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Lignin is one of the main components in wood and during the chemical pulping processes it is degraded and dissolved into the cooking liquor. The current challenge is to meet the need for energy and raw materials, and reform to a more environmentally sustainable society, so there is a great interest in using kraft lignin as a raw material for energy, materials and as source of chemicals. ) To meet this goal, it is essential to obtain kraft lignin with desirable properties. The overall goal of this master thesis project was to understand the relationship between kraft process conditions and the structure and properties of the dissolved lignin. Wood chips of pine, spruce and eucalyptus were pulped with the kraft process at constant temperature and similar alkali charge and sulphidity to different cooking times. From the collected black liquor, the dissolved kraft lignin was precipitated by acidification with sulphuric acid. It was observed that longer cooking time yields more precipitated material, where pine gave the highest yield. There was a significant difference in colour of the precipitated between eucalyptus and the softwood samples. Some the characteristic properties of the collected samples were investigated. Results from the Klason lignin and ionic chromatography showed variation in lignin and carbohydrate composition depending on raw material and cooking time. This was also indicated by results lignin carbohydrate ratio from analytical pyrolysis. However, the analytical pyrolysis data showed that the relative composition of lignin and carbohydrates was similar independent on pulping time and raw material. The sulphur content was higher for eucalyptus lignin compared to the softwood lignin. Pine lignin with the longest pulping time had the highest total phenolic content. Spruce lignin with the longest cooking time had the highest glass transition temperature. / Lignin är en av de största byggstenarna i träd och andra växtmaterial, både till storlek och mängd. Under kemiska massaframställningsprocesser, som sulfatprocessen, bryts strukturen ned och lignin löses ut i kokvätskan. Ligninets värmevärde tas till vara, genom att det förbränns i sodapannan. Med den utmaning som dagens samhälle står inför, där fossila råvaror ska ersättas med förnyelsebara, finns ett allt större intresse att se vilka andra användningsområden som kan finnas för lignin, som grön råvara för energi, material och kemikalier. Det krävs därför kunskap om hur lignin med lämpliga egenskaper ska kunna utvinnas. Målet med detta examensarbete var att undersöka hur vedråvara och koktid under sulftakoket påverkar egenskaper hos det utlösta ligninet. I denna studie kokades vedflis av tall, gran och eukalyptus enligt sulfatprocessen och det utlösta ligninet analyserades efter tre olika koktider. Längre koktid ledde till mer utfällt material. Det var en tydlig skillnad i färg mellan lignin från eukalyptus och de från barrveden, gran och tall Eukalyptusligninet var mörkare med en tydlig grönaktig färgskiftning. Längre koktid medförde även ett mer lättfiltrerbart lignin. Mängden lignin, bestämt som mängd Klason lignin efter sur hydrolys, var högre i utfällningen efter kok av eukalyptus jämfört med efter kok av barrved. Resultaten från den analytiska pyrolysen visar däremot på rakt motsatt förhållande. Enligt den analytiska pyrolysen är det något mindre mängd lignin i utfällningen efter eukalyptuskok. Orsaken kan vara att vid kvantitativ bestämning av lignin som Klason lignin, kommer det oorganiska materialet att fällas ut tillsammans med ligninet, varvid mängden Klason lignin även inbegriper askmängden. Mängden lignin som lösts ut under koket ökar med ökad koktid, men andelen lignin i det utfällda materialet ändras inte med koktiden. Svavelhalten var högre för (utlöst) eukalyptuslignin än för granlignin och talllignin. Talllignin med den längsta koktiden hade den högsta totala halten fenol. Gran lignin med den längsta koktiden hade det högsta värdet på glastransitionstemperaturen.

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CO2 activation and conversion mediated by transition metal (TM) catalysts were investigated. Homogeneous catalysis of the reverse water gas shift reaction CO2+H2→H2O+CO was studied as a means to reduce CO2.  β-diketiminato metal models L'MI ( L' =C3N2H5-; M = first-row TMs) were considered as potential catalysts. The thermodynamics of prototypical reaction pathways were simulated using B3LYP/aug-cc-pVTZ. Results show that middle series metal complexes result in more thermodynamically favorable properties; therefore, more detailed thermodynamic and kinetic studies were carried out for Mn, Fe, and Co complexes. On the other hand, heterogeneous catalysis of the reduction of CO2 to CO was carried out on Fe, Co, Ni, and Cu surfaces, using the PBE functional. Reaction barriers were calculated using the climbing image nudged elastic band method. Late 3d and 4d transition metal ion (Fe, Co, Ni, Cu, Ru, Rh, Pd, and Ag) mediated activation of dimethyl ether was studied to investigate the intrinsic catalytic properties of metals for C-O bond cleavage. A set of density functional theory (DFT) methods (BLYP, B3LYP, M06, M06-L, B97-1, B97-D, TPSS, and PBE) with aug-cc-pVTZ basis sets was calibrated with CCSD(T)/CBS calculations on reaction energies and barriers.

Carbon fibres are used in many applications thanks to their exceptional tensile properties in relation to their relatively low weight. These thin strands of at least 90% carbon are mixed with a matrix such as epoxy to form composites used for cars, wind turbines, prosthetics, and many other things. Carbon fibres are often manufactured from polyacrylonitrile (PAN) based on fossil oil, an expensive and non-renewable resource. Developing carbon fibres from renewable resources, like products from the forest industry such as lignin and cellulose could reduce the environmental impact of carbon fibre production. Cellulose precursors have long been used for carbon fibre production, but adding lignin could potentially increase the yield and improve the tensile properties of the carbon fibres. The transition from PAN carbon fibres to lignin-cellulose carbon fibres might also lower the cost. Currently, the properties of cellulose- and lignin-based carbon fibres are poor compared to other fibres on the market. Research like this work focuses on improving the tensile properties of the carbon fibres to make them viable alternatives. The focus of this work was to further develop the three main parts of thermal conversion: stabilisation, low-temperature carbonisation and high-temperature carbonisation, by evaluating the impact of temperature and tension on the tensile properties of the fibre. The fibres were converted using a continuous setup for each process step. The stabilisation profiles tested ranged between 245-260 ⁰C, low-temperature carbonisation between 460-600 ⁰C and high- temperature carbonisation between 1100-1600 ⁰C. Batch conversion was conducted to compare conversion methods. The results showed that the temperature of the low-temperature carbonisation had a large impact on the ability to stretch the carbon fibre and increase the tensile properties with 600 ⁰C being the optimal temperature out of the temperatures tested on the setup used in this thesis. The stretching during the high-temperature carbonisation and the temperature of the stabilisation had less impact on tensile properties. The properties of the precursor fibre are not always indicative of the properties of the carbon fibre, but the methods used for creating the precursor fibres have a great impact on the behaviour during thermal conversion.

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京都大学 / 新制・課程博士 / 博士(農学) / 甲第23238号 / 農博第2445号 / 新制||農||1083(附属図書館) / 学位論文||R3||N5328(農学部図書室) / 京都大学大学院農学研究科応用生命科学専攻 / (主査)教授 渡邊 隆司, 教授 植田 充美, 教授 梅澤 俊明 / 学位規則第4条第1項該当 / Doctor of Agricultural Science / Kyoto University / DFAM

京都大学 / 新制・課程博士 / 博士(農学) / 甲第23939号 / 農博第2488号 / 新制||農||1089(附属図書館) / 学位論文||R4||N5374(農学部図書室) / 京都大学大学院農学研究科応用生命科学専攻 / (主査)教授 渡邊 隆司, 教授 梅澤 俊明, 教授 森 直樹 / 学位規則第4条第1項該当 / Doctor of Agricultural 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24712号 / エネ博第455号 / 新制||エネ||85(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 亀田 貴之, 教授 髙野 俊幸 / 学位規則第4条第1項該当 / Doctor of Energy Science / Kyoto University / DFAM