Carcinogenic health concerns over arsenic in drinking water caused the USEPA to reduce the maximum contaminant level (MCL) from 50 to 10 ppb, effective on January 23, 2006. This has forced many smaller utilities into expensive treatment or discontinuation of water distribution. Researchers throughout the world are working to develop an inexpensive method for arsenic removal to meet this MCL. Aluminum silicates, or zeolites, are naturally occurring ionic sorbents. Modification of a zeolite may enhance adsorption capacities and ion selectivity. This research investigates the arsenic adsorption capacities of a modified Chabazite. This adsorption, coupled with a hollow fiber, microfiltration membrane substrate, allows for the use of finer zeolite particles. Powdered zeolite creates a cake layer on the filtration surface through which the arsenic solution must filter. The research goal was to develop an overall mathematical model for the adsorption of arsenic through the adsorption equilibrium isotherms, the cake layer, and the microfiltration operational settings. Baseline adsorption isotherms where performed in distilled water. Solutions containing counter ions were then used to determine any counter-effects. The final isotherms were found using dechlorinated tap water, which is similar to many groundwaters found in the United States. Various runs were used to determine the most efficient modification and loading rate.Initial characterization of the membrane system defined membrane permeability and inherent arsenic rejection. Variable mass loading in both deadend and crossflow filtration determined that the cake layer was not compressible due to linear pressure increases. This process also determined the maximum cake layer permissible hydraulically on the membrane surface. Membrane system operational characteristics and arsenic dosing were chosen to adhere to these parameters as well as the adsorption isotherms. Adsorption runs were conducted which varied the flux through the membrane, the arsenic feed concentration, and the cake layer thickness. Through the data collected, a mathematical model based on irreversible adsorption was developed. This novel approach to arsenic removal and the predictive mathematical model can be used as an effective method for removal of aqueous arsenic, and may provide small water utilities with a cost effective way to meet the recommended new MCL.

Nesta pesquisa de doutorado, o processo de microfiltração tangencial com membranas cerâmicas é investigado visando à retenção de bactérias (Escherichia coli CCT 0549) e redução de sólidos suspensos de uma bebida à base de açaí (Euterpe oleracea Mart.). As membranas comerciais selecionadas foram manufaturadas com \'alfa\'-alumina (\'AL IND.2\'O IND.3\') e possuem tamanho nominal de poro, fornecido pelo fabricante no valor de 0,8\'mü\'m e 1,2\'mü\'m. O valor nominal da membrana de 1,2\'mü\'m é maior que a largura da Escherichia coli (0,8\'mü\'m). Como, a princípio, o microrganismo está fisicamente sujeito a passagem pela membrana de 1,2\'mü\'m, esta estrutura micro-porosa foi submetida à impregnação de prata. Este procedimento visou verificar a influência da prata como material bactericida para auxiliar na redução/eliminação das bactérias inoculadas na bebida à base de açaí. Para tanto, a estrutura cerâmica micro-porosa foi tratada quimicamente com solução de citrato de prata e submetida à queima até a temperatura de 600 graus Celsius para eliminação dos compostos orgânicos e conseqüente impregnação de nanopartículas de prata metálica nos poros da membrana. Este processo de impregnação proporcionou um discreto aumento no índice de retenção microbiana em regime de escoamento turbulento (Re=20000). A caracterização morfológica, a composição e a impregnação de prata nas membranas foram realizadas com o auxílio da Microscopia Eletrônica de Varredura (MEV) e do Detector de Energia Dispersiva de Raio-X (EDX). Estas mesmas técnicas foram utilizadas para caracterizar o fenômeno físico-químico de formação da camada polarizada sobre a superfície da membrana. A análise da retenção de bactérias foi realizada através da contagem de unidades formadoras de colônia (UFC/mL) em placas Petrifilm \'EC POT.TM\'. O desempenho das membranas na retenção de material particulado suspenso foi analisado pela técnica de espectroscopia de ultra-som e por comparação qualitativa, entre concentrado e permeado, via microscopia ótica. A redução de antocianina (cianidina-3-glicosídeo) e o conteúdo de polifenóis totais foram investigados via espectrofotometria, apresentando relação direta com o tamanho dos poros da membrana e com o regime de escoamento. Desta forma, parâmetros fluido-dinâmicos do processo, tais como: número de Reynolds, pressão transmembrana e fluxo transmembrana foram caracterizados para uma ampla faixa do escoamento turbulento e analisados com o modelo de resistência em série. Os resultados experimentais obtidos neste trabalho indicaram que o processo de microfiltração tangencial é uma boa alternativa à retenção de microrganismos e simultânea redução de sólidos suspensos da bebida à base de açaí. / In this doctoral research, the crossflow microfiltration process utilizing ceramic membranes was investigated aiming at the bacteria retention (Escherichia coli) and reduction of suspended solids of beverage based on açai (Euterpe oleracea Mart.). The selected commercial membranes of \'alfa\'-alumina (\'AL IND.2\'O IND.3\') had nominal pore sizes of 0.8 and 1.2 \'mü\'m and were manufactured by Andritz Group from Austria. The membrane nominal value of 1.2\'mü\'m is larger than the width of the Escherichia coli (0.8\'mü\'m). Therefore, as the microrganisms are subjected to pass through the pores of this membrane, it was submitted to silver impregnation. This procedure aimed to verify the silver influence as a bactericide material to assist in retention or elimination of bacteria during the microfiltration process. In this way, the microporous structure was chemically treated with a silver citrate solution and then, subjected to burning until 600 Celsius degrees to eliminate organic compounds and consequent impregnation of nanoparticles of metallic silver in the membrane pores. The morphology characterization, composition, and impregnation of silver in membranes were analyzed by Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray fluorescence (EDX) spectrometer. The same techniques were utilized to characterize the physicochemical phenomenon of polarization layer formation on the membrane surface. The analysis of bacteria retention was performed by the counting of colony forming units (CFU/mL) in Petrifilm Plates \'EC POT.TM\'. The performance of the membranes in the retention of solids in suspension was analyzed by Ultrasound Spectroscopy - APS100 and Optical Microscopy. The variations of the anthocyanin concentration and the total polyphenol content were investigated by spectrophotometry, showing direct relationship with the membrane pore size and flow regime. Therefore, fluid-dynamical parameters, such as Reynolds number, transmembrane pressure, and permeate flux were characterized for a large range of turbulent flow and analyzed with the resistance-in-series model. The experimental results of this research indicated that the microfiltration process is a suitable alternative to retain microrganisms and simultaneously decrease suspended solids of the beverage based on açai.

Nesta pesquisa de doutorado, o processo de microfiltração tangencial com membranas cerâmicas é investigado visando à retenção de bactérias (Escherichia coli CCT 0549) e redução de sólidos suspensos de uma bebida à base de açaí (Euterpe oleracea Mart.). As membranas comerciais selecionadas foram manufaturadas com \'alfa\'-alumina (\'AL IND.2\'O IND.3\') e possuem tamanho nominal de poro, fornecido pelo fabricante no valor de 0,8\'mü\'m e 1,2\'mü\'m. O valor nominal da membrana de 1,2\'mü\'m é maior que a largura da Escherichia coli (0,8\'mü\'m). Como, a princípio, o microrganismo está fisicamente sujeito a passagem pela membrana de 1,2\'mü\'m, esta estrutura micro-porosa foi submetida à impregnação de prata. Este procedimento visou verificar a influência da prata como material bactericida para auxiliar na redução/eliminação das bactérias inoculadas na bebida à base de açaí. Para tanto, a estrutura cerâmica micro-porosa foi tratada quimicamente com solução de citrato de prata e submetida à queima até a temperatura de 600 graus Celsius para eliminação dos compostos orgânicos e conseqüente impregnação de nanopartículas de prata metálica nos poros da membrana. Este processo de impregnação proporcionou um discreto aumento no índice de retenção microbiana em regime de escoamento turbulento (Re=20000). A caracterização morfológica, a composição e a impregnação de prata nas membranas foram realizadas com o auxílio da Microscopia Eletrônica de Varredura (MEV) e do Detector de Energia Dispersiva de Raio-X (EDX). Estas mesmas técnicas foram utilizadas para caracterizar o fenômeno físico-químico de formação da camada polarizada sobre a superfície da membrana. A análise da retenção de bactérias foi realizada através da contagem de unidades formadoras de colônia (UFC/mL) em placas Petrifilm \'EC POT.TM\'. O desempenho das membranas na retenção de material particulado suspenso foi analisado pela técnica de espectroscopia de ultra-som e por comparação qualitativa, entre concentrado e permeado, via microscopia ótica. A redução de antocianina (cianidina-3-glicosídeo) e o conteúdo de polifenóis totais foram investigados via espectrofotometria, apresentando relação direta com o tamanho dos poros da membrana e com o regime de escoamento. Desta forma, parâmetros fluido-dinâmicos do processo, tais como: número de Reynolds, pressão transmembrana e fluxo transmembrana foram caracterizados para uma ampla faixa do escoamento turbulento e analisados com o modelo de resistência em série. Os resultados experimentais obtidos neste trabalho indicaram que o processo de microfiltração tangencial é uma boa alternativa à retenção de microrganismos e simultânea redução de sólidos suspensos da bebida à base de açaí. / In this doctoral research, the crossflow microfiltration process utilizing ceramic membranes was investigated aiming at the bacteria retention (Escherichia coli) and reduction of suspended solids of beverage based on açai (Euterpe oleracea Mart.). The selected commercial membranes of \'alfa\'-alumina (\'AL IND.2\'O IND.3\') had nominal pore sizes of 0.8 and 1.2 \'mü\'m and were manufactured by Andritz Group from Austria. The membrane nominal value of 1.2\'mü\'m is larger than the width of the Escherichia coli (0.8\'mü\'m). Therefore, as the microrganisms are subjected to pass through the pores of this membrane, it was submitted to silver impregnation. This procedure aimed to verify the silver influence as a bactericide material to assist in retention or elimination of bacteria during the microfiltration process. In this way, the microporous structure was chemically treated with a silver citrate solution and then, subjected to burning until 600 Celsius degrees to eliminate organic compounds and consequent impregnation of nanoparticles of metallic silver in the membrane pores. The morphology characterization, composition, and impregnation of silver in membranes were analyzed by Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray fluorescence (EDX) spectrometer. The same techniques were utilized to characterize the physicochemical phenomenon of polarization layer formation on the membrane surface. The analysis of bacteria retention was performed by the counting of colony forming units (CFU/mL) in Petrifilm Plates \'EC POT.TM\'. The performance of the membranes in the retention of solids in suspension was analyzed by Ultrasound Spectroscopy - APS100 and Optical Microscopy. The variations of the anthocyanin concentration and the total polyphenol content were investigated by spectrophotometry, showing direct relationship with the membrane pore size and flow regime. Therefore, fluid-dynamical parameters, such as Reynolds number, transmembrane pressure, and permeate flux were characterized for a large range of turbulent flow and analyzed with the resistance-in-series model. The experimental results of this research indicated that the microfiltration process is a suitable alternative to retain microrganisms and simultaneously decrease suspended solids of the beverage based on açai.

Die Querstrom-Mikrofiltration mit Kapillarmembranen kommt zunehmend in den Bereichen Lebensmittel-, Pharma-, Chemieindustrie sowie in der Umwelttechnik zum Einsatz. Eine vollständige Beschreibung der Deckschichtbildung innerhalb der Membrananlage ist jedoch noch nicht gelungen. Der erste Teil dieser Arbeit widmet sich der Kuchenbildung in einer Kapillarmembran. Dabei werden sowohl Änderungen der Strömungsverhältnisse entlang der Kapillarlänge als auch Klassiereffekte bei der Querstrom-Mikrofiltration von polydispersen Stoffsystemen berücksichtigt. Die Modellberechnungen wurden mit Experimenten validiert. Weiterhin erfolgte die Untersuchung des Einflusses von polymeren Flockungsmitteln (PFM) auf die Mikrofiltration und der Möglichkeiten einer Filtratstromerhöhung durch Flockung mittels PFM. Es wird gezeigt, dass eine optimale Zudosierung von PFM existiert und diese mit einer maximalen Filtratstromerhöhung verbunden ist. Eine Überdosierung von PFM soll jedoch verhindert werden.

Die Querstrom-Mikrofiltration mit Kapillarmembranen kommt zunehmend in den Bereichen Lebensmittel-, Pharma-, Chemieindustrie sowie in der Umwelttechnik zum Einsatz. Eine vollständige Beschreibung der Deckschichtbildung innerhalb der Membrananlage ist jedoch noch nicht gelungen. Der erste Teil dieser Arbeit widmet sich der Kuchenbildung in einer Kapillarmembran. Dabei werden sowohl Änderungen der Strömungsverhältnisse entlang der Kapillarlänge als auch Klassiereffekte bei der Querstrom-Mikrofiltration von polydispersen Stoffsystemen berücksichtigt. Die Modellberechnungen wurden mit Experimenten validiert. Weiterhin erfolgte die Untersuchung des Einflusses von polymeren Flockungsmitteln (PFM) auf die Mikrofiltration und der Möglichkeiten einer Filtratstromerhöhung durch Flockung mittels PFM. Es wird gezeigt, dass eine optimale Zudosierung von PFM existiert und diese mit einer maximalen Filtratstromerhöhung verbunden ist. Eine Überdosierung von PFM soll jedoch verhindert werden.

A non-reactive model system comprising a highly concentrated and unstable oil-in-water emulsion was used to investigate the retention of oil by the membrane in producing biodiesel with a membrane reactor. Critical flux was identified using the relationship between the permeate flux and transmembrane pressure along with the separation efficiency of the membrane. It was shown that separation efficiencies above 99.5% could be obtained at all operating conditions up to the critical flux. It was observed that the concentration of oil in all collected permeate samples using the oil-water system was below 0.2 wt% when operating at a flux below the critical flux. Studies to date have been limited to the characterization of low concentrated emulsions below 15 vol.%. The average oil droplet size in highly concentrated emulsions was measured as 3200 nm employing direct light scattering (DLS) measurement methods. It was observed that the estimated cake layer thickness of 20 to 80 mm was larger than external diameter of the membrane tube i.e. 6 mm based on a large particle size. Settling of the concentrated emulsion permitted the detection of a smaller particle size distribution (30-100 nm) within the larger particles averaging 3200 nm. It was identified that DLS methods could not efficiently give the droplet size distribution of the oil in the emulsion since large particles interfered with the detection of smaller particles. The content of the smaller particles represented 1% of the total weight of oil at 30°C and 5% at 70°C. This was too low to be detected using DLS measurements but was sufficient to affect ultrafiltration. In order to study the critical flux in the presence of transesterification reaction and the effect of cross flow velocity on separation, various oils were transesterified in another membrane reactor providing higher cross flow velocity. higher cross flow velocity provides better separation by reducing materials deposition on the surface of the membrane due to higher shearing. The oils tested were canola, corn, sunflower and unrefined soy oils (Free Fatty Acids (FFA< 1%)), and waste cooking oil (FFA= 9%). The quality of all biodiesel samples was studied in terms of glycerine, mono-glyceride, di-glyceride and tri-glyceride concentrations. The composition of all biodiesel samples were in the range required by ASTM D6751 and EN 14214 standards. A critical flux based on operating pressure in the reactor was reached for waste cooking and pre-treated corn oils. It was identified that the reaction residence time in the reactor was an extremely important design parameter affecting the operating pressure in the reactor. / Natural Sciences and Engineering Research Council of Canada (NSERC)

A non-reactive model system comprising a highly concentrated and unstable oil-in-water emulsion was used to investigate the retention of oil by the membrane in producing biodiesel with a membrane reactor. Critical flux was identified using the relationship between the permeate flux and transmembrane pressure along with the separation efficiency of the membrane. It was shown that separation efficiencies above 99.5% could be obtained at all operating conditions up to the critical flux. It was observed that the concentration of oil in all collected permeate samples using the oil-water system was below 0.2 wt% when operating at a flux below the critical flux. Studies to date have been limited to the characterization of low concentrated emulsions below 15 vol.%. The average oil droplet size in highly concentrated emulsions was measured as 3200 nm employing direct light scattering (DLS) measurement methods. It was observed that the estimated cake layer thickness of 20 to 80 mm was larger than external diameter of the membrane tube i.e. 6 mm based on a large particle size. Settling of the concentrated emulsion permitted the detection of a smaller particle size distribution (30-100 nm) within the larger particles averaging 3200 nm. It was identified that DLS methods could not efficiently give the droplet size distribution of the oil in the emulsion since large particles interfered with the detection of smaller particles. The content of the smaller particles represented 1% of the total weight of oil at 30°C and 5% at 70°C. This was too low to be detected using DLS measurements but was sufficient to affect ultrafiltration. In order to study the critical flux in the presence of transesterification reaction and the effect of cross flow velocity on separation, various oils were transesterified in another membrane reactor providing higher cross flow velocity. higher cross flow velocity provides better separation by reducing materials deposition on the surface of the membrane due to higher shearing. The oils tested were canola, corn, sunflower and unrefined soy oils (Free Fatty Acids (FFA< 1%)), and waste cooking oil (FFA= 9%). The quality of all biodiesel samples was studied in terms of glycerine, mono-glyceride, di-glyceride and tri-glyceride concentrations. The composition of all biodiesel samples were in the range required by ASTM D6751 and EN 14214 standards. A critical flux based on operating pressure in the reactor was reached for waste cooking and pre-treated corn oils. It was identified that the reaction residence time in the reactor was an extremely important design parameter affecting the operating pressure in the reactor. / Natural Sciences and Engineering Research Council of Canada (NSERC)

A non-reactive model system comprising a highly concentrated and unstable oil-in-water emulsion was used to investigate the retention of oil by the membrane in producing biodiesel with a membrane reactor. Critical flux was identified using the relationship between the permeate flux and transmembrane pressure along with the separation efficiency of the membrane. It was shown that separation efficiencies above 99.5% could be obtained at all operating conditions up to the critical flux. It was observed that the concentration of oil in all collected permeate samples using the oil-water system was below 0.2 wt% when operating at a flux below the critical flux. Studies to date have been limited to the characterization of low concentrated emulsions below 15 vol.%. The average oil droplet size in highly concentrated emulsions was measured as 3200 nm employing direct light scattering (DLS) measurement methods. It was observed that the estimated cake layer thickness of 20 to 80 mm was larger than external diameter of the membrane tube i.e. 6 mm based on a large particle size. Settling of the concentrated emulsion permitted the detection of a smaller particle size distribution (30-100 nm) within the larger particles averaging 3200 nm. It was identified that DLS methods could not efficiently give the droplet size distribution of the oil in the emulsion since large particles interfered with the detection of smaller particles. The content of the smaller particles represented 1% of the total weight of oil at 30°C and 5% at 70°C. This was too low to be detected using DLS measurements but was sufficient to affect ultrafiltration. In order to study the critical flux in the presence of transesterification reaction and the effect of cross flow velocity on separation, various oils were transesterified in another membrane reactor providing higher cross flow velocity. higher cross flow velocity provides better separation by reducing materials deposition on the surface of the membrane due to higher shearing. The oils tested were canola, corn, sunflower and unrefined soy oils (Free Fatty Acids (FFA< 1%)), and waste cooking oil (FFA= 9%). The quality of all biodiesel samples was studied in terms of glycerine, mono-glyceride, di-glyceride and tri-glyceride concentrations. The composition of all biodiesel samples were in the range required by ASTM D6751 and EN 14214 standards. A critical flux based on operating pressure in the reactor was reached for waste cooking and pre-treated corn oils. It was identified that the reaction residence time in the reactor was an extremely important design parameter affecting the operating pressure in the reactor. / Natural Sciences and Engineering Research Council of Canada (NSERC)

A non-reactive model system comprising a highly concentrated and unstable oil-in-water emulsion was used to investigate the retention of oil by the membrane in producing biodiesel with a membrane reactor. Critical flux was identified using the relationship between the permeate flux and transmembrane pressure along with the separation efficiency of the membrane. It was shown that separation efficiencies above 99.5% could be obtained at all operating conditions up to the critical flux. It was observed that the concentration of oil in all collected permeate samples using the oil-water system was below 0.2 wt% when operating at a flux below the critical flux. Studies to date have been limited to the characterization of low concentrated emulsions below 15 vol.%. The average oil droplet size in highly concentrated emulsions was measured as 3200 nm employing direct light scattering (DLS) measurement methods. It was observed that the estimated cake layer thickness of 20 to 80 mm was larger than external diameter of the membrane tube i.e. 6 mm based on a large particle size. Settling of the concentrated emulsion permitted the detection of a smaller particle size distribution (30-100 nm) within the larger particles averaging 3200 nm. It was identified that DLS methods could not efficiently give the droplet size distribution of the oil in the emulsion since large particles interfered with the detection of smaller particles. The content of the smaller particles represented 1% of the total weight of oil at 30°C and 5% at 70°C. This was too low to be detected using DLS measurements but was sufficient to affect ultrafiltration. In order to study the critical flux in the presence of transesterification reaction and the effect of cross flow velocity on separation, various oils were transesterified in another membrane reactor providing higher cross flow velocity. higher cross flow velocity provides better separation by reducing materials deposition on the surface of the membrane due to higher shearing. The oils tested were canola, corn, sunflower and unrefined soy oils (Free Fatty Acids (FFA< 1%)), and waste cooking oil (FFA= 9%). The quality of all biodiesel samples was studied in terms of glycerine, mono-glyceride, di-glyceride and tri-glyceride concentrations. The composition of all biodiesel samples were in the range required by ASTM D6751 and EN 14214 standards. A critical flux based on operating pressure in the reactor was reached for waste cooking and pre-treated corn oils. It was identified that the reaction residence time in the reactor was an extremely important design parameter affecting the operating pressure in the reactor. / Natural Sciences and Engineering Research Council of Canada (NSERC)