With the inevitable depletion of the petroleum supply and increasing energy demands in the world, interest has been growing in bioconversion of lignocellulosic biomass (e.g., sugarcane bagasse). Lignocellulosic biomass is an abundant, inexpensive, and renewable resource. Most of current conversion technologies require expensive enzymes and sterility. In contrast, the patented MixAlco process requires no enzymes or sterility, making it attractive to convert lignocellulosic biomass to transportation fuels and valuable chemicals. This study focuses on pretreatment and thermophilic fermentation in the MixAlco process. Ammonium bicarbonate (NH4HCO3) was discovered to be a better pH buffer than previously widely used calcium carbonate (CaCO3) in anaerobic fermentations under thermophilic conditions (55°C). The desired pH should be controlled within 6.5 to 7.5. Over 85% acetate content in the product was found in paper fermentations and bagasse fermentations. Hot-lime-water-treated bagasse countercurrent fermentations buffered by ammonium bicarbonate achieved 50–60% higher total product concentrations than those using calcium carbonate. It was nearly double in paper batch fermentations if the pH was controlled around 7.0. Ammonium bicarbonate is a “weak” methane inhibitor, so a strong methane inhibitor (e.g., iodoform) is still required in ammonium bicarbonate buffered fermentations. Residual calcium salts did not show significant effects on ammonium bicarbonate buffered fermentations. Lake inocula from the Great Salt Lake, Utah, proved to be feasible in ammonium bicarbonate buffered fermentations. Under mesophilic conditions (40°C), the inoculum from the Great Salt Lake increased the total product concentration about 30%, compared to the marine inoculum. No significant fermentation performance difference, however, was found under thermophilic conditions. The Continuum Particle Distribution Model (CPDM) is a powerful tool to predict product concentrations and conversions for long-term countercurrent fermentations, based on batch fermentation data. The experimental acid concentrations and conversions agree well with the CPDM predictions (average absolute error < 15%). Aqueous ammonia treatment proved feasible for bagasse. Air-lime-treated bagasse had the highest acid concentration among the three treated bagasse. Air-lime treatment coupled with ammonium bicarbonate buffered fermentations is preferred for a “crop-tofuel” process. Aqueous ammonia treatment combined with ammonium bicarbonate buffered fermentations is a viable modification of the MixAlco process, if “ammonia recycle” is deployed.

South Africa has an annual sugarcane milling capacity of about 22 million tonnes on average producing about 3.3 million tonnes of dry bagasse, of which one third is surplus to factory requirements. Currently surplus bagasse is used for furfural, pulp and paper and cogeneration but significant amounts still remain . This prompted the need to find viable alternative and appropriate technology to utilize the surplus. A laboratory pilot plant was used to investigate the production of activated carbon from bagasse. Experiments were carried out to investigate conditions for making the best activated carbon in a rotary batch kiln, and also to examine potential ene rgy recovery from process gases using Gas Chromatography. Derived results from the laboratory experiments were used to develop a conceptual design for a demonstration plant sited within a sugar mill. The conceptual design was evaluated for economic and environmental impacts using a robust Excel spreadsheet and GABI-3 modelling software respectively. Excellent activated carbon was produced from sugarcane bagasse by a two-stage physical process involving pyrolysis and gasification with steam. The best operating conditions were pyrolysis at 700°C for 1 hr and activation at 850°C for 1hr, a heating rate of 10°C/min and a steam flow of 15g/g of char per hour. The active carbon yield was 7% on dry bagasse basis with a Methylene Blue Number of 257mglg of carbon. The active carbon had a sugar decolourisation capacity of 20% at a carbon dosage rate of 0.7 wt% on Brix using clear juice (l2°Brix) and 70% at 0.5 wt% on Brix using brown liquor (65°Brix) . The Freundlich isotherm showed that the bagasse-based activated carbon was a suitable adsorbent for sugar colour bodies. Gas analysis results revealed that the off gases from the pyrolysis and activation stages had calorific values of about 63MJ and 31MJ per kg of activated carbon respectively . The total combustion energy of 94 MJ/kg of active carbon was enough to satisfy the process energy requirements for drying, pyrolysis and activation. By burning combustibles like tar, methane, carbon monoxide, ethylene and hydrogen for process thermal energy needs, the environmental impact of the manufacturing process was reduced to a Global Warming Potential of llkg CO2 Equiv per kg of carbon produced. The demonstration plant requires a capital investment of US$lOA million to give a competitive bagasse-based activated carbon (BPAC) selling price of US$1.80 per kg and IRR, ROI and Investment payback time of 17.93%, 23.93% and 3.80 years respectively. A sensitivity analysis was also carried out to investigate the effect of possible variation in the main project forecasts which are BPAe selling price , bagasse buying price, capital investment and production costs on IRR, ROI and payback time . The benefits of process integration within a sugar mill would be expected to improve the business feasibility ; If bagasse was free the IRR would increase to 28.59% and even better to 32.12% if extra boiler and electricity capacity was also available at the mill. / Thesis (M.Sc.Eng.)-University of KwaZulu-Natal, 2005.

This work has examined the thermochemical conversion of sugar cane processing wastes (bagasse and cane harvesting trash) for use in the design of pressurised entrained flow gasification power cycles (~20 Barg, 600-900oC). The two key parameters of interest were the residual char yield from initial pyrolysis and the heterogeneous reactivity of the char with respect to carbon dioxide. Char yield and gasification rates were measured by a conventional wire mesh reactor and thermogravimetric (TGA) technique, an in-situ sample charring TGA technique and with an entrained flow reactor specifically designed for this work. The new experimental reactor concept is one of the major contributions of the work. Chars from the entrained flow experiments were characterised by optical microscope, SEM/EDS, TEM/EDS and XPS techniques, to help elucidate the processes occurring during pyrolysis and gasification. The key findings and conclusions of the work were as follows: 1. Initial (pyrolysis) char yields were consistent with the data reported in literature for similar materials. Char yields varied with reaction conditions, from 6 to 49 wt% daf for cane trash and 4 to 40 wt% daf for bagasse. Ash content also had a significant effect on char yield. The char yield for both cane trash and bagasse increased in proportion to the logarithm of system pressure. 2. A relatively simple empirical model for char yield under pressurised entrained flow conditions was formulated. This could predict char yields for both the experimental data in this work and those reported in literature for similar biomass materials. While temperature, pressure and ash content were all significant parameters in the model, the primary fitting parameter was a measure of the contribution of secondary char forming reactions and ongoing pyrolysis to char yield. The identification of this parameter is one of the contributions of this work. 3. The measured initial rate of char gasification by carbon dioxide was 0.06 to 1.2 mg per gram of initial char, over the temperature range 750 to 900oC. The rate of gasification was so low as to not contribute significantly to overall fuel conversion in the reaction residence times iv expected of a commercial gasifier. In essence almost all of the experimentally measured fuel conversion could be attributed to pyrolysis, which resulted in 85-95% fuel conversion. 4. Both the raw materials and the residual chars had low surface areas and negligible microporosity. The majority of the measured surface area may have been associated with the ash component rather than the carbonaceous component, which supported the finding of low reactivity. 5. The silica component of the chars exhibited crystalline silicate formation by migration of metal species over time periods of minutes. These silicates displayed signs of sintering, but otherwise remained physically intact; leaving a characteristic skeleton that corresponded to the original structure in the raw materials. 6. The gasification rate showed a time dependent decrease in the entrained flow experiments. This was attributed to coke formation on the char surface, followed by carbon trapping in the ash component at high levels of conversion. Both findings are significant contributions from this work, because they highlight key mechanisms that hinder fuel conversion in the proposed gasification concept. The broad coverage achieved in this work has provided an overall picture of how fuel conversion progresses during the pressurised entrained flow gasification of sugar cane wastes. It is recommended that many of the aspects highlighted in this work be examined further, to confirm the findings and to investigate the means to avoid the factors identified in this work as hindering fuel conversion.

Thesis (Ph.D.) - James Cook University, 2003. / Typescript (photocopy). Appendices: leaves 156-172. Bibliiography: leaves 149-155.

With recent emphasis on development of alternatives to fossil fuels, sincere attempts are being made on finding suitable lignocellulosic feedstocks for biochemical conversion to fuels and chemicals. Sweet Sorghum is among the most widely adaptable cereal grasses, with high drought resistance, and ability to grow on low quality soils with low inputs. It is a C4 crop with high photosynthetic efficiency and biomass yield. Since sweet sorghum has many desirable traits, it has been considered as an attractive feedstock. Large scale sweet sorghum juice extraction results in excessive amounts of waste sweet sorghum bagasse (SSB), which is a promising low cost lignocellusic feed stock. The ability of two pretreatment methods namely conventional oven and microwave oven pretreatment for disrupting lignocellulosic structures of sweet sorghum bagasse with lime [Ca(OH)2] and sodium hydroxide [NaOH] was evaluated. The primary goal of this study was to determine optimal alkali pretreatment conditions to obtain higher biomass conversion (TRS yield) while achieving higher lignin reduction for biofuel production. The prime objective was achieved using central composite design (CCD) and optimization of biomass conversion and lignin removal simultaneously for each alkali separately by response surface method (RSM). Quadratic models were used to define the conditions that separately and simultaneously maximize the response variables. The SSB used in this study was composed of cellulose, hemicellulose, and lignin in the percentage of 36.9 + 1.6, 17.8 + 0.6, and 19.5 + 1.1, respectively. The optimal conditions for lime pretreatment in the conventional oven at 100 °C was 1.7 (% w/v) lime concentration (=0.0024 molL-1), 6.0% (w/v) SSB loading, 2.4 hr pretreatment time with predicted yields of 85.6% total biomass conversion and 35.5% lignin reduction. For NaOH pretreatment, 2% (w/v) alkali (=0.005 molL-1), 6.8% SSB loading and 2.3 hr duration was the optimal level with predicted biomass conversion and lignin reduction of 92.9% and 50.0%, respectively. More intensive pretreatment conditions removed higher amount of hemicelluloses and cellulose. Microwave based pretreatments were carried out in a CEM laboratory microwave oven (MARS 6-Xpress Microwave Reactions System, CEM Corporation, Matthews, NC) and with varying alkali concentration(0.3 - 3.7 % w/v) at varying temperatures (106.4 - 173.6 °C), and length of time (6.6 - 23.4 min). The NaOH pretreatment was optimized at 1.8 (% w/v) NaOH, 143 °C, 14 min time with predicted yields of 85.8% total biomass conversion and 78.7% lignin reduction. For lime pretreatment, 3.1% (w/v) lime, 138 °C and 17.5 min duration was the optimal level with predicted biomass conversion and lignin reduction of 79.9% and 61.1%, respectively. Results from this study were further supported by FTIR spectral interpretation and SEM images.

MBL 3 Research Report / This study investigated the economic significance of using bagasse as a source of raw material for pulp and paper manufacturing. The study also compared this issue with the currently undergoing practices of cogeneration, where bagasse is burnt in the sugar mill boilers to produce steam and generate electricity.

Made available in DSpace on 2014-06-11T19:32:51Z (GMT). No. of bitstreams: 0 Previous issue date: 2011-06-28Bitstream added on 2014-06-13T21:05:02Z : No. of bitstreams: 1 pereira_phf_dr_guara.pdf: 2105093 bytes, checksum: 21492c0b00e90725bc6e355369f70dd7 (MD5) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Atualmente, a necessidade de desenvolver e comercializar materiais baseados em constituintes de fibras vegetais tem crescido, devido à conscientização com relação a questões relacionadas ao impacto ambiental e ao desenvolvimento sustentável. Grandes quantidades de materiais lignocelulósicos são gerados em todo o mundo a partir de diversas atividades humanas. Pensando no aproveitamento do excedente do bagaço de cana-de-açúcar, esse trabalho tem como objetivo a obtenção da celulose branqueada a partir do bagaço do mesmo. Para essa aplicação, os componentes macromoleculares do bagaço de cana-de-açúcar foram separados, aplicando prétratamento químico para retirada da parte hemicelulósica e um tratamento com hidróxido de sódio para separação da lignina e obtenção da polpa bruta de celulose. Essa polpa bruta de celulose foi branqueada com clorito de sódio. Assim, pretendeu-se preparar híbridos utilizando derivados de bagaço de cana-de-açúcar: celulose branqueada (CB) e celulose não branqueada (CNB) com fosfato de nióbio hidratado. Para preparação do híbrido com o NbOPO4.nH2O estudou-se uma nova rota de preparação do fosfato de nióbio hidratado com adição de ácido bórico, o qual reduziu o tempo de síntese; formando-se um complexo com os íons fluoreto presentes no sistema e a esta solução foi adicionada ácido fosfórico, permitindo a geração de um precipitado que se formou após 6 horas de reação. A parti do desenvolvimento desse método preparou-se os híbridos utilizando a CB e CNB em diferentes proporções. Os híbridos foram preparados em diferentes proporções denominados de síntese A (5 g CB/ 5 g NbOPO4.nH2O), síntese B (5 g CB/ 3 g NbOPO4.nH2O) e síntese C (5 g CB/ 1 g NbOPO4.nH2O). A fim de verificar a influência do ácido fosfórico na preparação do híbrido, foram... / Currently, the need to develop and market materials based on constituents of natural fibers has grown due to increased awareness on issues related to environmental and sustainable development. Large quantities of lignocellulosic materials are generated worldwide from human activities. Thinking about the use for surplus bagasse of sugarcane, this work aims at obtaining the bleached pulp from bagasse the same. For this application, the macromolecular components of sugarcane bagasse were separated by applying chemical pretreatment for removal of hemicellulose and part of a treatment with sodium hydroxide to obtain separation of lignin and obtaining of crude cellulose. This pulp were bleached crude cellulose with sodium chlorite. Thus, we intended to prepare using hybrids derived from sugar cane bagasse: bleached cellulose (CB) and unbleached cellulose (CNB) with hydrated niobium phosphate. To prepare the hybrid with NbOPO4.nH2O studied whether a new route for the preparation of hydrated niobium phosphate with addition of boric acid, which reduced the synthesis time, forms a complex with fluoride ions present in the system and this solution added phosphoric acid was added, allowing the generation of a precipitate formed after 6 hours of reaction. From the development hybrids prepared using the CB and CNB in different proportions. The hybrids were prepared in different proportions called; synthesis A (5 g CB /5 g NbOPO4.nH2O), synthesis B (CB 5 g / 3 g NbOPO4.nH2O) and synthesis C (CB 5 g / 1 g NbOPO4.nH2O). In order to verify the influence of phosphoric acid in the preparation of the hybrid, were also prepared hybrid called: synthesis D (5 g CB / 5 g NbOPO4.nH2O) and synthesis E (5 g CB / 3 g NbOPO4.nH2O) and synthesis F (5 g CB / NbOPO4.nH2O 1 g) using twice the amount of phosphoric acid. All materials were characterized... (Complete abstract click electronic access below)

Made available in DSpace on 2014-06-11T19:35:06Z (GMT). No. of bitstreams: 0 Previous issue date: 2008-08-15Bitstream added on 2014-06-13T20:06:24Z : No. of bitstreams: 1 sacco_ap_dr_araiq.pdf: 974516 bytes, checksum: df003a2a3edadda2bab3403b7e91624e (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / A elucidação da estrutura da lignina, macromolécula natural amorfa, é um desafio para a pesquisa. Sua estrutura pode variar bastante de uma fonte vegetal para a outra, dependendo da sua origem. Neste trabalho, foi realizada a extração, a caracterização e o estudo cinético de decomposição térmica de ligninas obtidas a partir de duas fontes de biomassa: de bagaço de cana-de-açúcar (utilizada como referência) e dos resíduos sólidos urbanos (RSU) de leiras em diferentes estágios de compostagem. As técnicas utilizadas para a caracterização das ligninas foram: análise térmica (TG/DTA), FITR, RMN de 13C no estado sólido e fluorescência de raios-X. O estudo cinético de degradação térmica das ligninas foi realizado utilizando o método isoconversional de Flynn- Wall e Ozawa. A lignina obtida do bagaço de cana-de-açúcar apresentou-se como uma boa amostra de referência por possuir características de protolignina, sem impurezas de carboidratos associados à sua estrutura, o que pôde ser confirmado pela técnica de RMN de 13C. Já as ligninas obtidas dos RSU apresentaram decomposição térmica e grupos característicos da lignina e a presença de outros elementos complexados em sua estrutura, principalmente o íon ferro. No entanto, a presença de carbonos alifáticos comprovados pelas técnicas de TG/DTA e RMN de 13C, sugere que as ligninas extraídas dos RSU encontram-se fragmentadas. De acordo com o estudo cinético, para o primeiro evento de decomposição térmica da lignina, verificou-se o efeito de compensação cinética para as amostras de ligninas referências, bem como, para as ligninas extraídas dos RSU, levando à conclusão de que ambas apresentam a mesma composição orgânica básica. / The elucidation of the structure of lignin, amorphous natural macromolecule, is a challenge for the research. Its structure can vary a lost from a vegetable source to other, depending on its origin. In this work, it was made the extraction, the characterization and the kinetic study of thermal decomposition of lignins obtained from two biomass sources: sugarcane bagasse (used as reference) and the urban solid residues (RSU) of stacks in different stages of composting. The techniques used for the characterization of lignins were: thermal analysis (TG/DTA), FITR, NMR 13C in the solid state and fluorescence of ray-X. The kinetic study of thermal degradation of the lignins was made using the method isoconversional of Flynn - Wall and Ozawa. Lignin obtained from sugarcane bagasse was a good reference sample for owning protolignin characteristics, without carbohydrate impurities associated in your structure, what could be confirmed by the technique of RMN 13C. By other hand, lignin obtained from RSU presented thermal decomposition and characteristic groups of lignin and the presence of other elements complexed in your structure, mainly the ion iron. However, the presence of aliphatic carbons confirmed by techniques of TG/DTA and NMR 13C, suggests that lignins extracted from RSU are fragmented. In agreement to kinetic study, for the first event of thermal decomposition of the lignin, the effect of kinetic compensation was verified for the samples of reference lignins, as well as, for lignins extracted from RSU, taking to the conclusion that both present the same basic organic composition.

Made available in DSpace on 2015-05-14T16:52:53Z (GMT). No. of bitstreams: 0 Previous issue date: 2014-08-01Bitstream added on 2015-05-14T16:59:45Z : No. of bitstreams: 1 000807395.pdf: 2800331 bytes, checksum: d487e7138b00aaf70faf975ffccf521d (MD5) / Neste trabalho encontra-se apresentada a produção via misturador termocinético e injeção de compósitos de polipropileno reforçados com bagaço de cana de açúcar deslignificado e com bagaço hidrolisado por enzimas, em diferentes concentrações (5%, 10% e 25%, massa/massa, (m/m)). Em seguida, os compósitos poliméricos foram caracterizados via ensaios mecânicos de tração, flexão em três pontos e impacto Izod. Além disso, ensaios para a determinação das propriedades térmicas (temperaturas de fusão e de cristalização por calorimetria exploratória diferencial (DSC), temperatura de degradação por termogravimetria (TGA) e temperatura de transição vítrea (Tg) por análise dinâmico-mecânica (DMA)) foram realizadas. Análises de infravermelho (FTIR) e microscopia eletrônica de varredura (MEV) também foram realizadas nos compósitos produzidos. As amostras foram também submetidas ao condicionamento em câmara de radiação ultravioleta (UV) para avaliar a influência do intemperismo nas propriedades mecânicas e térmicas dos compósitos poliméricos produzidos. Os resultados de FTIR mostram a presença de boa interface entre a matriz (PP) e os materiais lignocelulósicos. As análises de DSC e TGA mostram que as temperaturas de fusão, de cristalização e degradação térmica estão dentro dos valores relatados na literatura, indicando que o processamento termocinético e a injeção não afetaram as propriedades térmicas dos compósitos. A temperatura de transição vítrea (Tg) medida por DMA não foi afetada pela introdução dos reforços. Porém, quando os compósitos foram submetidos à exposição a radiação UV os valores da Tg dos compósitos foram aumentados. As propriedades mecânicas avaliadas no presente trabalho não sofreram alterações ou ganhos significativos com a introdução dos reforços nos compósitos, ... (Resumo completo, clicar acesso eletrônico abaixo) / In this work is presented the production via kinetic term mixing and injection of polypropylene composites reinforced with both delignified and enzymatic hydrolyzed residue bagasse from sugarcane, at different concentrations (5%, 10% and 25%, (w / w)). Polymeric composites were characterized via mechanical tests of tensile, three points bending flexural and Izod impact. Furthermore, tests for determining the thermal properties were done (melting and crystallization temperatures by differential scanning calorimetry (DSC), temperature of degradation by thermogravimetric analysis (TGA) and glass transition temperature (Tg) by dynamic mechanical (DMA)). Analyses of Fourier transform infra-red spectroscopy (FTIR) and scanning electron microscopy (SEM) were done for the composites. After this, the polymeric composites were subjected to conditioning in the ultraviolet radiation camera (UV) to evaluate the wheathering influence on the mechanical and thermal properties. FTIR results showed the presence of interface between the matrix (PP) and lignocellulosic materials. DSC and TGA analyzes showed that the melting temperatures of crystallization and thermal degradation are within the values reported on literature, indicating that the kinetic term processing and injection did not affect the thermal properties of the composites. Tg was not affected by the introduction of reinforcement agents. However, when the composites were subjected to exposure to UV radiation, the values of Tg of the composites were increased. The mechanical properties evaluated in this study did not change or significant gains with the introduction of reinforcements in composites, however, when exposed to UV radiation for conditioning such properties suffered less significant reductions when compared with the samples of the polypropylene

Made available in DSpace on 2015-05-14T16:52:56Z (GMT). No. of bitstreams: 0 Previous issue date: 2014-09-05Bitstream added on 2015-05-14T16:59:40Z : No. of bitstreams: 1 000827719.pdf: 2308407 bytes, checksum: 0549076ca7b449f6e27baadefa9ed6af (MD5) / Com o crescimento da colheita mecanizada impulsionada pelas leis ambientais que restringem a queima da palha, houve um aumento na quantidade de palha deixada no campo. Tal fato tem sido objeto de estudos no setor sucroalcooleiro quanto à tecnologia empregada no recolhimento e transporte, bem como o aproveitamento dessa biomassa pela indústria, que pode ser misturada junto ao bagaço para incrementar a cogeração de energia elétrica ou para produzir o etanol celulósico. No presente trabalho, foi estudado o aproveitamento da palha com transporte até indústria em caminhões junto com a cana-de-açúcar, embora exista a possibilidade de enfardamento para o transporte. Por conseguinte, foram avaliados termodinamicamente diferentes casos de utilização da palha baseado em uma usina produtora de açúcar, etanol (anidro e hidratado) e eletricidade, considerando o aumento da produção de eletricidade, através da incorporação de uma caldeira e um turbogerador de condensação no sistema de cogeração, e, também, levando-se em conta a produção de etanol celulósico, através da instalação de planta anexa com este propósito. Para cada caso estudado foi apresentada uma análise econômica identificando os investimentos com taxa interna de retorno e valor presente líquido, a fim de obter condições de viabilidade. As considerações finais apresentaram situações de retorno de investimento para casos em que foram considerados valores de venda acima do praticado atualmente na comercialização do MWh em contrato e no preço do etanol anidro negociado com as distribuidoras de combustíveis / With the growth of mechanized harvesting driven by environmental laws that restrict the burning of straw, there was an increase in the amount of straw left in the field. This situation have been studied by the sugarcane mill factories with respect to the technology employed in gathering and transportation of straw, as well as the utilization of this biomass, which can be mixed with the bagasse to increase cogeneration of electricity or to produce cellulosic ethanol. In the present study, the use of straw transported with the sugarcane to industry by trucks was considered although there is the possibility of packing it before transporting. Therefore different cases for straw utilization in an industrial plant that produces sugar, ethanol (anhydrous and hydrated) and electricity were thermodynamically analyzed, considering the increase of electricity production, by means incorporation of a boiler and a condensation turbogenerator in the cogeneration system, and, also, taking into account the production of cellulosic ethanol, by installing an annexed plant for this purpose. For each case studied an economic analysis to identify investments, the internal rate of return and net present value, in order to obtain feasibility conditions, was carried out. The final considerations presented situations of return on investment for cases where sale values above the currently practiced in the marketing of MWh in contract and negotiated price of anhydrous ethanol with fuel distributors were considered