Thesis (Masters of Environmental Health)--Cape Peninsula University of Technology, 2018. / In the Western Cape, South Africa and other regions globally, grape pomace (GP) is one of the abundant agro-waste from the winery industry. This study reports on the hyper-extraction of fermentable sugars from GP treated with white rot fungi (WRF) Phanerochaete chrysosporium BKMF 1767 to facilitate improved biovalorisation for total reducing sugars (TRS) extraction in conjunction with Nepenthes mirabilis digestive fluids. TRS were quantified using the 3,5-dinitrosalicylic acid (DNS) reagent method. The free readily dissolvable sugars from the GP recorded for the bio-treated (BT) samples was 206.39 ± 0.06 mg/L and for the untreated (UT) samples was 271.05 ± 0.02 mg/L. Overall, the TRS yield for the Bio-treated (BT) and untreated (UT) samples was recorded as 205.68 ± 0.09 and 380.93 ± 0.14 mg/L, respectively, using hot water pretreatment (HWP) with 2266.00 ± 0.73 (BT) and 2850.68 ± 0.31 mg/L (UT), respectively, for dilute acid pretreatment (DAP); with 2068.49 ± 6.02 (BT) and 2969.61 ± 8.054 mg/L (UT) respectively, using the cellulase pretreatment (CP) method. Using the HWP as a reference, the relative increases imparted by the biotreatment was higher (51%) for DAP and low (33%) for CP. The combination of conventional used pre-treatment methods (hot water pretreatment, dilute acid pre-treatment, and cellulase pre-treatment) in a single pot system was also done while monitoring the total residual phenolics (TRPCs) in the samples. Furthermore, powder X-ray diffraction (pXRD) were used to measure the crystallinity index (CrI) and functional groups of pre- and post-pretreated GP to ascertain the efficiency of the pre-treatment methods, with quantification of lignin, holocellulose, and ash. Overall, the TRS yield for N. mirabilis pre-treated agro-waste was 951 mg/L ± 4.666 mg/L, with biomass having a lower CrI of 33%, and 62% residual lignin content. Furthermore, reduced TRPCs were observed in hydrolysate, suggesting limited inhibitory by-product formation during N. mirabilis pre-treatment

In the last decade there has been increasing research interest in the value of bio-sourced materials from lignocellulosic biomass. The dissolution of cellulose by ionic liquids (ILs) has led to investigations including the dissolution of cellulose, lignin, and complete biomass samples and the in situ processing of cellulose. Rapid quantitative measurement of cellulose dissolution in ILs is difficult. In this work, Fourier transform infrared spectroscopy (FTIR) spectra of cellulose dissolved in 1-ethyl-3-methylimidazolium acetate ([emim][OAc]) were subjected to partial least squares (PLS) regression to model dissolved cellulose content. PLS regression was used due to the ease in developing predictive models with this technique in addition to linear regression being ineffectual for modeling when applied to potentially thousands of variables. Applying a normalization data treatment, before regression, generated a model that estimated cellulose content within 0.533 wt%. The methods described provided the basis for a rapid methodology to determine dissolved cellulose content. Development of rapid and facile screening techniques to determine the effectiveness of various ILs as solvents for cellulose or lignin will aid in the development of lignocellulosic based bioproducts. In this work, optical microscopy with and without the use of cross-polarized lenses, was used to monitor cellulose and lignin dissolution in two imidazolium-based and two phosphonium-based ILs as well as n,n-dimethylacetamide/lithium chloride (DMAc/LiCl), demonstrating that this technique could be applied more broadly than solely for ILs. The described optical microscopy methodology was more rapid and sensitive than more traditional techniques, such as visual inspection. The viscosity of [emim][OAc] (162 cP) is 100 times that of water at 20°C and could inhibit its use as a solvent for cellulose. There is a need for simple, low-cost and environmentally benign methods to reduce the viscosity of ILs to aid in cellulose dissolution. In this work, 4 wt% cellulose dissolved in [emim][OAc] was subjected to 50 psi CO2 and 20 psi N2, as a control environment, at both 50°C and 75°C. After 24 hours a nearly 2-fold increase in dissolved cellulose over the N2 control was demonstrated through the application of a 50 psi CO2 environment for cellulose dissolution in [emim][OAc] at 50°C. / Thesis (Master, Chemical Engineering) -- Queen's University, 2011-05-25 22:58:17.744

Abstract Biomass conversion methods represent bioeconomic solutions for the sustainable production of value added commodities (chemicals and materials) as well as for energy purposes, either in solid (pellets), liquid (transport fuels) or gaseous (combustion gases e.g. biomethane) form. Lignocellulosic biomass as a renewable source available in immense quantity, is considered to be one of the most promising natural sources, with high potential in the replacement of conventional transportation fuels and reduction of greenhouse gas emissions. This thesis provides new insights into mechanocatalysis, which as yet is a novel technique in catalytic biomass conversion. The mechanocatalytic approach combines chemical catalysis and mechanical assisted processing driven by ball milling. Lignocellulosic barley straw was impregnated or merely mixed with the catalyst (formic acid, acetic acid, sulfuric acid, oxalic acid dihydrate and potassium pyrosulfate) and ball milled under various conditions yielding the selective depolymerization of lignocellulose into water-soluble xylo-oligosaccharides. Subsequent hydrolysis at moderate temperatures resulted in the formation of valuable reducing sugars, mainly xylose, galactose, arabinose and glucose, which constitute the basic materials for transportation fuel and chemical production. Reducing sugar release of 53.4 wt% with low by-product formation was observed within short milling durations using sulfuric acid as a catalyst in mechanocatalysis. Likewise, oxalic acid dihydrate and potassium pyrosulfate as a novel catalyst, successfully converted barley straw to reducing sugars (42.4 wt% and 39.7 wt%, respectively), however longer milling durations were required. In comparison, lower saccharification (<10 wt%) was obtained by employing formic acid and acetic acid in mechanocatalysis. Harsh milling conditions initiated a temperature increase within the reaction vessel resulting in enhanced sugar release. Likewise, greater sugar release was observed with increased catalyst amount and acidity. The results revealed that the balance of these factors is crucial for efficient catalytic conversion of barley straw. / Tiivistelmä Biomassan konvertointimenetelmät mahdollistavat biotalouden hengen mukaisesti uusia ratkaisuja kemikaalien ja materiaalien kestävään tuotantoon sekä biomassan energiakäyttöön eri muodoissa (kuten pelletit, biopolttoaineet ja biokaasu). Lignoselluloosapohjaista, uusiutuvaa biomassaa, kuten tässä työssä tutkittua ohran olkea, on runsaasti saatavilla. Lignoselluloosa onkin yksi lupaavimmista raaka-aineista korvaamaan fossiilisia polttoaineita ja vähentämään kasvihuonekaasupäästöjä. Väitöskirjatutkimus antaa uutta tietoa ohran oljen mekaanis–katalyyttisestä käsittelystä, mikä on suhteellisen uusi menetelmä biomassan katalyyttisessä muokkauksessa. Menetelmässä yhdistetään kemiallinen katalyysi ja mekaaninen muokkaus (jauhatus) kuulamyllyllä. Lignoselluloosa (ohran olki) impregnoitiin tai sekoitettiin tutkitun katalyytin (muurahaishappo, etikkahappo, rikkihappo, oksaalihappodihydraatti, kaliumpyrosulfaatti) kanssa ja käsiteltiin erilaisissa mekaanis–katalyyttisissä olosuhteissa. Lignoselluloosan selektiivinen depolymerointi muodosti vesiliukoisia oligosakkarideja ja edelleen hydrolyysin kautta pelkistyneitä sokereita (pääasiassa ksyloosia, galaktoosia, arabinoosia ja glukoosia), joita voidaan käyttää biopolttoaineiden ja -kemikaalien valmistuksessa. Tutkimuksen tulosten perusteella rikkihappokatalyytillä saatiin 53,4 massa-% ohran oljen sisältämistä pelkistyneistä sokereista vapautettua lyhyillä käsittelyajoilla. Lisäksi sivutuotteiden muodostuminen oli vähäistä. Vastaavasti oksaalihappodihydraatti (sokerisaanto 42,4 massa-%) ja kaliumpyrosulfaatti (sokerisaanto 39,7 massa-%) toimivat uusina katalyytteinä hyvin, mutta vaativat rikkihappokatalyyttiä pidemmät jauhatusajat. Sen sijaan muurahaishapolla ja etikkahapolla sokerisaanto oli erittäin alhainen (alle 10 massa-%) mekaanis–katalyyttisessä käsittelyssä. Tutkimuksessa todettiin, että voimakas jauhatus vaikutti selkeästi reaktiolämpötilan nousuun käsittelyn aikana, mikä edisti korkeampaa sokerisaantoa. Vastaavasti sokerisaantoa voitiin parantaa katalyyttimäärällä ja happamuudella. Tulokset osoittavat, että näiden muuttujien tasapaino on ratkaisevaa ohran oljen tehokkaan katalyyttisen muuntamisen kannalta.

This diploma thesis is focused on study of chemical and enzymatical hydrolysis of raw wood material. The aim of this work was to find the suitable method for pretreatment of selected lignocellulose materials. The theoretical part deals with characterization of lignocellulosic material and its components. There are also subscribed various pretreatment methods and their effect on hydrolysis of sawdust. In experimental part of the work the most appropriate approach of pretreatment and hydrolysis of sawdust was studied. Criteria for the selection of suitable method was concentration of saccharides as desired product of hydrolysis and also concentration of the most important microbial inhibitors - polyphenols. Application of 96% ethanol or 5% H2O2 were identified as the most promising pretreatment methods which enhanced yields of fermentable sugars about 30 %. Further, we also performed cultivation of bacteria Burkholderia cepacia and bacteria Burkholderia sacchari using solution obtained by hydrolysis of lignocellulose material.

The aim of this work was study of the detoxification of lignocellulose material hydrolysates and to investigate sawdust suitability as a substrate for microbial production of PHA by bacteria Burkholderia cepacia and Burkholderia sacchari. In the experimental part of the work the most suitable way of detoxification of model and real hydrolysate was studied. After that, detoxification methods used were evaluated. Criteria for evaluation were concentration of polyphenols as the most important microbial inhibitors and reduction saccharides as the main carbon substrate. Furthermore, fermentability of the hydrolysates was also tested by cultivation of two bacteria capable of PHA accumulation. Burkholderia sacchari demonstrated higher ability to accumulate PHA then Burkholderia cepacia. Then in the summary – most effective way for detoxification was ‚overliming‘. Major increase of PHB in biomass was obtained when Burkholderia sacchari was cultivated on media gained by application of overliming of real lignocellulose hydrolysate. However, total gains of PHB were more likely low and then sawdust can not be considered as a substrate for PHB production at industrial scale.

Syftet med detta examensarbete var att utveckla ett hållbart ersättningsmaterial till akrylnitrilbutadienstyren plast (ABS), genom att applicera principerna för grön kemi och teknik. ABS är en icke-nedbrytbar plast som till exempel används i slagtåliga produkter för hyttinteriörer. Att utveckla ett nytt material baserat på en kravspecifikation med en specifik produkt i åtanke är av stor betydelse då en initial teoretiska utvärdering kan ge resultat som driver ytterligare innovation och säkerställer en god överensstämmelse med förväntningarna på produkten. Baserat på den genomförda litteraturutvärderingen och kravspecifikationen för produkten valdes polylaktid (PLA) som matrismaterial och blandades med nanofibrer av lignocellulosa (LCNF) och naturgummi (NR), där maleinsyraanhydrid (MA) användes som kompatibilisator. Denna modifieringsstrategi syftade till att förbättra PLAs styrka och minska dess sprödhet. Flera olika parametrar undersöktes, vilka inkluderar olika torkningsmetoder för LCNF:en och olika metoder för MA tillsats före bearbetningen av blandningen. Termisk analys av blandningarna visade att tillsatsen av LCHF och NR inte påverkar nedbrytningstemperaturen för PLA-matrisen i någon större utsträckning, men att kristalliniteten påverkades av dem och de olika behandlingsmetoderna. Styvheten hos de PLA-baserade materialen var likvärdig ABS, medan elasticitet var generellt likvärdig PLA och där tillsatsen av naturgummi förbättrade materialens deformationskapacitet. SEM bilder indikerade att de tre komponenterna var kompatibiliserade, då fibrösa strukturer och sammanflätade nätverk av LCNF och NR i PLA-matrisen kunde observeras. SEM bilderna visade också att NR agglomererade då stora agglomerat och porösa strukturer uppstod, vilket understryker vikten av att optimera framtida blandningsstrategier. En livscykelbedömning (LCA), enligt en vagga-till-graven metod, förväntas visa lägre koldioxidutsläpp för det föreslagna alternativet jämfört med ABS tack vare tillämpningen av principerna för grön kemi vid produktutformningen. Detta bekräftar den ursprungliga hypotesen om en ökad miljövänligheten hos PLA-baserade ersättningsmaterial jämfört med ABS. / This thesis aims to develop sustainable replacement for Acrylonitrile Butadiene Styrene (ABS) in high-impact applications within construction equipment’s Cab interior. Adhering to the principles of Green Chemistry and Engineering, the study focused on developing and accessing an environmentally friendly substitute for ABS, a commonly used non-biodegradable plastic. Investigating novel materials with a tailored requirements list is vital in materials science and engineering. Theoretical approaches can yield results which drive further innovation, ensuring comprehensive alignment with application expectations through a holistic approach to address critical factors. Following this guideline, the chosen alternative was Polylactide (PLA), fortified with a blend of lignocellulose nanofibers (LCNFs) and natural rubber (NR) at a 10 wt.% concentration, with the addition of Maleic Anhydride (MA) as a compatibilizer. This modification strategy aimed to enhance PLA's strength and reduce its brittleness. The investigation encompassed various parameters, including different LCNF drying methods and variations in additive treatment before melt-mixing with PLA. The outcomes from thermal analysis indicated that the inclusion of reinforcements does not significantly affect the degradation temperature of the PLA matrix. Crystallinity, on the other hand, was found to be influenced by the presence of lignocellulose reinforcements and natural rubber, with intriguing nuances emerging from the interplay of these components and different treatment methods. PLA-based alternatives performed similarly to low grade ABS and had similar stiffness levels. In terms of elasticity, most materials behaved similarly to neat PLA, but the addition of natural rubber enhanced their deformation capacity. Successful compatibilization between lignocellulose reinforcements, natural rubber, and PLA was assumed from the observed fibrous structures and interwoven networks within the PLA matrix. Additionally, the presence of aggregates and porous structures highlighted the challenges posed by rubber agglomeration. Finally, the observation of larger agglomerates beyond typical interphase sizes raised concerns about brittle behavior, emphasizing the need for optimizing blend toughening strategies. The input for a Life Cycle Assessment (LCA), following a cradle-to-gate approach, is anticipated to show lower carbon emissions for the proposed alternative in comparison to ABS due to the principles of Green Engineering applied in the product design, denoting the environmental viability of the PLA-based substitute.

No description available.

När befolkningsmängden ökar och teknisk och ekonomisk utveckling sker så påverkas även energianvändningen. Detta ställer krav på att energitillförseln är säker, stabil och hållbar. I dag är det fossila bränslen som dominerar globalt sett vilket får konsekvenser för den miljö vi lever i, och dessutom är det en ändlig, ohållbar resurs. Därför behöver dessa ersättas av hållbara alternativa energikällor, vilket också är centralt för miljömål i både Sverige och i den Europeiska Unionen. Förhoppningar finns om att processer som omvandlar lignocellulosa till fasta, flytande och gasformiga drivmedel och bränslen kan bidra till omställningen från fossilt till förnybart. I detta examensarbete som utförts i samarbete med KTH och IVL Svenska Miljöinstitutet har främst en av dessa omvandlingsprocesser undersökts närmare – pyrolys. Pyrolys är en termisk process som omvandlar lignocellulosa under temperaturer mellan cirka 300-650 °C under syrefria förhållanden. Tre faser kan erhållas. En gasfas som kan kondenseras till pyrolysolja, en fast fas som benämns biokol eller kol (beroende på slutanvändning) och en okondenserbar gasfas. Utbytet av produkter och kvalitet på dessa styrs främst av: typ av råvara, typ av reaktor och av vilka processförhållanden som råder. En undersökning av olika pyrolysprocessers status på marknaden har gjorts. Graden av kommersialisering och status i nuläget och hur framtiden kan se ut för både tekniken och produkterna har uppskattats genom litteraturstudier, internetsökningar och intervjuer med utvalda företag och personer med kunskaper inom pyrolys. Rapporten visar att pyrolys inte ännu är en helt kommersiell process, men att den har möjlighet att bli det med rätt förutsättningar. Det är svårt att säga när det sker, då det förutom fortsatt teknisk utveckling, ökad kunskap kring pyrolysprocessen och resultat av demonstrationer beror på olika externa faktorer. Yttre faktorer för kommersialisering av pyrolys i Sverige har identifierats som ökad säkerhet kring politiska styrmedel och beslut kring långsiktiga sådana (osäkerhet och kortsiktiga beslut skrämmer bort investerare), vikten av att etablera en värdekedja för att säkra investeringen, och priser på fossila drivmedel och biomassa som råvara. Processer för produktion av biokol verkar dock ha hunnit längre än de för pyrolysolja och är i ett tidigt stadium av kommersialisering.  Den enda tillämpningen som är fullt kommersiell idag är produktion av träkol och för detta tillämpas ofta traditionella satsvisa processer. Många möjliga användningsområden för produkterna finns där de har potential att reducera koldioxidutsläpp och bidra till en mer hållbar framtid. Standardisering och certifiering av produkter är då viktigt, samt demonstration av användning. Stabilisering och vidare förädling av pyrolysoljan är en annan viktig faktor för kommersialisering. Ännu verkar processer för katalytisk uppgradering inte vara tillräckligt tekniskt eller ekonomiskt utvecklade för att ge en konkurrenskraftig produkt, men forskning pågår kring detta. Integrering av processen ser ut att kunna öka energieffektiviteten, samt bidra till minskade produktionskostnader. / The population growth as well as a rapid technical and economic development globally affects the energy consumption. This requires a secure, stable and sustainable supply of energy. Today fossil fuels dominate globally and this results in environmental problems. Fossil fuels are also a finite, unsustainable resource. Thus, there is a need to replace fossil fuels with sustainable alternative sources of energy. This is also central for environmental goals both in Sweden and in the European Union. There are expectations that processes for the conversion of lignocellulosic biomass to solid, liquid and gaseous fuels can contribute to a transition from fossil to renewable fuels. In this thesis, carried out in collaboration between KTH and IVL Swedish Environmental Research Institute, one of the conversion processes is investigated in detail – pyrolysis. Pyrolysis is a thermal process that converts lignocellulose under anaerobic conditions at temperatures between about 300-650°C. Three phases can be obtained as products. A volatile which can be condensed into pyrolysis oil, a solid which may be termed biochar or charcoal depending on the end use, and a gas phase. The yield and the quality of the products is dependent upon the type of raw material, the type of reactor and the process conditions. An examination of the status of different pyrolysis processes on or on the way to the market has been made. The current degree of commercialization and what the future may look like for both the technology and the products have been assessed through literature studies, internet searches, and interviews with selected companies and individuals with expertise in pyrolysis.   This report reveals that continuous pyrolysis is not yet a fully commercial process, but that it has the opportunity to reach commercialization during the right conditions. It is difficult to say when it occurs, due to various external factors, continued technical development, increased knowledge of the pyrolysis process and results of the current demonstrations. In this report, several critical factors for the commercialization of pyrolysis in Sweden have been identified, e.g. increased stability for policy instruments and that will limit the risk for investments (uncertainty and short-term decisions frightens investors) and the establishment of a value chain for the products, i.e. a stable market. Prices on fossil fuels and biomass feedstock are also important factors. Processes for the production of biochar is in the early stages of commercialization, and seem to have reached further in their development than processes for pyrolysis oil. The only fully commercial application of pyrolysis today is the production of charcoal that commonly is performed in traditional batch-wise processes. There are many possible uses for the products in which they have the potential to reduce carbon emissions and contribute to a more sustainable future. Standardization and certification of products is important, and demonstration of the use. Stabilization and further upgrading of pyrolysis oil is another important factor for commercialization. It seems like processes for catalytic upgrading are not yet sufficiently technically or financially developed to be able to provide a competitive product. Research and development in this area are ongoing. Integration of the process with incumbent industrial processes seems to be able to offer increased energy efficiency and reduced production costs.

La biomasse lignocellulosique comprend les sous-produits agricoles et industriels pouvant être utilisés comme matière première dans des bioprocédés variés destinés à produire des molécules d'intérêt énergétique ou chimique. Ces ressources lignocellulosiques, peuvent notamment être fournies par l'industrie papetière qui est particulièrement adaptée pour les bio-raffineries modernes car elle est en capacité de produire en grande quantité un substrat ayant une faible teneur en lignine et sans composés inhibiteurs. La bagasse de canne à sucre est également un substrat prometteur par sa composition chimique simple et son abondance dans les pays tropicaux. Lors de l'utilisation de ces substrats, l'hydrolyse enzymatique constitue une étape cruciale permettant la transformation des fibres de cellulose en une source de carbone fermentescible. Si les aspects biochimiques de cette étape d'hydrolyse font l'objet de nombreuses recherches et de développements, les réactions sous haute teneur en matière sèche font apparaître des limitations physiques qui sont beaucoup moins étudiées et analysées mais constituent des verrous scientifiques et technologiques qui freinent actuellement l'utilisation de cette ressource abondante et durable. Ce travail s'inscrit dans ce contexte et propose l'étude de cette étape d'hydrolyse enzymatique de la lignocellulose en s'intéressant conjointement aux aspects biochimiques et physiques de façon à aller vers une compréhension et une maîtrise des transferts (de masse, de chaleur) dans les réactions à forte concentration en substrat. La stratégie adoptée a consisté à réaliser et analyser des réactions d'hydrolyse sous différentes conditions opératoires en travaillant dans un premier temps sur des concentrations intermédiaires (suspension semi-diluée), c'est-à-dire en introduisant, mais de façon limitée, les complexités dues aux interactions entre particules/fibres de lignocellulose. Les résultats obtenus sont ensuite utilisés pour élaborer une stratégie adaptée aux fortes concentrations. Les aspects physiques analysés sont essentiellement le comportement rhéologique du milieu réactionnel ainsi que la morpho-granulométrie des objets en suspension. Différentes métrologies, tant in-situ que ex-situ, ont été mises en œuvre et apportent des résultats complémentaires. Les études ont été menées sur un substrat de référence, le papier Whatman, et deux substrats à vocation industrielle: la pâte à papier et la bagasse de canne à sucre. La stratégie d'étude porte sur les aspects suivants: (i) le suivi de l'évolution des comportements rhéologiques et des propriétés morphologiques des suspensions au cours de l'hydrolyse, (ii) l'étude des mécanismes d'hydrolyse lors de la dégradation des substrats, (iii) l'étude de l'impact de la composition et de la structure des substrats sur les cinétiques de solubilisation et d'hydrolyse, (iv) la quantification de la contribution des différentes activités enzymatiques, seules ou en mélange par une approche physique multi-échelle et (v) le contrôle et l'optimisation des conditions d'alimentation dans un procédé discontinu alimenté (fed-batch) afin d'atteindre des conditions de milieu concentré. Les chapitres 1 et 2 de ce document sont consacrés à une étude bibliographique du sujet et à la présentation des matériels et méthodes mis en œuvre. Le troisième chapitre présente les résultats obtenus et leur analyse. Il est constitué de trois sections: tout d'abord une étude des propriétés des différents enzymes ou cocktail d'enzymes utilisés, des substrats retenus et des suspensions avec, notamment, la détermination des régimes semi-dilués et concentrés. Ensuite sont présentées et analysées les hydrolyses effectuées en milieu semi-dilué. Les mécanismes d'hydrolyse (fragmentation, solubilisation, hydratation et séparation des agglomérats) sont étudiés pour diverses concentrations et divers enzymes/cocktails. Enfin les résultats en milieu concentré sont présentés dans une dernière section. / Lignocellulosic biomass consists of several agriculture and industrial by-products that can be used as raw material for several bioprocesses to obtain range of products. Among lignocellulosic sources, the pulp & paper industry is appropriated for modern bio-refining thank to pulp with low lignin content and free of inhibitory compounds. Besides, sugarcane bagasse is a very promising feedstock because of its simple chemical composition and its abundancy especially in tropical countries. In the bioconversion of lignocellulose, enzymatic hydrolysis is a crucial step that allows the transformation of cellulosic and hemicellulosic fibers into fermentable carbon sources. The lack of knowledge about physical limitations and hydrolysis mechanisms, especially at high dry matter content, stands as the main barrier which forbids the scale-up of bio-refinery processes. Thus, the efficient and sustainable use of lignocellulosic resources is currently a major challenge and need to be investigated. In this context, this PhD focused on the enzymatic hydrolysis of lignocellulose by both physical and biochemical approaches. The strategy consisted in carrying out and in analyzing the hydrolysis reactions under different operating conditions with semi-dilute suspensions. Then, obtained results were used to develop a hydrolysis strategy for concentrated suspensions. Different methodologies, in- and ex-situ analyses, were implemented and provided complementary results. From physical approach, analyses consisted in rheological behavior of suspensions as well as the morpho-granulometry of particles. The study was carried out on a reference substrate, Whatman paper, and on two industrial substrates, paper pulp and sugarcane bagasse. The strategy aimed to investigate different stakes: (i) evolution of rheological behaviors and the morphological properties of suspensions, (ii) hydrolysis mechanisms during the degradation of substrates, (iii) impact of substrate composition and structure on solubilization and hydrolysis kinetics, (iv) quantification of the contribution of single enzyme and enzyme mixture activities by multi-scale physical approaches and (v) control and optimization of feeding parameters for fed-batch process in order to access to concentrated suspension. Chapters 1 and 2 of this document are devoted to a research bibliographic and presentation of materials and methods. The third chapter presents obtained results and discussion in three sections. The first one is a study of the properties of different enzymes and substrates, in particular, the determination of semi-dilute and concentrated regime. Subsequently the enzymatic hydrolysis at semi-dilute regime is presented to highlight the hydrolysis mechanisms (fragmentation, solubilization, solvation and agglomerate separation) in relationship with enzyme mixtures and dosages. Finally, results in concentrated regime are discussed in the final section.

The two main sources of biomass for energy generation are purpose-grown energy crops and waste materials. Energy crops, such as Miscanthus and short rotation woody crops (coppice), are cultivated mainly for energy purposes and are associated with the food vs. fuels debate, which is concerned with whether land should be used for fuel rather than food production. The use of residues from agriculture, such as barley, canola, oat and wheat straw, for energy generation circumvents the food vs. fuel dilemma and adds value to existing crops. In fact, these residues represent an abundant, inexpensive and readily available source of renewable lignocellulosic biomass. In order to reduce industrys operational cost as well as to meet the requirement of raw material for biofuel production, biomass must be processed and handled in an efficient manner. Due to its high moisture content, irregular shape and size, and low bulk density, biomass is very difficult to handle, transport, store, and utilize in its original form. Densification of biomass into durable compacts is an effective solution to these problems and it can reduce material waste. Upon densification, many agricultural biomass materials, especially those from straw and stover, result in a poorly formed pellets or compacts that are more often dusty, difficult to handle and costly to manufacture. This is caused by lack of complete understanding on the natural binding characteristics of the components that make up biomass. An integrated approach to postharvest processing (chopping, grinding and steam explosion), and feasibility study on lab-scale and pilot scale densification of non-treated and steam exploded barley, canola, oat and wheat straw was successfully established to develop baseline data and correlations, that assisted in performing overall specific energy analysis. A new procedure was developed to rapidly characterize the lignocellulosic composition of agricultural biomass using the Fourier Transform Infrared (FTIR) spectroscopy. In addition, baseline knowledge was created to determine the physical and frictional properties of non-treated and steam exploded agricultural biomass grinds. Particle size reduction of agricultural biomass was performed to increase the total surface area, pore size of the material and the number of contact points for inter-particle bonding in the compaction process. Predictive regression equations having higher R2 values were developed that could be used by biorefineries to perform economic feasibility of establishing a processing plant. Specific energy required by a hammer mill to grind non-treated and steam exploded barley, canola, oat and wheat straw showed a negative power correlation with hammer mill screen sizes. Rapid and cost effective quantification of lignocellulosic components (cellulose, hemicelluloses and lignin) of agricultural biomass (barley, canola, oat and wheat) is essential to determine the effect of various pre-treatments (such as steam explosion) on biomass used as feedstock for the biofuel industry. A novel procedure to quantitatively predict lignocellulosic components of non-treated and steam exploded barley, canola, oat and wheat straw was developed using Fourier Transformed Infrared (FTIR) spectroscopy. Regression equations having R2 values of 0.89, 0.99 and 0.98 were developed to predict the cellulose, hemicelluloses and lignin compounds of biomass, respectively. The average absolute difference in predicted and measured cellulose, hemicellulose and lignin in agricultural biomass was 7.5%, 2.5%, and 3.8%, respectively. Application of steam explosion pre-treatment on agricultural straw significantly altered the physical and frictional properties, which has direct significance on designing new and modifying existing bins, hoppers and feeders for handling and storage of straw for biofuel industry. As a result, regression equations were developed to enhance process efficiency by eliminating the need for experimental procedure while designing and manufacturing of new handling equipment. Compaction of low bulk density agricultural biomass is a critical and desirable operation for sustainable and economic availability of feedstock for the biofuel industry. A comprehensive study of the compression characteristics (density of pellet and total specific energy required for compression) of ground non-treated and steam exploded barley, canola, oat and wheat straw obtained from three hammer mill screen sizes of 6.4, 3.2 and 1.6 mm at 10% moisture content (wb) was conducted. Four preset pressures of 31.6, 63.2, 94.7 and 138.9 MPa, were applied using an Instron testing machine to compress samples in a cylindrical die. It was determined that the applied pressure (60.4%) was the most significant factor affecting pellet density followed by the application of steam explosion pre-treatment (39.4%). Similarly, the type of biomass (47.1%) is the most significant factor affecting durability followed by the application of pre-treatment (38.2%) and grind size (14.6%). Also, the applied pressure (58.3%) was the most significant factor affecting specific energy required to manufacture pellets followed by the biomass (15.3%), pre-treatment (13.3%) and grind size (13.2%), which had lower but similar effect affect on specific energy. In addition, correlations for pellet density and specific energy with applied pressure and hammer mill screen sizes having highest R2 values were developed. Higher grind sizes and lower applied pressures resulted in higher relaxations (lower pellet densities) during storage of pellets. Three compression models, namely: Jones model, Cooper-Eaton model, and Kawakita-Ludde model were considered to determine the pressure-volume and pressure-density relationship of non-treated and steam exploded straws. Kawakita-Ludde model provided the best fit to the experimental data having R2 values of 0.99 for non-treated straw and 1.00 for steam exploded biomass samples. The steam exploded straw had higher porosity than non-treated straw. In addition, the steam exploded straw was easier to compress since it had lower yield strength or failure stress values compared to non-treated straw. Pilot scale pelleting experiments were performed on non-treated, steam exploded and customized (adding steam exploded straw grinds in increments of 25% to non-treated straw) barley, canola, oat and wheat straw grinds obtained from 6.4, 3.2, 1.6 and 0.8 mm hammer mill screen sizes at 10% moisture content (wb). The pilot scale pellet mill produced pellets from ground non-treated straw at hammer mill screen sizes of 0.8 and 1.6 mm and customized samples having 25% steam exploded straw at 0.8 mm. It was observed that the pellet bulk density and particle density are positively correlated. The density and durability of agricultural straw pellets significantly increased with a decrease in hammer mill screen size from 1.6 mm to 0.8 mm. Interestingly, customization of agricultural straw by adding 25% of steam exploded straw by weight resulted in higher durability (> 80%) pellets but did not improve durability compared to non-treated straw pellets. In addition, durability of pellets was negatively correlated to pellet mill throughput and was positively correlated to specific energy consumption. Total specific energy required to form pellets increased with a decrease in hammer mill screen size from 1.6 to 0.8 mm and also the total specific energy significantly increased with customization of straw at 0.8 mm screen size. It has been determined that the net specific energy available for production of biofuel is a significant portion of original agricultural biomass energy (89-94%) for all agricultural biomass.