MBR process consists of a suspended growth biological reactor combined with a membrane unit. The widespread of this system for waste water treatment is contained by membrane fouling, which is strongly influenced by three factors: biomass characteristics, operating conditions and membrane characteristics. Fouling control techniques mainly include low-flux operation (sub-critical flux operation) and/or high-shear slug flow aeration in submerged. configuration. Based on the concept of the critical flux (Jo), the flux-step method has been developed to more fully characterise transmembrane pressure (TMP) behaviour during constant-fluxoperation. A zero rate of TMP increase was never attained during the trial, such that no critical flux, in its strictest definition, could be defined in this study for a submerged MBRs challenged with real and simulant sewage. Under similar operating conditions, Jc was obtained around 18 and 10 L.m-2.h-1 for a submerged MBR fed by real and synthetic sewage respectively. Three TMP-based parameters have been defined, all indicating the same flux value at which fouling starts to be more significant (the weak form of Jo). Results from factorial experimental designs revealed the relative effect of MLSS levels, aeration rate and membrane pore size on J, The MLSS effect on Jc was generally around double that of the aeration effect. The calculation of mean sub-critical values for the different TMP-based parameters suggest lower short-term fouling resistance for large pore sized membranes. A direct comparison between the two MBR configurations revealed a greater J, for the submerged compared to the SS MBR (22 and 11 L.m-2.h-1 respectively) under similar hydraulic conditions. The fluid hydrodynamics has been studied for both configurations, leading to an accurate calculation of shear at the membrane surface in SS MBR and to the determination of the minimum gas velocity required for Taylor bubble formation in submerged MBR (around 0.1 m.s-1). Finally, the effect of operating conditions such as process configuration, feed nature, and aeration type on biomass characteristics has been assessed and link to membrane fouling. Key words: Fouling, MBR, critical flux, process configuration, biomass characterisation.

In this study the fouling mechanisms of various microfiltration and ultrafiltration membranes were studied when subjected to crossflow filtration using various protein solutions. Experimentation was carried out using controlled flux experiments and fouling phenomena was investigated via the monitoring of the transmembrane pressure (TMP) and rejection. Electron microscopy was employed to study fouling on microfiltration membranes when single protein solutions were filtered while a novel method involving Matrix-Assisted Laser Desorption Ionisation Mass Spectrometry (MALDI-MS) was developed to qualitatively and quantitatively analyse mixed proteins fouled on ultrafiltration membranes. An apparent critical flux was identified whereby fouling was shown to occur at fluxes where there was no increase in TMP. TMP increase is one of the common indicators of fouling in controlled flux operation. Microfiltration experiments showed that the imposition of the apparent critical flux is accompanied by rapid increases in hydraulic resistance and the membrane wall concentration. Pore blockage and narrowing occurred at somewhat higher fluxes as indicated by increases in the observed rejection. Fouling was not influenced greatly by the addition of electrolytes for microfiltration membranes but observed transmissions were found to be greater than 100% when ultrafiltration membranes were employed. For all membranes used, the actual value of the apparent critical flux was shown to be independent of the salt concentration but dependent on pH. Sub apparent-critical constant flux microfiltration showed the existence of an aggregation/deposition time lag after which the membrane experiences a rapid increase in resistance due to protein aggregates blocking a majority of pores. This phenomenon was shown to be dependent on pH and ionic strength and was concluded to be the product of a balance between electrostatic, solubility and hydrophobic interactions.

The work described by this thesis is a comparison of pore opening geometry for true surface microfilters. True surface microfilters can be thought of as very fine sieves, with pore sizes less than 10 microns. All other types of so-called microfiltration membranes do not rely on sieving, but obtain their pore retention rating by particle collection mechanisms similar to depth filters. Particle deposition within such microfilters results in permeate flow rate dechne, for a fixed pressure filtration, or pressure drop rise, for a fixed rate filtration. The true surface microfilter pore geometnes considered were circular and slotted, and microfilters with filtering dimension of less than 10 microns were used. The slotted pore microfilters are not commercially available and had to be made in the laboratory as part of this study. The technique used was to plate nickel onto an existing substrate, thereby reducing the pore dimension until It was within the microfiltration range. The plating was by electroless nickel solution and not by galvanic means. Significant development of the electroless platmg technique led ultimately to the successful manufacture of process scale slotted surface microfilters.

Made available in DSpace on 2014-06-11T19:29:13Z (GMT). No. of bitstreams: 0 Previous issue date: 2010-03-19Bitstream added on 2014-06-13T19:38:24Z : No. of bitstreams: 1 bezerra_lf_me_ilha.pdf: 1874770 bytes, checksum: b6f02018abe581f4724626202c471af4 (MD5) / Universidade Estadual Paulista (UNESP) / As atividades industriais, principalmente as indústrias químicas e alimentícias que se utilizam dos processos fermentativos, geram efluentes com altas concentrações de matéria orgânica carbonácea e nitrogenada. Estas necessitam de sistemas complexos para o tratamento de suas águas residuárias, pois a emissão excessiva de nutrientes no corpo d’água pode resultar na ocorrência da eutrofização que interfere nos usos desejáveis do recurso hídrico e altera o equilíbrio ambiental. Neste sentido, o presente avaliou da remoção de matéria orgânica carbonácea e nitrogenada, bem como a determinação do fluxo crítico, em biorreator de membranas (MBR) tratando águas residuárias industriais do processo de produção de aminoácidos. Pelos resultados obtidos, constatou-se a viabilidade técnica no uso do MBR para ao tratamento dessas águas residuárias contendo 2505 mg DQO/L de material carbonáceo e 277 mg NTK/L de material nitrogenado. O biorreator foi operado com carga orgânica volumétrica de 1,91 ± 0,13 kg DQO/m³ dia e carga nitrogenada volumétrica de 0,18 ± 0,02 kg NTK/m³ dia, com recirculação interna de 4 vezes a vazão afluente. O efluente tratado apresentou concentrações médias de 59 ± 27 mg DQO/L, 0,60 ± 0,24 mg N-NH4 +/L e 20,5 ± 11,9 mg N-total/L, com eficiências médias de remoção de DQO, NTK e NT de 97,5%, 98,6% e 92,1%, respectivamente. O sistema de ultrafiltração foi testado em vários fluxos entre 25 e 37 LMH e determinou-se o fluxo crítico de 28 LMH para o sistema operando com 11,4 g/L de SST / Industrial activities, especially the chemical and food industries, that use fermentation processes, generate effluents with high concentrations of carbonaceous organic matter and nitrogen. These require complex systems to treat its wastewater, since the emission of excessive nutrients in the water body can result in the occurrence of eutrophication, which interferes with the desirable uses of water resource and changes the environmental balance. In this sense, this paper evaluated the carbonaceous organic matter and nitrogen removal as well as the determination of critical flux in membrane bioreactor (MBR) treating industrial wastewater from amino acids production. By the obtained results, it found the technical feasibility of MBR for the wastewater treatment containing 2505 mg COD / L of organic material and 277 mg TKN / L of nitrogen material. The bioreactor was operated with organic loading rate of 1.91 ± 0.13 kg COD / m³ day and nitrogen volumetric load of 0.18 ± 0,02 kg TKN / m day, with internal recirculation of 4 times. The treated effluent showed concentrations of 59 ± 27 mg COD / L, 0.60 ± 0.24 mg N-NH4 + / L and 20.5 ± 11.9 mg total N / L, with average removal efficiencies of COD , TKN and TN of 97.5%, 98.6% and 92.1%, respectively. The ultrafiltration system was tested at various flow rates between 25 and 37 LMH, to determine the critical flux of 28 LMH with the system operating at 11.4 g / L of TSS

Orientador: Tsunao Matsumoto / Banca: Milton Dall'Aglio Sobrinho / Banca: Marcelo Zaiat / Resumo: As atividades industriais, principalmente as indústrias químicas e alimentícias que se utilizam dos processos fermentativos, geram efluentes com altas concentrações de matéria orgânica carbonácea e nitrogenada. Estas necessitam de sistemas complexos para o tratamento de suas águas residuárias, pois a emissão excessiva de nutrientes no corpo d'água pode resultar na ocorrência da eutrofização que interfere nos usos desejáveis do recurso hídrico e altera o equilíbrio ambiental. Neste sentido, o presente avaliou da remoção de matéria orgânica carbonácea e nitrogenada, bem como a determinação do fluxo crítico, em biorreator de membranas (MBR) tratando águas residuárias industriais do processo de produção de aminoácidos. Pelos resultados obtidos, constatou-se a viabilidade técnica no uso do MBR para ao tratamento dessas águas residuárias contendo 2505 mg DQO/L de material carbonáceo e 277 mg NTK/L de material nitrogenado. O biorreator foi operado com carga orgânica volumétrica de 1,91 ± 0,13 kg DQO/m³ dia e carga nitrogenada volumétrica de 0,18 ± 0,02 kg NTK/m³ dia, com recirculação interna de 4 vezes a vazão afluente. O efluente tratado apresentou concentrações médias de 59 ± 27 mg DQO/L, 0,60 ± 0,24 mg N-NH4 +/L e 20,5 ± 11,9 mg N-total/L, com eficiências médias de remoção de DQO, NTK e NT de 97,5%, 98,6% e 92,1%, respectivamente. O sistema de ultrafiltração foi testado em vários fluxos entre 25 e 37 LMH e determinou-se o fluxo crítico de 28 LMH para o sistema operando com 11,4 g/L de SST / Abstract: Industrial activities, especially the chemical and food industries, that use fermentation processes, generate effluents with high concentrations of carbonaceous organic matter and nitrogen. These require complex systems to treat its wastewater, since the emission of excessive nutrients in the water body can result in the occurrence of eutrophication, which interferes with the desirable uses of water resource and changes the environmental balance. In this sense, this paper evaluated the carbonaceous organic matter and nitrogen removal as well as the determination of critical flux in membrane bioreactor (MBR) treating industrial wastewater from amino acids production. By the obtained results, it found the technical feasibility of MBR for the wastewater treatment containing 2505 mg COD / L of organic material and 277 mg TKN / L of nitrogen material. The bioreactor was operated with organic loading rate of 1.91 ± 0.13 kg COD / m³ day and nitrogen volumetric load of 0.18 ± 0,02 kg TKN / m day, with internal recirculation of 4 times. The treated effluent showed concentrations of 59 ± 27 mg COD / L, 0.60 ± 0.24 mg N-NH4 + / L and 20.5 ± 11.9 mg total N / L, with average removal efficiencies of COD , TKN and TN of 97.5%, 98.6% and 92.1%, respectively. The ultrafiltration system was tested at various flow rates between 25 and 37 LMH, to determine the critical flux of 28 LMH with the system operating at 11.4 g / L of TSS / Mestre

La clarification des vins par procédés membranaires en particulier la microfiltration tangentielle a toujours été limitée par le colmatage, générant des flux de perméation faibles incompatibles avec la rentabilité économique. La compréhension, la maîtrise, ainsi que l'anticipation des phénomènes de colmatage font l'objet de ce travail. Dans un premier temps, la contribution individuelle puis en mélange des composés du vin (tannins, pectines, mannoprotéines et levures) au colmatage d'une membrane céramique multicanaux a été évaluée. Une approche fondamentale a permis de proposer des mécanismes de colmatage : la présence des pectines induit les flux de perméation les plus faibles en formant un gel à la surface de la membrane tandis que les levures semblent au contraire avoir un effet protecteur dans le cas d'un vin brut. Parce qu'il représente le flux au-delà duquel un colmatage irréversible apparaît à la surface de la membrane, le flux critique pour l'irréversibilité est un paramètre clef pour contrôler le colmatage. Dans le cas de la filtration de vin, aucun flux critique n'a pu être déterminé ce qui a conduit à définir un critère identifiant une zone de travail où le degré de colmatage reste acceptable. La dernière partie de cette thèse est consacrée à l'étude de la filtration dynamique (RVF) pour une éventuelle application dans le secteur vinicole. Cette technique est testée en présence de deux membranes organiques différentes: PES (hydrophile) et PTFE (hydrophobe). Les observations ont permis de mettre en évidence l'efficacité du système contre le colmatage des membranes PES induite par l'action de l'agitateur. Le colmatage des membranes PTFE est énormément affecté par les interactions molécules/membrane rendant la filtration dynamique inefficace pour lutter contre le colmatage de ces membranes. / Wine clarification by membrane processes mainly cross-flow microfiltration has been limited by membrane fouling generating low permeate fluxes with economic efficiency. Understanding, controlling and anticipation of fouling are the main goals of this work. In a first time, the individual contribution of wine compounds (tannins, pectins, mannoproteins and yeasts) to a multichannel ceramic membrane fouling was evaluated. The fouling mechanisms were analyzed using a fundamental approach. The presence of pectins induce the lowest fluxes by a gel-type formation at the membrane surface while yeasts presence tends to reduce fouling in the case of crude wine (case of mixed components). Because it represents the flux beyond which irreversible fouling appears on the membrane surface, the critical flux for irreversibility is a key parameter to control fouling. No critical flux for irreversibility could be measured, hence a criterion that identifies a range of operating conditions where the degree of fouling remains acceptable was proposed. The last part of this work was devoted to the study of dynamic filtration (RVF) for further application in wine sector. This technique was tested with two different membranes: hydrophilic PES and hydrophobic PTFE. Results have allowed to demonstrate the efficiency of the system to reduce fouling in the case of PES membrane. Fouling of PTFE membrane is greatly influenced by molecules / membrane interaction making dynamic filtration ineffective in reducing of membrane fouling.

This thesis describes the rejection efficiency and the fouling behaviour of calcium sulphate solutes in a 1 nm tubular ceramic titanium dioxide nanofiltration membrane. Calcium sulphate is considered as one of the greatest scaling potential inorganic salts that responsible for membrane fouling which represents a main challenge in the expansion of membrane processes for desalination of brackish and saline water. The surface charge type and magnitude for the composite amphoteric TiO_2 membrane were characterised using streaming potential measurements. Electrokinetic membrane experiments were conducted in a background electrolyte comprising 0.01 M (NaCl). The zeta potential was estimated from the measured streaming potential using the Helmoholtz-Smoluchowski equation and the surface charge density was subsequently calculated using the Gouy-Chapman and Graham equations. The experimental results showed that the membrane was negatively charged at neutral pH and its iso-electrical point (i.e.p) was at pH of 4.0. The rejection behaviour of calcium sulphate at three different initial concentrations (0.001, 0.005 and 0.01 M) were investigated compared to other naturally occurring minerals (NaCl, Na_2 SO_4, CaCl_2) in single salt solutions. The rejection experiments were conducted at five different applied trans-membrane pressures ranged from 1.0 to 5.0 bars. Salt retention measurements showed that the rejection sequence was R (CaSO_4) > R (Na_2 SO_4) > R (CaCl_2) > R (NaCl). This rejection sequence behaviour showed an inverse relationship with the diffusion coefficients of the four salts. The salt with the lowest diffusion coefficient (CaSO_4) showed the highest rejection (43.3%), whereas that with the highest diffusion coefficient showed the lowest rejection. The rejection of calcium sulphate solution at saturation concentration was also conducted after a suspension solution of 0.015 M (CaSO_4) was prepared and filtered. The ionic analysis for calcium sulphate permeates indicated that, for the negatively charged TiO_2 membrane, the rejection for bivalent anion (SO_4^(2-) ) was higher than that of the bivalent cation (Ca^(2+) ).The critical flux (CF) experiments were carried out at six trans-membrane pressure ranged from 1.0 to 6.0 bars to identify the form and the onset of calcium sulphate fouling (as gypsum) using different concentrations below saturation concentration (0.001, 0.005, 0.01 M) and at saturation concentration. Two different flux-pressure techniques have been applied and compared to determine the critical flux values; these are: step by step technique and standard stepping technique. The obtained critical flux results from both measuring techniques (for all the four sessions) confirmed that the critical flux was reached and exceeded. The present work indicated that the resulting critical flux values from both measuring procedures were decreased as the ionic strengths of the calcium sulphate solutes were increased. A mathematical model has been proposed to identify the key parameters that affect the transport performance inside the TiO_2 nanofiltration membrane. The original Donnan steric pore model (DSPM) was used to simulate the rejection of 0.01 M sodium chloride as a reference solution. The membrane effective pore radius was estimated using two different transport models, both of these models depend on the permeation test of uncharged solute (glucose). The Donnan potential was determined based on the membrane effective fixed charge density which was determined by supposing that the membrane surface charge was uniformly distributed in the void volume of cylindrical pores. The theoretical rejection of NaCl solute for the present DSPM model was found to be in agreement with the experimental data.

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)