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Bioreactor landfills have become a feasible alternative to the typical "dry tomb" landfill. By recirculating leachate and/or adding additional liquid wastes, bioreactor landfills operate to rapidly degrade and transform organic wastes. The reactions within a bioreactor landfill create elevated temperatures. The intent of this study was to determine the effect of elevated temperature on the degradation of lignocellulose compounds. In order to observe the effects of temperature on lignin, small bioreactors were created in the laboratory. Several experiments were performed by the authors. Solubility of lignin based on temperature and time of thermal exposure were conducted. In addition, degradation studies were conducted based on biological treatment of lignin as well as a combination of biological and thermal treatment. Samples were collected at specified intervals to determine the amount of water soluble lignin (WSL), volatile fatty acids (VFAs), lignin monomers, and/or methane present. Lignin solubility increased as temperature rose in the thermal solubility experiments. The rate of solubility increased 15 times for office paper and 1.5 times for cardboard in the biological experiments when compared to the thermal treatment. The thermal and biological study indicates that as lignin is solubilized, it breaks down into lignin monomers, which can be converted easily by anaerobic bacteria into VFAs and subsequently, methane. These experiments indicate that temperature is crucial to the degradation of lignin compounds in a bioreactor landfill. / Master of Science

After cellulose, lignin is the second most abundant natural polymer in the world. It has multiple functional groups, providing great potential for polymer production. In this project, we explored the use of this renewable and valuable resource in two different adhesive applications to displace petroleum-based additives, thereby providing a more sustainable and “green” product. In this regard, two types of lignin, water-soluble (Amalin LPH) and non-water-soluble lignin (Amalin HPH) provided by the British Columbia Research Institute (BCRI) were used. In the first case, lignin was added to a pressure-sensitive adhesive (PSA) formulation via in-situ seeded semi-batch emulsion polymerization. It was seen that lignin does not readily take part in the polymerization reaction; rather, its presence results in reaction inhibition. Therefore, Amalin LPH lignin was modified via acrylation to overcome this issue. In another modification approach, maleic anhydride was used to produce maleated Amalin HPH lignin. Both the acrylated and maleated lignins were used in butyl acrylate/methyl methacrylate emulsion copolymerizations to produce PSA films. A series of controlled experiments with different lignin loadings was conducted. Adhesive properties of the PSA films were measured and compared with the corresponding acrylic base case formulation. The incorporation of lignin in the PSA formulation was a “green” solution to conventional PSA production and led to a simultaneous increase in tack and shear strength. Further characterization of the latex films via transmission electron microscopy (TEM) showed that lignin was successfully incorporated into the polymer particles. It also showed that the use of maleated lignin at a higher concentration led to a core-shell morphology. In the second application, unmodified Amalin LPH lignin was used to create a starch-based adhesive through the Stein-Hall process, a two-step process involving a “carrier” portion and a “slurry” portion. Several formulations with lignin loadings up to 35 wt% distributed in varying ratios in the carrier and slurry portions were prepared. It was shown that the addition of lignin to the starch-based adhesive formulation increases the water-resistance of the adhesive. Therefore, lignin addition is a solution for a common issue in starch-based adhesives, their lack of water-resistance due to the high affinity of starch toward water. Lignin incorporation solely in the slurry portion significantly increased the strength of the glued joints in a paper board adhesive test. The use of lignin as a renewable replacement of petroleum-based components in two different adhesive formulations was demonstrated successfully. This research strongly suggests that lignin can be used as a high value-added property modifier in adhesive applications.

No description available.

Thesis (Ph. D.)--Institute of Paper Chemistry, 1942. / Includes bibliographical references (p. 68).

The use of fossil fuels is depleting the petroleum resources and the emissions exhausted during the use is contributing to the planets temperature rise, glaciers reciding and rised sea level etc. In a global perspective, the liquid petroleum fuels are dominating the fuel market. In the coming ten years, the use of liquid fuels is expected to grow.   In this work a method of preparing a biodiesel microemulsion between petroleum diesel and kraft lignin has been examined. Lignin is a renewable by-product from the pulp- and paper industry, extracted from black liquor. In its natural appearance, lignin is not soluble in water and has to be modified to work as the hydrophilic phase in the microemulsion. The modification is achieved in a oxidative ammonolysis process. As an indication of how well the modification is performing, the amount of dissolved lignin in water were measured. The influence by the reaction time, pH-value and water content on the amount of dissolved lignin were examined in a statistical model in the software MODDE. A screening examination was performed to find the most influential factors. The MODDE model was optimized and could thereafter be used as a predictive tool and predict the outcome of responses within the experimental range. Ultrasonication was used to create the microemulsion. A stabilization test was performed by observing the created lignin diesel samples during three weeks. The operational cost of producing lignin diesel was calculated based on the chemical cost and the cost of electricity consumed during the production process.   A microemulsion was not created between diesel and modified lignin, rather an emulsion was achieved. The highest amount of dissolved lignin in the oxidative ammonolysis process were 99.77 %. The most influential factor was the pH-value in the oxidative ammonolysis process. The water content also affected the amount of dissolved lignin, while the reaction time factor within its range did not affect the amount of dissolved lignin. The statistical model design, execution and predictive ability were evaluated in MODDE and given a satisfying grade. In the stability test, a separation in the bottom of the samples were observed after 0.5 h time. After one week, there was a small colour gradient in the top of one of the samples. After two weeks, the same colour gradient were observed in all of the samples. In none of the samples, a total phase separation was observed under the three weeks. / Användningen av fossila bränslen utarmar jordens petroleum resurser och under användning utsöndras emissioner som bland annat bidrar till den globala uppvärmningen, smältande glaciärer och höjda havsnivåer. Globalt sätt dominerar de flytande petroleum bränslena bränslemarknaden och dess användning förväntas inom de närmsta tio åren öka.   I detta examensarbete undersöks och testas en metod för framställning av lignindiesel. Lignindieseln består av petroleumdiesel och lignin, vilka hålls ihop med hjälp av en mikroemulsion. Lignin är en förnybar restprodukt från pappers- och massaindustrin som utvinns från svartlut. I naturligt utförande är lignin inte blandbart med vatten och behöver därför modifieras för att kunna agera som hydrofil fas i mikroemulsionen. Modifieringen görs genom en oxidativ ammonolysprocess. Som indikation på hur modifieringen verkade på ligninet mättes mängden löst lignin i vatten. Påverkan av faktorerna reaktionstid, pH-värde och vatteninnehåll på ligninets löslighet i vatten undersöktes i en statistisk modell som gjordes i programvaran MODDE. Den statistiska modellens design, utförande och predikteringskapacitet utvärderades. En screeningundersökning utfördes för att identifiera hur de olika faktorerna påverkade lignets löslighet i vatten. Modellen i MODDE optimerades och kunde därefter användas som en predikterande modell inom undersökningens omfattning. Ultraljudssonikering användes för att skapa mikroemulsionen. Ett stabiliseringstest gjordes genom att de olika lignindieslarna placerades i provrör som observerades under tre veckors tid. Driftkostnaden i form av kemikaliekostnad och kostnad för konsumerad elektricitet under produktionen beräknades.   En mikroemulsion kunde inte framställas. Dock skapades en emulsion mellan diesel och modifierat lignin. Den högsta halten av löst lignin i vatten var 99.77 %. pH-värdet under reaktionen var den faktor som påverkade ligninets löslighet mest. Vatteninnehållet i det modifierade ligninet påverkade också lösligheten samtidigt som reaktionstiden inte påverkade lösligheten nämnvärt inom det givna spannet. Den statistiska modellens design och utförande var tillfredställande och den prediktiva kapaciteten var mycket bra. Stabilitetstestet visade att en separation observerades i botten ett av lignindieselproverna efter 0.5 h. Efter en vecka observerades en liten färggradient i toppen av ett av provrören. Efter två veckor syntes samma sorts färggradient i alla lignindieselproverna. Inget av lignindieselproverna undergick fullständig fasseparation under the tre veckornas separationstest.

農林水産研究情報センターで作成したPDFファイルを使用している。

Thesis (MSc)--Stellenbosch University, 2015. / ENGLISH ABSTRACT: Lignocellulosic material is composed of three major macromolecule components i.e., cellulose, hemicelluloses and lignin. These components are chemically associated and directly linked to each other through covalent bonding which is scientifically denoted as lignin-carbohydrate complexes (LCCs) and their interaction is fundamentally important as to understand wood formation and reactivity during chemical and biological processing e.g. pulping and enzymatic hydrolysis. The association of lignin with polysaccharides (covalent linkages) has been surrounded by contradictions and controversy in several wood chemistry studies. These linkages exist in lignocellulosic materials from wood to herbaceous plants. In woody plants, they consist of ester and ether linkages through sugar hydroxyl to α-carbonyl of phenyl-propane unit on lignin. However, in herbaceous plants ferulic and p-coumaric acids are esterified to hemicelluloses and lignin respectively. In recent studies, the existence of the bonds has been shown by applying indirect analysis strategies which resulted to low yields and contaminations. The general aim of the current study was to isolate and fractionate LCCs from raw lignocellulosic materials (E. grandis and sugarcane bagasse) and corresponding processed materials (chemical pulps and water-insoluble residues (WIS)) in order to determine the chemical structure of the residual lignin associated with polysaccharides and how they affected industrial processing. The objective of the study is to compile a document that when the development of pulping and bio-ethanol bio-refinery will greatly depends on the detailed wood chemistry on how the components interact with each before and after hemicelluloses pre-extraction prior to pulping and steam explosion pre-treatment prior to enzymatic hydrolysis. The current study was focusing on understanding the effect LCCs isolated from two different industrial processing methods, i.e. pulping and enzymatic hydrolysis (EH). There were two lignocelluloses feedstocks used for pulping, i.e. Eucalyptus grandis and sugarcane bagasse whereas sugarcane bagasse was the only feedstock used for enzymatic hydrolysis. Hemicelluloses pre-extracted (mild alkali or dilute acid and autohydrolysis for sugarcane bagasse) pulps of Kraft or soda AQ from E. grandis and sugarcane bagasse were used to understand the effect of xylan pre-extraction prior to pulping on lignin-carbohydrate complexes has not been reported to the best knowledge of the primary author. Also prior to EH the material was subjected to two different treatment methods, i.e. steam explosion and ionic liquid fractionation in varying conditions. The study illustrated the types of extracted and fractionated LCCs from hemicelluloses pre-extracted pulps and WIS in comparison to the non-extracted pulps and reports from the literature. Lignin-carbohydrate complexes (LCCs) were isolated and fractionated by an inorganic method which yielded reasonable quantification quantities and no contamination and low yields for the hardwood compared to reports of using an enzymatic method. To the best knowledge of the authors, no work has been done on WIS material. The lignocelluloses were subjected to ball milling which was followed by a sequence of inorganic solvents swelling and dissolution into 2 fractions i.e. glucan-lignin and xylan-lignin-glucan. Characterisation of the isolated LCCs was made using a variety of analytical tools such as FTIR-PCA, HPLC, GPC and GC-MS. LCCs were evident when FTIR and HPLC studies were conducted. Residual lignin isolated from the lignocelluloses was assumed to be chemically bonded to carbohydrates and mostly to xylan. Approximately 60% and 30% of the lignin was linked to xylan while for the second and first fractions respectively. It is reported that lignin associated with xylan is more resistant and reduce the delignification process than when linked to glucan that is easily hydrolysable. With the FTIR and GPC analyses of LCC fractions, it was evident that the ester bonds of LCCs were destroyed through pre-extraction and pre-treatment, where this resulted to more cellulose being more accessible to alkaline pulping and enzymatic hydrolysis respectively. The linkages were either partially broken down or completely destroyed leading to significant changes of chemical structures. The polydispersity of the LCCs assisted in determining the structure of lignin, either existing as monolignols on the surfaces of fibres or a as complex two or three-dimensional structure that is linked to carbohydrates as the Mw increased or decreased. In general, these findings may have an important implication for the overall efficiency on bio-refinery. The molecular weights (Mw) of the extracted LCCs were measured by gel permeation chromatography. From the chromatograms, it was observed that the materials that were subjected to pre-processing prior to further processing, the Mw shifted to lower Mws regions. It was found that LCCs isolated from mild alkali pre-extracted pulps had high lignin syringyl to guaiacyl lignin contents than LCCs isolated from dilute acid pre-extracted pulps. High syringyl/guaiacyl ratio (S/G ratio) was an indication of low lignin content as a result of processing which will result to high product yields after downstream processing. The 5 average S/G ratio for the pulps from E. grandis and sugarcane bagasse was ranging between 1.1 to 19.01 and 1.4 to 18.16 respectively, while for the WIS-material generated from ionic liquid fractionated and steam exploded materials ranged from 3.29 to 9.27 and 3.5 to 13.3 respectively. The S/G ratios of the LCCs extracted from E. grandis and sugarcane bagasse pulps ranged from 0.42 to 2.39 and 0.041 to 0.31 was respectively while for the LCCs extracted from water-insoluble-solids (WIS) material generated from steam exploded material was from 4.87 to 10.40. The determination of S/G ratio is recommended for the LCC extraction and characterisation study as an evaluation of residual lignin in processed materials such as pulps and WIS. The obtained saccharifications were low, possibly due to the severity of the steam explosion pre-treatment and ionic liquid fractionation conditions which resulted on high accumulation of acetic acid and increased in cellulose crystallinity respectively. From quantitative analysis of the LCCs perspective it could be concluded that free lignin was present in mild alkali pre-extracted pulps than for the dilute acid pre-extracted pulps. / AFRIKAANSE OPSOMMING: Cellulose materiaal is saamgestel uit drie groot makromolekule komponente naamlik, sellulose, hemisellulose en lignien. Hierdie komponente is chemies verwante en direk met mekaar verbind deur kovalente binding wat wetenskaplik aangedui as lignien-koolhidraat komplekse (LCCs) en hul interaksie is fundamenteel belangrik as hout vorming en reaktiwiteit tydens chemiese en biologiese verwerking bv om te verstaan verpulping en ensiematiese hidrolise. Die vereniging van lignien met polisakkariede (kovalente verbindings) is omring deur teenstrydighede en omstredenheid in verskeie hout chemie studies. Hierdie skakeling bestaan in cellulose materiaal uit hout te kruidagtige plante. In houtagtige plante, hulle bestaan uit ester en eter bindings deur suiker hidroksiel te α-karboniel van feniel-propaan eenheid op lignien. Maar in kruidagtige plante ferulic en p-coumaric sure veresterd te hemisellulose en lignien onderskeidelik. In onlangse studies, het die bestaan van die bande is getoon deur die toepassing van indirekte analise strategieë wat gelei tot lae opbrengste en kontaminasie. Die algemene doel van die huidige studie was om te isoleer en fraksioneer LCCs van rou cellulose materiaal (E. grandis en suikerriet bagasse) en die ooreenstemmende verwerkte materiaal (chemiese pulp en water-oplosbare residue (WIS)) ten einde die chemiese struktuur van die te bepaal oorblywende lignien wat verband hou met polisakkariede en hoe hulle geaffekteerde industriële verwerking. Die doel van die studie is 'n dokument op te stel dat wanneer die ontwikkeling van verpulping en bio-etanol bio-raffinadery sal grootliks afhang van die gedetailleerde hout chemie oor hoe om die komponente met mekaar voor en na hemisellulose pre-onttrekking voor verpulping en stoom ontploffing pre-behandeling voor ensiematiese hidrolise. Die huidige studie was die fokus op die begrip van die effek LCCs geïsoleerd van twee verskillende industriële verwerking, maw verpulping en ensiematiese hidrolise (EH). Daar was twee lignocelluloses voerstowwe gebruik vir verpulping, dws Eucalyptus grandis en suikerriet bagasse terwyl suikerriet bagasse was die enigste grondstof gebruik vir ensiematiese hidrolise. Hemisellulose pre-onttrek (ligte alkali of verdunde suur en autohydrolysis vir suikerriet bagasse) pulp van Kraft of soda AQ van E. grandis en suikerriet bagasse is gebruik om die effek van Xylan pre-onttrekking te voor verstaan verpulping op lignien-koolhidraat komplekse het nie aan die berig is beste kennis van die primêre outeur. Ook voor EH die materiaal is onderworpe aan twee verskillende behandeling metodes, naamlik stoom ontploffing en ioniese vloeistof fraksionering in wisselende toestande. Die studie geïllustreer die tipes onttrek en gefractioneerd LCCs van hemisellulose pre-onttrek pulp en WIS in vergelyking met die nie-onttrek pulp en verslae van die literatuur. Lignien-koolhidraat komplekse (LCCs) is geïsoleer en gefraksioneer deur 'n anorganiese metode wat redelike kwantifisering hoeveelhede en geen besoedeling en lae opbrengste opgelewer vir die hardehout vergelyking met verslae van die gebruik van 'n ensiematiese metode. Na die beste kennis van die skrywers, het geen werk op WIS materiaal gedoen. Die lignocelluloses is onderworpe aan die bal maal wat gevolg is deur 'n reeks van anorganiese oplosmiddels swelling en ontbinding in 2 breuke dws glucan-lignien en Xylan-lignien-glucan. Karakterisering van die geïsoleerde LCCs is gemaak met behulp van 'n verskeidenheid van analitiese gereedskap soos FTIR-PCA, HPLC, GPC en GC-MS. LCCs was duidelik wanneer FTIR en HPLC studies is uitgevoer. Residuele lignien geïsoleerd van die lignocelluloses is aanvaar moet word chemies gebind aan koolhidrate en meestal te xylan. Ongeveer 60% en 30% van die lignien is gekoppel aan xylan terwyl dit vir die tweede en eerste breuke onderskeidelik. Dit is gerapporteer dat lignien wat verband hou met Xylan is meer bestand en die delignification proses as wanneer gekoppel aan glucane wat maklik hidroliseerbare verminder. Met die FTIR en GPC ontledings van LCC breuke, was dit duidelik dat die ester bande van LCCs is deur pre-ontginning en pre-behandeling, waar dit gelei tot meer sellulose om meer toeganklik te alkaliese verpulping en ensiematiese hidrolise onderskeidelik vernietig. Die skakeling is óf gedeeltelik afgebreek of heeltemal vernietig lei tot beduidende veranderinge van chemiese strukture. Die polydispersity van die LCCs bygestaan in die bepaling van die struktuur van lignien, hetsy bestaande as monolignols op die oppervlak van die vesel of 'n as komplekse twee of drie-dimensionele struktuur wat gekoppel is aan koolhidrate as die Mw vermeerder of verminder. In die algemeen, kan hierdie bevindinge het 'n belangrike implikasie vir die algehele doeltreffendheid op bio-raffinadery. Die molekulêre gewigte (Mw) die onttrek LCCs gemeet deur gelpermeasie- chromatografie. Van die chromatograms, was dit opgemerk dat die materiaal wat blootgestel is aan die pre-verwerking voor verdere verwerking, die Mw verskuif MWS streke te verlaag. Daar is gevind dat LCCs geïsoleerd van ligte alkali pre-onttrek pulp het hoë lignien syringyl lignien inhoud as LCCs geïsoleerd van verdunde suur vooraf onttrek pulp te guaiacyl. Hoë syringyl / guaiacyl verhouding (S/G-verhouding) was 'n aanduiding van 'n lae lignien inhoud as 'n resultaat van verwerking wat sal lei tot 'n hoë produk opbrengste ná stroomaf verwerking. Die gemiddelde S/G-verhouding vir die pulp van E. grandis en suikerriet bagasse was wat wissel tussen 1,1-19,01 en 1,4-18,16 onderskeidelik, terwyl dit vir die WIS-materiaal gegenereer uit ioniese vloeistof gefraksioneer en stoom ontplof materiaal het gewissel 3,29-9,27 en 3.5 13,3 onderskeidelik. Die S/G verhoudings van die LCCs onttrek uit E. grandis en suikerriet bagasse pulp gewissel 0,42-2,39 en ,041-,31 was onderskeidelik terwyl dit vir die LCCs onttrek uit water-oplosbare-vastestowwe (WIS) materiaal gegenereer uit stoom ontplof materiaal was van 4,87-10,40. Die bepaling van S/G-verhouding word aanbeveel vir die LCC ontginning en karakterisering studie as 'n evaluering van die oorblywende lignien in verwerkte materiaal soos pulp en WIS. Die verkry saccharifications was laag, moontlik as gevolg van die erns van die stoom ontploffing pre-behandeling en ioniese vloeistof fraksionering voorwaardes wat gelei op 'n hoë opeenhoping van asynsuur en vermeerder in sellulose kristalliniteit.