Submitted in fulfilment of the requirements of the degree of Master of Engineering - Chemical, Durban University of Technology, Durban, South Africa, 2015. / Industrial wastewater containing organic compounds and/or substances is an increasing problem due to its increasing toxic threat to humans and the environment. The removal of organic compounds has become an imperative issue due to stringent measures that are introduced by the Department of Environmental Affairs in South Africa to enforce regulations concerning wastes that emanate from petrochemical industries. Thus, wastewater containing these compounds must be well understood so as to device adequate treatment processes. In this study, the adsorptive capacity of PAD 910 polystyrenic resin originating from China and granular activated carbon (GAC) was evaluated for the removal of benzene, toluene, ethylbenzene and isomers of xylene (BTEX) from an aqueous solution. Batch studies were performed to evaluate the effects of various experimental parameters such as mixing strength, contact time, internal diffusion, adsorbates and initial concentration on the removal of the BTEX compounds. The experiments were conducted at the mixing strength of 180 rpm, in order to comfortably assume negligible external diffusion. The equilibrium isotherms for the adsorption of the adsorbates on the PAD 910 polystyrenic resin were analyzed by the Langmuir, Freundlich and linearized Dubinin-Radushkevich models at a pH of 5.86. The Langmuir model fitted the data adequately; this result was supported by the work done by Site (2001) which concluded that the Langmuir is the most practical model in representing the adsorption of aromatic compounds. The Langmuir model indicated that resin has the highest adsorption capacity of 79.44 mg/g and GAC has 66.2 mg/g. Resin was found to adsorb 98% of benzene, 88% of toluene, 59% of ethylbenzene, 84% m-;p-xylene and 90% o-xylene at an initial concentration of 14.47 mg/l. BTEX adsorption was a two-stage process: a short, fast initial period then followed by a longer, slow period corresponding to the intra-particle diffusion of BTEX molecules in macropores and micropores. The adsorption capacity was determined by total surface area accessible to BTEX and the availability of active surface chemical groups. The dependence of adsorption capacity on the surface of the two adsorbents and temperature was observed, suggesting the chemical nature of the BTEX adsorption. The interaction between BTEX/activated carbon was however weak and energetically similar to that of hydrogen bonds. Generally, BTEX adsorption was an exothermic process that combined physisorption and chemisorption. The PAD 910 polystyrenic resin had a greater specific surface area (SSA) of 1040 m2/g which yielded in higher capacity compared to GAC which had a low SSA of 930 m2/g. The normalized adsorption capacity was found to be higher for PAD 910 polystyrenic resin than GAC (0.66 and 0.27 mg/m2 respectively) which suggests that the resin has a good potential of the adsorbent for removing BTEX compound compared to GAC. Fixed bed columns were used to evaluate the dynamic adsorption behaviour of BTEX/PAD 910 polystyrenic resin through a dynamic column approach. The performance of small-scale fixed bed columns, each containing PAD 910 polystyrenic resin and the other containing GAC were evaluated using 14.47 mg/L of BTEX concentration. The columns with 32 mm diameter, studied bed depths of 40, 80 and 120 mm and flow rate of 6 ml/min were used in order to obtain experimental breakthrough curves. The bed depth service time (BDST) model was used to analyze the experimental data and design parameters like adsorption capacity, adsorption rate and service time at 20% and 60% breakthrough. BDST was also used to predict the service times of columns operated under different influent concentrations and flow rates to produce theoretical values that were compared to the experimental values. Adsorption model by Dubinin and colleagues (Dubinin, 1960), based on the theory of volume filling micropores was used to fit the measured adsorption isotherms. Agreement between the modelled and experimental results for GAC and PAD 910 polystyrenic resin using Dubinin-Radushkevich equation generally improved with increasing the surface area and produced reasonable fits of the adsorption isotherms for both GAC and PAD 910 polystyrenic resin. Granular activated carbon had a lesser performance compared to the PAD 910 polystyrenic resin, in terms of kinetic studies, and this finding was attributed to the pore structure which made accessibility of BTEX molecules more difficult in this study. The results indicate that PAD 910 polystyrenic resin show potential as an adsorbent for removing low concentrations of BTEX from wastewater. It is suggested that necessary treatment of GAC might improve the performance of this adsorbent by creating more mesopore volume and fraction which is essential to enhance adsorption rate. A substantial different SSA could be achieved through high porosity development in GAC by using templating method with a higher potassium hydroxide mixture ratio.

O interesse na remoção de material orgânico no tratamento de águas de abastecimento surgiu em decorrência do aumento na poluição dos mananciais, da descoberta de novas doenças de veiculação hídrica e do melhor conhecimento das propriedades mutagênicas e carcinogênicas de poluentes orgânicos, entre eles os agroquímicos. Na presente pesquisa foi estudada a seqüência de processos de tratamento: pré-filtração; pré-oxidação com ozônio e ozônio associado ao peróxido de hidrogênio e filtração lenta com leito de areia e leito de carvão ativado granular. Para concentração de atrazina no afluente entre 2,2 e 110,3 µg/L o filtro lento de areia com camada intermediária de carvão ativado granular apresentou para a condição de não utilização de pré-oxidação valores para atrazina no efluente inferiores a 2,0 µg/L e para dose de ozônio entre 0,9 e 3,7 mg/L e para relação de peróxido de hidrogênio entre 0,1 e 1,1 valores para atrazina inferiores a 0,1 µg/L. O sistema de tratamento com pré-filtração, pré-oxidação com ozônio e ozônio associado ao peróxido de hidrogênio seguido da filtração lenta com camada intermediária de carvão ativado granular, mostrou-se eficiente na remoção de atrazina para concentrações inferiores a 0,1 µg/L. / The interest in removing organic matter in supplying waters treatment processes emerged from the increasing levels of water pollution worldwide, the discovery of new water-born diseases and of a better knowledge of mutating (mutagenic) and carcinogenic features of organic pollutants, including the pesticides. The two sequential arrangements for the water treatment process considered in this research were: 1) pre-filtration, slow sand filtration and granular activated carbon filtration; and 2) pre-filtration, pre-oxidation with ozone and ozone associated to hydrogen peroxide, slow sand filtration and granular activated carbon filtration. For concentrations of atrazine between 2.2 and 110.3 µg/L in the affluent, its concentration in the effluent was lower than 2.0 µg/L for the first arrangement, and lower than 01 µg/L for the second one, in this case for consumed doses of ozone between 0.9 and 3.7 mg/L and ratio H2O2/O3 between 0.1 and 1.1. The treatment system used composed of pre-filtration, pre-oxidation with ozone and ozone associated to hydrogen peroxide followed by the slow filtration, with an intermediate layer of granular activated carbon, was found efficient in reducing atrazine to levels inferior to 0.1 µg/L.

O interesse na remoção de material orgânico no tratamento de águas de abastecimento surgiu em decorrência do aumento na poluição dos mananciais, da descoberta de novas doenças de veiculação hídrica e do melhor conhecimento das propriedades mutagênicas e carcinogênicas de poluentes orgânicos, entre eles os agroquímicos. Na presente pesquisa foi estudada a seqüência de processos de tratamento: pré-filtração; pré-oxidação com ozônio e ozônio associado ao peróxido de hidrogênio e filtração lenta com leito de areia e leito de carvão ativado granular. Para concentração de atrazina no afluente entre 2,2 e 110,3 µg/L o filtro lento de areia com camada intermediária de carvão ativado granular apresentou para a condição de não utilização de pré-oxidação valores para atrazina no efluente inferiores a 2,0 µg/L e para dose de ozônio entre 0,9 e 3,7 mg/L e para relação de peróxido de hidrogênio entre 0,1 e 1,1 valores para atrazina inferiores a 0,1 µg/L. O sistema de tratamento com pré-filtração, pré-oxidação com ozônio e ozônio associado ao peróxido de hidrogênio seguido da filtração lenta com camada intermediária de carvão ativado granular, mostrou-se eficiente na remoção de atrazina para concentrações inferiores a 0,1 µg/L. / The interest in removing organic matter in supplying waters treatment processes emerged from the increasing levels of water pollution worldwide, the discovery of new water-born diseases and of a better knowledge of mutating (mutagenic) and carcinogenic features of organic pollutants, including the pesticides. The two sequential arrangements for the water treatment process considered in this research were: 1) pre-filtration, slow sand filtration and granular activated carbon filtration; and 2) pre-filtration, pre-oxidation with ozone and ozone associated to hydrogen peroxide, slow sand filtration and granular activated carbon filtration. For concentrations of atrazine between 2.2 and 110.3 µg/L in the affluent, its concentration in the effluent was lower than 2.0 µg/L for the first arrangement, and lower than 01 µg/L for the second one, in this case for consumed doses of ozone between 0.9 and 3.7 mg/L and ratio H2O2/O3 between 0.1 and 1.1. The treatment system used composed of pre-filtration, pre-oxidation with ozone and ozone associated to hydrogen peroxide followed by the slow filtration, with an intermediate layer of granular activated carbon, was found efficient in reducing atrazine to levels inferior to 0.1 µg/L.

M. Tech (Department of Chemistry, Faculty of Applied and Computer Sciences) Vaal University of Technology. / A simple and rapid method for determination of estrone (E1) and β-estradiol (E2) was developed and validated using high performance liquid chromatography (HPLC). The solutions of standards and sample were prepared with distilled water. HPLC separation was performed in isocratic method 50/50 (water/methanol) using 4.6 mm x 250 mm id film thickness 5 µm) XDB-C18 capillary column, detector DAD, UV on 254 nm, temperature 20 ºC with flow rate of 2 mL/min, sample volume 20 µL and run time of 10 min. Calibration curves were linear between concentration range 1.0 - 15.0 ppm. The method was validated for limit of detection and quantification, linearity, precision, trueness and specificity. Also the method was applied to directly and easily to the analysis of the E1 and E2. Adsorption experiments were carried out in batch mode using multistirrer in a series of Erlenmeyer flasks of 50 ml capacity covered to prevent contamination having concentration ranges of E1 and E2 from 1 to 10 mg/L with adsorbent dose range 0.01 to 1 g at pH range 1 to 10 and temperature range 15°C to 35°C, placed on multistirrer. The results of the batch studies showed that simultaneous adsorption shows the maximum percent (91%) removal of E1 and (86 %) E2 at optimum temperature 25 °C of adsorbent dose 0.1 g, and pH 7. The mechanism, isotherms and kinetics of removal of two endocrine disrupting chemicals, estrone (E1) and β-estradiol (E2) by activated carbon adsorption were investigated in an agitated non-flow batch adsorption studies. Mathematical models were used to describe the adsorption phenomenon with the kinetic and thermodynamic parameters evaluated using the adsorption equilibrium data at varying temperatures. Higher adsorption rates were achieved at acidic to neutral pH ranges, with the sorption kinetic data showing a good fit to the pseudo second order rate equation and the Langmuir adsorption isotherm model for both E1 and E2. The Gibbs free energy were –16.68 kJ/mol and –17.34 kJ/mol for E1 and E2 respectively. The values of enthalpy for both E1 (84.50 kJ/mol) and E2 (90 kJ/mol) indicated a chemical nature of the sorption process. Both the isotherm and thermodynamic data obtained all supported the mechanism of adsorption of E1 and E2 to be mainly chemisorption’s supported by some physical attractions.

A crescente taxa de urbanização com descarga de esgoto sem tratamento prévio nos ecossistemas aquáticos e o aumento do uso de fertilizantes para desenvolvimento agrícola são causas da aceleração da floração de cianobactérias em águas de mananciais destinadas ao consumo humano. Cabe ao tratamento de água para abastecimento atender as especificações da legislação em relação à potabilidade necessitando remover as cianobactérias e suas toxinas. Este trabalho teve por objetivo estudar a utilização de bagaço de cana-de-açúcar in natura para adsorção de microcistina-LR da Microcystis aeruginosa em comparação com o carvão ativado. Foram realizados ensaios de adsorção a temperatura ambiente, com três concentrações iniciais de microcistina-LR: 3,83, 3,33 e 2,36 μg.L-1 no tempo total de 10 h, e a caracterização físico-química dos adsorventes para analisar a remoção da microcistina-LR. O desempenho da adsorção foi avaliado pela capacidade adsortiva e pela eficiência da remoção de toxina. Os resultados para o bagaço de cana-de-açúcar in natura não possibilitaram o alcance do limite inferior de concentração de microcistina de 1,0 μg.L-1 estabelecido na Portaria MS 2914/2011, porém, permitiram eficiência 8% maior de remoção da microcistina no bagaço de cana-de-açúcar comparado ao carvão ativado para maior concentração de adsorvato, mesmo apresentando área superficial de 1,28 m2.g-1 e superfície menos porosa e heterogênea que o carvão. A melhor taxa de remoção foi de 65%. de microcistina para concentração de 2,36 μg.L-1 no carvão ativado. Verificou-se também que o desempenho dos adsorventes foi melhor representado pelo Modelo da Isoterma de Freundlich do que pelo Modelo da Isoterma de Langmuir. De modo geral, a utilização do bagaço de cana-de-açúcar in natura para remoção de microcistina demonstra ser uma alternativa no tratamento de água comparado a outros adsorventes, porém, necessitando ser melhor estudada. / Increasing urbanization rate with untreated sewage discharge in aquatic ecosystems, and the increased use of fertilizers for agricultural development are causes of the acceleration of cyanobacterial bloom in water fountains which are intended for human consumption. It is important that the treatment for water supply meets the specifications of legislation for the potability that requires removing cyanobacteria and their toxins. This work aimed to study the use of in natura sugarcane bagasse for microcystin-LR adsorption of Microcystis aeruginosa compared to activated carbon. Adsorption experiments were carried out at room temperature with three initial concentrations of microcystin-LR: 3.83, 3.33 and 2.36 μg.L-1 total time of 10 h, and physico-chemical characterization of adsorbents analyzing the removal of microcystin-LR. The performance was evaluated by the adsorption capacity and adsorption by the toxin removal efficiency. The results for in natura sugarcane bagasse did not allow the scope of microcystin concentration lower limit of 1.0 μg.L -1 established in the MS 2914/2011, however, it allowed 8% higher efficient removal of microcystin in bagasse sugarcane compared to activated carbon to higher concentration of adsorbents, even with surface area of 1.28 m2.g-1 and less porous and heterogeneous surface than coal. The best removal rate was 65% microcystin concentration to 2.36 μg.L-1 on activated carbon. It was also found that the performance of adsorbents was best represented by the Freundlich Isotherm of Model than the Model Langmuir Isotherm. In general, the use of in natura sugar bagasse for removing microcystin proves to be an alternative water treatment compared to other adsorbents, however, it needs further studies.

O alto custo do carvão ativado tem motivado a busca por materiais adsorvedores de baixo custo, como os subprodutos industriais. Neste sentido, o uso dos subprodutos industriais de xisto: finos de xisto (XC), xisto retortado (XR) e xisto retortado com pneus (XRP), proveniente do processo PETROSIX/PETROBRAS, e o catalisador exaurido (CAT), da unidade de FCC (Craqueamento Catalítico em Leito Fluidizado), foram caracterizados e utilizados neste trabalho na adsorção de compostos orgânicos de efluente líquido industrial. O objetivo geral deste estudo é modelar matematicamente o processo de adsorção de compostos orgânicos em xisto, catalisador exaurido de FCC e carvão ativado em pó, utilizando o modelo HSDM (Modelo de Difusão por Superfície Homogênea), e o comportamento hidráulico do sistema adsorvedor. A caracterização estrutural e química de várias amostras de xisto (finos de xisto, xisto retortado e xisto retortado com pneus) e do catalisador exaurido de FCC, além do desenvolvimento de um modelo computacional para a simulação do processo de adsorção são contribuições adicionais ao trabalho. Os resultados de caracterização dos adsorventes de xisto mostram que estes materiais são basicamente macroporosos e com área superficial em torno de 0,51 a 3,36 2 . 1 m g , além de apresentarem as mesmas estruturas cristalinas, e micrografias características dos argilominerais. Já o adsorvente CAT mostrou-se formado basicamente por faujasita, sílica e alumina, apresentando-se na forma de grânulos esféricos, irregulares e microporosos, com área superficial característica de materiais zeolíticos (148 e 155 2 . 1 m g ). Os ensaios de adsorção realizados nos efluentes sintéticos e industriais (Fenólico e Petroquímico) mostraram que existe potencial de aplicação dos subprodutos industriais de xisto e CAT na remoção de compostos orgânicos (corantes, fenóis e COT) destes efluentes. Os resultados das simulações obtidos do modelo proposto mostraram que o tratamento unicamente por adsorção em xisto ou CAT, tendo em vista os padrões ambientais de descarte de efluente (resolução CONAMA 357), é inviável. Isto por que a quantidade de adsorvente requerida é muito elevada. Entretanto, tais adsorventes podem ser utilizados na redução da carga orgânica de ambos os efluentes. Por questões de transporte, é indicado que cada subproduto industrial seja utilizado na própria indústria que lhe deu origem. Ou seja, o CAT é indicado para o tratamento do efluente Petroquímico e os adsorventes de xisto para o Fenólico. / The high cost of the activated carbon has motivated the search of low cost adsorbents such as industrial by-products. In this sense, the use of industrial by-products of oil shale: Oil Shale (XC), Pirolized Oil Shale (XR) and Pirolized Oil Shale with Tires (XRP), from PETROSIX/PETROBRAS, and the spent catalyst (CAT), from FCC (Fluid Catalytic Cracking) unit were characterized and used in this work in the adsorption of organics compounds of industrial liquid effluent. The main contribution of this thesis is to propose a mathematical model to the adsorption process of organic compounds in oil shale, spent catalyst of FCC and powdered activated carbon. This model is based on HSDM (Homogeneous Surface Diffusion Model) model and on the hydraulic behavior of the adsorbent system. Other contribution is the structural and chemical characterization of several samples of oil shale (oil shale, Pirolized oil shale and Pirolized oil shale with Tires) and of the spent catalyst of FCC. A computational model to simulate the adsorption process of these materials is also developed and can be considered an additional contribution of this work. Experimental and simulated results allow characterization of the oil shale adsorbent as basically macroporous and with superficial area about 0.51 to 3.36 m2.g-1. In addition, they present the same crystal structures and clay micrografies characteristics. The adsorbent CAT is composed basically by Faujasite, silica and alumina. They present spherical beads, irregular forms and micropores, with superficial area characteristics of zeolitic materials (148 and 155 m2.g-1). The adsorption tests realized in the synthetic and industrial effluents (Phenolic and Petrochemical) showed the potential of application of the industrial by-products of oil shale and CAT in the removal of organics compounds (dyes, Phenol and COT) of these effluents. In respect of environmental standards to effluents disposal (CONAMA resolution 357), simulations results, obtained with the proposed model, has demonstrated that the use of only oil shale or CAT is not viable, because the high quantity of adsorbents required. However, such adsorbents can be used in the reduction of organic loads in both effluents, when combined with other processes. Each adsorbent showed be used where it is produced because of transportation cost. The CAT is indicated for the treatment of Petrochemical effluent while the others adsorbents may be applied in the phenolic effluent treatment.

A crescente taxa de urbanização com descarga de esgoto sem tratamento prévio nos ecossistemas aquáticos e o aumento do uso de fertilizantes para desenvolvimento agrícola são causas da aceleração da floração de cianobactérias em águas de mananciais destinadas ao consumo humano. Cabe ao tratamento de água para abastecimento atender as especificações da legislação em relação à potabilidade necessitando remover as cianobactérias e suas toxinas. Este trabalho teve por objetivo estudar a utilização de bagaço de cana-de-açúcar in natura para adsorção de microcistina-LR da Microcystis aeruginosa em comparação com o carvão ativado. Foram realizados ensaios de adsorção a temperatura ambiente, com três concentrações iniciais de microcistina-LR: 3,83, 3,33 e 2,36 μg.L-1 no tempo total de 10 h, e a caracterização físico-química dos adsorventes para analisar a remoção da microcistina-LR. O desempenho da adsorção foi avaliado pela capacidade adsortiva e pela eficiência da remoção de toxina. Os resultados para o bagaço de cana-de-açúcar in natura não possibilitaram o alcance do limite inferior de concentração de microcistina de 1,0 μg.L-1 estabelecido na Portaria MS 2914/2011, porém, permitiram eficiência 8% maior de remoção da microcistina no bagaço de cana-de-açúcar comparado ao carvão ativado para maior concentração de adsorvato, mesmo apresentando área superficial de 1,28 m2.g-1 e superfície menos porosa e heterogênea que o carvão. A melhor taxa de remoção foi de 65%. de microcistina para concentração de 2,36 μg.L-1 no carvão ativado. Verificou-se também que o desempenho dos adsorventes foi melhor representado pelo Modelo da Isoterma de Freundlich do que pelo Modelo da Isoterma de Langmuir. De modo geral, a utilização do bagaço de cana-de-açúcar in natura para remoção de microcistina demonstra ser uma alternativa no tratamento de água comparado a outros adsorventes, porém, necessitando ser melhor estudada. / Increasing urbanization rate with untreated sewage discharge in aquatic ecosystems, and the increased use of fertilizers for agricultural development are causes of the acceleration of cyanobacterial bloom in water fountains which are intended for human consumption. It is important that the treatment for water supply meets the specifications of legislation for the potability that requires removing cyanobacteria and their toxins. This work aimed to study the use of in natura sugarcane bagasse for microcystin-LR adsorption of Microcystis aeruginosa compared to activated carbon. Adsorption experiments were carried out at room temperature with three initial concentrations of microcystin-LR: 3.83, 3.33 and 2.36 μg.L-1 total time of 10 h, and physico-chemical characterization of adsorbents analyzing the removal of microcystin-LR. The performance was evaluated by the adsorption capacity and adsorption by the toxin removal efficiency. The results for in natura sugarcane bagasse did not allow the scope of microcystin concentration lower limit of 1.0 μg.L -1 established in the MS 2914/2011, however, it allowed 8% higher efficient removal of microcystin in bagasse sugarcane compared to activated carbon to higher concentration of adsorbents, even with surface area of 1.28 m2.g-1 and less porous and heterogeneous surface than coal. The best removal rate was 65% microcystin concentration to 2.36 μg.L-1 on activated carbon. It was also found that the performance of adsorbents was best represented by the Freundlich Isotherm of Model than the Model Langmuir Isotherm. In general, the use of in natura sugar bagasse for removing microcystin proves to be an alternative water treatment compared to other adsorbents, however, it needs further studies.

O alto custo do carvão ativado tem motivado a busca por materiais adsorvedores de baixo custo, como os subprodutos industriais. Neste sentido, o uso dos subprodutos industriais de xisto: finos de xisto (XC), xisto retortado (XR) e xisto retortado com pneus (XRP), proveniente do processo PETROSIX/PETROBRAS, e o catalisador exaurido (CAT), da unidade de FCC (Craqueamento Catalítico em Leito Fluidizado), foram caracterizados e utilizados neste trabalho na adsorção de compostos orgânicos de efluente líquido industrial. O objetivo geral deste estudo é modelar matematicamente o processo de adsorção de compostos orgânicos em xisto, catalisador exaurido de FCC e carvão ativado em pó, utilizando o modelo HSDM (Modelo de Difusão por Superfície Homogênea), e o comportamento hidráulico do sistema adsorvedor. A caracterização estrutural e química de várias amostras de xisto (finos de xisto, xisto retortado e xisto retortado com pneus) e do catalisador exaurido de FCC, além do desenvolvimento de um modelo computacional para a simulação do processo de adsorção são contribuições adicionais ao trabalho. Os resultados de caracterização dos adsorventes de xisto mostram que estes materiais são basicamente macroporosos e com área superficial em torno de 0,51 a 3,36 2 . 1 m g , além de apresentarem as mesmas estruturas cristalinas, e micrografias características dos argilominerais. Já o adsorvente CAT mostrou-se formado basicamente por faujasita, sílica e alumina, apresentando-se na forma de grânulos esféricos, irregulares e microporosos, com área superficial característica de materiais zeolíticos (148 e 155 2 . 1 m g ). Os ensaios de adsorção realizados nos efluentes sintéticos e industriais (Fenólico e Petroquímico) mostraram que existe potencial de aplicação dos subprodutos industriais de xisto e CAT na remoção de compostos orgânicos (corantes, fenóis e COT) destes efluentes. Os resultados das simulações obtidos do modelo proposto mostraram que o tratamento unicamente por adsorção em xisto ou CAT, tendo em vista os padrões ambientais de descarte de efluente (resolução CONAMA 357), é inviável. Isto por que a quantidade de adsorvente requerida é muito elevada. Entretanto, tais adsorventes podem ser utilizados na redução da carga orgânica de ambos os efluentes. Por questões de transporte, é indicado que cada subproduto industrial seja utilizado na própria indústria que lhe deu origem. Ou seja, o CAT é indicado para o tratamento do efluente Petroquímico e os adsorventes de xisto para o Fenólico. / The high cost of the activated carbon has motivated the search of low cost adsorbents such as industrial by-products. In this sense, the use of industrial by-products of oil shale: Oil Shale (XC), Pirolized Oil Shale (XR) and Pirolized Oil Shale with Tires (XRP), from PETROSIX/PETROBRAS, and the spent catalyst (CAT), from FCC (Fluid Catalytic Cracking) unit were characterized and used in this work in the adsorption of organics compounds of industrial liquid effluent. The main contribution of this thesis is to propose a mathematical model to the adsorption process of organic compounds in oil shale, spent catalyst of FCC and powdered activated carbon. This model is based on HSDM (Homogeneous Surface Diffusion Model) model and on the hydraulic behavior of the adsorbent system. Other contribution is the structural and chemical characterization of several samples of oil shale (oil shale, Pirolized oil shale and Pirolized oil shale with Tires) and of the spent catalyst of FCC. A computational model to simulate the adsorption process of these materials is also developed and can be considered an additional contribution of this work. Experimental and simulated results allow characterization of the oil shale adsorbent as basically macroporous and with superficial area about 0.51 to 3.36 m2.g-1. In addition, they present the same crystal structures and clay micrografies characteristics. The adsorbent CAT is composed basically by Faujasite, silica and alumina. They present spherical beads, irregular forms and micropores, with superficial area characteristics of zeolitic materials (148 and 155 m2.g-1). The adsorption tests realized in the synthetic and industrial effluents (Phenolic and Petrochemical) showed the potential of application of the industrial by-products of oil shale and CAT in the removal of organics compounds (dyes, Phenol and COT) of these effluents. In respect of environmental standards to effluents disposal (CONAMA resolution 357), simulations results, obtained with the proposed model, has demonstrated that the use of only oil shale or CAT is not viable, because the high quantity of adsorbents required. However, such adsorbents can be used in the reduction of organic loads in both effluents, when combined with other processes. Each adsorbent showed be used where it is produced because of transportation cost. The CAT is indicated for the treatment of Petrochemical effluent while the others adsorbents may be applied in the phenolic effluent treatment.

Self-activation is a process that takes advantage of the gases emitted from the pyrolysis process of biomass to activate the converted carbon. The pyrolytic gases from the biomass contain CO2 and H2O, which can be used as activating agents. As two common methods, both of physical activation using CO2 and chemical activation using ZnCl2 introduce additional gas (CO2) or chemical (ZnCl2), in which the CO2 emission from the activation process or the zinc compound removal by acid from the follow-up process will cause environmental concerns. In comparison with these conventional activation processes, the self-activation process could avoid the cost of activating agents and is more environmentally friendly, since the exhaust gases (CO and H2) can be used as fuel or feedstock for the further synthesis in methanol production. In this research, many types of biomass were successfully converted into activated carbon through the self-activation process. An activation model was developed to describe the changes of specific surface area and pore volume during the activation. The relationships between the activating temperature, dwelling time, yield, specific surface area, and specific pore volume were detailed investigated. The highest specific surface area and pore volume of the biomass-derived activated carbon through the self-activation process were up to 2738 m2 g-1 and 2.209 cm3 g-1, respectively. Moreover, the applications of the activated carbons from the self-activation process have been studied, including lithium-ion battery (LIB) manufacturing, water cleaning, oil absorption, and electromagnetic interference (EMI) shielding.

D. Tech. Chemical Engineering / Aims of this research project was to add value to largely wasted South African sawdust by development of low-cost AC of high efficiency for removal of toxic Cr (VI), phenol and glutaraldehyde from dilute aqueous media. The main objectives of the research project were: a) To develop low-cost AC based on South African P. patula sawdust using economical physical superheated steam activation.Characterization of carbon samples for selection of optimum preparation conditions for development of low-cost AC of effective microporosity mesoporosity and surface functionality for enhanced adsorption capacity of Cr (VI) and/or phenol and/or glutaraldehyde from dilute aqueous solution. Acid-amine surface groups modification of optimally developed AC for further enhancement of adsorption capacity for mixed polarized glutaraldehyde molecules from aqueous solution. b) To evaluate the aqueous phase batch adsorption properties of developed AC for Cr (VI) and phenol and, of acid-amine modified developed AC for glutaraldehyde. Determination of optimum pH for adsorption; accurate adsorption isotherm modelling for determination of maximum adsorption capacity, comparison of maximum adsorption capacities for Cr (VI) and phenol of developed AC with commercial AC and literature ACs, and attempt to establish average micropore size for enhanced capacity for Cr (VI) and phenol from dilute aqueous solution.Kinetics reaction and diffusion modelling for determination of adsorption rate constants and diffusion parameters; and determination of adsorption thermodynamic parameters.Evaluation of equilibrium selectivity of developed AC for Cr (VI) and/or phenol in binary aqueous solutions. c) To evaluate aqueous phase fixed-bed adsorption characteristics of developed AC for single Cr (VI) and mixed solution using Rapid Small Scale column Tests (RSSCTs). Generation of breakthrough curves at optimum adsorption conditions for evaluation of column performance indicators at different process conditions, bed regeneration-reusability potential, and dynamic adsorption selectivity of developed AC for Cr (VI) from solution of base metals. Determination of column diffusion parameters; accurate mass transfer and empirical modelling of breakthrough data; determination of applicable RSSCT scaling equation; and optimization of breakthrough data for accurate RSSCT scale-up.