A indústria têxtil utiliza elevados volumes de água em seus processos, principalmente na etapa de tingimento, em que são utilizadas também quantidades elevadas de corantes e auxiliares têxteis. A presença desses produtos no efluente gera um efeito prejudicial e claramente visível ao ambiente, pois causam alteração nos parâmetros da qualidade da água do corpo receptor. O presente estudo apresenta o pós-tratamento de um efluente têxtil, objetivando o reciclo deste efluente para água de processo de tingimento. Para isso foi utilizada uma combinação de processo físico-químico de coagulação/floculação (CF) e processo de separação por membrana (PSM) de Ultrafiltração (UF) e Osmose Inversa (OI). Os parâmetros analisados antes e após os tratamentos foram: turbidez, condutividade elétrica, demanda química de oxigênio (DQO), carbono orgânico total (COT) e cor. Na etapa de CF foram testados dois tipos de coagulantes, o Sulfato de Alumínio e o Cloreto Férrico, nas concentrações de 30, 50, 70 e 100 mg.L-1. Foram testadas três concentrações de floculante comercial: 0,2, 0,3 e 0,4 mg.L-1. Os experimentos foram conduzidos em pH 7. As etapas de PSM foram conduzidas em módulo plano de Ultrafiltração e em módulos plano e espiral na membrana de Osmose Inversa. O melhor desempenho foi obtido com a dosagem de 50 mg.L-1 do coagulante cloreto férrico e a de 0,3 mg.L-1 de floculante comercial, que apresentou uma redução de 98% na turbidez com relação ao efluente de alimentação. No PSM de Ultrafiltração a remoção de cor não foi satisfatória por ainda apresentar coloração. No PSM de Osmose Inversa com o módulo plano o objetivo da remoção de cor foi atingido com sucesso na análise visual, porém, a vazão de permeado mostrou-se muito baixa inviabilizando o processo. No PSM de Osmose Inversa em módulo espiral a cor foi removida com sucesso, a turbidez ficou abaixo de 1 NTU, a DQO ficou abaixo do limite de detecção do equipamento e a vazão de permeado foi satisfatória. Assim, o estudo aponta como resultado a aplicação CF combinado à OI no tratamento eficaz deste efluente. / The textile industry uses large volumes of water in their processes, especially in the dyeing step, which are also used large quantities of coloring agents and textile auxiliaries. The presence of these products in the effluent generates a harmful effect and clearly visible to the environment because they cause changes in the parameters of the receiving body of water. This paper presents the post-treatment effluent from a textile industry, in order to recycle it as process water for dyeing. A combination of physico-chemical process were carried out applying coagulation / floculation (CF) and Ultrafiltration (UF) membrane separation process (MSP) and reverse osmosis (RO). The parameters analyzed before and after treatments were: turbidity, electrical conductivity, chemical oxygen demand (COD), total organic carbon (TOC) and color. In CF stage two types of coagulants were tested, aluminum sulphate and ferric chloride at concentrations of 30, 50, 70 e 100 mg.L-1. Three concentrations of commercial floculants were evaluated: 0,2, 0,3 e 0,4 mg.L-1. The experiments were conducted at pH 7. MSP steps were conducted in plan Ultrafiltration module, and in the Reverse Osmosis membrane, plan and spiral modules were tested. The best performance was obtained with a dosage of 50 mg.L-1 of the coagulant ferric chloride and 0.3 mg.L-1 commercial flocculant, which showed a 98% reduction in turbidity in respect to the raw effluent. MSP Ultrafiltration color removal was not satisfactory because color was still present. In MSP Reverse Osmosis using the plan module the goal of color removal was successfully achieved in the visual analysis, however, the membrane flow was extremely low compared with the UF permeate flow and prevented the process. The color in MSP Reverse Osmosis spiral module has been successfully removed, the turbidity was below 1 NTU, the COD was below the detection limit of the the equipment and the permeate flow was satisfactory. In this way, the study showed the best application for this effluent is CF combined with RO.

Abstract The aim of this work was to formulate separation process models with both predictive capabilities and robust solution strategies. Although all separation process models should have predictive capabilities, the current literature still has multiple applications in which predictive models having the combination of a clear phenomenon base and robust solving strategy are not available. The separation process models investigated in this work were liquid-liquid phase separation and membrane separation models. The robust solving of a liquid-liquid phase separation model typically demands the solution of a phase stability analysis problem. In addition, predicting the liquid-liquid phase compositions reliably depends on robust phase stability analysis. A phase stability analysis problem has multiple feasible solutions, all of which have to be sought to ensure both the robust solving of the model and predictive process model. Finding all the solutions with a local solving method is difficult and generally inexact. Therefore, the modified bounded homotopy methods, a global solving method, were further developed to solve the problem robustly. Robust solving demanded the application of both variables and homotopy parameter bounding features and the usage of the trivial solution in the solving strategy. This was shown in multiple liquid-liquid equilibrium cases. In the context of membrane separation models, predictive capabilities are achieved with the application of a Maxwell-Stefan based model. With the Maxwell-Stefan approach, multicomponent separation can be predicted based on pure component permeation data alone. On the other hand, the solving of the model demands a robust solving strategy with application-dependent knowledge. These issues were illustrated in the separation of a H2/CO2 mixture with a high-silica MFI zeolite membrane at high pressure and low temperature. Similarly, the prediction of mixture adsorption based on pure component adsorption data alone was successfully demonstrated. In the context of membrane separation models, predictive capabilities are achieved with the application of a Maxwell-Stefan based model. With the Maxwell-Stefan approach, multicomponent separation can be predicted based on pure component permeation data alone. On the other hand, the solving of the model demands a robust solving strategy with application-dependent knowledge. These issues were illustrated in the separation of a H2/CO2 mixture with a high-silica MFI zeolite membrane at high pressure and low temperature. Similarly, the prediction of mixture adsorption based on pure component adsorption data alone was successfully demonstrated. / Tiivistelmä Työn tavoitteena oli muotoilla prosessin käyttäytymisen ennustamiseen kykeneviä erotusprosessimalleja ja niiden ratkaisuun käytettäviä luotettavia strategioita. Vaikka kaikkien erotusprosessimallien tulisi olla ennustavia, on tällä hetkellä useita kohteita, joissa prosessin käyttäytymistä ei voida ennustaa siten, että käytettävissä olisi sekä ilmiöpohjainen malli että ratkaisuun soveltuva luotettava strategia. Tässä työssä erotusprosessimalleista kohteina tarkasteltiin neste-neste-erotuksen ja membraanierotuksen kuvaukseen käytettäviä malleja. Neste-neste-erotusmallien luotettava ratkaisu vaatii yleensä faasistabiilisuusongelman ratkaisua. Lisäksi faasien koostumusten luotettava ennustaminen pohjautuu faasistabiilisuusanalyysiin. Faasistabiilisuusongelmalla on useita mahdollisia ratkaisuja, jotka kaikki tulee löytää, jotta voitaisiin varmistaa luotettava mallin ratkaisu sekä prosessimallin ennustuskyvyn säilyminen. Kaikkien ratkaisujen löytäminen on sekä vaikeaa että epätarkkaa paikallisesti konvergoituvilla ratkaisumenetelmillä. Tämän vuoksi globaaleihin ratkaisumenetelmiin kuuluvia modifioituja rajoitettuja homotopiamenetelmiä kehitettiin edelleen, jotta faasistabiilisuusongelma saataisiin ratkaistua luotettavasti. Ratkaisun luotettavuus vaati sekä muuttujien että homotopiaparametrin rajoittamista ja ongelman triviaalin ratkaisun käyttöä ratkaisustrategiassa. Tämä käyttäytyminen todennettiin useissa neste-nestetasa-painoa kuvaavissa esimerkeissä. Membraanierotusta tarkasteltaessa ennustava malli voidaan muotoilla käyttämällä Maxwell-Stefan pohjaista mallia. Maxwell-Stefan lähestymistavalla voidaan ennustaa monikomponenttiseosten erotusta perustuen puhtaiden komponenttien membraanin läpäisystä saatuun mittausaineistoon. Toisaalta mallin ratkaisu vaatii luotettavan ratkaisustrategian, jossa hyötykäytetään kohteesta riippuvaa tietoa. Näitä kysymyksiä havainnollistettiin H2/CO2 seoksen erotuksessa MFI-zeoliitti-membraanilla korkeassa paineessa. Samoin seosten adsorboitumiskäyttäytymistä ennustettiin onnistuneesti pelkästään puhtaiden komponenttien adsorptiodatan pohjalta. Kokonaisuutena voidaan todeta, että tarkasteltujen erotusprosessimallien ennustavuutta voidaan parantaa yhdistämällä malli, jolla on selkeä ilmiöpohja ja luotettava ratkaisustrategia. Lisäksi mallien käytettävyys erotusprosessien suunnittelussa on parantunut työn tulosten pohjalta.

A busca por tecnologias cada vez mais eficazes no tratamento de águas e efluentes fez com que o desenvolvimento de membranas desempenhasse um papel importante nos processos de separação. A nanofiltração apresenta-se como uma tecnologia promissora para remoção de sais multivalentes em soluções aquosas. O preparo de membranas poliméricas pela técnica de inversão de fases permite a obtenção de estruturas distintas. Neste estudo avaliou-se o uso de diferentes não-solventes no preparo de membranas de poli(fluoreto de vinilideno) pelo método de inversão de fases, quanto às características estruturais e propriedades funcionais. Foram utilizados como não-solventes: água destilada, solução de dodecil sulfato de sódio e etanol/água, resultando nas membranas denominadas MT1, MT2 e MT3, respectivamente. O uso de um surfactante aniônico, como o dodecil sulfato de sódio, no preparo de membranas de poli(fluoreto de vinilideno) apresenta-se como uma inovação tecnológica. O uso de diferentes não-solventes alterou a taxa de precipitação do polímero, o que ocasionou alterações na estrutura química, morfológica, cristalina e nas propriedades de transporte das membranas. Análises de microscopia eletrônica de varredura e porosimetria de deslocamento líquido-líquido mostraram a obtenção de estruturas assimétricas, com poros na ordem de 1-2 nm para as membranas MT1 e MT2, e estrutura simétrica, com alta porosidade, para a membrana MT3. A análise de espectroscopia de infravermelho com transformada de Fourier mostrou a presença das fases cristalina α e β nas três membranas e no polímero. Análise termogravimétrica realizada em atmosfera inerte apresentou massa residual em torno de 20-30 % referente ao material carbonáceo, o qual foi eliminado com a utilização de atmosfera oxidante na análise. Os valores de cristalinidade aparente, do polímero e das membranas, apresentaram grandes variações quando determinados pela técnica de calorimetria exploratória diferencial, porém quando determinados a partir dos difratogramas obtidos pela técnica de difração de raios X, a variação foi pequena, apresentando valores em torno de 47%. A avaliação da composição química da superfície das membranas, por espectroscopia de fotoelétrons induzidos por raio X, mostrou que houve variação na quantidade de ligações C-F quando diferentes não-solventes foram utilizados. Essas variações contribuíram para alterações na hidrofobicidade das membranas. As membranas MT1 e MT2 apresentaram características hidrofílicas, com ângulo de contato em torno de 70°, e a membrana MT3 apresentou característica hidrofóbica, com ângulo de contato em torno de 142°. A maior hidrofobicidade da membrana MT3 é resultante da rugosidade superficial e da maior composição relativa de ligações C-F na superfície desta membrana. Ensaios de permeação realizados até a pressão de 20 bar mostraram que a membrana MT2 sofreu maior efeito de compactação e apresentou menor fluxo de permeado. Os ensaios realizados com soluções de cloreto de sódio, de cálcio e férrico mostraram diferentes eficiências de retenção. Para as membranas MT1 e MT2 a retenção de sais mono e divalentes foi praticamente igual, em torno de 5%. Para a solução de cloreto férrico, a retenção apresentou valores médios em torno de 16% e 27% para as membranas MT1 e MT2, respectivamente. Em função do tamanho de poros apresentados e da pressão transmembrana aplicada nos ensaios de permeação, as membranas MT1 e MT2 podem ser utilizadas em processos de nanofiltração. / The search for increasingly efficient technologies in water and effluent treatment made the development of membranes take on an important role in separation processes. The nanofiltration is presented as a promising technology for removal of multivalent salt in aqueous solution. The polymeric membranes preparation by phase inversion technique allows the obtaining of different structures. This study evaluated the use of different nonsolvents in the poly(vinylidene fluoride) membrane preparation, by phase inversion method, on the structural characteristics and functional properties. Were used as nonsolvents: distilled water, solution of sodium dodecyl sulfate and ethanol/water, resulting in the membranes called MT1, MT2 and MT3, respectively. Use of an anionic surfactant, like as sodium dodecyl sulfate, in the preparation of poly(vinylidene fluoride) membranes is presented as a technological innovation. The use of different non-solvents changed the rate of polymer precipitation which caused changes in chemical, morphology and crystalline structures, and transport properties of the membranes. Scanning electron microscopy and liquid-liquid displacement porosimetry analysis showed asymmetric structures, with pores on the order of 1-2 nm for the MT1 and MT2 membrane, and symmetrical structure, with a high porosity for MT3 membrane. The analysis by Fourier transform infrared spectroscopy showed the presence of α and β crystalline phases in the three membranes and in the polymer. Thermogravimetric analysis carried out in an inert atmosphere showed residual mass around 20-30% from the carbonaceous material, which was eliminated with the use of an oxidizing atmosphere in the analysis. The values of apparent crystallinity of the polymer and the membranes showed large variations, by differential scanning calorimetry technique, but when determined from the diffractograms obtained by X-ray diffraction technique, the variation was small, showed values around 47%. The evaluates of the membranes chemical surface composition by X-ray photoelectron spectroscopy showed that there was variation in the amount of C-F bonds, where different non-solvents were used. These variations contributed to changes in membranes hydrophobicity. The MT1 and MT2 membranes showed hydrophilic characteristics with contact angle around 70°, and the MT3 membrane showed hydrophobicity characteristics with contact angle around 142°. The highest hydrofobicity of the MT3 membrane is result of the surface roughness and the relative composition of CF bonds on this membrane surface. Permeation tests performed until a pressure of 20 bar, it was found that the MT2 membrane has a greater effect compression and showed a lower permeate flux. Tests conducted with solutions of sodium, calcium and ferric chloride showed different retention efficiencies. For MT1 and MT2 membranes the retention of mono and divalent salts was practically equal, around 5%. For the solution of ferric chloride, the retention showed medium values around 16% and 27% for the MT1 and MT2 membranes, respectively. Due to the pore size presented and transmembrane pressure applied on permeation tests, the MT1 and MT2 membranes may be used in nanofiltration processes.

This diploma thesis deals with the wastewater treatment technologies by means of which high quality of the treated wastewater is attained, especially with regard to removing nutrients. The introduction of the thesis contains, among others, descriptions of the reserves in the Czech Republic where it is extremely important to insist on the highest quality of the discharged wastewaters. Then follows a summary of the quality requirements on the discharged wastewaters as stipulated in the legislation. Furthermore, I analyse the impact of the nutrients – nitrogen and phosphorus – on the environment and the principles of their removal from the wastewaters. In the next section I concentrate on the technological processes by means of which the required quality of the wastewater is achieved. The conclusion includes a list of technologies used as the tertiary wastewater treatments with emphasis on membrane technologies. The second part of my thesis is a study of a project of a wastewater treatment plant (WWTP) with membrane technology for the villages of Sloup and Šošůvka located within the protected landscape area of Moravian Karst.

Thesis aims to design suitable technology for biogas treatment so that its output can be used as a fully equivalent fuel for vehicles. First part introduces reader into an area of biogas treatment. Second part describes in detail chosen method, technology of membrain separation. In third part, current conditions in Czech republic were discussed. Fourth part adresses the aplication of membrane technology into existing biogas station via side-standing reaserch container. The end of the thesis is focused on selection and proper desing of blower, which will be transporting raw biogas from biogas fermenters into research container.

The thesis deals with the issue of removing carbon dioxide from biogas using membrane separation. Addresses the impact of the implementation of a small research facility at the existing operation of the biogas plant. Assessment of the impact on traffic is solved in terms of technical and economic.

Die vorliegende Arbeit beschäftigt sich mit dem Einsatz eines Membranverfahrens zur Extraktabtrennung unter Hochdruckbedingungen. Die in einem zu koppelnden Prozess extrahierten Naturstoffsubstanzen sollen dabei ohne große Energieverluste, wie sie bei der herkömmlichen Methode der Druckentspannung entstehen, in nahezu isobarer und isothermer Fahrweise aus dem verdichteten Lösungsmittel gewonnen werden. Für den Einsatz oxid-keramischer, integral-asymmetrisch aufgebauter Einkanal-Rohrmembranen wurden vor allem grundlegende Daten zum Transportverhalten hinsichtlich der beiden eingesetzten Gase CO2 und dem Frigen Tetrafluorethan ermittelt. Dies geschah für zwei Nanofiltrationsmembranen mit trennaktiven Schichten aus TiO2 und SiO2. Die Filtrationsleistung der Membranen wurde für drei beispielhafte Wertstoffe (Koffein, Aescin, Inulin), deren Extraktionsverhalten im Vorfeld untersucht wurde, u.a. anhand von Rückhalt und Deckschichtbildung bewertet.

No description available.

Studies were conducted to evaluate the impact of landfill leachate discharge on the operation of waste water treatment plants (WWTPs). Two aspects of interferences were found: one is UV quenching substances, which are bio-refractory and able to penetrate the biological treatment processes, consequently interfere the UV disinfection in WWTPs. The other one is organic nitrogen, which can pass the nitrification-denitrification process and contribute to the effluent total nitrogen (TN). Also, treatability study was conducted for landfill gas (LFG) condensate. In a laboratory study, leachate samples were fractionated into humic acids (HA), fulvic acids (FA) and Hydrophilic (Hpi) fractions, the specific UV254 absorbance (SUVA254) of the three fractions follows: HA > FA > Hpi. However, the overall UV254 absorbance of the Hpi fraction was important because there was more hydrophilic organic matter than humic or fulvic acids. It was found that the size distribution of the three fractions follows: HA > FA > Hpi. This indicates that membrane separation following biological treatment is a promising technology for the removal of humic substances from landfill leachates. Leachate samples treated in this manner could usually meet the UV transmittance requirement of the POTWs. Also, nitrogen species in landfill leachates under various stabilization states were investigated. Although the effect of landfill stabilization state on the characteristics of organic matter and ammonia is well documented, there are few investigations into the landfill leachate organic nitrogen under different stabilization stages. Ammonia was found to leach out slower than organic matter and can maintain a constant level within the first a couple of years (< 10 years). The concentration and biodegradability of organic nitrogen were found to decrease with landfill age. A size distribution study showed that most of organic nitrogen in landfill leachates is < 1 kDa. The protein concentration was analyzed and showed a strong correlation with the organic nitrogen. Different slopes of regression curves of untreated and treated leachates indicate that protein is more biodegradable than the other organic nitrogen species in landfill leachates. XAD-8 resin was employed to isolate the hydrophilic fraction of leachate samples, hydrophilic organic nitrogen was found to be more biodegradable/bioavailable than the hydrophobic fractions. Furthermore, biological and physical-chemical treatment methods were applied to a landfill biogas (LFG) condensate to explore the feasible treatment alternatives for organic contaminant and arsenic removal efficiency. Sequencing batch reactor (SBR) showed effectiveness for the degradation of organic matter, even in an environment containing high levels of arsenic. This indicated a relatively low toxicity of organic arsenic as compared to inorganic arsenic. However, for arsenic removal, oxidation-coagulation, including biological oxidation, conventional oxidation and advanced oxidation followed by ferric salt coagulation, and carbon adsorption were not effective for what is believed to be tri-methyl arsenic. Among these, advanced oxidation-coagulation showed the best treatment efficiency (15.1% removal). Only reverse osmosis (RO) could reduce the arsenic concentration to an acceptable level to meet discharge limits. These results implied high stability and low toxicity of organic arsenic. / Ph. D.

A produção de petróleo no pré-sal pode ser associada a contaminantes como o CO2. As plataformas instaladas neste polo possuem o sistema de remoção de CO2 usando permeação em membrana polimérica, que separa a corrente de gás em uma pobre em CO2 e outra rica neste. Este trabalho propõe um modelo para simulação da separação de gases utilizando permeador de gases do tipo espiral em contra-corrente. Este modelo utiliza equações baseadas em fenômenos de transporte e termodinâmica, tais como: comportamento real dos gases, variação da permeância com temperatura, transferência de calor dentro do equipamento e efeito Joule-Thomson. A validação foi feita utilizando dados da literatura para separações isotérmicas e dados obtidos em permeador instalado em plataforma de petróleo. Utilizou-se metodologia de reconciliação de dados e agrupamento para tratamento dos dados industriais, o que permitiu maior eficiência na reconciliação dos parâmetros do modelo. A partir da modelagem proposta determinaram-se os parâmetros de processos mais relevantes, permitindo a simulação de condições operacionais diferentes das utilizadas na regressão e a verificação da influência da variação de cada uma das condições operacionais. / The production of oil in pre-salt field is associated with contaminants such as CO2. The rigs installed in this field have a CO2 removal system using permeation on polymer membrane, which separates the gas stream in a stream with low CO2 content and another one with high CO2 content. This paper proposes a model for simulation of gas separation using spiral type permeator of gases in countercurrent flow. This model uses equations based on transport and thermodynamic phenomena such as: real behavior of gases, permeance dependence with temperature, heat transfer inside the equipment and Joule-Thomson effect. The validation was performed using literature data for isothermal separations and data from permeator installed on the oil rig. Was used data reconciliation methodology and clusterization for treatment of industrial data, allowing more efficient reconciliation of the model parameters. From the proposed model were determined the most relevant process parameters, allowing the simulation of operating conditions different than those used in the regression and verification of the influence of the change of each of the operating conditions.