Les papiers et cartons récupérés sont aujourd’hui recyclés en nouveaux matériaux similaires, en particulier les vieux cartons sont transformés en nouveaux cartons. Riches en matière lignocellulosique, les cartons récupérés pourraient remplacer le bois dans la production de produits de plus haute valeur ajoutée. Ainsi la thèse a exploré le potentiel de procédés existants de délignification, blanchiment et purification, appliqués sur des mélanges fibreux simulant la composition de différents cartons, pour la production de pâte papetière blanchie et de pâte à dissoudre.Le traitement appliqué est composé d’une cuisson Kraft, suivie d’une séquence de blanchiment classique D0-Ep-D1 puis, dans le cas de la production de pâte à dissoudre, d’une purification de type CCE. Les cartons à traiter ayant des compositions fibreuses variables, toute l’étude a été conduite sur des mélanges fibreux modèles, composés de fibres de pâte Kraft écrue et de pâte mécanique. Dans tous les cas, des pâtes blanchies ont été produites, même si leur degré de polymérisation est parfois en deçà des standards. En revanche, les pâtes sont difficiles à purifier. Par ailleurs, il a été montré que la qualité du produit final, les performances des procédés et leur impact environnemental, dépendent de la composition fibreuse du mélange. Enfin le traitement d’un carton industriel a révélé que les charges minérales contenues dans le matériau limitent sa revalorisation.La faible qualité des pâtes blanchies obtenues a conduit à tester une autre voie de valorisation, la production de cellulose oxydée pour MFC. Un nouveau procédé de pré-oxydation pour les pâtes Kraft écrue a été développé : il combine blanchiment et oxydation du substrat dans un stade unique en utilisant le catalyseur TEMPO avec du dioxyde de chlore et de l’hypochlorite de sodium. Des MFC de qualité équivalente à celles produites à partir de pâte blanchie préoxydée par le système TEMPO/NaClO/NaBr ont été obtenues. / Today recovered papers and boards are recycled into similar products; in particular old corrugated boards are transformed into new corrugated boxes. Rich in lignocellulosic material, recovered carton boards might replace wood for the production of hgiher added-value products. The thesis investigated the potential of existing delignification, bleaching and purification processes, applied on fibre mixes simulating the composition of various carton boards, for the production of bleached paper pulp and dissolving pulp grades.The treatment was composed of a Kraft cook, followed by a conventional D0-Ep-D1 bleaching sequence, and in the case of dissolving pulp production, a CCE stage for cellulose purification. Because carton boards exhibit various fiber compositions, all the study has been conducted on model mixes, made of fibres from unbleached Kraft pulp and mechanical pulp. In all cases, bleached pulps have been successfully obtained, although pulp viscosity was sometimes below the standards. However the bleached pulps were found difficult to purify. Moreover, it has been shown that the quality of the final product, the performances of the processes and their environmental impact, depended on the fiber composition of the mix. Finally, the treatment of an industrial carton board revealed that mineral fillers contained in the material limit its upcycling.Because of the low quality of the bleached pulp produced, another valorization way was tested: the production of oxidized cellulose for MFC. A new pre-oxidation process for unbleached Kraft pulp has been developed, combining bleaching and oxidation of the substrate in a single stage combining stage combining the use of TEMPO as a catalyst, chlorine dioxide and sodium hypochlorite. MFC of same quality as those produced from bleached Kraft pulp pre-oxidized by the classical TEMPO/NaClO/NaBr system have been obtained.

The three main components of wood, namely, cellulose, hemicellulose, and lignin, can be used in various areas. However, since lignin covalently crosslinks with wood polysaccharides creating networks that is an obstacle for extraction, direct extraction of different wood components in high yield is not an easy matter. One potential approach to overcome such obstacles is to treat the wood with specific enzymes that degrade the networks by specific catalysis. However, the structure of wood is so compact that the penetration of the wood fibers by large enzyme molecules is hindered. Thus, the pretreatment of wood prior to the application of enzymes is necessary, for “opening” the structure. One pretreatment method that was performed in this thesis is based on kraft pulping, which is a well-established and industrialized technique. For untreated wood, the wood fibers cannot be attacked by the enzymes. A relatively mild pretreatment was sufficient for wood polysaccharides hydrolyzed by a culture filtrate. A methanol-alkali mixture extraction was subsequently applied to the samples that were pretreated with two types of hemicellulases, Gamanase and Pulpzyme HC, respectively. The extraction yield increased after enzymatic treatment, and the polymers that were extracted from monocomponent enzyme-treated wood had a higher degree of polymerization. Experiments with in vitro prepared lignin polysaccharide networks suggested that the increased extraction was due to the enzymatic untying. However, the relatively large loss of hemicellulose, particularly including (galacto)glucomannan (GGM), represents a problem with this technique. To improve the carbohydrate yield, sodium borohydride (NaBH4), polysulfide and anthraquinone were used, which increased the yields from 76.6% to 89.6%, 81.3% and 80.0%, respectively, after extended impregnation (EI). The additives also increased the extraction yield from approximately 9 to 12% w/w wood. Gamanase treatment prior to the extraction increased the extraction yield to 14% w/w wood. Sodium dithionite (Na2S2O4) is an alternative reducing agent for the preservation of hemicelluloses because it is less expensive than metal hydrides and only contains sodium and sulfur, which will not introduce new elements to the recovery system. Moreover, Na2S2O4has the potential to be generated from black liquor. Na2S2O4 has some preservation effect on hemicelluloses, and the presence of Na2S2O4 also contributed to delignification. The extraction yield increased to approximately 15% w/w wood. Furthermore, Na2S2O4 has been applied in the kraft pulping process of spruce. The yield and viscosity increased, while the Klason lignin content and kappa number decreased, which represents a beneficial characteristic for kraft pulp. The brightness and tensile strength of the resulting sheets also improved. However, the direct addition of Na2S2O4 to white liquor led to greater reject content. This problem was solved by pre-impregnation with Na2S2O4 and/or mild steam explosion (STEX) prior to the kraft pulping process. Following Na2S2O4 pre-impregnation and mild STEX, the obtained kraft pulp had substantially better properties compared with the properties exhibited after direct addition of Na2S2O4 to the white liquor. The wood structure opening efficiency of mild STEX alone was also tested. The accessibility of the wood structure to enzymes was obtained even at very modest STEX conditions, according to a reducing sugar analysis, and was not observed in untreated wood chips, which were used as a reference. The mechanical effect of STEX appears to be of great importance at lower temperatures, and both chemical and mechanical effects occur at higher STEX temperatures. / <p>QC 20140903</p>

Le renouveau des biocarburants pourrait être aussi celui de l’industrie chimique de la pâte àpapier, en diversifiant l’éventail des produits fabriqués à partir de bois. Cette étude porte surl’intégration d’une extraction des hémicelluloses du bois au procédé Kraft dans le cadre d’une coproductionde fibres cellulosiques et de bioéthanol.Le travail expérimental de cette étude balaie l’ensemble du procédé depuis l’extraction de plus dela moitié des hémicelluloses de bois de résineux, par autohydrolyse ou par hydrolyse à l’acidedilué, jusqu’à la production de fibres cellulosiques blanchies et d’éthanol obtenu par la fermentationdes hydrolysats.Les pâtes de bois préhydrolysé se sont distinguées par de très bonnes aptitudes à ladélignification lors de la cuisson Kraft et lors du blanchiment à l’oxygène. Une analyse desconstituants des pâtes de bois préhydrolysé a permis de comprendre pourquoi la préhydrolyseconduit à une diminution du rendement de cuisson (perte de lignine et de la totalité deshémicelluloses dont les xylanes). L’analyse des lignines de pâtes écrues de bois préhydrolysé apermis d’émettre une hypothèse quant à l’excellente aptitude de ces pâtes à la délignification lorsdu blanchiment à l’oxygène.En définitive, l’intégration d’une extraction des hémicelluloses à une usine Kraft telle qu’elle estproposée par cette étude permet d’obtenir à partir de 100 kg de bois de résineux, 27 à 36kilogrammes de fibres cellulosiques blanchies et jusqu’à 6 litres de bioéthanol. Ces fibrescellulosiques blanchies présentent des caractéristiques attrayantes pour la production de cellulose àusage chimique ou de nanocristaux de cellulose. / Biofuel revival could be a great opportunity for the chemical pulp industry to widen the range ofits products made from wood. This thesis deals with the integration of a softwood hemicelluloseextraction step prior to the Kraft pulping process in order to produce both cellulose fibres andbioethanol.In this study the experimental work covers the entirety of the process: from the extraction ofmore than half of the hemicelluloses from wood either by autohydrolysis or dilute acid hydrolysis tothe production of bleached cellulosic fibres as well as ethanol from fermentated wood hydrolyzates.Prehydrolyzed wood and their subsequent pulps stood out by their excellent delignification abilityduring Kraft cooking and oxygen bleaching. Quantitative analysis of the main constituants of thepulps showed why prehydrolysis leads to decreased Kraft pulp yields (extra lignin loss andhemicelluloses loss including xylans). A range of hypotheses to explain the good delignificationability of prehydrolyzed wood Kraft pulps during oxygen bleaching was narrowed to one by Kraftlignin analysis.The overall results of the hemicellulose extraction prior to Kraft pulping as it has been defined inthis study showed that from 100 kg of softwood, 27 to 36 kg of bleached cellulosic fibres and 6litres of ethanol could be produced. The bleached cellulosic fibres are of great interest for dissolvingpulp or cellulose nanocrystals production.

Lignin är en av de vanligaste naturliga råvarorna på jorden och finns mestadels i trä. Nuförtiden är valoriseringen av lignin en av processutvecklingarna för teknologier inom massa- och pappersindustrin. Denna utveckling syftar till att öka värdet av lignin. Traditionellt förbränns genererat lignin, känt som tekniskt lignin, som bränsle i sodapannan som en del av svartlutskomponenter, och denna praxis är används kontinuerligt inom massa- och pappersindustrin. Syftet med detta examensarbete är att undersöka det tekniska ligninet från två specifika träslag, Acacia crassicarpa (Acra) och Eucalyptus Hybrids (Euca), för att öka kunskapen om det tekniska ligninet och hitta lämpliga tillämpningar för dessa råvaror i framtiden. I denna studie isolerades lignin från svartlut som genererats från två olika kokningsmetoder, kraftkokning- och kraftbased dissolvingkokning (KP och DP). Karakteriseringsmetoderna inkluderade molekylviktsfördelning (THF-SEC), analys av ligninets funktionella grupper med fosfor-31 Nuclear Magnetic Resonance (31P-NMR) kvantifiering och ligninets trukturella elementanalys via Two-Dimensional Heteronuclear Single Quantum Correlation NMR (2D-HSQC NMR). Utbytet erhållet från kraftkokning (KP) och kraftbased dissolvingkokning (DP) visade inga skillnader för samtliga prover och resultaten visas inom samma intervall (cirka 0,06-0,08 g/mol svartlut). Molekylviktsfördelningen för KP och DP-kokning ligger fortfarande inom intervallet för kraftlignin Mw (1500-5000 g/mol) och polydispersitetsindex (PDI) för KP hade ett högre värde än DP för båda typerna av undersökta råvaror. För de funktionella grupperna hade Eucalyptus Hybrids högre -OH-halt än Acacia crassicarpa oavsett kokningstyp. 31P-NMR kvantifieringsdata visade tydligt att KP-Euca innehöll den högsta halten av  alifatisk-OH (1,4 mmol/g). DP-Euca hade den högsta halten C5-kondenserad (2,5 mmol/g), medan den högsta mängden Guaiacyl-OH identifierades i DP-Acra (1,2 mmol/g). Fingeravtrycket av kopplingarna som kvantifierades från 2D-NMR HSQC visade att KP hade högre β-O-4', β-5' och β-β' interenhetskopplingar än DP. Dessutom hade Acacia crassicarpa en högre andel interenhetskopplingar än Eucalyptus Hybrids för båda kokmetoderna. De högsta β-O-4'-, β-5'- och β-β'-kopplingarna detekterades i KP-Acra med 3,4 %, 0,5 % respektiv 4,3 %. / Lignin is one of the most abundant natural raw materials on Earth and is mostly found in wood. Nowadays, the valorization of lignin is one of the continual process developments for technologies in the pulp and paper industry. This development is intended to increase the value of lignin. In the traditional approach, generated lignin known as technical lignin is burnt as fuel in the recovery boiler as part of black liquor components, and this practice is still common in the pulp and paper industry. The objective of this thesis work is to explore the technical lignin from specific wood species, Acacia crassicarpa (Acra) and Eucalyptus Hybrids (Euca), to emphasize the knowledge about the technical lignin and finding suitable application for the mentioned raw materials in the future. In this study, lignin was isolated from black liquor generated from two different cooking methods, kraft and kraft dissolving pulp cooking (KP and DP). The Characterization methods included molecular weight distribution by THF-SEC, lignin functional groups analysis via Phosphorus-31 Nuclear Magnetic Resonance (31P-NMR) quantification, and lignin structural elements analysis via Two-Dimensional Heteronuclear Single Quantum Correlation NMR (2D-HSQC NMR). The isolation yield obtained from kraft cooking (KP) and kraft dissolving pulp cooking (DP) did not have drastic differences for all the samples and therefore the results are within the same ranges (around 0.06-0.08 g/mol of black liquor). The molecular weight distribution values of KP and DP cooking are still within the range of kraft lignin Mw (1500-5000 g/mol) and the polydispersity index (PDI) of KP had a higher value than DP for both types of raw material investigated.  For the functional groups, Eucalyptus Hybrids had the higher -OH content than Acacia crassicarpa regardless of the cooking type. The 31P-NMR quantification data showed clearly that KP-Euca was the richest in Aliphatic-OH (1.4 mmol/g). DP-Euca had the greatest amount of C5-Condensed (2.5 mmol/g), while the highest amount of Guaiacyl-OH was identified in DP-Acra (1.2 mmol/g). The fingerprint of the linkages that was quantified from 2D-NMR HSQC showed that KP cooking had a higher β-O-4’, β-5’ and β-β’ interunit linkages than DP cooking. Furthermore, Acacia crassicarpa had a higher interunit linkages percentage than Eucalyptus Hybrids for both cooking methods. The highest β-O-4’, β-5’ and β-β’ linkages were detected in KP-Acra with 3.4 %, 0.5 %, and 4.3 % respectively.