In the production of biodiesel via the transesterification of vegetable oils, purification to international standards is challenging. A key measure of biodiesel quality is the level of free glycerol in the biodiesel. In order to remove glycerol from fatty acid methyl ester (FAME or biodiesel), a membrane separation setup was tested. The main objective of this thesis was to develop a membrane process for the separation of free glycerol dispersed in FAME after completion of the transesterification reaction and to investigate the effect of different factors on glycerol removal. These factors included membrane pore size, pressure, temperature, and methanol, soap and water content. First, a study of the effect of different materials present in the transesterification reaction, such as water, soap, and methanol, on the final free glycerol separation was performed using a modified polyacrylonitrile (PAN) membrane, with 100 kD (ultrafiltration) molecular weight cut off for all runs at 25°C. Results showed low concentrations of water had a considerable effect in removing glycerol from the FAME. The mechanism of separation of free glycerol from FAME was due to the removal of an ultrafine dispersed glycerol-rich phase present in the untreated (or raw) FAME. The size of the droplets and the free glycerol separation both increased with increasing water content of the FAME. Next, three types of polymeric membranes in the ultrafiltration range with different molecular weight cut off, were tested at three fixed operating pressures and three operating temperatures (0, 5 and 25oC) to remove the free glycerol from a biodiesel reactor effluent. The ASTM standard for free glycerol concentration was met for the experiments performed at 25°C. The results of this study indicate that glycerol could be separated from raw FAME to meet ASTM and EN standards at methanol feed concentrations of up to 3 mass%. The process was demonstrated to rely on the formation of a dynamic polar layer on the membrane surface. Ceramic membranes of different pore sizes (0.05 µm (ultrafiltration (UF) range) and 0.2 µm (microfiltration (MF) range)) were used to treat raw FAME directly using the membrane separation set up at temperatures of 0, 5 and 25°C. The results were encouraging for the 0.05 µm pore size membrane at the highest temperature (25°C). The effect of temperature on glycerol removal was evident from its relation with the concentration factor (CF). Higher temperatures promoted the achievement of the appropriate CF value sooner for faster separation. Membrane pore size was also found to affect separation performance. A subsequent study revealed the effect of different variables on the size of the glycerol droplets using dynamic light scattering (DLS). A key parameter in the use of membrane separation technology is the size of the glycerol droplets and the influence of other components such as water, methanol and soaps on that droplet size. The effect of water, methanol, soap and glycerol on the size of suspended glycerol droplets in FAME was studied using a 3-level Box-Behnken experimental design technique. Standard statistical analysis techniques revealed the significant effect of water and glycerol on increasing droplet size while methanol and soap served to reduce the droplet size. Finally, a study on the effect of trans-membrane pressure (TMP) at different water concentrations in the FAME phase on glycerol removal using UF (0.03 µm pore size, polyethersulfone (PES)) and MF (0.1 and 0.22 µm pore sizes, PES) membranes at 25, 40 and 60°C was performed. Results showed that running at 25°C for the two membrane types produced the best results for glycerol removal and exceeded the ASTM and EN standards. An enhancement of glycerol removal was found by adding small amounts of water up to the maximum solubility limit in biodiesel. An increase in temperature resulted in an increase in the solubility of water in the FAME and less effective glycerol removal. Application of cake filtration theory and a gel layer model showed that the gel layer on the membrane surface is not compressible and the specific cake resistance and gel layer concentration decrease with increasing temperature. An approximate value for the limiting (steady-state) flux was reported and it was found that the highest fluxes were obtained at the lowest initial water concentrations at fixed temperatures. In conclusion, dispersed glycerol can be successfully removed from raw FAME (untreated FAME) using a membrane separation system to meet the ASTM biodiesel fuel standards. The addition of water close to the solubility limit to the FAME mixture enables the formation of larger glycerol droplets and makes the separation of these droplets straightforward.

Biodiesel ses som ett av de främsta substituten för fossila bränslen, då den relativt enkelt kan appliceras i redan existerande dieselmotorer. Dagens produktion av biodiesel använder sig av homogena katalysatorer som inte återanvänds i processen, men för en mer cirkulär och i längden en billigare process ses heterogena katalysatorer som ett alternativ. Syftet med denna studie var att undersöka litium dopad kalciumoxid katalytiska egenskaper, de optimala förhållandena för reaktionen och även kinetiken för reaktionen. Den valda katalysatorn syntetiserades med kalcinering och sedan testades den katalytiska förmågan i reaktionen vid olika reaktionsförhållanden, för att finna de optimala förhållandena. Även katalysatorns fysiska egenskaper analyserades och kinetiken för reaktionen. De optimala förhållanden för transesterifieringen bestämdes till 3 h, 1:6 olja- metanolförhållande, 60°C och 5 vikts% katalysator, där 96% utbyte av biodiesel uppnåddes. Övriga utbyten från de andra försöken var betydligt lägre, vilket kan bero på icke optimala förhållanden, men även relativ dålig katalytisk förmåga. Ytarea och porstorlek konstateras vara små, vilket påverkar den katalytiska förmågan negativt. Anledningen till katalysatorns egenskaper beror huvudsakligen på tillverkningsprocessen, men även mängden litium i dopningen. Kinetiken visar en oväntad reaktionsutveckling med initialt hög koncentration FAME (Fatty acid Methylester), vilket troligen beror på felkällor.

Huvudmålet i projektet var att analysera det vanligt förekommande additivet glycerolmonostearat, GMS, i plastprover. Projektet är en del av ett samarbete mellan KTH och det norska företaget Norner. Projektgruppen har jobbat för att utvärdera och optimera företagets nuvarande analysmetod samt att identifiera glycerolmonostearat i polypropylen. Olika lösningsmedel och derivatiseringsreagens testades, såväl som olika temperaturprofiler, för gaskromatografen jämfördes under projektet. Resultaten visade att glycerolmonostearat kunde derivatiseras genom silylering. Alla prover har sammanfattats i en slutgiltig metod som är lämpad för analys av polyolefiner som innehåller glycerolmonostearat. Slutmetoden saknade möjligheten för kvantitativ analys och kan därför förbättras i framtiden. / The main task was to analyze the very common additive, glycerol monostearate, GMS in plastic samples. The project was a collaboration between KTH students and the Norwegian company Norner. The goal was to evaluate and optimize the company's current method of analysis and identification of the content of GMS in polyolefins. Different solvents, derivatization agents and methods for gas chromatography were compared to find an effective process by which additives in polypropylene samples can be analyzed. The results showed that glycerol monostearate can be derivatized through a process called silylation. All different attempts have been summarized into one final method that was most suitable for the analysis of polyolefins containing glycerol monostearate. The final method was reproducible but lacked a properly determined quantification analysis. The final method can be improved further after this project. To give a few examples there are a lot more potential derivatization agents and solvents that can be substituted which requires further research.

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Biomass is one of the most promising replacements for fossil fuels as a feedstock for chemical and transportation fuel production. The combination of low vapor pressure and high polarity of most biomass derived molecules makes water the ideal solvent for biomass upgrading reaction schemes. Metal oxide and metal oxide supported catalysts are heavily used in oil refining and petrochemical production, and are capable of upgrading biomass molecules as well. However, the surface chemistries that dictate the behavior of aqueous phase biomass upgrading reactions over metal oxide catalysts are not nearly as well understood as in the case of gas phase hydrocarbon refining systems. This dissertation aims to investigate the surface chemistries of biomass derived oxygenate molecules on metal oxide and metal oxide supported metal catalysts. There are three main objectives in this dissertation: to understand how two and three carbon polyols interact with metal oxide surfaces, to elucidate the role of various surface sites on polyol-metal oxide interactions, and to discover the surface species of kinetic importance in aqueous phase reforming reactions of biomass molecules. Transmission infrared spectroscopy and density functional theory modeling were the major techniques used to demonstrate that polyols with alcohol groups on the first and third carbons, 1,3-propanediol and glycerol, form a multidentate surface species with a bridging alkoxide bond and an acid/base interaction through their two primary alcohol groups with Lewis acid sites of g-Al₂O₃. These interactions occur in the presence of bulk water. Polyols with alcohol groups only on the first and second carbons, ethylene glycol and 1,2-propanediol, only formed alkoxy bonds with the g-Al₂O₃ surface when bulk water was not coadsorbed, and these bonds were removed by re-adsorbing water. Glycerol also forms the same surface species on other metal oxides with strong Lewis acidic character: TiO₂ anatase, ZrO₂, and CeO₂. Glycerol only forms hydrogen bonds with MgO, which lacks strongly Lewis acidic sites. Basic surface hydroxyls and surface oxygen atoms of the metal oxides only played a minor role in interacting with the adsorbed glycerol. In-situ attenuated total reflectance infrared spectroscopy demonstrated that the aqueous phase reforming of glycerol over a 5 wt% Pt on g-Al₂O₃ catalyst is hindered by residual platinum bound hydrogen or oxygen atoms from commonly utilized catalyst reduction or cleaning procedures, respectively. A pretreatment consisting of multiple iterations of dissolved oxygen, dissolved hydrogen, and dissolved helium in water flow periods provides the cleanest Pt surface for monitoring carbon monoxide formation dynamics, and allows for observing the rate limiting step of the aqueous phase reforming reactions water-gas shift removal of Pt bound carbon monoxide. The bridging bound carbon monoxide is preferentially removed over the linearly bound species via water gas shift reactions even at room temperature.

La recherche de sources d’énergie fiables ayant un faible coût environnemental est en plein essor. L’hydrogène, étant un transporteur d’énergie propre et simple, pourrait servir comme moyen de transport de l’énergie de l’avenir. Une solution idéale pour les besoins énergétiques implique une production renouvelable de l’hydrogène. Parmi les possibilités pour un tel processus, la production biologique de l’hydrogène, aussi appelée biohydrogène, est une excellente alternative. L’hydrogène est le produit de plusieurs voies métaboliques bactériennes mais le rendement de la conversion de substrat en hydrogène est généralement faible, empêchant ainsi le développement d’un processus pratique de production d’hydrogène. Par exemple, lorsque l’hydrogène est produit par la nitrogénase sous des conditions de photofermentation, chaque molécule d’hydrogène constituée requiert 4 ATP, ce qui rend le processus inefficace. Les bactéries photosynthétiques non sulfureuses ont la capacité de croître sous différentes conditions. Selon des études génomiques, Rhodospirillum rubrum et Rhodopseudomonas palustris possèdent une hydrogénase FeFe qui leur permettrait de produire de l’hydrogène par fermentation anaérobie de manière très efficace. Il existe cependant très peu d’information sur la régulation de la synthèse de cette hydrogénase ainsi que sur les voies de fermentation dont elle fait partie. Une surexpression de cette enzyme permettrait potentiellement d’améliorer le rendement de production d’hydrogène. Cette étude vise à en apprendre davantage sur cette enzyme en tentant la surexpression de cette dernière dans les conditions favorisant la production d’hydrogène. L’utilisation de résidus organiques comme substrat pour la production d’hydrogène sera aussi étudiée. / The search for alternative energy sources with low environmental impact is in great expansion. Hydrogen, an elegant and simple energy transporter, could serve as means of transporting energy in the future. An ideal solution to the increasing energy needs would imply a renewable production of hydrogen. Out of all the existing possibilities for such a process, the biological production of hydrogen, also called biohydrogen, is an excellent alternative. Hydrogen is the end result or co-product of many pathways in bacterial metabolism. However, such pathways usually show low yields of substrate to hydrogen conversion, which prevents the development of efficient production processes. For example, when hydrogen is produced via nitrogenase under photofermentation conditions, each hydrogen molecule produced requires 4 molecules of ATP, rendering the process very energetically inefficient. Purple non-sulfur bacteria are highly adaptive organisms that can grow under various conditions. According to recent genomic analyses, Rhodospirillum rubrum and Rhodopseudomonas palustris possess, within their genome, an FeFe hydrogenase that would allow them to produce hydrogen via dark fermentation quite efficiently. Unfortunately, very little information is known on the regulation of the synthesis of this enzyme or the various pathways that require it. An overexpression of this hydrogenase could potentially increase the yields of substrate to hydrogen conversion. This study aims to increase our knowledge about this FeFe hydrogenase by overexpressing it in conditions that facilitate the production of hydrogen. The use of organic waste as substrate for hydrogen production will also be studied.

Cette thèse s’intéresse à la conversion du glycérol en acide lactique (AL) et 1,2-propanediol (1,2-PDO) par catalyse hétérogène. Le mécanisme de la réaction fait débat, particulièrement au sujet de la première étape, qui peut être une déshydratation ou une déshydrogénation. Il est attendu que ces étapes élémentaires soient influencées par le pH et la nature de l’atmosphère. Ces paramètres ont donc été étudiés expérimentalement, en présence d’un catalyseur au rhodium supporté sur charbon. D’autre part, il y avait un manque de connaissances sur le comportement du glycérol à la surface métallique du catalyseur. Une approche théorique sur une surface modèle a donc été mise en oeuvre dans le champ de la théorie de la fonctionnelle de la densité (DFT), pour examiner les étapes élémentaires et calculer les états de transition correspondants. La combinaison de ces études a montré que la déshydrogénation du glycérol en glycéraldéhyde est la première étape de la réaction sur le catalyseur Rh/C en milieu basique sous atmosphère d’hélium et d’hydrogène. Cette étude a ensuite été étendue à un catalyseur iridium supporté sur charbon, qui a mené à de meilleurs rendements en 1,2-PDO et AL. L’utilisation de ce métal supporté sur carbonate de calcium a permis d’améliorer le rendement en AL, mais l’activité est plus faible. Cependant, ce catalyseur s’est révélé relativement actif dans l’eau à pH neutre, ce qui pourrait conduire à une synthèse plus verte de l’AL. Enfin, les aspects prédictifs de la chimie théorique ont été examinés, pour voir si la réactivité de ce polyol complexe (du point de vue de la chimie théorique) pouvait être modélisée par celle d’un monoalcool sur la surface. / This thesis reports a study of the heterogeneously catalysed conversion of glycerol into 1,2-propanediol (1,2-PDO) and lactic acid (LA). The mechanism and the first step of the reaction are especially debated, as it can be either dehydration or dehydrogenation. It is expected that these elementary steps can be influenced by pH variations and by the nature of the gas phase. These parameters were consequently investigated experimentally in the presence of a carbon supported rhodium catalyst. On the other hand, there was a lack of knowledge in the behaviour of glycerol at the surface of the metallic catalyst. A theoretical approach on a model Rh(111) surface was thus implemented in the framework of Density Functional Theory (DFT) to look over the alementary reactions and to calculate the corresponding transition states. The combination of experimental and theoretical results has shown that dehydrogenation into lyceraldehyde is the first step of the reaction on the Rh/C catalyst in basic media under He or H2 atmosphere. The study was then extended to carbon supported iridium catalyst that lead to the best 1,2-PDO and LA yields. The use of iridium catalyst supported on calcium carbonate allowed obtaining higher yields in LA, but catalytic performances were lower. This latter catalyst was surprisingly quite active when performing the reaction in neutral water, which provides opportunities for a greener synthesis of LA. Last, the predictive aspects of the theoretical chemistry were investigated to determine whether the reactivity of this polyalcohol can be modelized by the reactivity of a simpler monoalcohol on the surface.

La biomasse représente l’une des principales alternatives à l’utilisation du pétrole dans la plasturgie. Grâce à leurs propriétés fonctionnelles, les caséinates sont une matière première prometteuse pour la fabrication de films plastiques pour des applications dans l’emballage biodégradable et hydrosoluble. La transformation du caséinate de sodium par les techniques habituellement utilisées dans la plasturgie a été démontrée. Des extrudats de caséinate plastifié au glycérol ont été obtenus au moyen d’une extrudeuse bi-vis corotative. La caractérisation physico-chimique du matériau obtenu a confirmé la thermostabilité de cette protéine et a montré la dépendance du comportement du matériau vis-à-vis de l’humidité ambiante. Pour une variation du taux d’Humidité Relative, de 40 à 90% et une augmentation de la concentration du glycérol, plastifiant hygroscopique, le matériau passe d’un état vitreux (rigide) à un état caoutchouteux (mou). Des films fins ont été ensuite réalisés, à partir des extrudats thermoplastiques, par extrusion gonflage. La perméabilité à la vapeur d’eau des films de caséinate de sodium a été étudiée et a montré que ces matériaux sont de mauvaises barrières à l’humidité. La deuxième partie a été consacré à l’étude de mélanges caséinate de sodium/caséinate de calcium d’un côté et caséinate de sodium/PBAT de l’autre. Le mélange des deux caséinates a permis d’augmenter la tenue mécanique du mélange, à partir de 50% de caséinate de calcium, et de retarder le transfert hydrique à travers le film. Dans le même sens, l’ajout du PBAT, a augmenté jusqu’à deux fois plus, le module d’Young des mélanges mais a baissé la résistance au transfert d’humidité du film à cause de l’incompatibilité des deux polymères / Biomass is one of the main alternatives to the use of oil in plastics field. Due to their various functional properties, caseinates are considered as an interesting raw material for making biodegradable and water-soluble packaging. The transformation of sodium caseinate by the processes used for synthetic plastics industry has been demonstrated. A corotating twin-screw extruder was used to get glycerol plasticized caseinate pellets. The physicochemical properties of the obtained material have confirmed the thermal stability of this protein and demonstrated the influence of surrounding moisture on material behavior. With the Relative Humidity varying from 40 to 90% and increasing the glycerol content, an hydrous plasticizer, the mechanical properties of sodium caseinate based materials changed from those of glassy (rigid) to rubbery (soft) plastics. The pellets were then taken over to make film using a blown-film extruder. The water vapour permeability of blown film was studied and showed that sodium caseinate based films are a poor moisture barrier. The second part dealt with the sodium caseinate blend. Sodium caseinate/calcium caseinate and sodium caseinate/PBAT blends was performed. Adding calcium caseinate, started from 50%, improved the mechanical properties and delayed hydrous transfer through the film. Concerning the sodium caseinate/PBAT blends, adding PBAT increased until twice more the material’s Young modulus but decreased the moisture transfer resistance because of the incompatibility between the two polymers