Este trabajo ha sido realizado en el contexto de los proyectos PPQ2000-0240 y BQU2002-03357, financiados por el Ministerio de Educación y Ciencia, así como las estancias breves de investigación realizadas en el Institut Européen des Membranes (Montpellier, Francia) bajo la supervisión de la Dra. Anne Julbe y en el Departamento de Ingeniería Química de la Universidad de Hiroshima (Japón) bajo la dirección del Prof. Masashi Asaeda.La pervaporación es la evaporación selectiva de un componente de una alimentación líquida al poner ésta en contacto con una membrana semi-permeable. Esta tesis propone la utilización de membranas cerámicas para mejorar la deshidratación de disolventes orgánicos mediante pervaporación. Con este propósito, este trabajo se divide en las etapas siguientes:1. Caracterización funcional de membranas cerámicas comerciales de PV, en ensayos de separación de una mezcla estándar agua/isopropanol. 2. Síntesis de membranas de sílice-zirconia, SiO2-ZrO2. Las membranas de SiO2-ZrO2 han sido preparadas mediante dos rutas del método sol-gel: (1) la ruta del gel polimérico y slip casting y (2) la ruta del sol coloidal y hot coating. Se ha caracterizado la morfología y estructura de estas membranas. La caracterización funcional en PV ha sido llevada a cabo en la separación de mezclas sintéticas de agua y disolvente orgánico.3. Desarrollo de aplicaciones industriales utilizando las membranas cerámicas, en especial, la valorización de una corriente cetónica residual procedente del proceso de fabricación de antioxidantes para el caucho, y la recuperación de tetrahidrofurano y acetona de efluentes industriales contaminados con agua. En el primer caso, se estudió el comportamiento de dos membranas des sílice comerciales y en el segundo caso, el funcionamiento de una membrana comercial de zeolita NaA. 4. Modelado matemático del flujo de agua a través de membranas cerámicas de PV, en función de la temperatura y de la actividad de agua en la alimentación.5. Validación de este modelado con los datos de PV obtenidos para las membranas comerciales y las membranas de desarrollo propio de SiO2-ZrO2, con precisión aceptable. / This work has been performed within the projects PPQ2000-0240 and BQU2002-03357, financed by the Spanish Ministry of Science and Education, as well as the short research stays performed at the Institut Européen des Membranes (Montpellier, France) under the supervision of Dr. Anne Julbe and at the Chemical Engineering Department of the Hiroshima University (Japan) under the direction of Prof. Masashi Asaeda. Pervaporation is the selective evaporation of one component of a liquid mixture by a membrane, which is in direct contact with the liquid phase. This work proposes the use of ceramic membranes to improve the pervaporative dehydration of organic solvents. With this purpose, the work has been developed into several stages:1. Functional characterisation of PV commercial ceramic membranes. 2. Synthesis of silica-zirconia, SiO2-ZrO2, membranes, as the literature points out to a higher stability of mixed oxide membranes at high water contents and temperatures. SiO2-ZrO2 membranes were prepared by two routes of the sol-gel method: (1) polymeric gel route and slip casting and (2) colloidal sol route and hot coating, The morphology and structure of these membranes were characterised by static procedures (FE-SEM, N2 adsorption-desorption, FTIR, XRD). The functional characterisation in PV of these membranes was performed.3. Development of PV ceramic membranes on industrial applications, mainly the valorisation of a residual ketonic stream coming from the production process of rubber antioxidants, and the recovery of THF and acetone from industrial effluents contaminated with water. In the case of the ketonic mixture, the performance of the commercial PV silica membranes was analysed at different working temperatures. 4. Mathematical modelling of water flux across PV ceramic membranes, as a function of the temperature and water activity in the feed.5. Validation of this model to the PV data obtained for the commercial silica membranes and also for the SiO2-ZrO2 non-commercial membranes, with acceptable accuracy. This work contributes to achieve a deeper insight on the structure-performance relationship of PV ceramic hydrophilic membranes, in order to improve their qualities towards implementation into actual industrial processes where these membranes can solve significant problems within economic and environmental contexts.

Submitted by Johnny Rodrigues (johnnyrodrigues@ufcg.edu.br) on 2018-10-17T20:04:39Z No. of bitstreams: 1 DIVANIRA FERREIRA MAIA - TESE PPGEP 2006..pdf: 9063307 bytes, checksum: 4a8a7f017dc5bdd4ff2e4624de86ba98 (MD5) / Made available in DSpace on 2018-10-17T20:04:39Z (GMT). No. of bitstreams: 1 DIVANIRA FERREIRA MAIA - TESE PPGEP 2006..pdf: 9063307 bytes, checksum: 4a8a7f017dc5bdd4ff2e4624de86ba98 (MD5) Previous issue date: 2006-04-20 / A presença de óleo na água produzida durante a extração de petróleo, causa sérios problemas tanto ao ser descartada no meio ambiente como ao ser reinjetada nos poços produtores de petróleo. Os métodos convencionais utilizados na separação óleo/água não conseguem limpar toda a água com eficiência e baixo custo. Assim sendo, a busca por novas alternativas para solucionar este problema foi a motivação principal deste trabalho, sendo este parte integrante de uma série de pesquisas, financiadas pela Agência Nacional de Petróleo (ANP), que visa otimizar todas as etapas de produção de petróleo. Assim o objetivo deste trabalho foi produzir membranas cerâmicas visando a sua aplicação na separação óleo/água. Inicialmente foram obtidos dois tipos de membranas tubulares de alumina, denominadas tipo 1 e tipo 2, com diferentes tamanhos de poros de aproximadamente 0,9\im e 15,5nm e com eficiências mínimas de aproximadamente 97,5% e 93,8%, respectivamente. Porém a membrana tipo 2 apresentou um fluxo 40 vezes maior que a membrana tipo 1. Assim, visando melhorar mais ainda o desempenho da membrana tipo 2 depositou-se sobre a mesma uma camada fina de zircônia, de forma que pudesse melhorar sua eficiência sem alterar significativamente seu fluxo. O pó de zircônia foi obtido com sucesso pelo método Pechini. Com este método foi possível a obtenção da zircônia cristalina cujos tamanhos de aglomerados indicaram que este material pode ser usado na obtenção de membranas de ultrafiltração. Para obtenção da camada de zircônia foi preparada uma suspensão com a zircônia obtida e esta foi depositada na parte interna da membrana de alumina tipo 2 usando a técnica de deposição "dip coating". A camada de zircônia formada apresentou uma espessura de 23,9 ^im, um fluxo superior a membrana de alumina tipo 1 e uma eficiência mínima de 97,8%. Para todas as membranas obtidas, a concentração de óleo no permeado foi abaixo de 7 ppm, usando concentração máxima de 1000 ppm na alimentação. A água permeada através das membranas estudadas se enquadraram nas especificações para uso na reinjeção e no descarte. / The presence of oil in water produced during the petrol extraction can cause serious problems during the discharge in the environment as well as in the re-injection in the oil well. The conventional methods used to remove oil from water can not clean with efficiency and low cost. So, the search for new alternatives to solve this problem is the motivation of this work. This study is part of a series of researches supported by Agência Nacional de Petróleo (ANP), with the aim to optimize ali the steps in the oil production. The aim of this work is to make ceramic membrane to be applied in the oil/water separation. Firstly, it was prepared two types of tubular alumina membranes, called type I and type 2, with different pore size of approximately 0.9nm and 15, 48nm, respectively. The minimal efficiency of these membranes was approximately 97.5% and 93.8% for membrane type I and type 2, respectively. However, the membrane type 2 shown a flux 40 times greater than the membrane type 1. To improve the use of the membrane type 2 it was coating the internai surface with a thin layer of zircônia to get better efficiency without to decrease the flux. The zircônia powder was prepared with success by Pechini method and it was obtained a crystalline zircônia with agglomerates that indicate the use to make ultrafiltration membranes. To obtain the zircônia layer it was prepared dispersion and deposited in the internai surface of the membrane type 2 by dip coating technique. The zircônia layer presented a thickness of 23.88}im, a flux grater than the alumina type 1 and a minimal efficiency of 97.8%. Ali studied membrane presented oil content in permeate below 7ppm, using a maximum concentration of lOOOppm in the feed tank. The permeate water through the studied membranes is in agreement with the norms to be discharge in the environment or to be re-injected in the oil well. / PRH 25.

Esta tese descreve o projeto e manufatura de membranas cerâmicas para separação de emulsões óleo/água. A escolha correta do material para a fabricação de membranas é importante para processos cujo desempenho depende da afinidade entre o meio poroso e o fluido. As condições de manufatura são também importantes, pois determinam a morfologia da membrana, que influencia fortemente as propriedades de transporte e conseqüentemente, a eficiência da membrana. Tendo isso em vista, este trabalho teve como objetivo desenvolver membranas cerâmicas tubulares (porosas e densas) por prensagem isostática, aplicáveis em processos de microfiltração para a separação de emulsões óleo-água. Para tanto, foi realizado um controle rigoroso do tamanho e distribuição dos poros através do uso da sacarose como agente porogênico. Suspensões de alumina e zircônia com sacarose de diferentes dimensões foram preparadas. Após esse processo a barbotina foi seca e granulada para obtenção do pó usado na conformação das membranas porosas ou como suporte das membranas densas. Para a manufatura das membranas densas, uma fina camada da suspensão foi depositada no núcleo do molde que foi preenchido com o pó (de alumina ou zircônia) e então submetido à co-prensagem (isostática) para obter simultaneamente o suporte e o filme de zircônia. Posteriormente, as membranas (porosas e densas) sofreram um tratamento térmico (para queima parcial da sacarose) e foram sinterizadas (a 1500°C). As membranas foram caracterizadas por MEV, porosimetria por intrusão de mercúrio, medidas de peso por imersão (para obtenção da porosidade e densidade aparente), ensaios de permeabilidade ao ar e à água. A caracterização morfológica das membranas constatou a formação de membranas porosas de alumina e de zircônia e de membranas densas: uma integral (\'ZR\'\'O IND.2\'/\'ZR\'\'O IND.2\') e outra composta (\'ZR\'\'O IND.2\'/\'AL IND.2\'\'O IND.3\'). A análise de porosimetria por intrusão de mercúrio apresentou tamanho médio de poros de 1,8 \'mü\'m para as membranas porosas e de 0,01-0,03 \'mü\'m e 1,8 \'mü\'m para as membranas densas, respectivamente para camada seletiva e suporte. Todas as membranas obtiveram porosidade total de aproximadamente 50%, que é considerada uma porosidade satisfatória. Os ensaios de permeabilidade ao ar demonstraram que as membranas de zircônia obtiveram maior permeabilidade do que as membranas de alumina. Já os ensaios de permeação de água, na condição de fluxo tangencial, mostraram que as membranas porosas apresentaram maior fluxo transmembrana do que as membranas densas, na mesma velocidade de escoamento. As membranas densas e porosas foram testadas na separação óleo-água e a maioria apresentou bom desempenho no processo de microfiltração e alta rejeição da fase óleo (entre 98 e 99%). Dentre essas membranas, a membrana densa composta (sinterizada a 1400°C) foi a que obteve melhor desempenho, pois apresentou fluxo permeado de aproximadamente 230 L/h.\'M POT.2\' e coeficiente de rejeição médio de 99,77%, os quais são valores desejáveis para a aplicação de membranas em processos industriais. / This thesis describes the project and manufacture of ceramic membranes for separation of oil/water emulsions. The selection of raw material for the manufacture of membranes is fundamental in processes whose performance depends on the affinity between the porous medium and the fluid. The manufacturing conditions are also important as they determine the membrane\'s morphology. Such morphology strongly influences the transport properties hence the membrane\'s performance. In this context, this work aims to develop tubular ceramic membranes (porous and asymmetric) by isostatic pressing which will be applicable to microfiltration processes for the oil-water emulsions separation. For such a purpose, a rigorous control was realized on the distribution and size of pores by use of the sucrose as porogenic agent. Suspensions of zirconia and alumina with sucrose of different dimensions were prepared. After that process, the slurry was dried and granulated to obtain the dust used in the manufacture of the membranes. For the manufacture of the supported zirconia membranes, a thin layer of suspension was deposited onto the nucleus of the mould, which was filled with the dust (of alumina or zirconia) and then, it was subjected to co-pressing (isostatic) to obtain the support and the zirconia top-layer, simultaneously. Next, the porous and supported membranes underwent a thermal treatment (for a partial burning of sucrose) and were sintered (until 1500°C). They were characterized by SEM, porosimetry by mercury intrusion, measurements of weight by immersion (for the determination of the apparent porosity and density) and water and air permeability tests. The morphologic characterization of membranes identified the formation of zirconia and alumina porous membranes, an asymmetric \'ZR\'\'O IND.2\' membrane (zirconia top-layer on the porous zirconia support) and a supported \'ZR\'\'O IND.2\'/\'AL IND.2\'\'O IND.3\' composite membrane. The results of porosimetry analysis by mercury intrusion presented a mean pore size of 1,8 \'mü\'m for the porous membranes and for the other membranes, 0,01-0,03 \'mü\'m and 1,8 \'mü\'m, respectively, for the top-layer and support. All membranes achieved a total porosity of about 50%, which is considered a satisfactory porosity. The air permeability tests showed that the zirconia membranes achieved higher permeability than the alumina membranes. Otherwise, the water permeation tests in cross-flow condition showed that the porous membranes (of alumina and zirconia) presented higher transmembrane flow than the asymmetric \'ZR\'\'O IND.2\' and supported \'ZR\'\'O IND.2\'/\'AL IND.2\'\'O IND.3\' composite membranes in the same flow average velocity. Such membranes were applied to oil-water emulsions separation and the most they presented good performance in the microfiltration process and high rejection of oil phase (between 98 and 99%). Among those membranes, the zirconia supported membrane (sintered until 1400°C) obtained the most performance because it showed transmembrana flow of about 230 L/h.\'M POT.2\' e rejection coefficient of 99,77%, which are appreciable values for the application of membranes in industrial processes.

<p>U radu je ispitivana mogucnost unapređenja membranske filtracije mleka primenom promotora turbulencije razlicitog geometrijskog oblika i dimenzije. Eksperimentalna istraživanja su izvedena na keramickoj membrani velicine 100 nm koja se najce&scaron;ce koristi u procesu mikrofiltracije mleka. Istraživanja su obuhvatila ispitivanje uticaja<br />promotora helikoidne geometrije (uvrnuta traka i Keniks mikser) i geometrije u obliku seciva (Koflo mikser) razlicitih karakteristicnih dimenzija na fluks permeata, prljanje i selektivnost membrane. Efikasnost primene razlicitih promotora analizirana<br />je kako sa aspekta povecanja fluksa tako i sa aspekta smanjenja potro&scaron;nje energije.<br />Istraživanje uticaja tipa promotora turbulencije na mikrofiltraciju proteina mleka<br />pokazalo je da se izborom geometrije, karakteristicne dimenzije i radnih uslova mogu<br />postici znacajna i energetski isplativa povecanja fluksa permeata.<br />Primenom uvrnute trake kao promotora Uticaj tipa promotora turbulencije na unapređenjemembranskefiltracije tubulencije ostvarena su povecanja fluksa i od 200<br />do 600% u zavisnosti od karakteristicne dimenzije uvrnute trake, i rad pri dva ili tri puta manjim protocima u odnosu na rad bez promotora. Najvece povecanje fluksa od oko 600% ostvareno je primenom najgu&scaron;ce uvrnute trake karakteristicne dimenzije 1,0 (UT1,0). UT1,0 kao promotor turbulencije uzrokuje najvece ubrzanje fluida tj. nivo turbulencije i najdužu helikoidnu putanju strujnica &scaron;to doprinosi intenzivnom odno&scaron;enju cestica sa povr&scaron;ine membrane. Ispitivanje primene Keniks miksera kao<br />promotora turbulencije je pokazalo da se znacajna i isplativa povecanja fluksa postižu vec pri veoma malim protocima. Keniks mikser je takođe helikoidne geometrije kao i uvrnute trake, ali se razlikuje po tome &scaron;to su helikoidni elementi<br />postavljeni pod uglom od 90o i levo desno jedan u odnosu na drugi. Ovakva orjentacija elemenata uzrokuje preraspodelu i promenu smera stujnica posle svakog elementa zbog cega je pad pritiska za Keniks mikser i do cetiri puta veci u odnosu na<br />uvrnutu traku iste karakteristicne dimenzije, ali uz veci utro&scaron;ak energije. Promotori geometrije u obliku seciva (Koflomikseri) takođe obezbeđuju povecanje fluksa od<br />200 do 650% pri nižem protoku u odnosu na rad bez promotora. Vece povecanje fluksa od 500 do 600% postignuta su primenom Koflo miksera manje karakteristicne dimenzije 1,3. Koflo mikseriobezbeđuju promenu slike strujanja u membrani koja se manifestuje takođe raspodelom toka fluida i pojavom helikoidnih strujnica, ali i sudaranjem i me&scaron;anjem struja usled udara o seciva pod određenim uglom. Po sudaranju struja se ovaj tip miksera razlikuje u odnosu na uvrnute trake i Keniks mikser. Ipak pad pritiska ovog miksera je veci u odnosu na pad pritiska uvrnute trake, a manji u odnosu na pad pritiska Keniks miksera. Ispitivanje smanjenja prljanja membrane pokazalo je da se primenom promotora smanjuje otpor prljanja membrane kao i otpori usled povratnog i nepovratnog prljanja. Naročito je zapaženo smanjenje otpora usled povratnog prljanja koje se javlja na povr&scaron;ini membrane. Na ovaj nacin potvrđeno je da svi tipovi miksera uzrokuju promenu nacina strujanja u membrani koja obezbeđuje pobolj&scaron;anje prenosa mase u graničnom sloju. U granicnom sloju najintenzivnije deluje Uticaj tipa promotora turbulencije na unapređenje membranske filtracije. Keniks mikser kod kog sem preraspodele stujanja dolazi i do promene smera strujnica nakon svakog elementa. Izvođenje procesa primenom promotora je energetski isplativije u odnosu na konvencionalan nacin rada i važi za sve ispitivane tipove promotora bez obzira na geometriju i karakterističnu dimenziju. Za vrednosti flukseva do 60 Lm-2h-1 uvrnute trake sve tri karakteristicne dimenzije zahtevaju istu potro&scaron;nju energije. Primena uvrnute trake UT1,0 je najisplativija za flukseve vece od 60 do 100 Lm-2h-1 iako uzrokuje veci pad pritiska u odnosu na UT1,5 i UT2,5, ali obezbeđuje i proporcionalno veci fluks pri protocima tri puta manjim u odnosu na rad bez promotora. Primenom UT1,0 moguće su u&scaron;tede energije u rasponu od 50 do 75 % u odnosu na rad bez promotora. Potro&scaron;nja energije kod primene Keniks miksera je veća u odnosu na uvrnutu traku iste karakterisitčne dimenzije, a opseg radnih protoka i TMP uslovljen velikim padom pritiska. U&scaron;tede energije u slučaju primene Keniks miksera su od 30 do 65% u odnosu na rad bez promotora. Međutim, primenom UT1,0 umesto Keniks miksera iste dimenzije obezbeđuju se od 10 do 35 % vece u&scaron;tede energije pri istom radnom fluksu. Sa aspekta potro&scaron;nje energije, Koflo mikseri su najmanje efikasni. KF1,3 mikser je manje efikasan u odnosu na KF2,5 zbog većeg pada pritiska i ne proporcionalno veceg fluksa. Primenom ovih promotora se postižu u&scaron;tede energije od 20 do 70% u odnosu na konvencionalan način rada, ali je ipak njihova efikasnost manja u odnosu na uvrnutu traku iste dimenzije zbog razlike u padu pritiska Pravilnim izborom geometrije promotora može postici povecanje fluksa uz nisku potro&scaron;nju energije odnosno niže padove pritiska. Slika strujanja koja zavisi od geometrije promotora najvi&scaron;e utice na povecanje fluksa pri čemu je najbitnije da se pored povećanja brzine obezbedi pojave strujnica helikoidnog oblika u graničnom sloju. Upravo ovakav nacin strujanja najvi&scaron;e doprinosi odno&scaron;enju cestica istaloženih na povr&scaron;ini membrane i povecanju prenosa mase. Pojave radijalnog me&scaron;anja ili sudaranja struja mogu se smatrati sporednim pojavama u odnosu na to koliko doprinose povecanju fluksa međutim, njihovo postojanje doprinosi povećanju pada pritiska i smanjuju energetsku efikasnost promotora. Uticaj tipa promotora turbulencije na unapređenje membranske filtracije. Rezultati istraživanja su potvrdili polaznu pretpostavku, definisanu ciljem istraživanja, da helikoidna putanja strujanja kod uvrnutih traka obezbeđuje najintenzivnije odno&scaron;enje istaloženog materijala sa povr&scaron;ine membrane uz najmanji pad pritiska odnosno gubitak energije. Sa druge strane, pojava me&scaron;anja koje je primarno kod Keniks i Koflo miksera izaziva, pored odno&scaron;enja istaloženih čestica i dodatno vrtloženje koje za posledicu ima veći pad pritiska i manju energetsku efikasnost.</p> / <p> This work investigates influence of tubulence promotor geometry and its characteristic dimension on the improvement of membrane filtration of milk proteins. The investigation was performed using a ceramic tubular membrane with 100 nm pore size which is commonly used in the dairy industry. As turbulence promoters two main geometry types were chosen: a helical (twisted tape and Kenics mixer) and a blade shaped (Koflo mixer). Except the geometry type, influence of an aspect ratio was studied, also. Efficiency of turbulence promoters was evaluated from the point of view of flux improvement and specific energy consumption. The experimental results clearly show that microfiltration process can be improved by proper choice of a turbulence promoter geometry, its aspect ratio and operating conditions. The process efficiency is increased by achievement of a significant flux increase and lowered energy consumption. Application of twisted tapes as turbulence promoters yields in the flux improvement of 200 to 600% depending on the aspect ratio of twisted tape but at two or three times lower cross-flow rates compared to conventional MF. The higher flux improvement of 600% was achieved by using twisted tape with aspect ratio 1.0, which induces the highest turbulence and the longest helical stream path so the scouring of particles from the membrane surface is the most intensive.<br /> By applying Kenics mixer as turbulence promoter significant flux improvement can be<br /> achieved at five fold lower cross-flow rates. Kenics mixer is also helical insert but its elements are right and left-hand orientated what causes the local resistances and much higher pressure drop compared to the twisted tape of the same aspect ratio. This resulted in higher energy consumption and in lower efficiency of the process fitted with Kenics mixer. Application of blade type insert, such is Koflo mixer, enables flux improvement of 200 to 650% and operation at lower cross-flow rates compared to conventional MF. The higher flux improvement, 500 to 600%, was yielded using the<br /> mixer of lower aspect ratio, 1.3. Blade mixers divide and redistribute streamlines after each element and also induce helical flow path near the membrane surface. Flow field defers from the flow field of twisted tape and Kenics mixer by the appearance of stream collision in the center of blade structure. This causes grater pressure gradient than for the twisted tape but lower than for the Kenics mixer. Investigation of membrane fouling confirmed that the membrane fitted with promoter is less fouled compared to the plane membrane. The reversible fouling resistance is reduced for<br /> order of magnitude especially for the case of Kenics mixer application. All types of promoters improve the mass transfer in the boundary layer at membrane surface inducing the helical path streamlines which take away deposited material. Energy consumption analysis has shown that the energy consumption can be significantly<br /> reduced by proper promoter geometry and aspect ratio. Operation with promoters proved to be more efficient from energy consumption point of view compared to the conventional operation. Using twisted tape of 1.0 aspect ratio energy can be saved for 50 to 75%. Blade type mixers are the less efficient, but still more efficient than the<br /> conventional filtration. In general, when the twisted tapes were used as promoters generated helical streamline path enables the most intensive fouling reduction with lowest pressure drop i.e. energy consumption. On the other hand, when the Kenics<br /> and blade mixers were used, except helical streamline path the secondary flows and mixing are induced what along with fouling reduction causes the higher pressure loss making these promoters energetically less efficient.</p>

Die Entsalzung ist eine der wichtigsten Technologien, um den Frischwasserbedarf in vielen Regionen der Welt sicherzustellen. Bevölkerungswachstum, der Klimawandel und stetig steigender Konsum werden die Bedeutung von Entsalzungstechnologien weiterwachsen lassen. Die Möglichkeit des Einsatzes etablierter konventioneller Verfahren wird begrenzt durch die hohen ökologischen und ökonomischen Kosten dieser Verfahren. Unkonventionelle Entsalzungsverfahren wie die Membrandestillation (MD) bieten einige Vorteile, mit denen sie konventionelle Verfahren jenseits dieser Limitationen ergänzen können. Die MD ist ein thermisch angetriebener Prozess, in welchem eine hydrophobe Membran das warme, flüssige Feed räumlich von der kälteren Permeatseite trennt, während nur dampfförmige Moleküle durch die Membran permeieren können. Wie in allen membranbasierten Trennprozessen bestimmen die Charakteristika der verwendeten Membran die Leistungsfähigkeit (Massentransport, Rückhaltevermögen und Energieeffizienz) des Prozesses und das damit verbundene kommerzielle Interesse. Durch ihre intrinsisch hydrophoben Materialeigenschaften und ihren guten Massentransfercharakteristika ist die Verwendung von Polymermembranen in der MD aktuell Stand der Technik. Um die Einsatzmöglichkeiten von MD Verfahren auf aggressive Lösungen zu erweitern, werden thermisch, mechanisch und chemisch stabile Membranen benötigt. Obwohl keramische Membranen im Vergleich zu Polymermembranen eine höhere Stabilität aufweisen (wodurch die Behandlung von aggressiven Lösungen mit MD-Verfahren prinzipiell möglich wird) muss die Eignung von keramischen Membranen für MD-Verfahren wissenschaftlich belegt und ein Konzept zur Membranoptimierung entwickelt werden. Im Rahmen dieser Arbeit wurden verschiedene Typen modifizierter keramischer Membranen (z.B. Materialauswahl und Schichtaufbau) vollständig im Hinblick auf ihre spezifischen Membraneigenschaften (z.B. Porengröße, Wärmeleitfähigkeit und hydrophobe Eigenschaften) charakterisiert und anschließend unter Verwendung von salzhaltigen Lösungen in der Direktkontaktmembrandestillation (DCMD) und der Vakuummembrandestillation (VMD) getestet. Diese Daten wurden genutzt, um den Stofftransport von asymmetrischen keramischen Membranen unter Verwendung eines anerkannten VMD-Modells (basierend auf dem Dusty-Gas-Modell) zu berechnen und um die Leistungsfähigkeit (d.h. Stabilität, Stofftransport, Selektivität und Energieeffizienz) von modifizierten keramischen Membranen in der MD in Hinblick auf spezifische Membraneigenschaften und Verfahrensparameter zu bewerten. Anschließend wurde die Eignung von keramischen Membranen für MD-Prozesse evaluiert und Optimierungskonzepte für keramische Membranen vorgeschlagen. Damit wurde mit dieser Arbeit die Grundlage gelegt, die Kommerzialisierung von keramischen Membranen in der MD voranzutreiben. Keramische Membranen wurde mit verschiedenen Molekülen hinsichtlich ihrer Oberflächeneigenschaften modifiziert. Dadurch konnte ein nicht-fluorisiertes Molekül als potenzielle Alternative zu den üblicherweise verwendeten fluorierten Molekülen identifiziert wurde. Für alle modifizierten Membranen (unabhängig von dem Hydrophobierungsmittel) mit Porengrößen kleiner oder gleich 400 nm, wurde ein Flüssigkeitseindringdruck (LEP) über 2,5 bar gemessen, welcher jedoch eine starke Abhängigkeit von den Eigenschaften der Testlösung zeigt. Während symmetrisch aufgebaute keramische Membranen modifiziert mit einem fluorierten Hydrophobierungsmittel die Behandlung mit heißer, salzhaltiger Lösung über 96 Stunden standhielten, zeigten diese deutlich geringere Permeatflüsse in der VMD als asymmetrisch strukturierte keramische Membranen. Der Stofftransport von asymmetrischen keramischen Membranen war in der VMD höher ausgeprägt als in der DCMD. Der Stofftransport von asymmetrischen keramischen Membranen wird in der VMD vorwiegend von den Supporteigenschaften beeinflusst, während der Strofftransport in der DCMD erheblich von den Eigenschaften der trennaktiven Membranschicht (z. B. die Porengröße) bestimmt wird. Ein in der Literatur beschriebenes VMD-Modell in Bezug vorhandener Defizite durch Korrekturfaktoren erfolgreich erweitert und zur Berechnung des Strofftransportes für asymmetrische TiO2 Membranen angewandt. TiO2 und Al2O3 Membranen wurden in der VMD erfolgreich zur Behandlung hochkonzentrierter Salzlösungen (synthetische und reale Lösungen) verwendet. TiO2 Membranen zeigten höhere Permeateflüsse als Al2O3 Membranen in der DCMD und der VMD. Das begründet sich insbesondere bedingt durch die bessere Moderierung von Temperaturpolarisationseffekten aufgrund der geringen Wärmeleitfähigkeit von TiO2 Membranen. Beispielsweise wurden bei der Behandlung einer hochkonzentrierte NaCl-Lösung (350 g NaCl pro kg H2O) mit einer TiO2 Membran (Finale Porengröße: 100 nm) in der VMD hervorragende Salzrückhalte von über 99,9 % und Permeatflüsse von bis zu 35 kg/( m² h) erreicht. Die Stofftransportraten der modifizierten keramischen Membranen in der VMD sind im Vergleich zu den Permeatflüssen von Polymermembranen (Literaturwerte) unter ähnlichen Testbedingungen wettbewerbsfähig. Es wurde gezeigt, dass die geringe Energieeffizienz von keramischen Membranen weiterhin die größte Herausforderung für deren kommerzielle Nutzung in MD-Prozessen darstellt und diese der Fokus der Membranoptimierung darstellen sollte.

M. Tech. (Department of Mechanical Engineering, Faculty of Engineering and Technology), Vaal University of Technology. / The developed oil-water separation membranes used in membrane technology are currently inefficient due to their poor morphological and topographical properties during nanoparticle coating. Researchers have developed different wettable membrane surfaces using jet spray coating. Most of these developed membranes are inadequate due to poor morphological and topographical properties normally observed as clusters, creating a rougher membrane surface that hinders wettability. This has resulted in the existing membrane fouling and degradation during the oil/water separation process and again due to different responses to corrosion and rusting. In the current study, membrane clusters were minimised on the ceramic membranes to create a smoother surface, improving membrane wettability. These clusters were minmised at optimal coating force, optimal coating distance and optimal coating angle. Part one of the study was to model and simulate different parameters that decreased clusters using the jet-spray coating. A theoretical model was derived from the first principles and all the external and internal forces that impact membrane clusters were considered during the model derivation. These forces are the force due to applied pressure from the spray gun, the force of nano-particles, the force of viscosity, the upward force on solid wall due to nanoparticles, the downward force on solid wall due to nanoparticles and the reaction force on the solid wall due to nanoparticles. The tools of stochastic theory and the concept of fluid dynamics were used in the modelling process. The total coating force from the jet spray gun nozzle was increased from 0,2x107 kN to 2,4x107 kN, which gave optimal coating force. The coating distance from the jet spray gun nozzle to the membrane surface was increased from 10 mm to 24 mm, which gave optimal coating distance. The jet spray angle in the spray region was also increased from 1⁰ to 9⁰ with reference from the vertical axis to the membrane surface, which gave optimal coating angle. This lead to optimal spread of nanoparticles on the membrane surface thus resulting to optimal cluster minimisation during the coating process. This decreased cluster sizes during nanoparticle coating, resulting in a smooth membrane surface, thus leading to lowered surface energy on the membrane. Part two of the study was to fabricate the ceramic membrane with fewer clusters on the surface for improved wettability using the jet-spray coating. It was important to produce the ceramic membrane surfaces with minimised membrane clusters by considering the optimal parameters revealed to minimise these membrane clusters during coating. Nanoparticle coating was performed under a controlled laboratory environment, and the optimal parameters that were studied to minimise membrane clusters were revealed. These parameters are coating force, coating distance and coating angle. More coating rounds were applied on ceramic samples and clusters were minimised during these coating rounds. The coated samples were analyzed by a scanning electron microscope and the nanoparticles on the membrane surfaces were characterised for optimal performance during oil-water separation. The scattering, orientation, morphology, spatial distribution, surface roughness, surface smoothness, contact angles, surface density of the particles, pore size network, mean size of the coated nanoparticle on the membrane surface after different coating rounds were characterised and analysed to minimise membrane cluster during nanoparticle coating. It was shown that more clusters were observed in 1st LP, 2nd LP, 3rd LP and 4th LP coating rounds when compared to 1st HP, 2nd HP, 3rd HP and 4th HP coating rounds. It was also shown that material surface roughness increased the formation of clusters in membrane surface as more clusters were observed in rough membrane surface when compared to the smooth membrane surface. The microstructure revealed a smoother membrane surface where membrane clusters were minimised. Part three of the study was to compare the newly designed ceramic membrane with the previously designed ceramic membrane from previous the literature. The correlation was done on the experimental results obtained in this study with the experimental results obtained from the previous literature. Different coating rounds were performed from the current study and the previous literature to design nanostructured ceramic membranes with fewer clusters on the surface. The results in the last coating round in this study, revealed a smooth membrane with a homogeneous substrate with fewer clusters and small sizes compared to other coating rounds.

Este trabalho trata do estudo da introdução de fibras poliméricas como agente porogênico na manufatura de membranas cerâmicas de alta resistência mecânica. Membranas cerâmicas são utilizadas para a separação de substâncias onde a estabilidade química e a resistência à alta temperatura são requeridas; na engenharia mecânica é também aplicada como mancais aerostáticos. A escolha do processo de manufatura destas membranas e o projeto da porosidade da estrutura cerâmica é de grande importância. Quando se utiliza da adição de elementos porogênicos, que são substâncias que se decompõem durante a queima deixando poros (abertos e fechados), altera não somente a porosidade como também a seletividade e permeabilidade da membrana, bem como diminui suas propriedades mecânicas. Este trabalho objetiva membranas com poros micrométricos e submicrométricos para aplicações em microfiltração ou em mancais aerostáticos, porém que tenham a maximização da sua resistência mecânica. Para isso foi idealizada a obtenção de membranas permeáveis com a menor porosidade possível. Então, propôs-se a adição de fibras poliméricas (fibras de polipropileno, fibras de carbono e fibras de álcool polivinílico) como agentes porogênicos em uma massa cerâmica de alumina que após granulada foi prensada na forma de pastilhas e sinterizadas. As membranas foram caracterizadas por ensaios de permeabilidade ao ar, resistência mecânica por flexão a 3 pontos, volume de poros pelo Princípio de Arquimedes e morfologicamente por MEV. A caracterização morfológica das membranas e os resultados de porosidade indicaram que a percolação foi melhorada pela adição de fibras em relação a trabalhos equivalentes que se utilizaram de particulados. As melhores condições de permeação, integridade da matriz e resistência mecânica foram encontradas para as membranas com 1 vol. % de fibras de álcool polivinílico, seguida das membranas com 2 vol. % de fibras de carbono. Com base nos resultados obtidos, foi comprovado que a morfologia alongada das fibras aumenta a probabilidade de contato entre os poros, pois com apenas 2 vol. % de fibras de PVAl, obteve-se uma porosidade total de 33,3%, porosidade aparente de 17,4% e permeabilidade específica de 6,32x10-12 m², apresentando resistência à flexão de 134,3 MPa, valor este o dobro de quando utilizado 50 vol. % de sacarose como agente precursor com equivalente permeabilidade. As propriedades físicas do agente porogênico como: expansão térmica, dimensões, relação comprimento versus diâmetro afetam enormemente a porosidade, percolação dos poros e integridade da matriz. / This work deals with the study of the introduction of polymeric fibers as porogenic agent in the manufacture of ceramic membranes with high mechanical strength. Ceramic membranes are used for separation of substances where chemical stability and high temperature resistance are required, in mechanical engineering is also applied as an aerostatic bearings. The choice of these membranes manufacturing process and design the porosity of the ceramic structure is of great importance. When using addition of porogenic components, which are substances that decompose during the burning leaving pores (open and closed), not only alters the porosity and also the permeability and the selectivity of the membrane, as well as decreases their mechanical properties. This work aims membranes with micrometric pores and submicrometrics for microfiltration applications or aerostatic bearings, however they having the maximization their mechanic strength. To this was designed to obtain porous membranes with the lowest porosity possible. Then proposed the addition of polymeric fibers (polypropylene fiber, carbon fiber and polyvinyl alcohol fiber) as porogenic agents on a ceramic alumina mass that was granular and pressed the form of discs and sintered. The membranes were characterized by testing the air permeability, mechanical strength by three points flexural, pore volume by Archimedes principle and morphologically by SEM. Morphological characterization of membrane and the results of porosity indicated that the percolation has been improved by adding fibers in relation to the corresponding work where particulates were used. The best conditions of permeation, matrix integrity and mechanical strength were found for the membranes with 2 vol. % of polyvinyl alcohol fibers and membranes with 2 vol. % carbon fibers. Based on these results, it was proven that the elongated morphology of the fibers increases the probability of contact between the pores, because with only 2 vol. % of PVAl fibers, we obtained a total porosity of 33.3%, apparent porosity of 17.4% and the specific permeability of 6.32x10-12 m², flexural strength of 134.3 MPa, this value is twice than when it is used 50 vol. % sucrose as a precursor agent with equivalent permeability. The physical properties of porogenic agent such as thermal expansion, dimensions and relation length versus diameter affect greatly the porosity, pore percolation and integrity of the matrix.

Este trabalho trata do estudo da introdução de fibras poliméricas como agente porogênico na manufatura de membranas cerâmicas de alta resistência mecânica. Membranas cerâmicas são utilizadas para a separação de substâncias onde a estabilidade química e a resistência à alta temperatura são requeridas; na engenharia mecânica é também aplicada como mancais aerostáticos. A escolha do processo de manufatura destas membranas e o projeto da porosidade da estrutura cerâmica é de grande importância. Quando se utiliza da adição de elementos porogênicos, que são substâncias que se decompõem durante a queima deixando poros (abertos e fechados), altera não somente a porosidade como também a seletividade e permeabilidade da membrana, bem como diminui suas propriedades mecânicas. Este trabalho objetiva membranas com poros micrométricos e submicrométricos para aplicações em microfiltração ou em mancais aerostáticos, porém que tenham a maximização da sua resistência mecânica. Para isso foi idealizada a obtenção de membranas permeáveis com a menor porosidade possível. Então, propôs-se a adição de fibras poliméricas (fibras de polipropileno, fibras de carbono e fibras de álcool polivinílico) como agentes porogênicos em uma massa cerâmica de alumina que após granulada foi prensada na forma de pastilhas e sinterizadas. As membranas foram caracterizadas por ensaios de permeabilidade ao ar, resistência mecânica por flexão a 3 pontos, volume de poros pelo Princípio de Arquimedes e morfologicamente por MEV. A caracterização morfológica das membranas e os resultados de porosidade indicaram que a percolação foi melhorada pela adição de fibras em relação a trabalhos equivalentes que se utilizaram de particulados. As melhores condições de permeação, integridade da matriz e resistência mecânica foram encontradas para as membranas com 1 vol. % de fibras de álcool polivinílico, seguida das membranas com 2 vol. % de fibras de carbono. Com base nos resultados obtidos, foi comprovado que a morfologia alongada das fibras aumenta a probabilidade de contato entre os poros, pois com apenas 2 vol. % de fibras de PVAl, obteve-se uma porosidade total de 33,3%, porosidade aparente de 17,4% e permeabilidade específica de 6,32x10-12 m², apresentando resistência à flexão de 134,3 MPa, valor este o dobro de quando utilizado 50 vol. % de sacarose como agente precursor com equivalente permeabilidade. As propriedades físicas do agente porogênico como: expansão térmica, dimensões, relação comprimento versus diâmetro afetam enormemente a porosidade, percolação dos poros e integridade da matriz. / This work deals with the study of the introduction of polymeric fibers as porogenic agent in the manufacture of ceramic membranes with high mechanical strength. Ceramic membranes are used for separation of substances where chemical stability and high temperature resistance are required, in mechanical engineering is also applied as an aerostatic bearings. The choice of these membranes manufacturing process and design the porosity of the ceramic structure is of great importance. When using addition of porogenic components, which are substances that decompose during the burning leaving pores (open and closed), not only alters the porosity and also the permeability and the selectivity of the membrane, as well as decreases their mechanical properties. This work aims membranes with micrometric pores and submicrometrics for microfiltration applications or aerostatic bearings, however they having the maximization their mechanic strength. To this was designed to obtain porous membranes with the lowest porosity possible. Then proposed the addition of polymeric fibers (polypropylene fiber, carbon fiber and polyvinyl alcohol fiber) as porogenic agents on a ceramic alumina mass that was granular and pressed the form of discs and sintered. The membranes were characterized by testing the air permeability, mechanical strength by three points flexural, pore volume by Archimedes principle and morphologically by SEM. Morphological characterization of membrane and the results of porosity indicated that the percolation has been improved by adding fibers in relation to the corresponding work where particulates were used. The best conditions of permeation, matrix integrity and mechanical strength were found for the membranes with 2 vol. % of polyvinyl alcohol fibers and membranes with 2 vol. % carbon fibers. Based on these results, it was proven that the elongated morphology of the fibers increases the probability of contact between the pores, because with only 2 vol. % of PVAl fibers, we obtained a total porosity of 33.3%, apparent porosity of 17.4% and the specific permeability of 6.32x10-12 m², flexural strength of 134.3 MPa, this value is twice than when it is used 50 vol. % sucrose as a precursor agent with equivalent permeability. The physical properties of porogenic agent such as thermal expansion, dimensions and relation length versus diameter affect greatly the porosity, pore percolation and integrity of the matrix.

High temperature proton conducting perovskite oxides are very attractive materials for applications in electrochemical devices, such as solid oxide fuel cells (SOFCs) and hydrogen permeation membranes. A better understanding of the hydrogen oxidation mechanism over the metal/proton conductor interface, is critical for rational design to further enhance the performances of the applications. However, kinetic studies focused on the metal/proton system are limited, compared with the intensively studied metal/oxygen ion conductor system, e.g., Ni/YSZ (yttrium stabilized zirconia, Zr₁-ₓYₓO₂-δ). This work presents an elementary kinetic model developed to assess reaction pathway of hydrogen oxidation/reduction on metal/proton conductor interface. Individual rate expressions and overall hydrogen partial pressure dependencies of current density and polarization resistance were derived in different rate limiting cases. The model is testified by tailored experiments on Pt/BaZr₀.₁Ce₀.₇Y₀.₁Yb₀.₁O₃-δ (BZCYYb) interface using pattern electrodes. Comparison of electrochemical testing and the theoretical predictions indicates the dissociation of hydrogen is the rate-limiting step (RLS), instead of charge transfer, displaying behavior different from metal/oxygen ion conductor interfaces. The kinetic model presented in this thesis is validated by high quantitative agreement with experiments under various conditions. The discovery not only contributes to the fundamental understanding of the hydrogen oxidation kinetics over metal/proton conductors, but provides insights for rational design of hydrogen oxidation catalysts in a variety of electrochemical systems.

Submitted by Johnny Rodrigues (johnnyrodrigues@ufcg.edu.br) on 2018-04-30T17:51:31Z No. of bitstreams: 1 TELLYS LINS DE ALMEIDA BARBOSA - DISSERTAÇÃO PPGEQ 2014..pdf: 2340446 bytes, checksum: 3a2ea16e16c4359a82b431379410d16c (MD5) / Made available in DSpace on 2018-04-30T17:51:31Z (GMT). No. of bitstreams: 1 TELLYS LINS DE ALMEIDA BARBOSA - DISSERTAÇÃO PPGEQ 2014..pdf: 2340446 bytes, checksum: 3a2ea16e16c4359a82b431379410d16c (MD5) Previous issue date: 2014-09-26 / O presente trabalho visa estudar o desempenho e validação de um sistema com automação para processos de separação de águas oleosas com membranas cerâmicas. O trabalho foi dividido em duas partes: testes em escala de bancada e no sistema com automação. Nos ensaios em escala de bancada foram realizados experimentos de caracterização da membrana cerâmica com água deionizada e com efluente sintético, com intuito de estimar o comportamento das membranas para auxiliar no desenvolvimento do sistema com automação. Para avaliar o desempenho dos sistemas de separação água/óleo com membranas cerâmicas os seguintes parâmetros foram analisados: fluxo do permeado (J, em L/h.m2) e taxa de rejeição de óleo. Nos experimentos no sistema com automação foi avaliado o desempenho no processo de separação água/óleo com membranas cerâmicas, o efluente sintético utilizado obedeceu às mesmas condições do sistema de bancada. Os experimentos com efluente sintético foram simulados com concentração de óleo fixada em 20 mg/L. Observou-se que a redução do fluxo de permeado com o tempo de operação é fortemente dependente da pressão e do teor de óleo emulsionado, podendo ser relacionada aos fenômenos de polarização por concentração, inerentes aos PSM. Contudo, a redução do fluxo no permeado foi atenuada no sistema com automação que possui processos de limpeza backpulse e backwash. Quanto à taxa de rejeição da fase dispersa, para todas as condições analisadas, apresentou-se maior que 97%. A utilização do backwash tendo como agente de limpeza uma solução de hidróxido de sódio não foi eficaz na recuperação do fluxo do permeado, porém o comportamento do processo de limpeza foi extremamente satisfatório o que indica com a mudança do agente de limpeza no processo terá uma melhor recuperação do fluxo do permeado. A partir dos experimentos realizados no sistema com automação os resultados obtidos demostram potencial para separação com membranas cerâmica, para o tratamento de águas oleosas. / This work aims to study the performance and validation of system with automation to oily water separation processes with ceramic membranes. It was divided into two phases: laboratory-scale tests and tests with the system with automation. In the laboratory-scale tests, experiments to characterize the ceramic membrane were carried out with deionized water and synthetic effluent, aiming to estimate the behavior of membranes to assist the developing of the system with automation. To evaluate the performance of the water-oil separation systems with ceramic membranes the following parameters were analyzed: permeate flow (J, L/h.m2) and oil rejection rate. In the experiments with the automatic system the performance was evaluated in oil-water separating process with ceramic membrane, the synthetic effluent used followed the same conditions as the benchtop system. The experiments with synthetic effluent were simulated with oil concentration set at 20 mg/L. It was observed that the reduction of the permeate flux with the operation time is strongly dependent of the pressure and emulsified oil content, may be related to concentration polarization, inherent to membrane separation processes. However, the reduction of permeate flow was attenuated in the system with automation where backpulse and blackwash cleaning processes were used. The dispersed phase rejection rate, for all conditions analyzed, was greater than 97%. The backwash cleaning system having sodium hydroxide as cleaning agent was not effective to increase the permeate flow, but the cleaning agent performance was extremely satisfactory which indicates that the change of the cleaning agent in the process will increase the flow in the permeate stream. From the experiments carried out with the system with automation results demonstrate the potential for separation with ceramic membranes, for oily water treatment.