industrial-scale applications. / Tiivistelmä Rajalliset öljyvarannot, huoli ympäristöstä sekä uusiutuvaa energiaa tukeva ja hiilidioksidipäästöjä rajoittava lainsäädäntö ovat lisänneet biomassapohjaisten polttoaineiden ja kemikaalien valmistusta ja käyttöä viime vuosina. Jatkuvasti kasvavan polttoainetarpeen täyttämiseksi tarvitaan myös muita vaihtoehtoja nykyisin käytössä olevien bioetanolin ja -dieselin lisäksi. Tuotantoprosessien tulisi olla materiaali-, energia- ja kustannustehokkaita sekä kestäviä aiheuttaen mahdollisimman vähän haitallisia taloudellisia, sosiaalisia ja ympäristöllisiä vaikutuksia. Biokemiallisissa, käymisen avulla tapahtuvissa polttoaineiden valmistusprosesseissa on kuitenkin vielä rajoitteita ja kehitystarpeita, jotka tulee ratkaista kannattavan teollisen mittakaavan tuotannon mahdollistamiseksi. Tässä työssä tutkittiin biopolttoaineiden, erityisesti biobutanolin ja -etanolin, valmistusta. Tuotantoprosesseja on esitelty työssä haasteiden ja kehitystarpeiden näkökulmasta. Lisäksi on käsitelty biopolttoaineiden tuotannon kestävyyden arviointia ja osoitettiin tapa verrata eri raaka-aineiden kestävyyttä valittujen indikaattoreiden avulla. Työn kokeellisessa osuudessa tutkittiin pervaporaatiota tuotteiden (asetoni, n-butanoli, etanoli) erotuksessa ja puhdistuksessa. Kahta eri sovellusta testattiin: hybrofobista polydimetyylisiloksaani- ja polyakrylonitriili-kerroksista koostuvaa komposiittikalvoa käytettiin asetonin, n-butanolin ja etanolin erottamiseen erilaisista vesiliuoksista laboratoriomittakaavan laitteistolla sekä hydrofiilistä, polyvinyylialkoholi-kalvoa bioetanolin vedenpoistoon pilot-mittakaavassa. Lisäksi testattiin aktiivihiilisuodatuksen käyttöä bioetanolin esipuhdistuksessa haitallisten komponenttien osalta ennen pervaporaatiota. Koetulokset osoittavat, että pervaporaatiota voidaan käyttää biopolttoaine-sovellusten erotusmenetelmänä. Tutkimuksen aikana saatu uusi tieto edistää biomassapohjaisten polttoaineiden ja kemikaalien tehokasta ja kestävää tuotantoa ja kehitystä kohti teollisen mittakaavan sovelluksia.

Les hydroxyapatites (HAps) sont des matériaux basiques qui présentent des propriétés catalytiques atypiques, notamment une sélectivité importante en butanol à partir de l’éthanol. Leur versatilité en termes de composition et de morphologie, facilement contrôlée par la synthèse, s’accompagne d’une grande modularité des propriétés acido-basiques de la surface, ce qui nous a permis d’établir des relations structure-réactivité dans l’objectif de rationaliser son mode de fonctionnement au niveau moléculaire. Certes, la stœchiométrie qui traduit le rapport Ca/P est un paramètre clé pour l’activité de ces matériaux dans ce type de réaction mais il s’avère que c’est plus précisément la concentration massique des OH des colonnes qui gouverne le niveau de la réactivité, ce qui oriente vers l’implication de ces espèces en tant que sites basiques. Au delà de cet aspect macroscopique, une approche visant la discrimination des contributions des OH-, PO43- et PO-H de surface et de cœur a été menée par IR et RMN du solide via des échanges isotopiques H-D, des prétraitements thermiques et des séquences RMN spécifiques. L’implication dans les interactions acides ou basiques des sites présents en surface a été suivie par adsorption de molécules sonde. L’adsorption du CO2 a révélé le caractère basique faible de la surface des HAps en générant des hydrogénocarbonates et des carbonates, respectivement suite à l’implication des OH basiques de terminaison en surface et des oxygènes de groupements phosphates. Seuls les OH qui émergent des colonnes sont impliqués dans l’interaction avec l’acétylène, conjointement avec les acides de BrØnsted PO-H (phosphates de terminaisons protonés). Les ions calcium sont peu accessibles (adsorption de CO et données XPS) et l’augmentation de leur accessibilité relative via la modulation de paramètres post-synthèse ne favorise pas la formation du n-butanol. Le suivi de la réaction de conversion d’éthanol en mode operando appuie la participation de la paire acide-base PO-H/OH dans le processus catalytique. L’étude de l’influence de la morphologie sur le comportement catalytique des HAps nous a incités à proposer qu’au-delà d’une réactivité favorisée sur les faces (001), l’allongement des particules bénéficie aussi au processus catalytique. Plus largement, le rôle joué par la mobilité des protons qui est un processus activé en température, permettrait d’unifier l’ensemble des données expérimentales qui rendent compte d’une sensibilité à la structure. / StructureHydroxyapatites (HAps) are basic materials which exhibit atypical catalytic properties, particularly a high selectivity in n-butanol from ethanol’s conversion. Versatility in terms of composition and morphology, easily tuned by synthesis, is accompanied by a high modularity of acid-base properties of the surface, which allowed us to establish structure-reactivity relationships in order to rationalize how the system works at a molecular level. Certainly stoichiometry, represented by the bulk Ca/P ratio, is a key parameter for the activity of these materials for this type of reaction, but it seems that the concentration of OH in the columns governs the conversion level, highlighting the role of these species as basic sites. Beyond this macroscopic aspect, an approach intended for the discrimination of the bulk and surface spectroscopic contributions of OH, PO43- and PO-H was implemented by IR and solid state NMR via H-D isotopic exchanges, thermal pretreatments and specific NMR sequences. The involvement of the present sites on the surface was investigated by adsorption of probe molecules. The CO2 adsorption revealed the low basicity of the surface generating hydrogenocarbonates and carbonates, respectively as a result of the interaction with the basic surface OH and oxygens of the phosphate groups. Only basic OH sites emerging from the columns are involved in the interaction with the acetylene, in association with Brönsted acids PO-H (protonated terminated phosphates). Calcium ions are inaccessible (CO adsorption and XPS data) and the increase of its relative accessibility via the modulation of the post-synthesis parameters does not promote the formation of n-butanol. Monitoring the reaction conversion of ethanol in operando mode supports the participation of the acid-base pair PO-H/OH in the catalytic process. The study of the influence of the morphology on the catalytic behavior of HAps led us to propose that beyond the enhancement of the reactivity on the (001) surfaces, the elongation of the particles is also beneficial to the catalytic process. The role of the protons mobility, activated by temperature, may unify all the experimental data that reflect a good sensitivity to the structure.

Abstract Volatile Organic Compounds (VOCs) in wastewaters from the chemical industry are of major concern because of their environmental and health impacts. The reclamation of VOCs from wastewaters would not only reduce the hazard to the environment but also contribute to an efficient use of resources. The thesis explores the reclamation of n-butanol and dichloromethane from sodium chloride containing mixtures by pervaporation. Another aim was to gain understanding of mass transport phenomena during the pervaporation of multicomponent systems, and the effect of sodium chloride on the pervaporation performance. In this work, the reclamation of n-butanol and dichloromethane was conducted as a sequence of pervaporation stages which utilised first hydrophobic and then hydrophilic membranes. The objective was to segregate the mixture of n-butanol/dichloromethane/sodium chloride/water into three different streams: a re-use quality concentrate of VOCs, brine, and discharge quality purified water. The effect of the experimental variables, VOCs feed concentration, feed temperature and sodium chloride content on the performance of the pervaporation stages was studied. A statistical design, response surface methodology, was used to further resource efficiency. The results indicate the potential of pervaporation for the reclamation of n-butanol and dichloromethane from aqueous mixtures. A single step of pervaporation of n-butanol/dichloromethane/sodium chloride/water systems using the CMX-GF-010-D (Celfa) and PERTHESE® 500-1 (P 500-1) membranes does not sufficiently concentrate the VOCs for direct re-use. It is also demonstrated that the electrolyte does not permeate through the membranes and does not affect their separation effectiveness significantly. The pervaporation of the water/dichloromethane/n-butanol system using the hydrophilic poly(vinyl alcohol)-titanium dioxide/polyacrylonitrile/polyphenylene sulfide (PVA-TiO2/PAN/PPS) membrane is effective for dewatering purposes. The membrane shows impermeable features towards dichloromethane in the studied conditions. The analysis of the mass transport phenomena demonstrates that, under the experimental conditions studied, the resistance towards the mass transport of the compounds through the membrane is mainly exhibited by the membrane itself. This study also shows the advantage of analysing the effect of temperature on membrane permeation by the permeation activation energy instead of by the apparent activation energy.