Abstract The chemical characteristics of spent wash, an effluent from the distillation of ethanol from molasses, can vary, depending on the initial feed stock and the operations of the factory. Spent wash from Australia contained large quantities of dissolved organic carbon (DOC), K, N and Cl with moderate to low concentrations of Ca, Mg, Na, and S, and small amounts of trace elements (Fe, Al, Mn, Cu, Zn). Spent wash from Thailand was obtained from whisky distillation and generally had similar chemical attributes to the spent wash from ethanol production, although the Zn concentration was much higher (399-974 mg Zn L-1). Large differences in EC and pH were found between Australian (pH: 4.08-4.49; EC: 40.4-42.2 dS m-1) and Thai spent wash (pH: 7.86-9.20; EC: 11.3-82.4 dS m-1). However, the high concentration of K in spent wash from both manufacturing processes indicates the unique chemical characteristic of wastewater produced from molasses-based distillation. While chemical characterisations of spent wash have shown its potential value as a fertilizer, its utility needs to be more practical than by direct application. This is due to its dilute nature, associated with the presence of organic carbon (OC) and nutrients in soluble form, thus making direct application susceptible to leaching losses of nutrients, especially in soils of low cation exchange capacity (CEC). It was hypothesized that capturing OC and nutrients on a high activity exchanger would overcome this problem. Since the charge on organic components in spent wash is important to the capturing process, pH manipulation is one of the major factors affecting the efficiency of this capture. The study of the influence of pH on development of charge on organic components in spent wash was undertaken using potentiometric titration. The potentiometric titration, and derived pH buffer curve, showed that the organic components in spent wash comprised a wide range of ionizable organic functional groups behaving like a mix of weak acids. While the inflection point (s) could not be obtained from the potentriometric titration, the absorbance of spent wash in the UV waveband (250 to 400 nm) confirmed the presence of phenolic groups in spent wash. The charge on organic components in spent wash was strongly pH dependent, and highest in the pH range of 4.0-5.0. The manipulation of pH and salt concentration (EC) was shown to have an effect on flocculation/dispersion and it is inferred that this was due to changes in the molecular arrangement of organic components in spent wash. A coiled configuration is suggested at acidic pH, whereas a linear flexible configuration and macromolecular structure tending to occur at neutral and alkaline pH respectively. Ca-saturated bentonite, originally sourced from Mantuan Downs, Central Queensland, was used in an investigation of the capture of OC and nutrients from Sarina spent wash at different pH values (4.5, 6.0, 8.0). This study demonstrated that manipulation of pH and electrolyte concentration had a small effect on adsorption of OC by the clay, probably the result of effects on the charge characteristics of both clay mineral surfaces and organic molecules and also on molecular sizes of the dissolved organic matter (DOM). The highest absorption of OC was only 28% for dewatered spent wash, suggesting Ca-saturated bentonite may not be a strong sorbent for DOM from a wastewater of high EC and which contains high concentration of DOC of the composition found in spent wash. The study of the adsorption of K by bentonite in a pure inorganic system (without DOM) indicated sufficiently high concentrations of K can compete with divalent Ca2+ for exchange sites on the clay surface. The adsorption of K in an organic system (the DOM component in spent wash) showed that DOM had a positive influence on adsorption of inorganic ions (e.g. K+). Characterisation of the spent wash/ clay mixture demonstrated its potential to be used as a soil ameliorant on the basis of the large quantity of OC and nutrients it contained (especially N and K). Wet and dry organic clays were produced and assessed as ameliorants in a glasshouse trial using forage oat (Avena sativa var. Coolobah) as test species. This pot study indicated a positive influence of application of either wet or dry organic clay on crop biomass at the high application rate (equivalent to 40 tonnes ha-1). The high proportional K recovery from this high application rate application suggests that organic clays can be used as K fertilizer. The crop nutrient uptake data also indicated its use as a source of S and Mn.

Made available in DSpace on 2014-10-09T12:41:34Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:56:02Z (GMT). No. of bitstreams: 0 / Dissertação (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Made available in DSpace on 2014-10-09T12:36:16Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:59:20Z (GMT). No. of bitstreams: 1 03766.pdf: 3809732 bytes, checksum: 161cbf8550f80b76813606d7f8abf4de (MD5) / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

Made available in DSpace on 2014-10-09T12:43:03Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:05:39Z (GMT). No. of bitstreams: 1 06173.pdf: 6069998 bytes, checksum: 60ab3760f99f6d97fd52766b4d449ab5 (MD5) / Dissertacao (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

Made available in DSpace on 2016-12-08T17:19:16Z (GMT). No. of bitstreams: 1 Cap 1.pdf: 354743 bytes, checksum: 0343c49a38673dd157dcd55a3475b0c2 (MD5) Previous issue date: 2012-02-16 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The environmental efficiency permeates all production sectors through a closed cycle of production and consumption of materials. The recycling of solid waste should be priorized against the consumption of natural raw materials as long as environmental and technical viability have been proved. The foundries are great ferrous scrap recyclers, but generate huge amount of waste, especially the foundry sand. In order to contribute to the sustainability of foundry and construction industries this work investigates the possibility of recycling spent foundry sand (ADF) in soilcement (SC) bricks. The soil-cement construction uses soil as natural raw material, sand and gravel if necessary correction, and cement as a stabilizer. The research involves the characterization of the raw materials by X-ray diffraction, thermal analysis, particle size, leaching and solubilization tests. In blends cement makes up 10% by weight and the soil, predominantly clayey, was partially replaced by spent foundry sand and gravel in different percents. The influence of the residue on the physico-chemical and mechanical properties of the mixtures was analyzed through compaction tests, isothermal conduction calorimetry, compressive strength, durability and water absorption in cylindrical specimens and modular bricks. The interface between the components was observed by electron microscopy scanning. The addition of spent foundry sand decreases the water absorption of the mixture and increases the maximum density with small changes in mechanical strenght. The bricks produced have water absorption and mass loss in the durability test in accordance with the current technical standards. The addition of ADF combined with gravel rises mechanical resistance to acceptable levels of soil-cement standards. The results attest the technical and environmental feasibility for the use of spent foundry sand in soil-cement bricks for masonry seal. / A eficiência ambiental permeia todos os setores produtivos através de um ciclo fechado de produção e consumo de materiais. A reciclagem de resíduos sólidos deve ser priorizada frente ao consumo de matérias-primas naturais, desde que comprovada viabilidade ambiental e técnica para tal. As fundições são grande recicladoras pois utilizam sucatas ferrosas como matéria-prima, porém geram enorme quantidade de resíduos, com destaque para as areias de moldagem. Buscando contribuir para a sustentabilidade das indústrias de fundição e da construção civil esse trabalho investiga a possibilidade da reciclagem de areia descartada de fundição (ADF) em tijolos de solo-cimento (SC). A construção com solo-cimento utiliza o solo como matéria-prima natural, se necessário areia e pedrisco para correção e o cimento como estabilizante. O estudo passa pela caracterização das matérias-primas utilizadas por difração de raios-X, análise térmica, granulometria, lixiviação e solubilização. Nas misturas o cimento compõe 10% em peso e o solo, de predominância argilosa, foi parcialmente substituído por areia descartada de fundição e pó de brita em diferentes percentuais. Assim foi analisada a influência da adição do resíduo nas propriedades físico-químicas e mecânicas das misturas através de ensaios de compactação, calorimetria de condução isotérmica, resistência à compressão, durabilidade e absorção de água em corpos de prova cilíndricos e tijolos modulares. A interface entre os materiais constituintes do solo-cimento foi observada por microscopia eletrônica de varredura. A adição do resíduo de areia de fundição diminui a absorção de água da mistura e aumenta a densidade máxima com pequenas alterações na resistência mecânica. Os tijolos produzidos apresentam absorção de água e perda de massa no ensaio de durabilidade em conformidade com as normas técnicas vigentes. A adição combinada de ADF e de pó de brita eleva a resistência mecânica a níveis aceitos pelas normas de solo-cimento. Os resultados obtidos atestam a viabilidade técnica e ambiental para a utilização da areia descartada de fundição em tijolos de solo-cimento para alvenaria de vedação.

Made available in DSpace on 2014-10-09T12:41:34Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:56:02Z (GMT). No. of bitstreams: 0 / O método mais comum de tratamento da resina de troca iônica radioativa é a imobilização em cimento, que reduz a liberação de radionuclídeos para o meio ambiente. Apesar de eficiente, esse método é custoso, pois a quantidade final de rejeito gerada é elevada, já que a capacidade de carga de imobilização é baixa. Este trabalho tem como objetivo desenvolver um método de degradação das resinas provenientes do reator de pesquisa nuclear do Instituto de Pesquisas Energéticas e Nucleares, utilizando o Processo Oxidativo Avançado (POA) com reagentes de Fenton. Isso permitiria uma incorporação maior no cimento. Três formas da resina foram avaliadas: catiônica, aniônica, e uma mistura de ambas as resinas. As reações foram realizadas variando a concentração do catalisador (25, 50, 100 e 150 mM), do volume de peróxido de hidrogênio (320 a 460 mL), e de três temperaturas diferentes, 50, 60 e 70 °C. A solução de catalisador mais eficiente foi a de concentração de 50 mM e volume de 330 mL de peróxido, degradando aproximadamente 98% da quantidade de resina. A temperatura mais eficiente foi a de 60 º C. / Dissertação (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Made available in DSpace on 2014-10-09T12:36:16Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:59:20Z (GMT). No. of bitstreams: 1 03766.pdf: 3809732 bytes, checksum: 161cbf8550f80b76813606d7f8abf4de (MD5) / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

Made available in DSpace on 2014-10-09T12:43:03Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:05:39Z (GMT). No. of bitstreams: 1 06173.pdf: 6069998 bytes, checksum: 60ab3760f99f6d97fd52766b4d449ab5 (MD5) / Dissertacao (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

O principal resíduo da indústria de café solúvel é a borra de café, gerada após a extração de sólidos solúveis com água, sendo usualmente queimada em caldeiras para geração de energia para a própria indústria. Entretanto, este co-produto pode conter de 15 a 20 % de óleo, componente de grande interesse na indústria alimentícia. Em paralelo, na indústria de produção de óleos vegetais o solvente frequentemente utilizado é o hexano. Contudo, por este ser um derivado de combustíveis fósseis, alternativas para sua substituição por solventes mais amigáveis ao meio ambiente, que podem ser obtidos por via biotecnológica, estão sendo estudadas. Deste modo, o objetivo principal desta dissertação de mestrado foi a viabilização técnica do emprego de solventes alcoólicos no processo de extração de óleo de borra de café proveniente da indústria de processamento de café solúvel. Foram realizadas extrações sólido-líquido em um estágio para estudar a influência das variáveis de processo temperatura (60 a 90 °C), tipo de solvente (etanol, ET ou isopropanol, IPA) e a hidratação do solvente (absoluto ou azeotrópico) nas características das fases extrato e rafinado, em termos de rendimento de extração de óleo, de ácidos clorogênicos (ACG), de carboidratos totais, teor de proteínas e índice de solubilidade de nitrogênio (ISN) da fase rafinado. Pré-tratamento enzimático ao processo de extração também foi realizado para investigar a sua atuação sobre o rendimento de extração de óleo e ACG, além do ISN das fases rafinado obtidas na temperatura de 70 °C. De forma geral, pode-se inferir que a temperatura favorece a extração de compostos lipídicos, mas a hidratação do solvente prejudica a extração destes compostos pelo aumento da polaridade do solvente. Do mesmo modo, como o ET é mais polar que o IPA, o primeiro solvente proporcionou a obtenção de menores rendimentos de extração de óleo. A temperatura de processo também influenciou a extração de ACG, a qual foi beneficiada a temperaturas mais baixas pelo aumento da polaridade dos solventes utilizados. De tal forma, que a 60 °C, nos experimentos utilizando etanol azeotrópico obteve-se os menores rendimentos de extração de óleo, porém maior rendimento de extração de ACG. O pré-tratamento enzimático apresentou diferenças significativas nas características das fases extrato e rafinado. No entanto, somente os experimentos com etanol absoluto resultaram em rendimentos de extração de óleo economicamente viáveis. De fato, será relevante um estudo mais aprofundado das variáveis de pré-tratamento enzimático para obter resultados mais expressivos em relação à extração de compostos lipídicos. Diante dos dados experimentais obtidos, conclui-se que é tecnicamente viável o emprego de solventes alcoólicos no processo de extração de óleo de borra de café. Entretanto, nota-se que as condições de processo devem ser avaliadas minuciosamente com o objetivo de se obter altos rendimentos de extração de óleo com maior teor de ACG. / Spent coffee grounds are the main residues of the soluble coffee industry, which are generated after the extraction of soluble solids with water. They are generally burned in boilers to generate energy for the coffee industry. However, this residue may contain 15 to 20 % oil, a component of interest to the food industry. Hexane is the most common solvent used in the vegetable oil industry; however, as it is a fossil fuel byproduct, biotechnology alternatives that replace it by more environmental-friendly solvents are being studied. Therefore, the main objective of this study was to determine technical viability of alcoholic solvents in oil extraction of spent coffee grounds. Solid-liquid extractions were carried out in one stage in order to analyzed the influence of the variables of the process (temperature, 60 to 90 °C; type of solvent, ethanol, ET or isopropanol, IPA; and solvent hydration level, absolute or azeotropic degree) in the characteristics of extract and raffinate phases, in terms of yield of oil extraction, chlorogenic acids (CGA), total carbohydrates, protein content, and nitrogen solubility index (NSI) of the raffinate phase. Enzymatic pre-treatment in the extraction process was also carried out to assess its effect on the oil and CGA yields, as well as NSI in the raffinate phase obtained at 70 °C. In general, it could be inferred that temperature favored lipid extraction, but solvent hydration level negatively affected extraction due to the increased polarity of the solvent. Similarly, as ET is more polar than IPA, the former solvent enabled lower yield of oil. The temperature of the process also influenced CGA extraction, which was favored by lower temperatures and increased solvent polarity. Therefore, at 60 °C, in the trials using azeotropic ethanol, oil extraction yield was lower, and CGA yield was greater. Enzymatic pre-treatment showed significant differences in the characteristics of the extract and raffinate phases. However, only the trials with absolute ethanol led to economically viable oil yields. In fact, further studies on pre-treatment variables of the enzymatic treatment should be carried out for more relevant results in relation to lipid compound extraction. Given the experimental data obtained here, it was concluded that the use of alcoholic solvents in oil extraction of spent coffee grounds is technically viable. However, the conditions of the process should be carefully analyzed for high yields of oil with greater levels of CGA to be obtained.

Os peitos de galinhas matrizes pesadas de corte, poedeiras comerciais brancas e frangos foram desossados manualmente, com o objetivo de avaliar e comparar as propriedades tecnológicas – capacidade de retenção de água e de emulsificação – bem como pH e composição centesimal, além de elaborar e avaliar sensorialmente um produto reestruturado empanado, tipo nugget. Os resultados das análises indicaram que não houve diferença significativa entre as carnes analisadas, nem entre produtos processados, implicando utilização regular desse tipo de matéria-prima na indústria de alimentos. O restante das carcaças das galinhas foi utilizado para extração de carne mecanicamente separada (CMS) para avaliação da estabilidade microbiológica. As CMSs foram submetidas a dois tratamentos: I) com 150ppm de nitrito, embaladas em saco de polietileno; e II) com 150ppm de nitrito e 500ppm de eritorbato, embaladas em saco de polietileno. Como controle, as amostras de CMS foram apenas acondicionadas em sacos de polietileno. Todas as embalagens foram estocadas e congeladas a –18ºC por 99 dias. Os resultados da análise de caracterização microbiológica indicaram que tanto as amostras de CMS de galinha matriz quanto de galinha poedeira atenderam os padrões de contagem requeridos pela legislação Brasileira. A avaliação da estabilidade microbiológica das CMSs no primeiro e no último dia para mesófilos, Escherichia coli, Staphylococcus aureus, Clostridium perfringens e Pseudomonas, bem como as análises quinzenais de microrganismos psicrotróficos, indicaram que não houve uma redução significativa nas contagens, independentemente do tratamento aplicado. Não foi detectada Salmonella em nenhuma das amostras analisadas. Tais resultados apontaram o tempo de estocagem como o principal fator na redução da carga bacteriana. / The breasts of heavy fowls, white commercial egg-layers and chickens were manually deboned in order to evaluate and compare technological properties—water hold and emulsifying capacity—and pH and centesimal composition, as well as to prepare and assess a restructured coated product. The results of the analyses indicated that there was not a significant difference between the meats analyzed, nor among the processed products, implying the regular use of such meat in the food industry. The remaining parts of the hens’ carcasses were mechanically deboned for the evaluation of microbiological stability. The mechanically deboned meat (MDM) was submitted to two treatments: I) 150ppm of nitrite, packed in polyethylene bags; II) 150ppm of nitrite and 500ppm of erythorbate, packed in polyethylene bags. The control meats were just packed in polyethylene bags. All samples were frozen-stored at –18ºC for 99 days. The results of microbiological characterization indicated that both samples from heavy fowls and egg-layers were in accordance with the Brazilian legislation. MDM microbiological stability evaluation on the first and last days for fecal coliforms, mesophiles, Staphylococcus aureus, Clostridium perfringens and Pseudomonas, as well as the analyses carried out every fifteen days for psychrotrophics bacteria indicated that there was not a significant reduction in the presence of the above, irrespective of the treatment applied. Salmonella was not detected in any of the samples. Such results indicated that freezing storage period was the main factor responsible for the reduction of the bacterial count in MDM.