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Submitted by Felipe Lange Shimizu null (felipe_lash@hotmail.com) on 2018-04-04T17:40:35Z No. of bitstreams: 1 Versão Final.pdf: 2417638 bytes, checksum: cbd92ea0f55b939141e8dbb758da327f (MD5) / Rejected by Adriana Aparecida Puerta null (dripuerta@rc.unesp.br), reason: Prezado Felipe Lange Shimizu, Solicitamos que realize uma nova submissão seguindo as orientações abaixo: - Capa - Faltou a capa no documento enviado. Este item é elemento obrigatório de acordo com as normas de trabalhos do seu Programa de Pós Graduação. Agradecemos a compreensão e aguardamos o envio do novo arquivo. Atenciosamente, Biblioteca Campus Rio Claro Repositório Institucional UNESP on 2018-04-05T13:45:30Z (GMT) / Submitted by Felipe Lange Shimizu null (felipe_lash@hotmail.com) on 2018-04-05T13:57:48Z No. of bitstreams: 1 Dissertação Final Biblioteca.pdf: 2476461 bytes, checksum: 98bb493283b6d060e268893b026507a0 (MD5) / Approved for entry into archive by Adriana Aparecida Puerta null (dripuerta@rc.unesp.br) on 2018-04-05T17:46:11Z (GMT) No. of bitstreams: 1 shimizu_fl_me_rcla.pdf: 2148045 bytes, checksum: 5ae73bad5319cc903eba26a7980c267c (MD5) / Made available in DSpace on 2018-04-05T17:46:11Z (GMT). No. of bitstreams: 1 shimizu_fl_me_rcla.pdf: 2148045 bytes, checksum: 5ae73bad5319cc903eba26a7980c267c (MD5) Previous issue date: 2018-02-26 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / A biomassa lignocelulósica, como a proveniente da cana-de-açúcar, é uma fonte abundante de resíduo que pode ser usado como matéria-prima na produção de energia. Para melhor aproveitar essa biomassa, moagem e pré-tratamentos podem ser usados para alterar a estrutura do material lignocelulósico, remover lignina e hemicelulose, expondo a celulose e assim aumentando sua acessibilidade. A acessibilidade à celulose tem sido indicada como uma das propriedades mais importantes para uma boa digestibilidade enzimática. Entretanto, as biomassas geradas da cana-de-açúcar possuem características físico-químicas diferentes, respondendo de modo diferente aos pré-tratamentos. Neste contexto, este estudo teve como objetivo verificar os efeitos da remoção de lignina e hemicelulose das biomassas da cana-de-açúcar (fração externa, entrenó, nó e folha) na acessibilidade à celulose. A cana-de-açúcar foi fracionada em fração externa, nó, entrenó e folha. Cada fração passou pelos pré-tratamentos ácido (5, 10, 20 %, m/m massa de ácido por massa de material, a 121°C/30 min), alcalino (5, 10, 20 e 30 % NaOH m/m) e oxidativo (0,5, 1, 2 e 3 horas com clorito de sódio 30 %). As amostras foram caracterizadas quanto ao seu conteúdo de celulose, hemicelulose e lignina. A determinação de acessibilidade foi realizada com corantes Direct, Orange (superfície específica externa), Direct Blue (superfície específica interna) e Vermelho Congo (superfície total). A hidrólise enzimática (15 FPU/g de material, Cellic Ctec 2 - Novozymes) foi realizada para avaliar o efeito dos pré-tratamentos e acessibilidade à celulose no rendimento em glicose. O efeito dos pré-tratamentos foi primeiramente analisado pela quantidade de massa recuperada. Todas as frações estudadas apresentaram uma tendência em perder massa com aumento da concentração de reagente utilizado no pré-tratamento. O pré-tratamento ácido resultou em menor recuperação de massa, o que ocorreu em função da solubilização de hemicelulose. A caracterização química apontou a remoção de hemicelulose e principalmente lignina dos materiais em função do pré-tratamento e das suas condições. A deslignificação com clorito de sódio (oxidativo) resultou em remoção de lignina, chegando a quase a sua totalidade em materiais como a folha. A determinação de acessibilidade com os corantes Vermelho Congo, Direct Blue e Direct Orange indicaram que o aumento da concentração de reagentes no pré-tratamento provoca aumento de acessibilidade à celulose. Entretanto, os corantes Direct Orange e Blue foram mais precisos na determinação da acessibilidade à celulose em comparação ao Vermelho Congo. A fração de menor recalcitrância, entrenó, apresentou adsorção de 525,9 mg/g no ensaio com Vermelho congo, o Direct Orange 1333,3 mg/g e o Direct Blue 746,3 mg/g. O rendimento em glicose na hidrólise enzimática seguiu a tendência de melhora com aumento da acessibilidade. Do mesmo modo, a remoção de lignina resultou em maior rendimento em glicose na hidrólise enzimática, o entrenó deslignificado resultou na quase completa conversão da celulose em glicose. Este estudo identificou a fração externa como mais recalcitrante, e entrenó como menos recalcitrante, resultando em menor rendimento e maior de glicose na hidrólise enzimática, respectivamente. A remoção de hemicelulose e lignina por meio de pré-tratamentos influenciou diretamente na acessibilidade à celulose, resultando em melhor ação das enzimas na hidrólise enzimática de todas as frações. / The lignocellulosic biomass, such as the provided by the sugarcane, is an abundant source of raw materials for energy production. In order to better use this biomass, milling and pretreatments can be employed to alter the structure of the materials, remove lignin and hemicellulose. This effect exposes the cellulose and raises its accessibility, which is is one of the most important property to ensure enzymatic digestibility. However, the biomass generated from the sugarcane have different physicochemical characteristics, giving different responses to the pretreatments. In this context, this study aimed to verify the effects of lignin and hemicellulose removal from the sugarcane biomass (external fraction, node, internode and leaf) on cellulose accessibility. The sugarcane was fractioned in external fraction, node, internode and leaf. Each fraction was pretreated with acid (5, 10, 20 % m/m acid mass per material mass, at 121°C/30 min), alkaline (5, 10, 20, 30 % NaOH m/m) oxidative (0,5, 1, 2 ,3 h charged with 30 % sodium chlorite). The chemical composition of the samples was determined based on cellulose, hemicellulose and lignin contents. Accessibility was determined by dye adsorption of Direct Orange (external specific surface), Direct Blue (internal specific surface) and Congo Red (total surface). Enzymatic hydrolysis (15 FPU/g of biomass, Cellic Ctec 2 – Novozymes) was used to verify the effects of pretreatments and cellulose accessibility on the glucose yield. All studied fractions showed tendency to lose mass with increasing reagent concentrations used in the pretreatments. Acid pretreatment resulted in low mass recovery due to hemicellulose solubilization. Chemical composition showed hemicellulose removal and significant lignin removal from the materials due to the pretreatments and their conditions. Delignification by sodium chlorite (oxidative) resulted in lignin removal, with almost completely removal with leaf samples. Accessibility determined by Congo Red, Direct Orange and Direct Blue dyes indicated that more aggressive pretreatments improved cellulose accessibility. However, Direct Orange and Direct Blue dyes were more precise than Congo Red while evaluating cellulose accessibility. The less recalcitrant fraction, the internode, showed 525,9 mg/g of Congo Red adsorption, 1333,3 mg/g of Direct Orange and 746,3 mg/g of Direct Blue. Glucose yield during enzymatic hydrolysis improved with higher cellulose accessibility. Lignin removal resulted in higher glucose yield, with delignified internode samples showing almost complete cellulose conversion. This study identified the external fraction as the most recalcitrant and the internode as the least recalcitrant, resulting in lower glucose yield and higher glucose yield, respectively. Hemicellulose and lignin removal by the pretreatments directly influenced cellulose accessibility, resulting in better enzymatic activity across all fractions.

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The suitability of water hyacinth (Eichornia crassipes) as a viable feedstock for renewable energy production was investigated in this project. Water hyacinth used in this study was harvested from the Vaal River near Parys in the northwest region of the Free State province, South Africa (26°54′S 27°27′E). The wet plants were processed in the laboratory at the North-West University by separating the roots from the leaves and the stems, thus obtaining two separate water hyacinth feedstock. Characterisation of the feedstock showed that the stems and leaves are more suitable for bio-energy production than roots, due to the higher cellulose and hemicellulose content and very low lignin content of the stems and leaves. Water hyacinth was evaluated as feedstock for the production of bio-ethanol gel, bio-ethanol, bio-oil and bio-char. The recovery of water from the wet plants for use in bio-refining or for use as drip-irrigation in agriculture was also investigated. Cellulose was extracted from water hyacinth feedstock to be used as a gelling agent for the production of ethanol-gel fuel. A yield of 200 g cellulose/kg dry feedstock was obtained. The extracted cellulose was used to produce ethanol-gel with varying water content. The gel with properties closest to the SANS 448 standard contained 90 vol% ethanol and 10 vol% water, with 38 wt% cellulose. This gel was found to ignite readily and burn steadily, without flaring, sudden deflagrations, sparking, splitting, popping, dripping or exploding from ignition until it had burned to extinction, as required by SANS 448. The only specifications that could not be met were the viscosity (23,548 cP) and the high waste residue (32 wt%) left after burning. The other major concern is the extremely high costs involved with the manufacturing of ethanol-gel from water hyacinth cellulose. It can be concluded that ethanol-gel cannot be economically produced using water hyacinth as feedstock. Chemical and enzymatic extraction of water from the feedstock, which is stems and leaves or roots, showed that the highest yield of water was obtained using a combination of Celluclast 1.5 L, Pectinex Ultra SP-L and additional de-ionised water. A yield of 0.89 ± 0.01 gwater/gwater in biomass was realised. This is, however, only 0.86 wt% higher than the highest yield obtained (0.87 ± 0.01 gwater/gwater in biomass) using only Pectinex Ultra SP-L and de-ionised water. It is recommended to use only Pectinex Ultra SP-L and de-ionised water at a pH of 3.5 and a temperature of 40°C. Using one enzyme instead of two reduces operating costs and simplifies the chemical extraction process. The extracted water, both filtered and unfiltered, was not found to be suitable for domestic use without further purification to reduce the total dissolved solids (TDS), potassium and manganese levels. Both the unfiltered and filtered water were, however, found to be suitable for industrial and agricultural purposes, except for the high TDS levels. If the TDS and suspended particle level can be reduced, the extracted water would be suitable for domestic, industrial and agricultural use. The potential fermentation of the sugars derived from the water hyacinth, using ultrasonic pretreatment, was investigated. Indirect ultrasonic treatment (ultrasonic bath) proved to be a better pretreatment method than direct sonication (ultrasonic probe). The optimum sugar yield for the ultrasonic bath pretreatment with 5% NaOH was found to be 0.15 g sugar/g biomass (0.47 g sugar/g available sugar) using an indirect sonication energy input of 27 kJ/g biomass. The optimum sugar yield is lower than those reported in other studies using different pretreatment methods. Theoretically a maximum of 0.24 g ethanol can be obtained per g available sugar. This relates to an ethanol yield of 0.08 g ethanol/kg wet biomass. The low yield implies that ethanol production from water hyacinth is not economically feasible. The production of bio-oil and bio-char from water hyacinth through thermochemical liquefaction of wet hyacinth feedstock was investigated. An optimum bio-char yield of 0.55 g bio-char/g biomass was achieved using an inert atmosphere (nitrogen) at 260°C and the stems and leaves as feedstock. With the roots as feedstock a slightly lower optimum yield of 0.45 g bio-char/g biomass was found using a non-reducing atmosphere (carbon monoxide) at 280°C. The bio-oil yield was too low to accurately quantify. As water is required during thermochemical liquefaction, it was found unnecessary to dry the biomass to the same extent as was the case with the pretreatment and fermentation of the water hyacinth, making this a more feasible route for biofuel production. Bio-char produced through liquefaction of roots as the feedstock and leaves and stems as the other feedstock had a higher heating value (HHV) of 10.89 ± 0.45 MJ/kg and 23.31 ± 0.45 MJ/kg respectively. Liquefaction of water hyacinth biomass increased the HHV of the feedstock to a value comparable to that of low grade coal. This implies a possible use of water hyacinth for co-gasification. The most effective route for bio-energy production in the case of water hyacinth was found to be thermochemical liquefaction (12.8 MJ/kg wet biomass). Due to the high production costs involved, it is recommended to only use water hyacinth as a feedstock for biofuel production if no alternative feedstock are available. / MIng (Chemical Engineering), North-West University, Potchefstroom Campus, 2014

The suitability of water hyacinth (Eichornia crassipes) as a viable feedstock for renewable energy production was investigated in this project. Water hyacinth used in this study was harvested from the Vaal River near Parys in the northwest region of the Free State province, South Africa (26°54′S 27°27′E). The wet plants were processed in the laboratory at the North-West University by separating the roots from the leaves and the stems, thus obtaining two separate water hyacinth feedstock. Characterisation of the feedstock showed that the stems and leaves are more suitable for bio-energy production than roots, due to the higher cellulose and hemicellulose content and very low lignin content of the stems and leaves. Water hyacinth was evaluated as feedstock for the production of bio-ethanol gel, bio-ethanol, bio-oil and bio-char. The recovery of water from the wet plants for use in bio-refining or for use as drip-irrigation in agriculture was also investigated. Cellulose was extracted from water hyacinth feedstock to be used as a gelling agent for the production of ethanol-gel fuel. A yield of 200 g cellulose/kg dry feedstock was obtained. The extracted cellulose was used to produce ethanol-gel with varying water content. The gel with properties closest to the SANS 448 standard contained 90 vol% ethanol and 10 vol% water, with 38 wt% cellulose. This gel was found to ignite readily and burn steadily, without flaring, sudden deflagrations, sparking, splitting, popping, dripping or exploding from ignition until it had burned to extinction, as required by SANS 448. The only specifications that could not be met were the viscosity (23,548 cP) and the high waste residue (32 wt%) left after burning. The other major concern is the extremely high costs involved with the manufacturing of ethanol-gel from water hyacinth cellulose. It can be concluded that ethanol-gel cannot be economically produced using water hyacinth as feedstock. Chemical and enzymatic extraction of water from the feedstock, which is stems and leaves or roots, showed that the highest yield of water was obtained using a combination of Celluclast 1.5 L, Pectinex Ultra SP-L and additional de-ionised water. A yield of 0.89 ± 0.01 gwater/gwater in biomass was realised. This is, however, only 0.86 wt% higher than the highest yield obtained (0.87 ± 0.01 gwater/gwater in biomass) using only Pectinex Ultra SP-L and de-ionised water. It is recommended to use only Pectinex Ultra SP-L and de-ionised water at a pH of 3.5 and a temperature of 40°C. Using one enzyme instead of two reduces operating costs and simplifies the chemical extraction process. The extracted water, both filtered and unfiltered, was not found to be suitable for domestic use without further purification to reduce the total dissolved solids (TDS), potassium and manganese levels. Both the unfiltered and filtered water were, however, found to be suitable for industrial and agricultural purposes, except for the high TDS levels. If the TDS and suspended particle level can be reduced, the extracted water would be suitable for domestic, industrial and agricultural use. The potential fermentation of the sugars derived from the water hyacinth, using ultrasonic pretreatment, was investigated. Indirect ultrasonic treatment (ultrasonic bath) proved to be a better pretreatment method than direct sonication (ultrasonic probe). The optimum sugar yield for the ultrasonic bath pretreatment with 5% NaOH was found to be 0.15 g sugar/g biomass (0.47 g sugar/g available sugar) using an indirect sonication energy input of 27 kJ/g biomass. The optimum sugar yield is lower than those reported in other studies using different pretreatment methods. Theoretically a maximum of 0.24 g ethanol can be obtained per g available sugar. This relates to an ethanol yield of 0.08 g ethanol/kg wet biomass. The low yield implies that ethanol production from water hyacinth is not economically feasible. The production of bio-oil and bio-char from water hyacinth through thermochemical liquefaction of wet hyacinth feedstock was investigated. An optimum bio-char yield of 0.55 g bio-char/g biomass was achieved using an inert atmosphere (nitrogen) at 260°C and the stems and leaves as feedstock. With the roots as feedstock a slightly lower optimum yield of 0.45 g bio-char/g biomass was found using a non-reducing atmosphere (carbon monoxide) at 280°C. The bio-oil yield was too low to accurately quantify. As water is required during thermochemical liquefaction, it was found unnecessary to dry the biomass to the same extent as was the case with the pretreatment and fermentation of the water hyacinth, making this a more feasible route for biofuel production. Bio-char produced through liquefaction of roots as the feedstock and leaves and stems as the other feedstock had a higher heating value (HHV) of 10.89 ± 0.45 MJ/kg and 23.31 ± 0.45 MJ/kg respectively. Liquefaction of water hyacinth biomass increased the HHV of the feedstock to a value comparable to that of low grade coal. This implies a possible use of water hyacinth for co-gasification. The most effective route for bio-energy production in the case of water hyacinth was found to be thermochemical liquefaction (12.8 MJ/kg wet biomass). Due to the high production costs involved, it is recommended to only use water hyacinth as a feedstock for biofuel production if no alternative feedstock are available. / MIng (Chemical Engineering), North-West University, Potchefstroom Campus, 2014

Lake Vättern has been contaminated with high levels of polychlorinated biphenyls (PCBs) for decades, which could be due to the release of wastes from industries and urban communities surrounding the water system. This has especially had a negative effect on fatty fishes, which could accumulate large amounts of persistent organic pollutants (POPs) and thereby also become a source of environmental toxicants to humans through consumption. Most PCB analysis only quantify a handful of congeners, the so called indicator-PCBs (I-PCBs), but this might leave out important information. In this study, an existing analytical method was improved by supplementing with additional congeners to detect a larger set of PCB congeners in Arctic char (Salvelinus salvelinus) and European whitefish (Coregonus acronius) caught from Lake Vättern, Sweden. New pre-packed multilayer silica columns from CAPE technologies were tested and used to pretreat the fish samples prior to analysis with a Gas Chromatograph coupled to low-resolution Mass Spectrometer using Atmospheric Pressure Ionization (API GC/MS). It was found that modifications of the clean up method for PCBs were necessary, such as lowering the amount of hexane in the washing step and combining the two eluent fractions. The Arctic char and the European whitefish showed a fat content of 0.18% and 0.74%, respectively. Concentrations of detected congeners ranged from 0.5 to 1470 pg g-1 fresh weight (fw) in Arctic char and varied between 1.2 to 6550 pg g-1 in European whitefish. For Arctic char and European whitefish, the WHO2005-TEQ values were 0.4 pg g-1 fw and 0.6 pg g-1 fw, respectively. The greatest total PCB concentration of 25900 pg g-1 was measured in European whitefish. The total concentration of I-PCBs (#28, 52, 101, 138, 153, 180) was 3710 pg g-1 for the Arctic char and 13900e pg g-1 for the European whitefish. All obtained results were lower than those reported from other studies. Constructed congener profiles show that the two species have similar ratios of PCB #138 and #153. Differences are observed of PCBs with a higher chlorination grade, probably due to differences in migration patterns, habitats of the lake, diets, metabolism or bioaccumulation.

Thesis (MSc)--Stellenbosch University, 2011. / ENGLISH ABSTRACT: The need to mitigate the twin crises of peak oil and climate change has driven a headlong rush to biofuels. This study was aimed at the development of a process to efficiently convert steam explosion pretreated (STEX) sugarcane bagasse into ethanol by using combinations of commercial enzyme cocktails and recombinant Saccharomyces cerevisiae strains. Though enzymatic saccharification is promising in obtaining sugars from lignocellulosics, the low enzymatic accessibility of the cellulose and hemicellulose is a key impediment thus necessitating development of an effective pretreatment scheme and optimized enzyme mixtures with essential accessory activities. In this context, the effect of uncatalysed and SO2 catalysed STEX pretreatment of sugarcane bagasse on the composition of pretreated material, digestibility of the water insoluble solids (WIS) fraction and overall sugar recovery was investigated. STEX pretreatment with water impregnation was found to result in a higher glucose recovery (28.1 g/ 100 bagasse) and produced WIS with a higher enzymatic digestibility, thus was used in the optimization of saccharification and fermentation. Response surface methodology (RSM) based on the 33 factorial design was used to optimize the composition of the saccharolytic enzyme mixture so as to maximize glucose and xylose production from steam exploded bagasse. It was established that a combination of 20 FPU cellulase/ g WIS and 30 IU -glucosidases/ g WIS produced the highest desirability for glucose yield. Subsequently the optimal enzyme mixture was used to supplement enzyme activities of recombinant yeast strains co-expressing several cellulases and xylanases in simultaneous saccharification and fermentations SSFs. In the SSFs, ethanol yield was found to be inversely proportional to substrate concentration with the lowest ethanol yield of 70% being achieved in the SSF at a WIS concentration of 10% (w/v). The ultimate process would however be a one-step “consolidated” bio-processing (CBP) of lignocellulose to ethanol, where hydrolysis and fermentation of polysaccharides would be mediated by a single microorganism or microbial consortium without added saccharolytic enzymes. The cellulolytic yeast strains were able to autonomously multiply on sugarcane bagasse and concomitantly produce ethanol, though at very low titres (0.4 g/L). This study therefore confirms that saccharolytic enzymes exhibit synergism and that bagasse is a potential substrate for bioethanol production. Furthermore the concept of CBP was proven to be feasible. / AFRIKAANSE OPSOMMING: Die behoefte om die twee krisisse van piek-olie en klimaatsverandering te versag, het veroorsaak dat mense na biobrandstof as alternatiewe energiebron begin kyk het. Hierdie studie is gemik op die ontwikkeling van 'n proses om stoomontplofde voorafbehandelde (STEX) suikerriet bagasse doeltreffend te omskep in etanol deur die gebruik van kombinasies van kommersiële ensiem mengsels en rekombinante Saccharomyces cerevisiae stamme. Alhoewel ensiematiese versuikering belowend is vir die verkryging van suikers vanaf lignosellulose, skep die lae ensiematiese toeganklikheid van die sellulose en hemisellulose 'n hindernis en dus is die ontwikkeling van' n effektiewe behandelingskema en optimiseerde ensiemmengsels met essensiële bykomstige aktiwiteite noodsaaklik. In hierdie konteks, was die effek van ongekataliseerde en SO2 gekataliseerde stoomontploffing voorafbehandeling van suikerriet bagasse op die samestelling van voorafbehandelde materiaal, die verteerbaarheid van die (WIS) breuk van onoplosbare vastestowwe in water (WIS), en die algehele suikerherstel ondersoek. Daar was bevind dat stoomontploffing behandeling (STEX) met water versadiging lei tot 'n hoër suikerherstel (21.8 g/ 100g bagasse) en dit het WIS met ‘n hoër ensimatiese verteerbaarheid vervaardig en was dus gebruik in die optimalisering van versuikering en fermentasie. Reaksie oppervlak metodologie (RSM), gebasseer op die 33 faktoriële ontwerp, was gebruik om die samestelling van die ‘saccharolytic’ ensiemmengsel te optimaliseer om sodoende die maksimering van glukose en ‘xylose’ produksie van stoomontplofde bagasse te optimaliseer. Daar was bevestig dat ‘n kombinasie van 20 FPU sellulase/ g WIS en 30 IU ‘ -glucosidases/ g’ WIS die hoogste wenslikheid vir glukose-opbrengs produseer het. Daarna was die optimale ensiemmengsel gebruik om ensiemaktiwiteit van rekombinante gisstamme aan te vul, wat gelei het tot die medeuitdrukking van verskillende ‘cellulases’ en ‘xylanases’ in gelyktydige versuikering en fermentasie SSFs. In die SSFs was daar bevind dat die etanol-produksie omgekeerd proporsioneel is tot substraat konsentrasie, met die laagste etanolopbrengs van 70% wat bereik was in die SSF by ‘n WIS konsentrasie van 10% (w/v). Die uiteindelike proses sal egter 'n eenmalige "gekonsolideerde" bioprosessering (CBP) van lignosellulose na etanol behels, waar die hidrolise en fermentasie van polisakkariede deur' n enkele mikroorganisme of mikrobiese konsortium sonder bygevoegde ‘saccharolytic’ ensieme bemiddel sal word. Die ‘cellulolytic’ gisstamme was in staat om vanself te vermeerder op suikerriet bagasse en gelyktydig alkohol te produseer, al was dit by baie lae titres (0.4 g/L). Hierdie studie bevestig dus dat ‘saccharolytic’ ensieme sinergisme vertoon en dat bagasse 'n potensiële substraat is vir bio-etanol produksie. Daar was ook onder meer bewys dat die konsep van CBP uitvoerbaar is. / The National Research Foundation (NRF) for financial support

Lignocellulosic materials provide a raw material source for biofuel conversion and offer several advantages over fossil fuels- usage of a renewable resource, reduced greenhouse emissions, a decreased dependence on foreign oil, and stimulation of the agricultural sector. However, a primary technological challenge in converting lignocellulosic biomass into fuel is overcoming the recalcitrance of its matrix to enzymatic hydrolysis. To overcome these problems for chemical processing, naturally occurring cellulose biomass must be pretreated before it can be further processed using enzymatic hydrolysis or bioconversion. The goal of this work was to develop a model that predicts the glucose yield (pretreatment and enzymatic digestibility) of dilute acid pretreated switchgrass as a function of pretreatment process conditions (acid loading, 0-1.5 vol%, temperature, 165-195oC, and residence time, 1-10 min). This project was the first study that used a multivariable design experimental series to directly compare the pretreatment effectiveness (product yield, biomass composition and appearance, pH, etc) of using conventional and microwave heated reactors. Microwave-pretreated switchgrass afforded up to a 100% higher total glucose yield (combined pretreatment and enzymatic-hydrolysis liquor yields) at equivalent pretreatment severity and at one tenth of the reaction time, relative to conventional pretreatment. Under best pretreatment conditions of 0.75 vol% acid, 195oC, 1 min residence time, 99% glucose yield and 99% hemicellulose removal were achieved. Kinetic parameters were estimated for the cellulose and xylan hydrolysis reactions in the pretreatment liquor and the solid residue. The kinetic model gave an average correlation coefficient of 0.93 for all reactions. In addition, the combined severity factors (CSF) were also determined for each experiment. Highest observed enzymatic glucose yield corresponded to a CSF of 1.7. A mass and energy balance, and economic analysis based on production scale was developed for both reactor systems. The microwave pretreatment process theoretically yielded 48% more ethanol relative to the conventional process. For microwave pretreatment to be commercially viable, two criteria must be met. One, the cost for largescale continuous microwave reactors would need to be significantly lower than current estimates. And second, higher solids content must be used (>20 wt% in the slurry) to maximize output.

Doctor of Philosophy / Department of Industrial & Manufacturing Systems Engineering / Zhijian Pei and Donghai Wang / Currently, transportation is almost entirely dependent on petroleum-based fuels (e.g. gasoline, diesel fuel, and jet fuel). Increasing demands for sustainable sources of liquid transportation fuels make it imperative to develop alternatives to petroleum-based fuels. Biofuels derived from cellulosic biomass (forest and agricultural residues and dedicated energy crops) have been recognized as promising alternatives to petroleum-based liquid fuels. Cellulosic biofuels not only reduce the nation’s dependence on foreign petroleum but also improve the environment through reduction of greenhouse gas emissions. In order to convert cellulosic biomass into biofuels, cellulosic biomass must go through a size reduction step first, because large size cellulosic biomass (whole stems of herbaceous biomass or chunks of woody biomass) cannot be converted to biofuels efficiently with the current conversion technologies. Native cellulosic biomass has limited accessibility to enzyme due to its structural complexity. Size reduction can reduce particle size and disrupt cellulose crystallinity, rendering the substrate more amenable to enzymatic hydrolysis. The purpose of this research is to provide knowledge of how size reduction alters biomass structural features, and understand the relationships between these biomass structural features and enzymatic hydrolysis sugar yield. This research is also aimed to investigate the impacts of process parameters in biomass size reduction on the conversion of cellulosic biomass to biofuels to help realize cost-effective manufacturing of cellulosic biofuels. This dissertation consists of eleven chapters. Firstly, an introduction of this research is given in Chapter 1. Secondly, Chapters 2 presents a literature review on cellulosic biomass size reduction. Thirdly, a preliminary experimental study is included in Chapter 3. Chapters 4 to 6 present a three-phase study on confounding effects of two important biomass structural features: particle size and biomass crystallinity. Chapters 7 and 8 investigate effects of sieve size used in size reduction of woody and herbaceous biomass, respectively. Chapters 9 and 10 focus on the relationship between particle size and sugar yield. Chapter 11 studies effects of cutting orientation in size reduction of woody biomass. Finally, conclusions and contributions are given in Chapter 12.

Doctor of Philosophy / Department of Biological & Agricultural Engineering / Donghai Wang / Grain sorghum is the second major starch-rich raw material (after corn) for bioethanol production in the United States. Most sorghum feedstock for bioethanol production is normal non-tannin sorghum. Waxy sorghum and tannin sorghum are rarely used due to lack of scientific information about waxy sorghum fermentation performance and the way to increase fermentation efficiency of tannin sorghum. The main objectives of this study were to investigate the fermentation performance of waxy sorghum and to improve fermentation efficiency of tannin sorghum using techniques such as germination and ozonation treatments. The ethanol fermentation performance on both waxy sorghum and tannin sorghum were evaluated using a dry grind ethanol fermentation procedure. Fermentation efficiencies of tested waxy sorghum varieties ranged from 86 to 93%, which was higher than normal (non-waxy) sorghum varieties. The advantages of using waxy sorghums for ethanol production include less energy consumption, higher starch and protein digestibility, shorter fermentation time, and less residual starch in distillers dried grains with solubles (DDGS). Results from germination study showed germination significantly increased fermentation efficiency of tannin sorghum. The laboratory results were further confirmed by those from five field-sprouted grain sorghum samples. Significantly increased free amino nitrogen (FAN) contents in sprouted sorghum samples accelerated the ethanol fermentation process. Results from both laboratory-germinated and fieldsprouted samples demonstrated that germination not only increased fermentation efficiency (higher than 90%) but also reduced fermentation time by about 50%, which could result in energy saving and increased production capacity without additional investment. The excellent performance of sprouted sorghums may provide farmers a new market for field-sprouted sorghum (poor quality as food or feed) in a bad year. A previous study showed ozone had a strong connection to degradation of lignin macromolecules. The hypothesis was that ozone treatment may also reduce tannin activity and increase fermentation efficiency of tannin sorghum. Results showed that the ethanol production performance (ethanol yield, fermentation efficiency, and fermentation kinetics) of the ozone-treated, tannin sorghum flours was significantly improved compared with the untreated control. The other effects of ozonation on sorghum flour include pH value decrease, discoloration, and inactivation of tannin. In summary, these studies showed sorghum, no matter it was waxy, field-sprouted, or tannin sorghum, can be an excellent feedstock for ethanol production.