The depletion of fossil fuels and the need to deal with climate change lead to an increasing interest in renewable resources. Lignocellulosic biomass in general, and agricultural residues in particular, could serve as an excellent starting material for the production of cellulose, basic chemicals, lignin and bioethanol in a biorefinery framework as they are abundant, do not compete with food production and are distributed worldwide. Two factors considerably influence the composition and properties of biorefinery products: biomass feedstock and pretreatment process. Their influence on the separability of raw material into a carbohydrate and lignin fraction as well as the composition and properties of these products are objectives of this study. Hereby, the focus is on lignin, as its structure is particularly dependent on the aforementioned factors complicating its further utilisation. Different agricultural biomass namely barley straw, coconut shell powder, hemp shives, horse manure, maize straw, miscanthus, oat husk, pretreated alfalfa, rape straw, sunflower stalks, tomato stalks and wheat straw were investigated regarding their suitability for lignocellulose separation using alkaline soda pulping. Best separation into a carbohydrate and lignin fraction was achieved for pretreated alfalfa, miscanthus, wheat and barley straw. The purity of the obtained lignin fractions varied in the wide range of 57% klason-lignin content for sunflower stalks and 81% for pretreated alfalfa prior to further purification by dialysis. Lignin fractions were characterised by means of FTIR spectroscopy, elementary analysis, thioacidolysis, size-exclusion-chromatography, thermodesorption, differential scanning calorimetry and different wet chemical methods for determination of functional groups. Lignins could be classified into groups, within which they show similar characteristics: (A) horse manure, rape straw, (B) sunflower stalks, tomato stalks, (C) barley-, maize- and wheat straw and (D) hemp shives, miscanthus. In addition, promising lignin candidates were found for several applications. Thus, by screening different agricultural residues, it is possible to choose a specific raw material, in order to produce lignin with desired properties and functionalities. The effect of the pretreatment process was studied based on wheat straw. It was subjected to conventional alkaline pulping, microwave-assisted alkaline pulping and organosolv pulping using formic acid and hydrogen peroxide. Pulping parameters were varied in order to attain best possible separation into a carbohydrate and lignin fraction. Of the varied parameters the concentration of both sodium hydroxide and formic acid has the highest impact on yield and purity of the products for alkaline and organosolv pulping, respectively. It additionally influences the content of functional groups of the lignin fraction and is hence, an important parameter for lignin customisation for subsequent utilisation. Furthermore, the possibility of reducing pulping time by using microwave-assisted pulping instead of conventional alkaline pulping is promising, as the obtained carbohydrate fraction has a low intrinsic viscosity, which may enhance enzymatic hydrolysis.

Utilisation of biomass resources and CO2 abatement systems in currently exploited fossil resource based energy systems are the key strategies in resolving energy sustainability issue and combating against global climate change. These strategies are affected by high energy penalty and high investment. Therefore, it is imperative to assess the viability of these energy systems and further identify niche problem areas associated with energy efficiency and economic performance improvement. The current research work has two parts. The first part presents techno-economic investigation of thermochemical conversion of biomass into the production of fuels (Fischer-Tropsch liquid or methanol) and electricity. The work encompasses centralised bio-oil integrated gasification plant, assuming that the bio-oil is supplied from distributed pyrolysis plant. Bio-oil is a high energy density liquid derived from biomass fast pyrolysis process, providing advantages in transport and storage. Various bio-oil based integrated gasification system configurations were studied. The configurations were varied based on oxygen supply units, once-through and full conversion configurations and a range of capacities from small to large scale. The second part of this thesis considers integration of various CO2 abatement strategies in coal integrated gasification systems. The CO2 abatement strategies under consideration include CO2 capture and storage, CO2 capture and reuse as well as CO2 reuse from flue gas. These facilities are integrated into cogeneration or polygeneration systems. The cogeneration concept refers to the production of combined heat and power while polygeneration concept is an integrated system converting one or more feedstocks into three or more products. Polygeneration is advocated in this work attributed to its high efficiency and lower emission. Furthermore, it can generate a balanced set of products consisting of fuels, electricity and chemicals. It is regarded as a promising way of addressing the future rapidly growing energy demands. A holistic approach using systematic analytical frameworks comprising simulation modelling, process integration and economic analysis has been developed and adopted consistently throughout the study for the techno-economic performance evaluation of decarbonised fossil and bio-oil based systems. Important design methodology, sensitivity analysis of process parameters and process system modifications are proposed. These are to enhance the efficiency as well as lower the economic and environmental impacts of polygeneration systems. A shortcut methodology has also been developed as a decision-making tool for effective selection from a portfolio of CO2 abatement options and integrated systems. Critical and comprehensive analyses of all the systems under considerations are presented. These embrace the impact of carbon tax, product price evaluation and recommendations for sustainability of low carbon energy systems.

Le hêtre est une essence très répandue sur le territoire français et plus particulièrement dans la région Grand-Est. Toutefois, son bois est peu exploité, notamment pour des utilisations en conditions extérieures en raison de sa faible durabilité et son instabilité dimensionnelle. Pour favoriser et développer son utilisation, il est nécessaire de le traiter afin de limiter sa reprise en humidité et de le protéger contre les champignons de pourriture. Par ailleurs, la réglementation actuelle sur les produits de traitement du bois impose la mise au point de solutions alternatives respectueuses de l’environnement et de la santé. Dans ce cadre, les travaux développés durant cette thèse visent la valorisation du hêtre en tant que matériau via sa protection par un traitement « non-biocide », la furfurylation. Cette méthode consiste à polymériser in situ de l’alcool furfurylique dans le bois de hêtre. La mise au point du procédé a permis d’aboutir à du hêtre composite dont la durabilité et la stabilité dimensionnelle sont nettement améliorées. D’autre part, le hêtre est une essence feuillue pour laquelle la fraction hémicellulosique est riche en pentoses et plus précisément en xylose, précurseur de furfural. Des travaux ont donc été menés pour produire du furfural par hydrodistillation acide à partir de connexes issus de l’industrie de la première transformation du hêtre. Le furfural a ensuite été réduit en alcool furfurylique par transfert d’hydrogène. Les résultats prometteurs obtenus montrent qu’il est possible de mettre en place une filière locale alliant le hêtre comme source de molécules furaniques et le bois de hêtre comme matériau / Beech is a wood species present in the French territory, particularly in the Grand-Est region. However, beech is a under used wood, especially for outdoor uses, because it is non durability and it is dimensional unstability. To promote and develop its use, it is necessary to limit its recovery in moisture and treat to protect it against fungi decay. Futhermore, current regulation on wood treatment products imposes the development of alternative wood treatments more respectful of the environment and health. In this context, the work developed during this thesis is focused on valorisation of beech as a material through its protection by a “non-biocide” treatment, furfurylation. This method consists in an polymerisation in situ by heating a furfuryl alcohol solution into beech solid wood. The development of process led to a bio-based beech composite with significantly improved durability and dimensional stability.On the other hand, beech is a hardwood species in which the hemicellulosic fraction is rich in pentoses, and more precisely in xylose, precursor of furfural. Work has been done to produce furfural by acidic steam distillation, from beech primary wood processing by products. This molecule is then chemically reduced to furfuryl alcohol by hydrogen transfer.These promising results to show that it is possible to set up a local production combining beech as a local source of furanic molecules and beech wood as a solid material

The main focus of this diploma thesis is the utilization of spent coffee ground (SCG) and its biorefinery products in agriculture primarly as a prospective organic fertilizer. The study verifies an influence of the addition of native SCG as well as its acid hydrolysed, defatted and oxidized forms to experimental clay soil on chemical and physical properties (ph, conductivity and mineral content). Growing experiments were realized by using Lactuca sativa to detect positive or negative effects on growth. Samples of basic soil and soil with the addition of commercial NPK fertilizer served as a reference to measuring data. Measurements showed that addition of SCG and products of its biorefinery to the soil caused a decrease of pH and an increase of conductivity of soil samples. Significant increase of extractable calcium, magnesium, manganese and moderate increase of potassium content was detected. 2 % addition of SCG to soil had no impact on plants growth. The number and visual appearance of lettuces were comparable with plants in basic soil. No seed on acid hydrolysed samples germinated, which was caused by an increase of conductivity and sulphate content in these samples. In defatted and oxidized samples the early germination and the highest number of lettuces was observed. The low content of phosphorus in all soil samples had a great impact on growth rate and visual appearance of cultivated lettuces. In comparison with soil with NPK addition, lettuces in samples with SCG and its form had a pink-grey colour and lower growth.

The depletion of fossil fuels and the need to deal with climate change lead to an increasing interest in renewable resources. Lignocellulosic biomass in general, and agricultural residues in particular, could serve as an excellent starting material for the production of cellulose, basic chemicals, lignin and bioethanol in a biorefinery framework as they are abundant, do not compete with food production and are distributed worldwide. Two factors considerably influence the composition and properties of biorefinery products: biomass feedstock and pretreatment process. Their influence on the separability of raw material into a carbohydrate and lignin fraction as well as the composition and properties of these products are objectives of this study. Hereby, the focus is on lignin, as its structure is particularly dependent on the aforementioned factors complicating its further utilisation. Different agricultural biomass namely barley straw, coconut shell powder, hemp shives, horse manure, maize straw, miscanthus, oat husk, pretreated alfalfa, rape straw, sunflower stalks, tomato stalks and wheat straw were investigated regarding their suitability for lignocellulose separation using alkaline soda pulping. Best separation into a carbohydrate and lignin fraction was achieved for pretreated alfalfa, miscanthus, wheat and barley straw. The purity of the obtained lignin fractions varied in the wide range of 57% klason-lignin content for sunflower stalks and 81% for pretreated alfalfa prior to further purification by dialysis. Lignin fractions were characterised by means of FTIR spectroscopy, elementary analysis, thioacidolysis, size-exclusion-chromatography, thermodesorption, differential scanning calorimetry and different wet chemical methods for determination of functional groups. Lignins could be classified into groups, within which they show similar characteristics: (A) horse manure, rape straw, (B) sunflower stalks, tomato stalks, (C) barley-, maize- and wheat straw and (D) hemp shives, miscanthus. In addition, promising lignin candidates were found for several applications. Thus, by screening different agricultural residues, it is possible to choose a specific raw material, in order to produce lignin with desired properties and functionalities. The effect of the pretreatment process was studied based on wheat straw. It was subjected to conventional alkaline pulping, microwave-assisted alkaline pulping and organosolv pulping using formic acid and hydrogen peroxide. Pulping parameters were varied in order to attain best possible separation into a carbohydrate and lignin fraction. Of the varied parameters the concentration of both sodium hydroxide and formic acid has the highest impact on yield and purity of the products for alkaline and organosolv pulping, respectively. It additionally influences the content of functional groups of the lignin fraction and is hence, an important parameter for lignin customisation for subsequent utilisation. Furthermore, the possibility of reducing pulping time by using microwave-assisted pulping instead of conventional alkaline pulping is promising, as the obtained carbohydrate fraction has a low intrinsic viscosity, which may enhance enzymatic hydrolysis.

The world population is growing exponentially. At the same time, the availability of natural resources decreases dramatically – an alarming trend which demands for a sustainable use of our resources in a circular economic framework and hence, for the valorization of wastes and by-products. Owing to its high annual abundance, lignocellulosic biomass has a promising potential as renewable resource for the development of high-value products, covering fuels, platform chemicals, and specialty polymers. Besides, lignocelluloses offer an attractive basis for material applications, considering their peculiarity as natural composites and their inherent modifiability. Therefore, targeted chemical modifications have been widely used to exploit this potential and to further increase their spectrum of characteristics and application prospects. The objective of this study was to fabricate lignocellulose-based hydrogels, with the prospect to be used as soil conditioners in agriculture. Considering this application, this study was striving for the development of a simple synthetic pathway that ideally guarantees non-toxic and biodegradable products. Besides, two key factors were involved in the development of the synthetic route and constitute the center of this study: the accessibility of lignocelluloses towards chemical modifications – in view of their inherent recalcitrance – and the envisaged properties of the hydrogel, including high swelling rates and structural stability. To comply with both key factors, three basic processing steps were carried out: (1) feedstock activation by chemical or mechanical pretreatments, (2) introduction of ionic groups to induce swelling properties and (3) gel network formation via chemical crosslinking. Furthermore, to elucidate the behavior of different biomass types, wheat straw and beech sawdust were exemplarily surveyed. In the first step, different chemical (ozonolysis, alkaline and sulfite pulping) or mechanical (short-time ball milling) pretreatment approaches were used to activate the feedstocks by inducing compositional and/or structural alterations. In the second processing step, two modification reactions – carboxymethylation and phosphorylation (with phosphoric acid/molten urea) – were examined with emphasis on their ability to access lignocellulosic matrices and to realize high contents of ionic groups. In the final step, covalently crosslinked gel networks were formed using either citric acid or electron beam irradiation. Both crosslinking approaches were evaluated in detail with respect to yield and properties of the resulting hydrogels. In view of the two key factors proposed for this study – the accessibility of lignocelluloses and the final hydrogel properties – and amongst the approaches examined, the following synthetic pathway delivered the most promising results: ball milling ⟶ carboxymethylation ⟶ citric acid crosslinking. In this process, the promoting effect of ball milling can be attributed to particle size reduction, a breakdown of plant cell structures, and a decline of the cellulose crystallinity. The effectivity of carboxymethylation was particularly based on its alcoholic-alkaline media. Therefore, the uptake of alkali induced a partial disintegration of the lignocellulosic matrix, facilitating both the introduction of ionic groups and high swelling rates of the final gels. Overall, this path delivered promising results for straw-based gels, whereas beech sawdust was hardly accessible.

La croissance de la population mondiale et son effet sur la sécurité alimentaire et l'urgence du changement climatique, sont des facteurs qui favorisent des diverses innovations pour accroître l'efficacité de l'utilisation des ressources naturelles. Parmi lesquelles la biomasse est une ressource renouvelable d’une grande disponibilité. Une bioraffinerie peut transformer la biomasse en énergie durable, matériaux et des produits chimiques. Par contre, au début d'un projet de bioraffinerie, des décisions stratégiques doivent être prises. Et ainsi, le processus de décision doit tenir en compte diverses aspects, comme des conditions spécifiques du territoire où le projet est destiné à être déployé. Une étude récente montre que, bien que ce problème ait été traité par la communauté scientifique, l'accent est mis sur les facteurs de rentabilité économique. Cependant, considérer toutes les dimensions de la durabilité, «Économique», «Social», «Environnemental», «Technologique» et «Politique» est essentielle dans ce type de projets. Dans ces conditions, tous les outils d'optimisation disponibles ne conviennent pas. Par conséquent, une étude préliminaire sur les outils d'optimisation multi-objectifs est réalisée. Par la suite, une stratégie d'optimisation intégrant les dimensions de durabilité dans la phase amont du projet a été développée. En fin, le modèle développé a été appliqué à l'étude du déploiement de bioraffineries en Colombie. Ce modèle et son optimisation permettent une meilleure visibilité pour les décideurs, grâce à sa capacité de proposer des scénarios et d’évaluer les compromis de la durabilité en intégrant les préférences des parties prenantes / The growing global population and its effect on food security and the urgency for climate change mitigation, are issues that foster innovations to increase the efficiency of the use of natural resources. Among them, biomass is a renewable resource highly available. A biorefinery can transform biomass in source of energy, materials and chemical products. However, at the early stage of a biorefinery project, strategic decisions have to be made, including location, production capacity or technology to be used, determining the project’s feasibility. As a consequence, the decision process needs to consider several aspects, as the specific conditions of the territory where the project is supposed to be deployed. A recent study shows that despite this problem has been treated by the multiple objective programming community, the main focus has been centered on factors of economic profitability. However, consider the whole dimensions of sustainability, “Economical”, “Social”, “Environmental”, “Technological” and “Political” is essential in this kind of project. Under these conditions, not all available optimization tools are suitable. Hence, a preliminary study about multi-objective optimization tools is realized. Then, a general optimization modeling strategy integrating the sustainability dimensions at the early stage of a biorefinery project is developed. To finish, the developed model is applied to the case study of biorefinery deployment in Colombia. It will permit a better visibility for decision makers, because its capability to propose scenarios and evaluate sustainability trade-offs by integrating stakeholders preferences

Now when the interest is increasing to reach a sustainable infrastructure, one possibility SCA is experimenting with is the possibility to produce renewable hydrocarbons from black liquor which can be extracted from a Kraft process. However, when extracting the black liquor, a lot of sodium-based compounds are removed from the recovery process and when hydrocarbons are produced in SCA’s biorefinery, these compounds are caught in an aqueous solution. The aqueous solution is received at 50°C, and the sodium-based compounds are mainly sodium sulfate and sodium carbonate, where the solution do also contain organic compounds and a solvent that is used in the biorefinery.  This thesis focused on building a concept to extract sodium sulfate from the aqueous solution. The thesis did also include if any additional preparatory work needs to be done to the solution before extracting sodium sulfate. Finally, a flow chart that maps the energy needed for the process was created.  The method that was used was crystallisation by cooling the solution. By cooling the solution, sodium sulfates solubility decreases which will result in that sodium sulfate falls out of the solution as crystals. It was determined that the solvent that the solution contains should be extracted if the solvents boiling temperature is below 100°C. Further, by cooling the solution under stirring to 15°C with a residence time of 3 hours, unwanted compounds can be extracted. By later cooling the solution under stirring to 5°C with a residence time of 1 hour, it gave sodium sulfate decahydrate (Na2SO4·10H2O) with small amounts of organic compounds. By removing the water, the dry product reached a purity of 94wt% sodium sulfate with a yield of 12% (mass of dry product/mass of aqueous solution). This result reached the specific objectives that were set at the start of this thesis, which was to reach a purity of 90wt% sodium sulfate with a yield of 5%.  The energy intensity for evaporating the solvent is expected to be high. It highly depends on which solvent is used. However, this process can use the lowest quality of steam that is available from the pulp mill. It is expected that the cooling will require high amounts of cooling water and a high investment cost for the heat exchanger. Yet, this is a vital part of the process to reduce the need for coolers which is powered by electricity. / Nu när intresset ökar, för att nå en hållbar infrastruktur, så experimenterat SCA med möjligheten att producera förnybara kolväten från svartlut som kan extraheras från en sulfatprocess. Vid extrahering av svartluten tas dock mycket natriumbaserade föreningar bort från återvinningsprocessen och när kolväten produceras i SCA:s bioraffinaderi fastnar dessa föreningar i en vattenlösning. Den lösningen tas emot vid 50°C och de natriumbaserade föreningarna är huvudsakligen natriumsulfat och natriumkarbonat, där lösningen också innehåller organiska föreningar och ett lösningsmedel som används i bioraffinaderiet. Denna avhandling fokuserade på att bygga ett koncept för att extrahera natriumsulfat från vattenlösningen. Avhandlingen omfattade också om ytterligare förberedande arbete måste göras av lösningen innan man extraherar natriumsulfat. Slutligen skapades ett flödesschema som kartlägger den energi som behövs för processen. Metoden som bestämde sig för att användas var kristallisering genom kylning av lösningen. Genom att kyla lösningen minskar lösligheten av natriumsulfater vilket leder till att natriumsulfat faller ut ur lösningen som kristaller. Det bestämdes att lösningsmedlet som lösningen innehåller skulle extraheras om lösningsmedlets koktemperatur är under 100°C. Vidare, genom att kyla lösningen under omrörning till 15°C med en uppehållstid på 3 timmar, kan oönskade ämnen extraheras. Genom att senare kyla lösningen under omrörning till 5°C med en uppehållstid på 1 timme gav natriumsulfatdekahydrat (Na2SO4·10H2O) med små mängder organiska föreningar. Genom att avlägsna vattnet nådde den torra produkten en renhet av 94 vikt% natriumsulfat med ett utbyte av 12% (massa torr produkt/massa vattenlösning). Detta resultat nådde de specifika mål som sattes i början av denna avhandling, vilket var att nå en renhet av 90 vikt% natriumsulfat med ett utbyte på 5%. Energiintensiteten för att förånga lösningsmedlet förväntas vara hög. Det beror mycket på vilket lösningsmedel som används. Denna process kan dock använda den lägsta ångkvaliteten som finns tillgänglig från massafabriken. Det förväntas att kylningen kommer att kräva stora mängder kylvatten och höga investeringskostnader för värmeväxlaren. Ändå är detta en viktig del av processen för att minska behovet av kylare som drivs av elektricitet.

With a growing demand for electrical energy storage materials, lignin-derived carbon materials have received increasing attention in recent years. As a highly abundant renewable carbon source, lignin can be converted to a variety of advanced carbon materials with tailorable chemical, structural, mechanical and electrochemical properties through thermochemical conversion (e.g. pyrolysis). However, the non-uniformity in lignin structure, composition, inter-unit linkages and reactivity of diverse lignin sources greatly influence lignin fractionation from plant biomass, the pyrolysis chemistry, and property of the resulting carbon materials. To introduce a better use of lignocellulosic biomass to biofuels and co-products, it is necessary to find novel ways to fractionate lignin and cellulose from the feedstock at high efficacy and low cost. Deep eutectic solvent (DES) was used to extract lignin from high lignin-content walnut and peach endocarps. Over 90% sugar yields were achieved during enzymatic hydrolysis of DES pretreated peach and walnut endocarps while lignins were extracted at high yields and purity. The molecular weights of the extracted lignin from DES pretreated endocarp biomass were significantly reduced. The native endocarp lignins were SGH type lignins with dominant G-unit. DES pretreatment decreased the S and H-unit which led to an increase in condensed G-units, which may contribute to a higher thermal stability of the isolated lignin. Lignin slow pyrolysis was investigated using a commercial pyrolysis–GC/MS system for the first time to link pyrolysis chemistry and carbon material properties. The overall product distributions, including volatiles and solid product were tracked at different heating rates (2, 20, 40 ℃/min) and different temperature regions (100-200, 200-300 and 300-600 ℃). Results demonstrate that changes in reaction chemistry as a factor of pyrolysis conditions led to changes in yield and properties of the resulting carbon materials. Physical and chemical properties of the resulting carbon material, such as porosity, chemical composition and surface functional groups were greatly affected by lignin slow pyrolysis temperature and heating rate. Lignin-derived activated carbons (AC) were synthesized from three different lignin sources: poplar, pine derived alkaline lignin and commercial kraft lignin under identical conditions. The poplar lignin-derived ACs exhibited a larger surface area and total mesopore volume than softwood lignin-derived AC, which contribute to a larger electrochemical capacitance over a range of scan rates. The presence of oxygen-containing functional groups in all lignin-derived ACs, which participated in redox reaction and thus contributed to an additional pseudo-capacitance. By delineating the carbonization and activation parameters, results from this study suggest that lignin structure and composition are important factors determining the pore structure and electrochemical properties of the derived carbon materials. A 3-dimensional, interconnected carbon/silicon nanoparticles composite synthesized from kraft lignin (KL) and silicon nanoparticles (Si NPs) is shown to have a high starting specific capacity of 2932 mAh/g and a retaining capacity of 1760 mAh/g after 100 cycles at 0.72 A/g as negative electrode in a half-cell lithium-ion battery (LIB) test. It was found the elemental Si and C of the C/Si NPs were most likely linked via Si-O-C rather than direct Si-C bond, a feature that helps to alleviate the mechanical degradation from Si volume change and assure a sound electronic and ionic conductivity for enhanced electrochemical performance. EGA-MS and HC-GC/MS analyses suggest that the interaction of the Si, O and C can be tailored by controlling pyrolysis conditions. This study systematically investigated the interconnecting aspects among lignin source, pyrolysis chemistry, characteristics of the derived carbon materials and electrochemical performance. Such knowledge on the processing-structure-function relationships serves as a basis for designing lignin-based carbon materials for electrochemical energy storage applications.

京都大学 / 0048 / 新制・課程博士 / 博士(農学) / 甲第18332号 / 農博第2057号 / 新制||農||1023(附属図書館) / 学位論文||H26||N4839(農学部図書室) / 31190 / 京都大学大学院農学研究科応用生命科学専攻 / (主査)教授 植田 充美, 教授 渡邊 隆司, 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