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The objective of this thesis is twofold - (1) to design the unit processes for treating the waste from a specific industrial plant using the best practicable technology, and (2) to critically examine the theory of these unit processes for utilization in design. The industrial waste was derived from a synthetic button and textile trimmings factory producing polyester and casein buttons. The effluent has a high pH and COD; contains metallic poisons; and is highly coloured. It exceeds the limitations for effluent quality promulgated by the Cape Town Municipality before discharge to the sewers. A certain measure of pretreatment before discharge to the sewers was therefore required. The treatment process eventually selected consists of neutralization; flocculation; sedimentation; sand filtration of the sludge; and atmospheric drying of the sludge.

This thesis investigates an application of immobilized lipase for pre-treating wastewater containing fats and oils, which is difficult to treat practically. The kinetics of soluble lipase was studied for establishing background of the lipase. The immobilization of lipase was adopted in order to repeatedly use the expensive lipase. The developed immobilization methods were based on the characteristics of carriers, but covalent bonding of lipase was preferred because of strong adsorption nature. Three types of materials, nylon membrane and polystyrene-divinylbenzene and silica gel beads, were used for studying the lipase immobilization characteristics. The lipase from Canada rugosa was chosen because of its relatively high catalytic activity and commercial availability. The oily wastewater sources used were a simulated mixture of olive oil and distilled water as well as actual restaurant oily wastewater. A packed bed reactor packed with immobilized lipase was suitable for the study. Moreover, a comparative study of anaerobic digestion of lipase treated and un-treated oily wastewater was undertaken to evaluate the efficiency of the lipase pre-treatment method due to lack of the relevant literature in the enzymatic wastewater treatment field. The kinetics of lipase catalyzed hydrolysis reactions was investigated in a stirred tank reactor. The experimental results confirmed that the lipase catalyzed reaction obeyed Michaelis-Menten model. The optimal pH and temperature of the lipase catalysed hydrolysis reaction were 7 and 37°C, respectively. The conversion of oil to fatty acid was dependent on the reaction time and mass of the enzyme used. The lipase activities depended on the concentrations of some selected additives. Calcium ion improved lipase activity significantly amongst the additives used. / The immobilization of lipase was carried out using different materials, nylon membranes, polystyrene-divinylbenzene beads, and silica gel. Covalent adsorption was simple and successful for immobilizing the lipase onto nylon membrane which was pre-treated with HC1 solution for releasing amino groups. The adsorption of lipase was completed after only a 2-hour reaction time. It was much more practical for this shorter adsorption time (2 hours) rather than the 24 hours required for physical capillary adsorption of lipase. The properties of the immobilized lipase and the performance of the reactors we compared amongst the soluble and immobilized lipase forms. The immobilization, particularly for covalent bonding, made lipase more resistant to thermal deactivation. It was evident that the optimum temperature was shifted from 37°C for the soluble lipase to 45 and 40°C for immobilized lipase adsorbed onto nylon and polystyrene-divinylbenzene beads, respectively. The immobilized lipase could be used repeatedly with only little activity loss. The repeatedly operational stability made the reuse of the immobilized lipase possible. Comparison was also made between two types of beads, polystyrene-divinylbenzene beads and silica gels. Though polystyrene-divinylbenzene beads showed higher lipase activity and shorter adsorption time when compared to silica gels, the forme beads were not suggested for large scale study because of high cost of the beads. On improvement achieved in this work was that the 24 hours required for silanization of silica gel was reduced to only a few hours using evaporating 3-APTES in acetone instead of refluxing 3-APTES in toluene. / It is worthwhile to point out that much higher enzyme activity was obtained using the packed bed reactor as against the membrane reactor when aqueous oil emulsion was fed into the reactors. The lipase activity was 64.2% of soluble lipase activity for the immobilized lipase in the packed reactor but its activity was hardly detectable in the membrane reactor. Moreover, the operation of the packed bed reactor solved the of separating problem that severely hampered the lipase catalytic activity in the membrane reactor in aqueous phase. This result suggests that the packed bed reacts with the immobilized lipase is applicable in treating oily wastewater. The intrinsic parameters, Vmax and Km, were evaluated to study the internal diffusional effects of the porous spherical silica gel on the immobilized lipase. The changes of Vmax and Km for the immobilized lipase from those of the soluble lipase indicated that some alteration in the lipase intrinsic properties was caused by the immobilization of lipase. However, the magnitude of Thiele modulus suggested the immobilized lipase was most likely reaction controlling. In addition, good agreement for Vmax and Km from experiments and numerical model estimations seemed to suggest that the numerical model could be used for estimating Vmax and Km for the immobilized lipase. / An application was tried for conducting the hydrolysis of oily restaurant wastewater by soluble and the immobilized lipase. Enzyme activity of both forms was severely inhibited by the oily wastewater. The enzymatic activity was only 20% and 15% for soluble and the immobilized lipase, respectively, when compared to the initial activity value for the hydrolysis of olive oil by soluble lipase. Evaluation of the efficiency for the proposed lipase pre-treatment method was carried out by monitoring the performance of two anaerobic digesters. These two digesters were fed with lipase treated and untreated restaurant wastewater that was neutralised with KOH solution prior to feeding. The oil-floating problem was minimised by this saponification of fatty acids with potassium hydroxide. However, there was no clear sign of an improvement for the treatment efficiency of the anaerobic digesters in terms of COD removal and methane production rate resulted in digesting lipase treated oily wastewater when compared to the one without lipase pre-treatment.

Thesis (M.S.)--University of Tennessee, Knoxville, 2001. / Vita. Includes bibliographical references (leaves 80-83). Also available via the Internet.

Rejeitos radioativos líquidos contendo compostos orgânicos precisam de atenção especial, porque os processos de tratamento disponíveis são caros e difíceis de serem gerenciados. A biossorção é uma potencial técnica de tratamento que tem sido estudada em rejeitos simulados. O termo biossorção é utilizado para descrever a remoção de metais, metalóides e/ou radionuclídeos por um material de origem biológica independentemente de sua atividade metabólica. Dentre as potenciais biomassas, os resíduos agrícolas apresentam características muito atraentes, pois possibilitam a remoção dos radionuclídeos presentes no rejeito utilizando um biossorvente de baixo custo. O objetivo deste estudo foi avaliar o uso potencial de diferentes biomassas originadas de produtos ou resíduos agrícolas (fibra de coco, casca de café e casca de arroz) no tratamento de rejeitos radioativos líquidos orgânicos reais. Foram realizados experimentos com essas biomassas incluindo i) Preparação, ativação e caracterização das biomassas; ii) Realização dos ensaios de biossorção e iii) Avaliação do produto da imobilização de biomassas em cimento. As biomassas foram testadas nas formas brutas e ativadas. A ativação foi realizada com soluções diluídas de HNO3 e NaOH. Os ensaios de biossorção foram realizados em frascos de polietileno, nos quais foram adicionados 10 mL do rejeito radioativo ou diluições do rejeito em água deionizada com o mesmo pH e 2 % da biomassa (m/v). No final do experimento, a biomassa foi separada por filtração e a concentração dos radioisótopos remanescente no filtrado foi determinada por ICP-OES e espectrometria gama. O rejeito estudado contém urânio natural (U (total)), amerício-241 e césio-137. Os tempos de contato adotados foram 30 min, 1, 2 e 4 horas e as concentrações estudadas variaram entre 10% e 100%. Os resultados foram avaliados por meio da capacidade máxima de sorção experimental e modelos ternários de isotermas e cinética. As maiores capacidades de sorção foram observadas com casca de café bruta, com valores aproximados de 2 mg/g de U (total), 40 x10-6 mg/g de Am-241 e 50 x10-9 mg/g de Cs-137 e, também, com fibra de coco ativada, com valores de 2 mg/g de U (total), 70 x10-6 mg/g de Am-241 e 40 x10-9 mg/g de Cs-137. As propriedades avaliadas na determinação da qualidade do produto de imobilização foram água livre, resistência mecânica, trabalhabilidade e tempo de pega. Os melhores produtos de imobilização para estas biomassas foram obtidos com uma relação água/cimento de 0,30, contendo 5%, 10% e 15% de casca café bruto, fibra de coco ativada e casca de café ativado, respectivamente. Estes resultados sugerem que a biossorção com casca de café bruta e fibra de coco sob a forma ativada podem ser aplicadas no tratamento de rejeitos radioativos líquidos orgânicos contendo urânio, amerício-241 e césio-137. / Radioactive liquid waste containing organic compounds need special attention, because the treatment processes available are expensive and difficult to manage. The biosorption is a potential treatment technique that has been studied in simulated wastes. The biosorption term is used to describe the removal of metals, non-metals and/or radionuclides by a material from a biological source, regardless of its metabolic activity. Among the potential biomass, agricultural residues have very attractive features, as they allow for the removal of radionuclides present in the waste using a low cost biosorbent. The aim of this study was to evaluate the potential use of different biomass originating from agricultural products (coconut fiber, coffee husk and rice husk) in the treatment of real radioactive liquid organic waste. Experiments with these biomasses were made including i) Preparation, activation and characterization of biomasses; ii) Conducting biosorption assays; and iii) Evaluation of the product of immobilization of biomasses in cement. The biomasses were tested in raw and activated forms. The activation was carried out with diluted HNO3 and NaOH solutions. Biosorption assays were performed in polyethylene bottles, in which were added 10 mL of radioactive waste or waste dilutions in deionized water with the same pH and 2% of the biomass (w/v). At the end of the experiment, the biomass was separated by filtration and the remaining concentration of radioisotopes in the filtrate was determined by ICP-OES and gamma spectrometry. The studied waste contains natural uranium, americium-241 and cesium-137. The adopted contact times were 30 min, 1, 2 and 4 hours and the concentrations tested ranged between 10% and 100%. The results were evaluated by maximum experimental sorption capacity and isotherm and kinetics ternary models. The highest sorption capacity was observed with raw coffee husk, with approximate values of 2 mg/g of U (total), 40 x10-6 mg/g of Am-241 and 50 x10-9 mg/g of Cs-137 and, also, with activated coconut fiber, with values of 2 mg/g of U (total), 70 x10-6 mg/g of Am-241 and 40 x10-9 mg/g of Cs-137. The properties evaluated to determine the quality of the immobilization product were free water, mechanical strength, workability and setting time. The best immobilization products for these biomasses were obtained with a water/cement ratio of 0.30, containing 5%, 10% and 15% of raw coffee husk, activated coconut fiber and activated raw coffee husk, respectively. These results suggest that biosorption with raw coffee husk and activated coconut fiber can be applied in the treatment of radioactive liquid organic wastes containing uranium, americium-241 and cesium-137.