Water scarcity is among the most serious, long-term challenges in the world. To an ever increasing degree, sustainable water supply depends on the utilization of water of impaired initial quality. This is particularly true in developing nations and in water-stressed areas such as the American Southwest. Water of impaired quality could be water of high salinity such as brackish groundwater. Traditionally, reverse osmosis (RO) would be chosen to desalinate the brackish groundwater, since RO costs are competitive with those of thermal desalination, even for seawater applications. However, both conventional thermal distillation and RO are energy intensive, complex processes that discourage decentralized or rural implementation. In addition, both technologies require enhanced expertise for operation and maintenance, and are susceptible to scaling and fouling unless extensive feed pretreatment is employed. Membrane distillation (MD), driven by vapor pressure gradients, can potentially overcome many of these drawbacks. MD can operate using low-grade, sub-boiling temperature heat sources. When it is driven by solar energy it does not require highly concentrating collection devices, non-aqueous working fluids, or complex temperature control systems, nor does it require extensive operational expertise. Membrane Distillation (MD) applications, background and modeling efforts are discussed in the first part of this dissertation. Two main studies are presented in this document: Firstly, Sweeping Gas Membrane Distillation (SGMD) through a hollow fiber membrane was studied both experimentally and modeled mathematically to describe performance of SGMD and extend results to predict membrane module efficiency and secondly, SGMD through a flat sheet MD module to study the effect of membrane characteristics in combination with operational variables. A final study was conducted to examine the effect of mesh spacer insertion in flat sheet membrane module on the permeate water production.

The spinning process of hollow fiber membranes was investigated with regards to two fundamental phenomena: flow (shear and elongation) and phase separation. Quantitative analysis of phase separation kinetics of binary (polymer/solvent) and ternary (polymer/solvent/volatile co-solvent) polymer solution was carried out with a newly developed microfluidic device. The device enables visualization of in situ phase separation and structure formation in controlled vapor and liquid environments. Results from these studies indicated that there was a weak correlation between phase separation kinetics and macroscopic defect (macrovoid) formation. In addition, the effect of shear and elongation on membrane morphology was tested by performing fiber extrusion through microfluidic channels. It was found that the membrane morphology is dominated by different factors depending on the rate of deformation. At high shear rates typical of spinning processes, shear was found to induce macrovoid formation through normal stresses, while elongation suppressed macroscopic defect formation. Furthermore, draw resonance, one of the key instabilities that can occur during fiber spinning, was investigated. It was found that draw resonance occurs at aggressive elongation condition, and could be suppressed by enhanced phase separation kinetics. These results can be used as guidelines for predicting hollow fiber membrane spinnability.

The main theme of this dissertation is the fabrication and analysis of modified mesoporous silica membranes for separation applications. Synthesis methods for mesoporous silica membranes have been developed to enhance the transport performance and quality of the membranes, such as permeability, pore volume, and surface area. Then, synthesized membranes were modified with different organic groups to tailor selectivity in separations. The collected studies of modified mesoporous silica membranes showed that appropriate functionalization on newly synthesized novel membranes leads to promising structural and permeation properties. First, a seeded growth method was developed for synthesis of MCM-48 membranes on alumina supports, thereby extending the seeded growth technique used for zeolite membranes to mesoporous silica membrane synthesis. The surface properties of the MCM-48 membranes were then modified by silylation with hexamethyldisilazane (HMDS). In comparison to MCM-48 membranes previously synthesized by the in situ growth technique, much less silica infiltration into the alumina support was observed. The pore structure of the MCM-48 membranes demonstrated that a large accessible pore volume was available for molecular permeation and pore modification to tailor selectivity. The gas permeation properties of the calcined and silylated MCM-48 membranes were consistent with a Knudsen-like mechanism, albeit with a substantial influence of gas-solid interactions in the mesopores. The silylated MCM-48 membranes were evaluated for pervaporative separation of ethanol (EtOH), methyl ethyl ketone (MEK), and ethyl acetate (EA) from their dilute aqueous solutions. The synthesized membranes exhibited high pervaporative separation factors and organic fluxes. The selective separation of organic/water mixtures with MCM-48 membranes were attributed to both the organophilic nature of the surface and the effective pore size of the silylated mesopores. Next, the synthesis and organic/water separation properties of mesoporous silica membranes supported on low-cost and scalable polymeric (polyamide-imide) hollow fibers and modified by trimethylsilylation with HMDS was studied. Thin, defect-free membranes that exhibited high gas permeances consistent with Knudsen-like diffusion through the mesopores were prepared. Silylation of these membranes did not affect the integrity of the mesoporous silica structure and the underlying polymeric hollow fiber, but led to capping of the surface silanol groups in the mesopores with trimethylsilyl groups. The silylated mesoporous membranes were evaluated for pervaporative separation of EtOH, MEK, EA, iso-butanol, and n-butanol from their dilute aqueous solutions. The membranes showed higher separation factors than those of flat membranes, along with high organic fluxes. The large increase in hydrophobicity of the membranes upon silylation allowed upgrading of the feed mixtures to permeate streams with considerably higher organic content. The selective separation of organic/water mixtures with the fiber-supported mesoporous silica membranes was attributed to both the organophilic nature of the surface (yielding good adsorption selectivity) and the effective pore size of the silylated mesopores (giving good fluxes). Comparison with other types of organic/water separation membranes revealed that the present silylated membrane platform shows good promise for use in organic/water separation applications due to its high flux, scalable and low-cost fabrication methodology, and good separation factors that can be further enhanced by tailoring the mesopore modification chemistry. Further, the gas transport properties of aziridine-functionalized mesoporous silica membranes on polymeric hollow fibers have also investigated. The mesoporous membranes were amine-functionalized with aziridine and their transport properties were studied to understand the effects of surface functionalization on gas separations. This new hybrid aminosilica membrane showed interesting and counter-intuitive N₂ selective permeation properties in dry CO₂/N₂ separations. Detailed characterization of the membrane structure and its permeation behavior showed that such behavior was due to the strong adsorption of CO₂, leading to reduced gas flux because of CO₂-induced amine crosslinking in the mesopores. This hyper-branched aminosilica membrane showed CO₂ selective properties when applied to humid gas permeation. Water molecules in the humid gas affected the adsorption of CO₂ molecules by causing a lower degree of crosslinking, allowing facilitated transport of CO₂.

Despite intrinsically high separation performance, conventional polymeric membranes suffer from CO₂ induced plasticization, which reduces CO₂/CH₄ separation efficiency significantly. Covalent ester-crosslinking can improve the plasticization resistance by controlling the segmental chain mobility in the polymer; however, only relatively thick selective skin layers and lower separation productivity have been reported to date. On the other hand, the high cost of crosslinkable polymers makes the approach challenging, especially for large-scale gas separations which require large membrane areas with high feed pressures. Dual-layer hollow fiber spinning can be used to reduce the cost of membrane production by integrating a low-cost supporting core polymer with the expensive crosslinkable sheath polymer. However, the complexity of interfacial interaction between the sheath/core layers and subsequent crosslinking required can delaminate the sheath/core layers and collapse the core layer polymer. This can reduce mechanical strength and the separation productivity significantly. This work aimed to develop thin-skinned high-performing ester-crosslinked hollow fiber membranes with improved CO₂ plasticization resistance. The skin layer thickness of hollow fibers was first optimized by simultaneous optimization of the polymer dope and spinning process variables. Moreover, this study also addresses the solutions of challenging in transitioning the monolithic hollow fiber to composite hollow fiber format. The ester-crosslinked hollow fibers were subjected to high feed pressures and high-level contaminants to probe their CO₂ plasticization and hydrocarbon antiplasticization resistance, respectively. The resultant ester-crosslinked monolithic hollow fibers show significantly reduced skin layer thickness and improved separation productivity under extremely challenging operation conditions. They also demonstrate strong stability under high feed pressures and reversibility after contaminant exposure. Moreover, this study presents a newly discovered core layer material, Torlon®, which demonstrates excellent compatibility with the crosslinkable polymer and superior thermal stability during crosslinking without sheath/core layer delamination or collapse. The characterization under aggressive feed conditions clearly suggests that ester-crosslinked composite hollow fibers can achieve high separation performance and reduce membrane cost simultaneously. This provides a significant advance in state of the art for natural gas separations under realistic operation environments

Novas tecnologias para o tratamento de água potável vêm sendo empregadas na medida em que a utilização de sais de alumínio tem apresentado correlação com doenças de envelhecimento mental nos seres humanos. Os coagulantes orgânicos de origem vegetal podem substituir de forma satisfatória estes sais no tratamento convencional de água potável. A utilização de processos combinados utilizando membranas de ultrafiltração com coagulação é uma alternativa aos métodos convencionais de potabilização. Com este cenário, o presente trabalho tem como objetivo comparar o desempenho operacional de uma planta piloto de ultrafiltração com membranas submersas para produção de água potável a partir do Lago Guaíba, utilizando o coagulante convencional poli (cloreto de alumínio) (PAC) e um coagulante orgânico oriundo da casca da Acácia Negra (Acacia maernsii) Tanfloc SG, com a análise da morfologia, massa molar de corte e permeabilidade hidráulica da membrana e com análises da água bruta e filtrada. As membranas de fibra oca de Poliéter Sulfona (PES) com massa molar de corte de 50 kDa, permearam sob pressão fixa de -500 mbar, com ação de borbulhamento em testes de 140 horas para avaliação da performance e testes de 10 horas para avaliação da qualidade de permeado. Os resultados indicaram semelhança no desempenho operacional dos dois coagulantes quanto à redução da permeância hidráulica relativa, e a qualidade do permeado indicou que mesmo com a ausência de flocos no tanque de alimentação, não houve passagem significativa de coagulante para o permeado. Os parâmetros de potabilidade indicaram o enquadramento da água produzida nos padrões organolépticos na atual Portaria 2914/2011 do Ministério da Saúde. / New technologies to water treatment have been applied as the aluminum salts commonly used have shown correlations with mental diseases in human beings. The organic coagulants from natural sources can satisfactorily replace those inorganic salts in drinking water treatment. The hybrid processes join ultrafiltration membranes with coagulation are alternatives to the standard potabilization. The present study compares the operational behavior of a submersed ultrafiltration (UF) pilot plant producing drinking water from Guaíba Lake, using poli (aluminum chloride) (PAC) and an organic coagulant extracted from Acacia maernsii Tanfloc SG. The membrane and the permeate were investigated. The polyether sulfone hollow fiber membranes filtered with a -500 mbar constant vacuum and air bubbles through 140 hours for performance test and for 10 hour for permeate quality verification. The results showed similarity of the relative hydraulic permeability of the two coagulants, and even with the absence of visible flocs in the membrane tank, there were no significant coagulant carryover through the membrane. The analytical data pointed that the water produced with both coagulants had concentration bellow the Brazilian organoleptic standards, according to the Portaria 2914/2011 of the Health Ministry.

Novas tecnologias para o tratamento de água potável vêm sendo empregadas na medida em que a utilização de sais de alumínio tem apresentado correlação com doenças de envelhecimento mental nos seres humanos. Os coagulantes orgânicos de origem vegetal podem substituir de forma satisfatória estes sais no tratamento convencional de água potável. A utilização de processos combinados utilizando membranas de ultrafiltração com coagulação é uma alternativa aos métodos convencionais de potabilização. Com este cenário, o presente trabalho tem como objetivo comparar o desempenho operacional de uma planta piloto de ultrafiltração com membranas submersas para produção de água potável a partir do Lago Guaíba, utilizando o coagulante convencional poli (cloreto de alumínio) (PAC) e um coagulante orgânico oriundo da casca da Acácia Negra (Acacia maernsii) Tanfloc SG, com a análise da morfologia, massa molar de corte e permeabilidade hidráulica da membrana e com análises da água bruta e filtrada. As membranas de fibra oca de Poliéter Sulfona (PES) com massa molar de corte de 50 kDa, permearam sob pressão fixa de -500 mbar, com ação de borbulhamento em testes de 140 horas para avaliação da performance e testes de 10 horas para avaliação da qualidade de permeado. Os resultados indicaram semelhança no desempenho operacional dos dois coagulantes quanto à redução da permeância hidráulica relativa, e a qualidade do permeado indicou que mesmo com a ausência de flocos no tanque de alimentação, não houve passagem significativa de coagulante para o permeado. Os parâmetros de potabilidade indicaram o enquadramento da água produzida nos padrões organolépticos na atual Portaria 2914/2011 do Ministério da Saúde. / New technologies to water treatment have been applied as the aluminum salts commonly used have shown correlations with mental diseases in human beings. The organic coagulants from natural sources can satisfactorily replace those inorganic salts in drinking water treatment. The hybrid processes join ultrafiltration membranes with coagulation are alternatives to the standard potabilization. The present study compares the operational behavior of a submersed ultrafiltration (UF) pilot plant producing drinking water from Guaíba Lake, using poli (aluminum chloride) (PAC) and an organic coagulant extracted from Acacia maernsii Tanfloc SG. The membrane and the permeate were investigated. The polyether sulfone hollow fiber membranes filtered with a -500 mbar constant vacuum and air bubbles through 140 hours for performance test and for 10 hour for permeate quality verification. The results showed similarity of the relative hydraulic permeability of the two coagulants, and even with the absence of visible flocs in the membrane tank, there were no significant coagulant carryover through the membrane. The analytical data pointed that the water produced with both coagulants had concentration bellow the Brazilian organoleptic standards, according to the Portaria 2914/2011 of the Health Ministry.

Le projet NEOPHIL a pour ambition d'élaborer une membrane d'ultrafiltration (UF) en fibre creuse de poly(fluorure de vinylidène) (PVdF) possédant une résistance au colmatage stable dans le temps. Cette propriété peut être acquise par l'ajout d'un copolymère à blocs nommé GEN dans la solution de préparation des fibres en plus de l'additif poly(vinyl pyrrolidone) (PVP) classiquement utilisé. Dans ce travail, nous nous sommes attachés à la détermination des additifs en surface, dans la masse et à établir des profils de concentration par ATR-FTIR, T%-FTIR et microscopie Raman. Ces analyses ont montré que la moitié de la PVP est lessivée dans le bain de coagulation alors que GEN reste quantitativement ancré dans la matrice. Dans le cas de la PVP, les paramètres d'élaboration comme la présence de solvant ou de PVP dans le bain de coagulation influent fortement sur le profil de concentration au niveau des interfaces. Par la suite, une analyse multicritère entre l'hydrophilie apportée par les additifs et le colmatage a été effectuée. Cette étude a été réalisée par des mesures d'angle de contact à l'eau, de rétention d'eau et de pression d'intrusion d'eau sur fibres sèches en relation avec la taille et la distribution des pores, la rugosité de surface (AFM) et la perméabilité à l'eau pure. La rétention d'eau et la pression d'intrusion d'eau semblent les deux techniques les plus pertinentes pouvant relier les propriétés physico-chimiques et les performances de filtration. Une étude préliminaire sur le comportement au vieillissement a également été effectuée qui montre que GEN est peu extrait alors que la PVP disparait en partie par extraction et/ou dégradation. Ce phénomène affecte fortement les différents paramètres étudiés dans l'analyse multicritère. / The project NEOPHIL aims to develop an ultrafiltration (UF) membrane hollow fiber from poly (vinylidene fluoride) (PVdF) that resists to fouling amide time. This property can be achieved by adding a block copolymer called GEN in the fiber preparation solution in addition to the classic additive, poly (vinyl pyrrolidone) (PVP). In this work, we focused on the quantification of additives on the surface, in the bulk and establishing the concentration profile by ATR-FTIR, T% -FTIR and Raman microscopy. These analyzes showed that half of the PVP is washed away into the coagulation bath while GEN quantitatively remains anchored in the matrix. In the case of PVP, the formulation parameters such as the presence of solvent or PVP in the coagulation bath greatly affects the concentration profile at the interfaces. In addition a multi-criteria analysis between hydrophilicity provided by the additives and the fouling was established. This study was carried out by measurement of the water contact angle, water retention and water intrusion pressure of dry fibers in relation to the size and distribution of pores, the surface roughness (AFM) and the permeability to pure water. Water retention and water intrusion pressure seem to be the two most relevant techniques that can connect the physicochemical properties and filtration performance. A preliminary study on the aging behavior was also performed showing that GEN is not extracted while the PVP is lost partly by extraction and/or degradation. This phenomenon strongly affects the different parameters studied in the multi-criteria analysis.

Coagulation/flocculation/sedimentation is a common pretreatment process prior to microfiltration (MF) or ultrafiltration (UF) to alleviate membrane fouling, however there has been limited research on floatation as the pretreatment separation process. The main objective of this study is to compare sedimentation with floatation as part of the pretreatment for ultrafiltration of Ottawa River water (ORW) with relatively high natural organic matter (NOM) content. Water samples pretreated at two full-scale plants were subjected to multiple-day UF membrane fouling tests (constant flux with backwash and chemical cleaning) using an automated bench-scale UF hollow fiber membrane system. For all the experiments, the transmembrane pressure (TMP) increased sharply during the beginning of the operation (~10 h), which indicated the adsorption was significant. In the later cycles, the TMP showed a more linear constant increase, which indicated the built up of the cake layers. The total fouling index (TFI), hydraulically irreversible fouling index (HIFI) and chemical irreversible fouling index (CIFI) for floated water were much smaller than those of settled waters during both summer and winter testing. Thus, for this type of water coagulation/floatation pretreatment was superior process compared to coagulation/sedimentation, the decreased fouling appears to be linked to greater hydrophobic NOM removal by the coagulation/floatation. For all the tests, HIFI/TFIs were less than 0.1, which is to mean most of the fouling was reversible by hydraulic backwashing.Large fluctuation of backwash efficiencies with time were found for all the tested waters. Enhanced chemical backwash with 100 ppm chlorine and chemical clean with 0.1N NaOH & 200 ppm chlorine were found to be very effective at reducing fouling for pretreated ORW. As expected longer filtration cycles resulted in greater fouling but with a slightly greater degree of hydraulically reversible fouling.

Orientador: Sergio Persio Ravagnani / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-07T19:00:28Z (GMT). No. of bitstreams: 1 Lavezo_AnaElisa_M.pdf: 1136570 bytes, checksum: e8e9754aa79e23bced02a8fa2d543e4c (MD5) Previous issue date: 2006 / Resumo: A separação de misturas gasosas é efetuada com o objetivo de obter um ou mais dos constituintes na forma altamente puros. Existem quatro métodos principais aplicados para a separação de gases: absorção, adsorção, destilação criogênia e membranas. A economia do processo determinará qual desses métodos é usado para alguma aplicação particular (Scott, 1995). A era moderna das membranas de separação de gases foi introduzída após 1980, quando as membranas poliméricas se tomaram economicamente viáveis (Robeson, 1999).Atualmente a separação baseada em membranas é utilizada largamente em escala industrial para produção de nitrogênio de alta pureza a partir do ar, tendo importante aplicação na inertização do ambiente para conservação de frutas e vegetais, reatores químicos e produção de NH3, assim como para segurança na operação com líquidos inflamáveis (Spillman, 1989). O objetivo deste trabalho é a otimização do custo total do processo de separação de misturas gasosas multicomponentes utilizando membrana de fibra oca. A otimização foi realizada utilizando o método "Constrained Rosenbrock (Hill AIgorithm)", para obter um produto final com alta qualidade e com um custo total minimizado. Para a otimização do custo total do processo são necessários os seguintes dados fornecidos pelo programa de Caramello (2002): pressão do permeado e da alimentação, taxa de fluxo do lado do alimentado, pureza e recuperação. A equação do custo total utilizada consiste em custo de instalação e custo operacional, ou seja, o custo total é o custo do módulo de permeação, custo de substituição da membrana (assumindo-se a vida útil da membrana a cada 3 anos), custo da energia elétrica e o custo de instalação do compressor.Otimizaram-se primeiramente dois parâmetros, número de cartuchos de membrana de fibra oca (QM) e pressão de alimentação (pt), em seguida fixou-se o número de cartuchos de membrana de fibra oca e foi otimizada a pressão de alimentação verificando se assim para cada análise o custo total otimizado para as seguintes purezas: 85%, 90%, 95% e 99% / Abstract: The separation of gas mixtures is made under the objective of obtaining one or more representatives in the highly pure form. Four methods can be used in gas separation: absorption, adsorption, distillation cryogenics and membranes. The economy of the process will determine which method will be used in a specific application (Scott, 1995). The modem era of gas-separation membrane was introduced in the early 1980s, when polymeric membranes became economically viable. (Robeson, 1999). Nowadays, membranes separation is used wide in industrial scale for the production of nitrogen in a high purity level from the air. This is an essential method for the inertization of the atmosphere air for fruits and vegetables storage, quimicos reactors and production of NH 3, as well as for safety when operating inflammable liquids (Spillman, 1989). The objective of this work is to optimization the cost related to the process of separation of multicomponents gas mixtures using membrane of hollow fiber. The optimization was made using "Constrained Rosenbrock (Hill Algorithm)", in order to obtain a high quality product with a reduced cost. For the process cost optimization the following data supplied for the program of Caramello (2002) is needed: feeding and permeated pressure, flow tax next to the feeder, purity and recovery. The equation of the cost used consists of: installation cost and operational cost. The total cost consists of the permeation module cost, the membrane substitution cost (assuming it useful life of the membrane to each 3 years), the electricity cost and finally the cost of the compressor installation. One first optimized two parameters: amount of membranes (QM) and pressure of feeding (P / Mestrado / Ciencia e Tecnologia de Materiais / Mestre em Engenharia Química

The diploma thesis is devoted to the separation of a pollutant (NH3) from a water solution using an experimental technology device - membrane contactor. The theoretical part is mostly focused on the recent progress in the field of membrane contactors. The theoretical part also contains theory of absorption, chemisorption and microreactions, which is needed to understand the subject properly. The experimental part focuses on the construction of the experimental device and what does experimental device consist of. The efficiency of the device in transfer of ammonia to an nitrate salt of nitric acid solution was tested. At the end, experimental data are further discussed.