Biodiesel is a re-emerging biofuel as an alternative to the traditional petroleum derived diesel. There are however, several factors that currently hinder the widespread uptake. Majority of the biodiesel are currently produced from edible oils thereby sparking the food versus fuel debate, the cost of feedstock is significantly high, there are problems experienced in the traditional production process and the resulting fuel is of inadequate quality. This work focused on addressing the issue of poor cold flow properties to improve the overall quality of biodiesel. The skeletal isomerisation of linear fatty acid methyl esters (FAMEs) into branched chain isomers, using solid acid catalysts, appears to be the most comprehensive solution in enhancing the cold flow properties of biodiesel. However, obtaining high branched chain yields, mitigation of undesired side reactions, achieving shorter reaction times, using fewer processing steps and lower operating conditions have still not been achieved to a large extent. Moreover, no studies were found to date investigating isomerisation of FAMEs as a continuous process. A trickle bed reactor (TBR) system has been identified to be an effective continuous reactor. Its key features of being a three phase system and allowing a high degree of contact between the reactant and the catalyst offering a high conversion per unit volume provides an encouraging opportunity to lower reaction times, reaction steps and conditions whilst increasing branched chain yields. This thesis explores the use of the TBR system, for the first time, to enhance the cold flow properties of biodiesel through molecular modification using zeolite beta catalyst with Si/Al ratios of 180 and 12.5. A range of reactions have been investigated including isomerisation, dewaxing (hydroisomerisation and hydrocracking) and decarboxylation on biodiesels derived from camelina, palm and coconut oils. Significant progress has been made in this research area with a 7 °C drop in MP being achieved upon the dewaxing of the coconut biodiesel at 250 °C, 1.01 bar pressure, 0.2 ml/min LF and 37.5 ml/min GF. To achieve greater drops in melting points it has been suggested to investigate mesoporous catalysts as they will ensure greater facilitated molecular access to the active sites, resulting in a higher conversion by preventing pore blockages. All in all, a series of key findings and serendipitous discoveries have brought to surface an array of new challenges as well as paving the way for a host of exciting opportunities for future research. The ability to continuously produce high quality renewable fuel offers a fascinating prospective for various industrial associates such as Argent Energy, Olleco, Neste Oil and ConocoPhillips.

Improvement of biodiesel’s cold flow properties still remains one of the major challenges for using it as an alternative fuel in diesel engines. Therefore, the main objective of the present research was to use newly developed liquid biofuels, 3-hydroxyl fatty acid esters and ethers, as an additive for improving biodiesel cold weather properties. Test results revealed that blending with 10% 3-hydroxyl fatty acid esters (C4, C6, C8 and C12) improved biodiesel volatility, cloud point, flash point and kinematic viscosity without a significant loss in LHV. However, blending biodiesel with 3-hydroxyl fatty acid esters negatively affected the oxidation stability which was then found to improve by blending with 3-hydroxyl fatty acid ethers (1,3-DMO and 1,3-DMD). The latter novel fuel substance (1,3-DMO and 1,3-DMD) exhibited much higher evaporation rate compared to biodiesel and only slightly lower than that of decane, gasoline or ethanol. Moreover, the LHV of 1,3-DMO and 1,3-DMD was found to be almost equal to that of canola biodiesel, and higher than that of methanol and ethanol. These findings suggest that 1,3-DMO and 1,3-DMD have the potential to be used as additive to improve biodiesel cold weather combustion performance or as standalone fuels. / February 2016

京都大学 / 0048 / 新制・課程博士 / 博士(エネルギー科学) / 甲第20478号 / エネ博第347号 / 新制||エネ||69(附属図書館) / 京都大学大学院エネルギー科学研究科エネルギー社会・環境科学専攻 / (主査)教授 坂 志朗, 教授 塩路 昌宏, 准教授 河本 晴雄 / 学位規則第4条第1項該当 / Doctor of Energy Science / Kyoto University / DGAM

京都大学 / 新制・課程博士 / 博士(エネルギー科学) / 甲第23535号 / エネ博第426号 / 新制||エネ||81(附属図書館) / 京都大学大学院エネルギー科学研究科エネルギー社会・環境科学専攻 / (主査)教授 河本 晴雄, 教授 石原 慶一, 教授 川那辺 洋 / 学位規則第4条第1項該当 / Doctor of Energy Science / Kyoto University / DFAM

Les gazoles, carburant automobile préféré des français, sont « additivés » afin de permettre leur utilisation en hiver. Les n-paraffines présentes dans ces gazoles cristallisent en effet à basse température. Ces cristaux peuvent alors entraîner le colmatage des filtres protecteurs situés en amont du moteur. Des polymères à base d'éthylène, notamment les copolymères éthylène-acétate de vinyle (EVA), sont utilisés pour abaisser la température à laquelle les problématiques de filtration adviennent. Un nouveau procédé de copolymérisation radicalaire d'éthylène et d'acétate de vinyle, à plus basse pression et à plus basse température, que le procédé industriel actuel, a été développé au cours de cette thèse. Une grande variété d'EVA a ainsi été obtenue. Ils présentent des caractéristiques structurelles et une efficacité, pour le traitement des gazoles, similaires aux EVA commerciaux. Ce procédé a, par ailleurs, permis la synthèse d'autres co- et terpolymères de l'éthylène variant par la nature des comonomères polaires utilisés ou par l'architecture. Des modèles de copolymères EVA ont été également synthétisés par métathèse. La grande diversité d'additifs polymères à disposition combinée à des techniques d'analyse thermique et de diffusion des rayons X mises en oeuvre au plus proche de l'application (en particulier dans le gazole), ont permis de mieux appréhender leur mode d'action sur la cristallisation des n-paraffines. Les spécificités structurelles, des polymères, conditionnant leur efficacité pour le traitement de la tenue à froid des gazoles ont également pu être établies / The additivation of diesel fuels allows operating engines at low temperatures without filter blocking and thus fulfilling legal requirements. Ethylene based copolymers such as ethylene-vinyl acetate copolymers, made by free radical polymerization at high pressure (above 2000 bars) and high temperature (above 200 °C) are frequently used as middle distillate cold flow improvers (MDFI). A new free radical copolymerization process of ethylene and vinyl acetate in organic solvent media has been developed. This process gives access to polymers close to commercial MDFI additives under tremendous less drastic conditions (under 250 bars of ethylene and 70 °C). Thanks to this process, a wide diversity (variation of the nature of the polar unit, of polymer architecture…) of ethylene based polymers was obtained. Moreover, EVA model copolymers have been synthesized by metathesis. Thanks to these numerous and diverse ethylene based polymers combined with thermal analysis and X-ray scattering studies a better understanding of the operating mode of these additives in a diesel fuel has been achieved. The structural characteristics of the polymers enabling their effectiveness as diesel fuel cold flow improvers have also been established