The use and research of renewable fuels has become more important due to the connection between climate changes and the use of fossil fuels. With risks of decline in petroleum production derived from fossil fuels due to limitation of resources in the future, the renewable fuels are even more important in the transport sector. Research regarding gasification of biomass to create a syngas that can be upgraded to a biodiesel for cars is one of the approaches. By gasifying black liquor, it is possible to create a 100 % green fuel diesel. However, as this black liquor might be in limited quantities the idea to create a synthetic black liquor was sparked. The pulp industry where the black liquor originated from also has quantities of wastewater, containing a biomass sludge. Otherwise containing water in so large quantities that it is not possible to combust it without ending up with a negative energy output. One of the paths could be to recover the biomass from the sludge and convert it to a liquid similar to black liquor. Catalytic hydrothermal liquefaction has been recognized as a potential method. While biocrude is usually the target in hydrothermal liquefaction for direct upgrade to biofuel, the aqueous product could prove to be used for the gasification process. This would create a combined liquefaction-gasification process. Using model compounds possibly existing in the waste sludge, hydrothermal liquefaction was performed at different temperatures, together with varied alkali loads (K2CO3) and water the content to see how the different compounds reacted. Model compounds included cellulose and lignin as major compounds. Although the temperature was increased from 240 °C to 340 ° the lignin conversion was lower at 340 °C than at 240 °C. Re-polymerization took place and around 40 % of resulted in solid residue, while the remaining 60 % was partially converted to aqueous phase, oil phase or gas in the process. By not performing the hydrothermal liquefaction it is however possible to dissolve Kraft lignin directly in water and alkali. Cellulose showed an almost full conversion at 290 °C with similar results at 340 °C, with 4 – 5 % remaining as solid. At the higher temperature more gas was produced, which is not optimal for this process where liquid product is wanted. This suggest that 290 °C is enough for cellulose conversion in this process. Using an alkali load of 0.3 times the cellulose mass in the solution the final aqueous product contained about 26 % alkali, which is similar to black liquor. Increase the alkali to 0.9 times however increased the sought aqueous product, in both terms of energy and carbon content. Fiber sludge from a pulp mill, containing mainly cellulose, could therefore most likely be converted to a liquid product that is similar to black liquor for further upgrade

As a first step in understanding the chemistry of toxic elements in sludged soil, this thesis presents a comprehensive model of their chemistry in the digester. A review of the literature had shown that heavy metals were likely to be held in 3 pools: as precipitated and detrital mineral phases 'Particulate'; as complexes with the flocculated biomass 'Biofloc'; and as complexes in solution 'Soluble'. A simple pragmatic fractionation procedure has been offered to separate these 3 pools based on their physical properties in water. A mass-balance between the pools showed that the 'Particulate' fraction held only 5-16% of the heavy metals but contained them in the highest concentration. The 'Biofloc' held 82-94% of the heavy metals. The 'Particulate' material was subdivided by density separation and examined by a combination of analytical SEM and XRD. Thirty-four minerals were identified by XRD, many of which were detrital. Secondary precipitates on the surface of detrital minerals were revealed by the SEM; of these only the sulphides were found to contain detectable levels of heavy metals. Eleven minerals were identified in the 'Biofloc', of which most were clays. The fractionation scheme defined 2 fractions that could hold heavy metals by complexation. The 'Soluble' had a CEC of 8.8 meq/gm and the 'Biofloc' 4 meq/gm. Complexation by the heavy metals and a few other important cations was measured. A thermodynamic model was built which describes the possible solution species, mineral phases and complexation by the biomass in terms of a set of 33 primary components. This model was solved by computer for an 'average' sludge based on published analyses, and considered 313 solution species, 42 exchange reactions and 129 possible minerals. The predicted speciation was broadly in line with observations and suggested that the majority of the heavy metals separating with the 'Biofloc' would have been held as fine enmeshed sulphide precipitates. The model may be used with existing programs such as MINEQL and GEOCHEM. Preliminary studies have shown that with a few additions the model may be used to describe the heavy metals in sludged soil.

Orientador: Marisa Spirandeli Crespi / Coorientador: Sonia de Almeida / Banca: Valdir Schalch / Banca: Wellington Cyro de Almeida Leite / Resumo: Com a crescente preocupação em preservação do meio ambiente e qualidade de vida da população, observa-se um aumento de 95% na quantidade de esgoto tratado no Brasil entre 2000 e 2008. Entretanto, tal evento acarreta na geração de um resíduo denominado lodo de esgoto que é geralmente disposto em aterros sanitários licenciados para este fim. A problemática atual é o fato de que tais aterros já não comportam mais tanto lodo, e é necessária uma alternativa viável de descarte desse resíduo. Para tanto, torna-se imprescindível a caracterização química e comportamento térmico do lodo de esgoto para futuros estudos de reaproveitamento e alocação. Neste estudo, apresentam-se a caracterização química e estudo de decomposição térmica dos lodos das estações de tratamento das cidades de Jaú e São Carlos, ambas no estado de São Paulo. As amostras foram coletadas e tratadas de acordo com cada técnica de análise. O lodo de Jáu apresentou 70% de sua massa de matéria orgânica, enquanto que o lodo de São Carlos apresentou 55%, segundo a análise termogravimétrica. A presença de matéria orgânica nos lodos foi confirmada através das técnicas de demanda química de oxigênio, difratometria de Raios-X e espectroscopia na região do infravermelho. Houve diferença no tamanho de partículas dos lodos, enquanto Jaú apresentou partículas maiores, com cerca de 860nm, São Carlos possui partículas em torno de 310nm. A partir da análise de espectroscopia de absorção atômica, obteve-se a concentração de metais nos lodos e observou-se que esta encontra-se dentro do limite máximo permitido pela legislação vigente no Brasil para reuso como fertilizante agrícola, de acordo somente com este parâmetro. Entretanto, a análise de compostos orgânicos através da cromatografia gasosa acoplada a espectrometria de... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: With the growing concern for environmental preservation and quality of life, there is increase of 95% in the amount of treated sewage in Brazil between 2000 and 2008. However, it leads in the generation of a residue named sewage sludge which is generally disposed in sanitary landfills licensed to this application. The current problem is the fact of such landfills no longer can storage much more sludge, and it is required a viable alternative for disposal of this waste. Therefore, chemical characterization and thermal behavior of sewage sludge becomes essential for posterior reuse studies and storage. This study presents the chemical characterization and study of thermal decomposition of sewage sludge from treatment plants of the cities of São Carlos and Jaú, both in the São Paulo state. The samples were collected and handled according to each analysis technique requirements. The amount of organic matter, in mass fraction, in the sludge of Jau was 70%, while the sludge of São Carlos was 55%, according to the thermal analysis. The presence of organic matter in the sludge was confirmed by the techniques of chemical oxygen demand, X-ray diffraction and infrared spectroscopy. The size of the sludge particles of Jaú was around 860nm, while the sludge of São Carlos was around 310nm. The analysis of atomic absorption spectroscopy showed that the concentrations of metals in the sludge samples were according the Brazilian law for reuse as agricultural fertilizer, according only to this parameter. However, the analysis of organic compounds by gas chromatography mass spectrometry indicated the presence of numerous compounds which are not cited in the law and are potentially harmful to the environment. The kinetic evaluation showed the effect of kinetics compensation on the reaction of degradation of organic matter... (Complete abstract click electronic access below) / Mestre

O principal impacto ambiental do processo de beneficiamento da casca de coco verde é a geração de resíduo líquido com elevada carga orgânica. Este trabalho teve como objetivo aplicar o sistema convencional de lodos ativados para o tratamento biológico do líquido gerado no beneficiamento da casca de coco verde, além de utilizar o teste de taxa de consumo de oxigênio (TCO) para avaliar a toxicidade do efluente ao lodo aeróbio. O reator de escala laboratorial foi inoculado com lodo proveniente de uma estação de tratamento de esgoto em escala plena. Inicialmente o sistema foi alimentado com efluente sintético contendo sacarose e nutrientes para posterior adição progressiva do resíduo líquido proveniente da reciclagem da casca de coco verde. Para o ensaio de respirometria, as composições testadas foram 25, 50, 75 e 100% de resíduo líquido em termos de carga orgânica e o teste se baseou na medição manual da TCO ao longo do tempo. Para cada composição de efluente se verificou o valor máximo de TCO, o nível de toxicidade devido ao líquido da casca de coco verde (LCCV) e a indicação de inibição permanente. O parâmetro usado nos cálculos de toxicidade e de inibição permanente foi a taxa de consumo de oxigênio específica (TCOe) máxima. Para o monitoramento do sistema de fluxo contínuo, foram empregados os parâmetros pH, índice volumétrico de lodo (IVL), oxigênio dissolvido (OD), demanda química de oxigênio (DQO), taninos totais e sólidos suspensos. O reator foi operado com carga orgânica volumétrica (COV) de 0,8 a 2,9 gDQO/L.d e tempo de detenção hidráulica (TDH) de 26,7 d. Devido à presença natural de leveduras no resíduo líquido, os testes de respirometria foram realizados com o efluente tanto esterilizado quanto in natura. Como os resultados preliminares de respirometria não foram conclusivos, optou-se por começar a adaptação do reator de fluxo contínuo com a menor porcentagem testada: 25% de resíduo líquido. Nos testes adicionais de respirometria não houve toxicidade ao lodo e a TCOe foi diretamente proporcional à concentração de resíduo líquido. A remoção média de DQO obtida durante a operação (LCCV a 100%) foi de 81% com amostra filtrada e 82% com amostra bruta. Houve diminuição significativa da concentração de taninos, de 5332 para 1206 mg/L, em média. No início da operação ocorreu o decaimento da concentração de oxigênio dissolvido (OD) no reator para valores menores que 1 mg/L em decorrência do aumento da concentração de biomassa, mas esta situação não afetou a remoção de matéria orgânica e nem a sedimentabilidade do lodo. A remoção de matéria orgânica obtida com o tratamento em escala laboratorial do LCCV mostra que o sistema convencional de lodos ativados pode ser aplicado como alternativa no tratamento biológico dos resíduos líquidos do beneficiamento da casca de coco verde, porém a demanda elevada de oxigênio pode ser um entrave na operação em escala plena. / The main disadvantage of coconut recycling is the highly pollutant wastewater generated during the process. The objectives of this study were to treat the coconut husk liquor (CHL) using a conventional activated sludge system (AS) and to use the oxygen uptake rate (OUR) test for determining the initial effluent composition of reactor feeding and for wastewater toxicity assessment. The laboratory-scale reactor was inoculated with sludge from a full-scale sewage treatment plant. Firtly the system was fed with synthetic effluent containing saccarose and nutrients which was substituted by CHL. For the OUR test the substrate compositions were 25, 50, 75 and 100% of CHL. For each substrate composition, it was verified the maximum OUR value, the toxicity level and permanent inhibition caused by CHL. The maximal specific oxygen uptake rate (SOUR) was the parameter applied for the toxicity assessment and permanent inhibition calculation. The lab-scale reactor was monitored on the basis of pH, sludge volume index, dissolved oxygen, chemical oxygen demand (COD), total tannins and suspended solids. The respirometry assays were carried out with sterilized and natural effluent because of yeast contamination in CRW. Because of the lack of conclusive results in the first respirometry test, it was chosen the lower composition for reactor adaptation beginning: CRW 25%. In the additional OUR tests it was not detected toxicity and the SOUR values were as higher as CRW concentration. After initializing the reactor adaptation with CRW 25%, the percentage changed to 30% and than increased by 10% each 2 or 3 days until the operation beginning. The mean COD removal values were 81% (filtered sample) and 82% (raw sample). The mean tannin concentration decreased from 5332 to 1206 mg/L. The organic removal and sludge settleability were not affected by the DO concentration decrease to less than 1 mg/L due to biomass increase. The organic removal obtained in the lab-scale AS treatment shows that this system can be an alternative for CHL biological treatment, even though the high oxygen demand could be a disadvantage at full-scale treatment.

Thesis (M.Ph.)--Chinese University of Hongkong. / Bibliography: leaves 366-391.

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Os lodos provenientes de estação de tratamento de água brasileira são, frequentemente, dispostos e lançados diretamente nos corpos d\'água, causando um impacto negativo no meio ambiente. Também, cinzas de carvão são produzidas pela queima de carvão em usinas termelétricas e é o resíduo sólido industrial mais gerado no sul do Brasil: cerca de 4 milhões ton/ano. A disposição eficiente das cinzas de carvão é um problema devido ao seu volume maciço e aos riscos nocivos para o ambiente. O objetivo deste trabalho foi estudar a viabilidade da incorporação desses dois resíduos industriais em uma massa utilizada na fabricação de tijolos ecológicos. As amostras de cinzas leve do filtro ciclone da usina termelétrica localizada no Município de Figueira, Estado do Paraná, Brasil e o lodo de estação de tratamento de água localizada no município de Terra Preta, Estado de São Paulo, Brasil, foram utilizados no estudo. Tijolos de cinzas leve-lodo e cinzas leve-lodo-solo-cimento foram moldados e testados de acordo com padrões brasileiros. Os materiais foram caracterizados por análises físico-químicas, difração de raios X, análise térmica, análise morfológica, espectroscopia no infravermelho com transformada de Fourier e análise granulométrica. Os resultados indicaram que o lodo de estação de tratamento de água e as cinzas de carvão podem ser usados na manufatura de tijolos prensados solo-cimento de acordo com a Norma Brasileira NBR 10836/94. / Sludge from treatment water Brazilian plant station are, frequently, disposed and launched directly in the water bodies, causing a negative impact in the environment. Also, coal ashes is produced by burning of coal in coal-fired power stations and is the industrial solid waste most generated in southern Brazil: approximately 4 million tons/y. The efficient disposal of coal ashes is an issue due to its massive volume and harmful risks to the environment. The aim of this work was study the feasibility of incorporating these two industrial wastes in a mass used in the manufacture of ecological bricks. Samples of fly ashes from a cyclone filter from a coal-fired power plant located at Figueira County in Paraná State, Brazil and waterworks sludge of Terra Preta County in São Paulo State, Brazil, were used in the study. Fly ash-sludge and fly ash-sludge-soil-cement bricks were molded and tested, according to the Brazilians Standards. The materials were characterized by physical-chemical analysis, X-ray diffraction, thermal analysis, morphological analysis, Fourier transform infrared spectroscopy and granulometric analysis. The results indicate that the waterworks sludge and coal ashes have potential to be used on manufacturing soil-cement pressed bricks according to the of Brazilians Standards NBR 10836/94.

Thesis. 1977. Ph.D.--Massachusetts Institute of Technology. Dept. of Mechanical Engineering. / MICROFICHE COPY AVAILABLE IN ARCHIVES AND ENGINEERING. / Vita. / Includes bibliographical references. / Ph.D.

O principal impacto ambiental do processo de beneficiamento da casca de coco verde é a geração de resíduo líquido com elevada carga orgânica. Este trabalho teve como objetivo aplicar o sistema convencional de lodos ativados para o tratamento biológico do líquido gerado no beneficiamento da casca de coco verde, além de utilizar o teste de taxa de consumo de oxigênio (TCO) para avaliar a toxicidade do efluente ao lodo aeróbio. O reator de escala laboratorial foi inoculado com lodo proveniente de uma estação de tratamento de esgoto em escala plena. Inicialmente o sistema foi alimentado com efluente sintético contendo sacarose e nutrientes para posterior adição progressiva do resíduo líquido proveniente da reciclagem da casca de coco verde. Para o ensaio de respirometria, as composições testadas foram 25, 50, 75 e 100% de resíduo líquido em termos de carga orgânica e o teste se baseou na medição manual da TCO ao longo do tempo. Para cada composição de efluente se verificou o valor máximo de TCO, o nível de toxicidade devido ao líquido da casca de coco verde (LCCV) e a indicação de inibição permanente. O parâmetro usado nos cálculos de toxicidade e de inibição permanente foi a taxa de consumo de oxigênio específica (TCOe) máxima. Para o monitoramento do sistema de fluxo contínuo, foram empregados os parâmetros pH, índice volumétrico de lodo (IVL), oxigênio dissolvido (OD), demanda química de oxigênio (DQO), taninos totais e sólidos suspensos. O reator foi operado com carga orgânica volumétrica (COV) de 0,8 a 2,9 gDQO/L.d e tempo de detenção hidráulica (TDH) de 26,7 d. Devido à presença natural de leveduras no resíduo líquido, os testes de respirometria foram realizados com o efluente tanto esterilizado quanto in natura. Como os resultados preliminares de respirometria não foram conclusivos, optou-se por começar a adaptação do reator de fluxo contínuo com a menor porcentagem testada: 25% de resíduo líquido. Nos testes adicionais de respirometria não houve toxicidade ao lodo e a TCOe foi diretamente proporcional à concentração de resíduo líquido. A remoção média de DQO obtida durante a operação (LCCV a 100%) foi de 81% com amostra filtrada e 82% com amostra bruta. Houve diminuição significativa da concentração de taninos, de 5332 para 1206 mg/L, em média. No início da operação ocorreu o decaimento da concentração de oxigênio dissolvido (OD) no reator para valores menores que 1 mg/L em decorrência do aumento da concentração de biomassa, mas esta situação não afetou a remoção de matéria orgânica e nem a sedimentabilidade do lodo. A remoção de matéria orgânica obtida com o tratamento em escala laboratorial do LCCV mostra que o sistema convencional de lodos ativados pode ser aplicado como alternativa no tratamento biológico dos resíduos líquidos do beneficiamento da casca de coco verde, porém a demanda elevada de oxigênio pode ser um entrave na operação em escala plena. / The main disadvantage of coconut recycling is the highly pollutant wastewater generated during the process. The objectives of this study were to treat the coconut husk liquor (CHL) using a conventional activated sludge system (AS) and to use the oxygen uptake rate (OUR) test for determining the initial effluent composition of reactor feeding and for wastewater toxicity assessment. The laboratory-scale reactor was inoculated with sludge from a full-scale sewage treatment plant. Firtly the system was fed with synthetic effluent containing saccarose and nutrients which was substituted by CHL. For the OUR test the substrate compositions were 25, 50, 75 and 100% of CHL. For each substrate composition, it was verified the maximum OUR value, the toxicity level and permanent inhibition caused by CHL. The maximal specific oxygen uptake rate (SOUR) was the parameter applied for the toxicity assessment and permanent inhibition calculation. The lab-scale reactor was monitored on the basis of pH, sludge volume index, dissolved oxygen, chemical oxygen demand (COD), total tannins and suspended solids. The respirometry assays were carried out with sterilized and natural effluent because of yeast contamination in CRW. Because of the lack of conclusive results in the first respirometry test, it was chosen the lower composition for reactor adaptation beginning: CRW 25%. In the additional OUR tests it was not detected toxicity and the SOUR values were as higher as CRW concentration. After initializing the reactor adaptation with CRW 25%, the percentage changed to 30% and than increased by 10% each 2 or 3 days until the operation beginning. The mean COD removal values were 81% (filtered sample) and 82% (raw sample). The mean tannin concentration decreased from 5332 to 1206 mg/L. The organic removal and sludge settleability were not affected by the DO concentration decrease to less than 1 mg/L due to biomass increase. The organic removal obtained in the lab-scale AS treatment shows that this system can be an alternative for CHL biological treatment, even though the high oxygen demand could be a disadvantage at full-scale treatment.