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AdsorÃÃo de MolÃculas Sulfuradas AromÃticas em Adsorventes Mesoestruturados à Base de SÃlica. / Adsorption of aromatic sulfur molecules on mesostructured silica adsorbents.Anne Kerolaine de Oliveira Rodrigues 22 February 2011 (has links)
CoordenaÃÃo de AperfeiÃoamento de Pessoal de NÃvel Superior / A exigÃncia de um maior controle na emissÃo de poluentes de automÃveis, com uma reduÃÃo na emissÃo de enxofre, tem levado a um intenso esforÃo de pesquisas sobre tÃcnicas de remoÃÃo de sulfurados nos combustÃveis. Nos Ãltimos anos, a adsorÃÃo à vista como uma tÃcnica alternativa adequada para atingir os nÃveis de dessulfurizaÃÃo das correntes das unidades de processo de hidrodessulfurizaÃÃo (HDS). O processo HDS à muito eficiente na remoÃÃo de mercaptanas e dissulfetos, porÃm maior severidade seria necessÃria para converter as molÃculas cÃclicas de enxofre, tais como tiofenos e benzotiofenos. Devido ao tamanho volumoso destes compostos refratÃrios de enxofre, adsorventes mesoporosos sÃo vistos como mais adequado para a adsorÃÃo do que sÃlidos microporosos convencionais, tais como zeÃlitas. A dessulfurizaÃÃo por adsorÃÃo com adsorventes modificados e seletivos à um processo alternativo promissor com relaÃÃo à hidrodessulfurizaÃÃo convencional por se tratar de um processo que nÃo necessita de condiÃÃes severas de operaÃÃo que comprometam a octanagem da gasolina e o custo final de operaÃÃo. Neste trabalho foi realizado um estudo de remoÃÃo de enxofre a partir de soluÃÃes de benzotiofeno em iso-octano, utilizando os adsorventes SBA-15 e SBA-15/PdCl2. Ãrea superficial BET, volume de poros e diÃmetro de poro dos materiais mesoporos, SBA-15 e SBA-15/PdCl2, foram medidos. A adsorÃÃo do benzotiofeno em iso-octano foi avaliada atravÃs do estudo dinÃmico usando uma coluna de leito fixo em escala de laboratÃrio, utilizando os adsorventes SBA-15 e SBA-15/PdCl2. Para a SBA-15/PdCl2 o estudo de adsorÃÃo em leito fixo foi realizado em quatro temperaturas: 25, 35, 45 e 60ÂC. Curvas de breakthrough foram simuladas de acordo com um modelo matemÃtico que considera as seguintes hipÃteses: operaÃÃo isotÃrmica, fluxo com dispersÃo axial, taxa de fluxo constante, resistÃncia à transferÃncia de massa externa Ãs partÃculas (filme) desprezÃvel, transferÃncia de massa descrita por uma aproximaÃÃo de forÃa motriz linear (LDF), isoterma de adsorÃÃo linear e equilÃbrio de adsorÃÃo atingido instantaneamente na superfÃcie externa das partÃculas adsorventes. Os resultados confirmaram a eficiÃncia da SBA-15/PdCl2 para a utilizaÃÃo em processos de adsorÃÃo de compostos sulfurados. / The demand of a larger control in the emission of pollutants from automobiles, with a reduction in the emission of sulfur, has led to an intense research effort on techniques of sulfur removal from fuels. In the last few years, adsorption is thought to be a suitable polishing technique to achieve a deep desulfurization of streams from hydrodesulfurization (HDS) units. The HDS process is very efficient in the removal of mercaptans and disulfides but higher severity would be required to convert cyclic sulfur molecules, such as tiophenes and benzotiophenes. Due to the bulky size of these refractory sulfur compounds, mesoporous adsorbents are thought to be best suited for adsorption than conventional microporous solids, such as zeolites. The desulfurization by adsorption with modified and selective sorbents is a promising alternative process when compared to the conventional hydrodesulfurization once that process does not need severe conditions of operation which compromise the octane of the gasoline and the final cost of operation. In this present work, a study was coducted to remove sulfur from benzothiophene solutions in isooctante, using the adsorbent SBA-15 and SBA-15/PdCl2. BET surface area, pore volume and pore diameter of SBA-15 and SBA-15/PdCl2 mesoporous materials were measured. Adsorptive desulfurization in benzothiophene/isooctane mixture was carried trough dynamic study using a column of fixed bed in laboratory scale, using sorbents SBA-15 and SBA-15/PdCl2. The adsorption study using SBA-15/PdCl2 was carried on four temperatures: 25, 35, 45 and 60ÂC. Breakthrough curves were simulated according to a mathematical model that assumes the following hypotheses: isothermal operation; flow with axial dispersion; constant fluid flow rate; negligible external film resistance to mass transfer; internal mass transfer described by LDF approximation; linear adsorption isotherm and equilibrium reached instantaneously at the external surface of adsorbent particles. The results confirmed the efficiency of SBA-15/PdCl2 for use in adsorption process of sulfur compounds.
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Efeito da composição físico-química e mineralógica de solos sobre a dinâmica dos íons nitrato, fósforo e potássio / Effect of physicochemical and mineralogical composition of soils on the dynamics of nitrate, phosphorus and potassium ionsGrecco, Katarina Lira 09 August 2019 (has links)
A adubação tem o intuito de fornecer nutrientes (solutos) às plantas em quantidades requeridas no momento adequado, visando obter produções agrícolas economicamente viáveis. Todavia, em alguns casos, o manejo da adubação não é feito de maneira correta, principalmente por se utilizar quantidades excessivas desses nutrientes. Juntando-se a esse fato, a água da irrigação e/ou da chuva, pode vir a ser um facilitador do escoamento superficial e da lixiviação através do perfil de solo, tornando-se, dessa forma, indisponível às plantas e, podem provocar a poluição de águas superficiais através da erosão hídrica e eutrofização, além da contaminação de águas subterrâneas e a acidificação de camadas do solo. Portanto, para evitar esses impactos ambientais, é necessário conhecer e entender a dinâmica de solutos no perfil de solo mediante a obtenção de informações que venham a caracterizar esses processos. Dentro dessas informações, tem-se a obtenção dos parâmetros de transporte de solutos. Tais parâmetros podem sofrer várias interferências do meio poroso, dentre elas a composição físico-química e mineralógica dos solos, a qual poderá determinar a capacidade de retenção ou dispersão desses íons. Dessa forma, o objetivo dessa pesquisa foi avaliar o efeito da composição físico-química e mineralógica de alguns tipos de solo sobre a dinâmica dos íons nitrato, fósforo e potássio, mediante a análise de seus parâmetros de transporte, obtidos pelo ajuste numérico das curvas de distribuição de efluentes (Breakthrough Curves, BTC) aplicando o código CFITIM dentro do software STANMOD (STudio of ANalytical MODels). Além disso, utilizando-se colunas com diferentes alturas (10 e 20 cm) e buscou-se recomendar qual altura de coluna possui acurácia sobre os parâmetros mediante simulações numéricas das BTC\'s pelo modelo HYDRUS-1D. A pesquisa foi conduzida junto ao Departamento de Engenharia de Biossistemas da Universidade de São Paulo (USP/ESALQ). Os tratamentos foram distribuídos em um esquema fatorial de 5 x 2, ou seja, cinco tipos de solo e duas alturas de colunas de solo para cada íon, individualmente. O delineamento experimental foi em blocos casualizados, com três blocos, totalizando 30 parcelas por soluto. Para a análise dos resultados, os parâmetros de transportes foram submetidos à análise de variância e a avaliação do desempenho do modelo pelos índices estatísticos: Raiz do Erro Quadrático Médio (RMSE), Erro Absoluto Médio (MAE) e o Coeficiente de Determinação (R2). Diante dos resultados obtidos, o solo PV foi diferente estatisticamente dos demais solos em todos os íons no coeficiente de dispersão. Diante das diferentes nas alturas das colunas, os solos PV, PVAe, NV e PVAd apresentaram diferenças significativas no fator de retardamento e os coeficientes de distribuição e dispersão nos íons nitrato e potássio. Sendo assim, recomendou-se a altura de 20 cm, pois os parâmetros determinados foram precisos em relação a 10 cm, pelo fato do modelo HYDRUS-1D ter alcançado um desempenho adequado nas simulações das BTC\'s nos solos arenosos e argilosos. / Fertilizer is applied to provide nutrients (solutes) for plants in required quantities, and at the right time, to facilitate economically viable agricultural production. However, in some cases excessive quantities of fertilizers are applied. Such overapplication can result in runoff and ions leaching through the soil profile, where they are unavailable to plants, and can cause surface water pollution by water erosion and eutrophication, besides of groundwater contamination and soil acidification. To avoid these environmental impacts, it is necessary to characterize the transport parameters that govern the dynamic of solutes in soil profile. These parameters are influenced by porous media properties, such as mineralogical composition of soils, that regulate the retention or dispersion of ions. The objective of this study was to evaluate the effect of physicochemical and mineralogical composition of soils on transport parameters of nitrate, phosphorus, and potassium, estimated by using the CFITIM code inside of STANMOD (STudio of ANalytical MODels) software to fit BTC\'s. Besides that, using of columns with different heights (10 and 20 cm) and recommended the columns height with accuracy under transport parameters by numerical simulations of the BTC\'s using the HYDRUS-1D model. The research was conducted in the Department of Biosystems Engineering, University of São Paulo (USP/ESALQ). The treatments were a 5 x 2 factorial with five soils and two column heights for each individual solute. The experimental design was random blocks, with three blocks, totaling 30 plots for each solute. For analysis of results, the transport parameters were submitted a variance analysis and the evaluation of model performance by statistical indexes: Root Mean Square Error (RMSE), Mean Absolute Error (MAE) and Determination Coefficient (R2). The dispersion coefficient for PV soil were significantly different from those for other soils, for all ions. In front of the different heights of the columns, PV, PVAe, NV and PVAd soils showed significant differences in retardation factor, and distribution and dispersion coefficients, for nitrate and potassium ions. The parameters obtained from 20 cm columns were accurate than those obtained from 10 cm height, based on adequate performance of HYDRUS-1D model in BTC\'s simulations of sandy and clay soils.
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Uso de adsorvente à base de lodo biológico na remoção de sulfeto de hidrogênio de corrente gasosa / Use of biological sludge-based adsorbent in removing gaseous stream of hydrogen sulfideSampaio, Carlos Danillo Cavalcante 25 September 2015 (has links)
O objetivo deste estudo foi realizar ensaios de adsorção dinâmica, em coluna de leito fixo sem etapa regenerativa, para tal finalidade utilizou-se como adsorventes o carvão ativado comercial e material adsorvente à base de lodo biológico, para o tratamento de sulfeto de hidrogênio em corrente gasosa e obtenção das capacidades de adsorção. O lodo foi obtido de forma bruta em estação de tratamento de efluentes de abatedouro de aves, e tratado por processos térmicos e químicos em laboratório, para a geração de adsorvente. A concentração de H2S alimentada foi de 500 ppm na coluna, presente em duas misturas gasosas, uma com N2 e H2S, e outra mistura simulando o biogás contendo CO2, CH4 e H2S. As concentrações de H2S foram monitoradas por meio de um analisador de gás conectado a saída da coluna. Usou-se a técnica de interpretação das curvas de efluência para a determinação da capacidade de adsorção dos adsorventes estudados. Os resultados obtidos nesse trabalho indicaram que o aparato experimental usado não se mostrou viável para a adsorção com adsorvente à base de lodo. No entanto foi possível aumentar sua área superficial por meio dos tratamentos submetidos, passando de 0,005 g/m² na condição de lodo seco, para 86,4 g/m² depois de tratado. O lodo tratado com ácido sulfúrico mostrou maior capacidade de adsorção para a vazão de 4,0 L/min, apresentando remoção média de 0,21 mg H2S/g lodo. O carvão ativado comercial se apresentou propício para a remoção de H2S nas duas correntes gasosas, apresentando uma capacidade de adsorção média de 2,70 mg H2S/g carvão para a mistura gasosa simulando biogás e 1,26 mg H2S/g carvão para a corrente gasosa formado por nitrogênio e sulfeto de hidrogênio. / The objective of this study was to perform dynamic adsorption tests in fixed-bed column without regenerative stage, for this purpose it was used as adsorbents commercial activated carbon and biological sludge-based adsorbent material, for the treatment of hydrogen sulfide in the gas stream and obtaining the adsorption capacities. The sludge was obtained in raw form in treatment effluent plant from slaughterhouse poultry, and treated by thermal and chemical processes in the laboratory, to generate adsorbent. The concentration of H2S fed was 500 ppm in the column, present in two gas mixtures, one with N2 and H2S, and other mixing simulating the biogas containing CO2, CH4 and H2S. The H2S concentration was monitored by a gas analyzer connected to the outlet of the column. It was used breakthrough curves to determine the adsorption capacity of the adsorbents studied. The results of this work indicated that the experimental apparatus used was not suitable for adsorption with sludge-based adsorbent. However it was possible to increase the surface area through of undergoing treatments, from 0.005 g/m² on dry sludge condition to 86.4 g/m² after treated. The treated sludge with sulfuric acid showed a higher adsorption capacity for the flow rate of 4.0 L/min, with an average removal of H2S 0.21 mg/g sludge. The commercial activated carbon proved itself suitable for the removal of H2S in the two gas streams, with an average adsorption capacity of 2.70 mg H2S/g carbon for the gaseous mixture simulating biogas and 1.26 mg/g carbon for the gaseous stream consisting of nitrogen and hydrogen sulfide.
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Montagem e operação de unidade de adsorção em leito fixo para remoção de H2S de corrente gasosa / Assembly and operation of the adsorption unit to a fixed bed to remove H2S from the gas streamGarcia, Carolina Gil 09 May 2014 (has links)
O H2S é um gás que causa preocupação devido aos efeitos que pode provocar a saúde, a corrosão sobre alguns materiais e a redução do poder calorífero no aproveitamento de biogás, mesmo quando presente em baixas concentrações. O uso de biogás como fonte energética tem crescido nos últimos anos, impulsionando a remoção do sulfeto de hidrogênio, uma vez que a presença de tal gás reduz a capacidade calorífica do biogás e causa danos às instalações. Diante disso, várias técnicas são utilizadas na remoção de H2S, sendo uma delas, a adsorção. Os processos de separação por adsorção são muito utilizados para a remoção de poluentes gasosos de misturas gasosas. Neste trabalho foram realizados experimentos da adsorção do H2S sobre lodo seco, em coluna de leito fixo, para obtenção da capacidade de adsorção dinâmica do lodo e como esta seria afetada pelas variáveis de processo: concentração de alimentação e vazão de alimentação. Para tanto, foi concebida e instalada uma unidade de bancada de adsorção em leito fixo, com facilidades experimentais necessárias para testes dinâmicos, com o emprego da técnica de interpretação de curvas de efluência, um método útil para a avaliação do desempenho de um adsorvente em colunas de leito fixo. Testes preliminares mostraram que a unidade de bancada apresentou versatilidade, podendo ser operada com vazões de até 5 L/ min e concentração de H2S na mistura gasosa de até 500 ppm. Os resultados obtidos mostraram que a capacidade de adsorção do lodo seco foi muito baixa, com valores variando de 3,30 x 10-5 a 2,54 x 10-3 mg de H2S/g de lodo seco e existência de caminhos preferenciais no leito. / It is widely known that H2S is a gas which causes preoccupation due to the potential risks to health, corrosion in materials and reduction of the calorific value, even when present in low concentrations. The application of biogas as an energetic source has increased in last years, promoting the hydrogen sulphide removal, so that H2S presence can reduce the biogas energetic capacity and cause damage in the installations. Therefore, many techniques are used to H2S removal, one them is adsorption. The adsorption separation processes are widely used in the removal of pollutants gaseous from gas mixtures. In this work, experiments were performed on the adsorption of H2S the dry sludge in a fixed bed column, aiming to obtain the dynamic adsorption capacity and how this would be affected by the process variables: feed concentration and feed flow rate . For that, we designed and installed a bench unit to fixed bed adsorption with necessary experimental facilities for dynamic tests with the use of the technique of interpretation breakthrough curves, an useful method for evaluating the performance of an adsorbent columns fixed bed . Preliminary tests showed that the bench unit has presented versatility and efficiency and it can be operated at flow rates up to 5 L/min and H2S concentration in the gas mixture up to 500 ppm. The results showed that the adsorption capacity of the dried sludge was very low , with values varied from 3.30 × 10-5 to 2.54 × 10-3 mg H2S/g of dry sludge and the existence of preferential paths in the bed .
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Development and Characterization of Novel Nanofibrous Metal–Organic Framework Adsorption Membranes for Water TreatmentEfome, Johnson Effoe 05 October 2018 (has links)
Membrane technology has become a predominant process in providing one of the key components of life (water), either through water and wastewater treatment for water quality purposes or desalination as seen in Ultra-filtration, Nano-filtration, Reverse osmosis, Membrane distillation, Pervaporation, among others. With the ever-increasing demand for portable water due to population increase, constant research has focused on the improvements of the performances of the different water treatment systems including enhancing the performance of the membrane. Among all the different membrane performance enhancement techniques exploited, incorporation of filler has gained much grounds in the last decades. Traditional fillers like silica gel, activated carbon, metal oxides and zeolites are now being challenged by the recent class of mesoporous materials known as Metal Organic Frameworks (MOFs), which are built of metal ions or metal ion clusters linked together by organic ligands giving these materials tunable pore geometries and pore volume, greatly improved surface area with extraordinary adsorptive properties. The membrane incorporating MOFs demonstrate enhance performances more than the other fillers due to the good coordination of the organic moiety and polymers.
The overall objective of this project is to develop and study a membrane incorporated MOFs nanofiber system vis-à-vis their applications in heavy metal contaminated water treatment, stability in aqueous media and the advantages and drawbacks of these composite membranes with regards to the quality of the water produced. The developed materials were characterized by SEM, FTIR, TEM, XPS, DSC, and TGA. The heavy metals earmarked for this study include; Lead, Mercury, Cadmium, and Zinc and were studied using flame atomic absorption spectrometry (FAAS). Upon successful fabrication of the nanofiber membranes, detailed adsorption studies were conducted (pristine MOF, pristine nanofibers, enmeshed MOFs) to establish adsorption kinetics and isotherm, which were used further to select the best performing membranes for filtration application. Two different MOFs were used, MOF808; made of Zirconium and Benzene Tricarboxylate) and MOF F300; made of Iron and Benzene Tricarboxylate) The adsorption capacities of the MOFs for the different heavy metal analyzed were; MOF 808 (Pb-170.74 mg g-1, Zn-287 mg g-1, Cd-225.05 mg g-1, Hg-276.96 mg g-1) and MOF F300 (Pb-148.13 mg g-1, Hg-229.66 mg g-1), while the membrane adsorption capacities were; PA808 (MOF 808 embedded within polyacrylonitrile (PA) nanofibers, (Pb-23.98 mg g-1, Hg-50.88 mg g-1), PA300, MOF F300 embedded within polyacrylonitrile nanofibers, (Pb-30.19 mg g-1, Hg-53.09 mg g-1). Upon activation of MOF 808 by water (hydractivation), the removal efficiency of MOF 808 was improved by 10% while the MOF membrane efficiency was increased by 30%. Filtration experiments could produce 577.5 L of treated water with a single layer of PAN/ MOF808 membrane at 0.1 bar using a 50 ppb Pb ion feed solution.
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Montagem e operação de unidade de adsorção em leito fixo para remoção de H2S de corrente gasosa / Assembly and operation of the adsorption unit to a fixed bed to remove H2S from the gas streamCarolina Gil Garcia 09 May 2014 (has links)
O H2S é um gás que causa preocupação devido aos efeitos que pode provocar a saúde, a corrosão sobre alguns materiais e a redução do poder calorífero no aproveitamento de biogás, mesmo quando presente em baixas concentrações. O uso de biogás como fonte energética tem crescido nos últimos anos, impulsionando a remoção do sulfeto de hidrogênio, uma vez que a presença de tal gás reduz a capacidade calorífica do biogás e causa danos às instalações. Diante disso, várias técnicas são utilizadas na remoção de H2S, sendo uma delas, a adsorção. Os processos de separação por adsorção são muito utilizados para a remoção de poluentes gasosos de misturas gasosas. Neste trabalho foram realizados experimentos da adsorção do H2S sobre lodo seco, em coluna de leito fixo, para obtenção da capacidade de adsorção dinâmica do lodo e como esta seria afetada pelas variáveis de processo: concentração de alimentação e vazão de alimentação. Para tanto, foi concebida e instalada uma unidade de bancada de adsorção em leito fixo, com facilidades experimentais necessárias para testes dinâmicos, com o emprego da técnica de interpretação de curvas de efluência, um método útil para a avaliação do desempenho de um adsorvente em colunas de leito fixo. Testes preliminares mostraram que a unidade de bancada apresentou versatilidade, podendo ser operada com vazões de até 5 L/ min e concentração de H2S na mistura gasosa de até 500 ppm. Os resultados obtidos mostraram que a capacidade de adsorção do lodo seco foi muito baixa, com valores variando de 3,30 x 10-5 a 2,54 x 10-3 mg de H2S/g de lodo seco e existência de caminhos preferenciais no leito. / It is widely known that H2S is a gas which causes preoccupation due to the potential risks to health, corrosion in materials and reduction of the calorific value, even when present in low concentrations. The application of biogas as an energetic source has increased in last years, promoting the hydrogen sulphide removal, so that H2S presence can reduce the biogas energetic capacity and cause damage in the installations. Therefore, many techniques are used to H2S removal, one them is adsorption. The adsorption separation processes are widely used in the removal of pollutants gaseous from gas mixtures. In this work, experiments were performed on the adsorption of H2S the dry sludge in a fixed bed column, aiming to obtain the dynamic adsorption capacity and how this would be affected by the process variables: feed concentration and feed flow rate . For that, we designed and installed a bench unit to fixed bed adsorption with necessary experimental facilities for dynamic tests with the use of the technique of interpretation breakthrough curves, an useful method for evaluating the performance of an adsorbent columns fixed bed . Preliminary tests showed that the bench unit has presented versatility and efficiency and it can be operated at flow rates up to 5 L/min and H2S concentration in the gas mixture up to 500 ppm. The results showed that the adsorption capacity of the dried sludge was very low , with values varied from 3.30 × 10-5 to 2.54 × 10-3 mg H2S/g of dry sludge and the existence of preferential paths in the bed .
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Uso de adsorvente à base de lodo biológico na remoção de sulfeto de hidrogênio de corrente gasosa / Use of biological sludge-based adsorbent in removing gaseous stream of hydrogen sulfideCarlos Danillo Cavalcante Sampaio 25 September 2015 (has links)
O objetivo deste estudo foi realizar ensaios de adsorção dinâmica, em coluna de leito fixo sem etapa regenerativa, para tal finalidade utilizou-se como adsorventes o carvão ativado comercial e material adsorvente à base de lodo biológico, para o tratamento de sulfeto de hidrogênio em corrente gasosa e obtenção das capacidades de adsorção. O lodo foi obtido de forma bruta em estação de tratamento de efluentes de abatedouro de aves, e tratado por processos térmicos e químicos em laboratório, para a geração de adsorvente. A concentração de H2S alimentada foi de 500 ppm na coluna, presente em duas misturas gasosas, uma com N2 e H2S, e outra mistura simulando o biogás contendo CO2, CH4 e H2S. As concentrações de H2S foram monitoradas por meio de um analisador de gás conectado a saída da coluna. Usou-se a técnica de interpretação das curvas de efluência para a determinação da capacidade de adsorção dos adsorventes estudados. Os resultados obtidos nesse trabalho indicaram que o aparato experimental usado não se mostrou viável para a adsorção com adsorvente à base de lodo. No entanto foi possível aumentar sua área superficial por meio dos tratamentos submetidos, passando de 0,005 g/m² na condição de lodo seco, para 86,4 g/m² depois de tratado. O lodo tratado com ácido sulfúrico mostrou maior capacidade de adsorção para a vazão de 4,0 L/min, apresentando remoção média de 0,21 mg H2S/g lodo. O carvão ativado comercial se apresentou propício para a remoção de H2S nas duas correntes gasosas, apresentando uma capacidade de adsorção média de 2,70 mg H2S/g carvão para a mistura gasosa simulando biogás e 1,26 mg H2S/g carvão para a corrente gasosa formado por nitrogênio e sulfeto de hidrogênio. / The objective of this study was to perform dynamic adsorption tests in fixed-bed column without regenerative stage, for this purpose it was used as adsorbents commercial activated carbon and biological sludge-based adsorbent material, for the treatment of hydrogen sulfide in the gas stream and obtaining the adsorption capacities. The sludge was obtained in raw form in treatment effluent plant from slaughterhouse poultry, and treated by thermal and chemical processes in the laboratory, to generate adsorbent. The concentration of H2S fed was 500 ppm in the column, present in two gas mixtures, one with N2 and H2S, and other mixing simulating the biogas containing CO2, CH4 and H2S. The H2S concentration was monitored by a gas analyzer connected to the outlet of the column. It was used breakthrough curves to determine the adsorption capacity of the adsorbents studied. The results of this work indicated that the experimental apparatus used was not suitable for adsorption with sludge-based adsorbent. However it was possible to increase the surface area through of undergoing treatments, from 0.005 g/m² on dry sludge condition to 86.4 g/m² after treated. The treated sludge with sulfuric acid showed a higher adsorption capacity for the flow rate of 4.0 L/min, with an average removal of H2S 0.21 mg/g sludge. The commercial activated carbon proved itself suitable for the removal of H2S in the two gas streams, with an average adsorption capacity of 2.70 mg H2S/g carbon for the gaseous mixture simulating biogas and 1.26 mg/g carbon for the gaseous stream consisting of nitrogen and hydrogen sulfide.
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Séparation des isomères de l’hexane par des solides hybrides poreux (MOFs) / Separation of Hexane Isomers in Metal-Organic Frameworks (MOFs)Pinto Mendes, Patricia Alexandra 09 September 2014 (has links)
Le principal objectif de cette recherche est l’évaluation de nouveaux adsorbants nommés Metal-Organic Frameworks (MOFs) pour la séparation des isomères de l'hexane afin d'améliorer l'indice d'octane de l’essence. La séparation des isomères de l'hexane est actuellement réalisée par Total Isomerization Processes (TIP) basé sur l’utilisation de la zéolithe 5A qui permet d’isoler les paraffines «non normales». Afin d'améliorer et de tester d’autres adsorbants, des structures MOFs flexibles et rigides ont été synthétisées et évaluées pour cette séparation au travers de séries de courbes de perçage avec des mélanges d’isomères de l’hexane nHEX, 3MP, 22DMB et 23DMB. Cela a permis d'obtenir des isothermes d'adsorption à l'équilibre et une analyse de leurs performances a permis de trouver les structures plus performantes. L’UiO-66(Zr) fonctionnalisé par des groupes –Br, –NO2, et –NH2, les solides mésoporeux MIL-100(Cr) et son analogue fonctionnalisé MIL-100(Cr) greffé avec des alkylamines, le solide microporeux MIL-125(Ti) fonctionnalisé avec un groupe –NH2 et le tétracarboxylate de fer(III) microporeux MIL-127(Fe) sont les solides rigides étudiés. Les structures flexibles sont les dicarboxylates de fer(III) MIL-53(Fe) fonctionnalisés –(CF3)2, –2CH3, le ZIF-8 à base d’imidazolate et un polymorphe MIL-88B(Fe) fonctionnalisé –2CF3. La caractérisation de ces adsorbants cristallins a été réalisée par combinaison de diffraction des rayons X (XRPD), spectroscopie infrarouge (IR), analyse thermogravimétrique (TGA) et la porosimétrie d’adsorption d’azote. Les solides MIL-53(Fe)–(CF3)2 et ZIF-8 démontrent un effect de tamis moléculaires avec un comportement remarquable. / The main goals of this research are the synthesis of new specific adsorbents named Metal-Organic Frameworks (MOFs) for the separation of hexane isomers in order to improve the octane number of the gasoline. The separation of hexane isomers is actually performed using the conventional Total Isomerization Processes (TIP) with zeolite 5A which isolates only «non-normal paraffins». In order to improve and to test other alternatives, flexible and rigid frameworks were synthesized, performing a set of breakthrough curves with hexane isomers nHEX, 3MP, 22DMB and 23DMB with the purpose of obtaining adsorption equilibrium isotherms and further analysis of their performances in order to find new frameworks that offer better results. This concerned first the rigid frameworks UiO-66(Zr) functionalized with the functional groups –Br, –NO2, and –NH2; the mesoporous MIL-100(Cr) and its functionalized analogue MIL-100(Cr) grafted with alkylamines, the microporous Ti MOF MIL-125 functionalized with the functional group –NH2 and the iron tetracarboxylate MIL-127(Fe). The flexible frameworks were the Zn imidazolate ZIF-8, the iron(III) dicarboxylates MIL-53(Fe) functionalized with the functional groups –(CF3)2 and –2CH3 and the MIL-88 functionalized with the functional group –2CF3. The characterization of these crystalline adsorbents was achieved by X-Ray Powder Diffraction (XRPD), Infra-Red spectroscopy (IR), Thermogravimetric Analysis (TGA) and nitrogen surface area measurement. MIL-53(Fe)–(CF3)2 and ZIF-8 demonstrated molecular sieve effects with interesting and promossing behaviour for hexane isomers separation.
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Describing and Predicting Breakthrough Curves for non-Reactive Solute Transport in Statistically Homogeneous Porous MediaWang, Huaguo 06 December 2002 (has links)
The applicability and adequacy of three modeling approaches to describe and predict breakthough curves (BTCs) for non-reactive solutes in statistically homogeneous porous media were numerically and experimentally investigated. Modeling approaches were: the convection-dispersion equation (CDE) with scale-dependent dispersivity, mobile-immobile model (MIM), and the fractional convection-dispersion equation (FCDE).
In order to test these modeling approaches, a prototype laboratory column system was designed for conducting miscible displacement experiments with a free-inlet boundary. Its performance and operating conditions were rigorously evaluated.
When the CDE with scale-dependent dispersivity is solved numerically for generating a BTC at a given location, the scale-dependent dispersivity can be specified in several ways namely, local time-dependent dispersivity, average time-dependent dispersivity, apparent time-dependent dispersivity, apparent distance-dependent dispersivity, and local distance-dependent dispersivity. Theoretical analysis showed that, when dispersion was assumed to be a diffusion-like process, the scale-dependent dispersivity was locally time-dependent. In this case, definitions of the other dispersivities and relationships between them were directly or indirectly derived from local time-dependent dispersivity. Making choice between these dispersivities and relationships depended on the solute transport problem, solute transport conditions, level of accuracy of the calculated BTC, and computational efficiency
The distribution of these scale-dependent dispersivities over scales could be described as either as a power-law function, hyperbolic function, log-power function, or as a new scale-dependent dispersivity function (termed as the LIC). The hyperbolic function and the LIC were two potentially applicable functions to adequately describe the scale dependent dispersivity distribution in statistically homogeneous porous media.
All of the three modeling approaches described observed BTCs very well. The MIM was the only model that could explain the tailing phenomenon in the experimental BTCs. However, all of them could not accurately predict BTCs at other scales using parameters determined at one observed scale. For the MIM and the FCDE, the predictions might be acceptable only when the scale for prediction was very close to the observed scale. When the distribution of the dispersivity over a range of scales could be reasonably well-defined by observations, the CDE might be the best choice for predicting non-reactive solute transport in statistically homogeneous porous media. / Ph. D.
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Assessment of soil water movement and the relative importance of shallow subsurface flow in a near-level Prairie watershedRoss, Cody 20 January 2017 (has links)
Near-level Prairie landscapes have received limited attention in hydrological research. For this thesis, hydrometric measurements and four tracing experiments were completed at three “riparian-to-stream” sites in the Catfish Creek Watershed (southeastern Manitoba) to enhance Prairie hydrology understanding. First, hydrologic state variables were examined to infer vertical and lateral water movement. Second, tracer data were analyzed to evaluate the relative importance of surface versus subsurface water movement. Results show that hydrologic state variables can be useful for inferring riparian-to-stream water movement. Tracer data also revealed that subsurface water movement can contribute significantly to streamflow during snowmelt- and rainfall-triggered events in the study watershed. This thesis demonstrated that subsurface flow is a significant runoff generation mechanism in Prairie landscapes, thus challenging surface water-focused conceptualizations and management strategies that are traditionally used. The findings summarized in this thesis will be critical to improve the performance of hydrological models when applied to the Prairies. / February 2017
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