No presente trabalho foram avaliados processos alternativos de dessalinização visando a recuperação e reuso da água contida em salmouras concentradas, sendo o processo de cristalização assistida por destilação por membranas (MDC) investigado com profundidade. Foi desenvolvido um modelo diferencial para o processo de destilação por membranas por contato direto (DCMD), contemplando métodos termodinâmicos rigorosos para sistemas aquosos de eletrólitos fortes, bem como mecanismos de transferência de calor e massa e efeitos de polarização de temperatura e concentração característicos deste processo de separação. Com base em simulações realizadas a partir do modelo matemático assim desenvolvido, foram investigados os principais parâmetros que influenciam o projeto de um módulo de membranas para DCMD. O modelo foi posteriormente estendido com equações de balanço de massa e energia adicionais para incluir a operação de cristalização e desta forma representar o processo de MDC. De posse dos resultados das simulações e do modelo estendido, foi desenvolvido um método hierárquico para o projeto de processos de MDC, com o objetivo de conferir características de rastreabilidade e repetibilidade a esta atividade. Ainda a partir do modelo MDC foram discutidos aspectos importantes em MDC como a possibilidade de nucleação e crescimento de cristais sobre a superfície das membranas, bem como o comportamento do processo com sais com diferentes características de solubilidade e largura da zona metaestável. Verificou-se que para sais cuja solubilidade varia muito pouco com a temperatura e que possuem zona metaestável com pequena largura, caso do NaCl, a operação com resfriamento no cristalizador não é viável pois aumenta excessivamente o consumo energético do processo, sendo nesses casos preferível a operação \"isotérmica\" - sem resfriamento no cristalizador - e o convívio com a possibilidade de nucleação no interior do módulo. No extremo oposto, observou-se que para sais com grande variabilidade da solubilidade com a temperatura, um pequeno resfriamento no cristalizador é suficiente para garantir condições de subsaturação no interior do módulo, sem grande ônus energético para o processo. No caso de sais com pequena variabilidade da solubilidade com a temperatura, mas com largura da zona metaestável elevada, existe certo ônus energético para a operação com resfriamento do cristalizador, porém não tão acentuado como no caso de sais com zona metaestável estreita. Foi proposto um fluxograma alternativo para o processo de MDC, onde foi introduzido um circuito de pré-concentração da alimentação antes do circuito de cristalização, para o caso de alimentação com soluções muito diluídas. Este esquema proporcionou um aumento do fluxo permeado global do processo e consequentemente uma redução na área total de membrana requerida. Verificou-se que através do processo com préconcentração da alimentação de 5% até 10% em massa - no caso de dessalinização de uma solução de NaCl - foi possível reduzir-se a área total da membrana em 27,1% e o consumo energético específico do processo em 10,6%, quando comparado ao processo sem pré-concentração. Foram desenvolvidas ferramentas úteis para o projeto de processos de dessalinização por MDC em escala industrial. / Alternative desalination processes aiming at the recovery and reuse of the water contained in concentrated brines were evaluated, being the membrane distillation crystallization (MDC) process investigated in depth. A differential model for the direct contact membrane distillation (DCMD) process was developed for that matter, comprising rigorous thermodynamic methods for strong electrolytes, heat and mass transfer mechanisms and temperature and concentration polarization effects. Based on simulations from the mathematical model thus developed, the main parameters that influence the design of DCMD membrane modules were investigated. The model was further extended with mass and energy balance equations in order to consider the crystallization unit operation and thus suitably represent the MDC process. Based on the simulations results and the extended model, a hierarchical method was developed for the MDC process design, adding traceability and repeatability characteristics to the design activity. Important aspects of the MDC process such as the possibility of nucleation and crystal growth on the membrane surface, as well as the behavior of the process with salts presenting different solubility characteristics and metastable zone widths were further discussed. It was observed that salts presenting negligible temperature dependence regarding their solubility and small metastable zone widths (i.e. NaCl) do not favor the operation with cooling in the crystallizer due to excessive increase in energy consumption, being the isothermal operation more indicated in such cases even at the risk of nucleation inside the membrane module. On the other hand, it was noticed that for salts whose solubility is highly temperature dependent a slight cooling in the crystallizer is enough to assure subsaturated conditions inside the membrane module with minimal energy consumption increase. In the case of salts with low temperature dependence regarding solubility but with large metastable zone widths, the operating strategy of applying cooling in the crystallizer may increase energy consumption but not as significantly as in the case of salts with small metastable zone widths. An alternative flowsheet for the MDC process was proposed, where a pre-concentration loop was introduced before the crystallization loop, showing good results for dilute feeds since it takes advantage of the higher water activity and consequently higher transmembrane fluxes due to the lower concentration. It was perceived a 27.1% reduction in the required membrane surface and a 10.6% energy consumption reduction for the modified flowsheet with the pre-concentration loop, for a feed comprised of 5% of NaCl. Useful tools aimed for the design of industrial scale processes based on MDC were developed.

Membrane Distillation (MD) is an emerging sustainable desalination technique. While MD has many advantages and can be powered by solar thermal energy, its main drawback is the low water production rate. However, the MD process has not been fully optimized in terms of its manipulated and controlled variables. This is largely due to the lack of adequate dynamic models to study and simulate the process. In addition, MD is prone to membrane fouling, which is a fault that degrades the performance of the MD process. This work has three contributions to address these challenges. First, we derive a mathematical model of Direct Contact Membrane Distillation (DCMD), which is the building block for the next parts. Then, the proposed model is extended to account for membrane fouling and an observer-based fouling detection method is developed. Finally, various control strategies are implemented to optimize the performance of the DCMD solar-powered process. In part one, a reduced-order dynamic model of DCMD is developed based on lumped capacitance method and electrical analogy to thermal systems. The result is an electrical equivalent thermal network to the DCMD process, which is modeled by a system of nonlinear differential algebraic equations (DAEs). This model predicts the water-vapor flux and the temperature distribution along the module length. Experimental data is collected to validate the steady-state and dynamic responses of the proposed model, with great agreement demonstrated in both. The second part proposes an extension of the model to account for membrane fouling. An adaptive observer for DAE systems is developed and convergence proof is presented. A method for membrane fouling detection is then proposed based on adaptive observers. Simulation results demonstrate the performance of the membrane fouling detection method. Finally, an optimization problem is formulated to maximize the process efficiency of a solar-powered DCMD. The adapted method is known as Extremum Seeking (ES). A Newton-based ES is designed and the proposed model is used to accurately forecast the distilled water flux. Although good results are obtained with this method, a practical modification to the ES scheme is proposed to enhance the practical stability.

No description available.

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.

This thesis presents investigations on air-cooled air gap membrane distillation for desalination and the application of radial waveguides based on total internal reflection for solar thermal desalination. Using an air-cooled design for an air gap membrane distillation (AGMD) process may result in significantly lower energy requirements for desalination. Experiments were conducted on AGMD module to study the effect of air gap, support mesh conductivity and hydrophobicity, condensing surface hydrophobicity. A novel modular design was used in which modules could be used in a series configuration to increase the flux value for the distillate. The output from the series configuration was found to have about three times the production from a single pass water-cooled system with the same temperature difference between the saline and clear water streams. The results also indicated that the mesh conductivity had a favorable effect on the flux value whereas the hydrophobicity of the mesh had no significant effect. The hydrophobicity of the condensing surface was favorable on two accounts: first, it led to an increase in the flux of the distillate at temperatures below 60 °C and second, the temperature difference of the saline feed when it enters and leaves the module is lower which can lead to energy savings and higher yields when used in a series configuration. The second part of the thesis considers use of low-cost radial waveguides to collect and concentrate solar energy for use in thermal desalination processes. The optical-waveguide-based solar energy concentrators are based on total internal reflection and minimize/eliminate moving parts, tracking structures and cost. The use of optical waveguides for thermal desalination is explored using an analytical closed-form solution for the coupled optical and thermal transport of solar irradiation through a radial planar waveguide concentrator integrated with a central receiver. The analytical model is verified against and supported by computational optical ray tracing simulations. The effects of various design and operating parameters are systematically investigated on the system performance, which is quantified in terms of net thermal power delivered, aperture area required and collection efficiency. Design constraints like thermal stress, maximum continuous operation temperature and structural constraints have been considered to identify realistic waveguide configurations which are suitable for real world applications. The study provides realistic estimates for the performance achievable with radial planar waveguide concentrator-receiver configuration. In addition to this, a cost analysis has been conducted to determine the preferred design configurations that minimize the cost per unit area of the planar waveguide concentrator coupled to the receiver. Considering applications to thermal desalination which is a low temperature application, optimal design configuration of waveguide concentrator-receiver system is identified that result in the minimum levelized cost of power (LCOP). / Master of Science

In this thesis, the potential to purify water utilizing waste heat from a unit which stores thermal energy and converts it to electricity is studied. The unit, called TES.POD, is developed by Azelio AB and is in this thesis used as a heat source to drive an air gap membrane distillation (AGMD) unit developed by Scarab Development AB. Heat from the TES.POD and ambient air temperature constitutes a temperature difference over a membrane used as a driving force to vaporize a part of the water that transfer through the membrane, and later condensates as clean distilled water as the contaminations stays in the hot stream of feed water. An analysis has been conducted to determine quasi-steady performance of the combined system for estimating the amount of purified water that can be supplied when the TES.POD unit is in peak electricity discharge mode. The 26 kW of waste heat accessible from the TES.POD is shown to enable two AGMD-modules producing purified water at a production of 7, 1l/h per unit having the feed water at 50°C and cooling water at 25°C. A correlation between the amount of waste heat and distilled water production is determined, as the TES.POD could be configured to produce less electricity and more waste heat at a higher temperature. The correlation showed that an 9% increase in cooling temperature, lead to an 30% increase in pure water output and a 33% decrease in electricity output. The results show that when implementing the two companies’ units together, a system that both provides electricity and distilled water is obtained. This is a system with a high demand, especially in off-grid areas with lack of both resources but with accessible renewable energy sources. Moreover, by using waste heat to purify water, it can also reduce the production cost compared to cases where conventional energy sources are used. The potential revenue of the production was estimated to 673 790 SEK/year with an implementation cost of 93 861 SEK with yearly operational expenses estimated to 14 080 SEK/year. / I detta arbete undersöks möjligheten att rena vatten med spillvärme från ett system vilket lagrar termisk energi och av den producerar elektricitet, när det behövs. Systemet är utvecklat av Azelio AB och har produktnamnet TES.POD. Vattendestillationen utförs med en så kallad air gap membrane distillation (AGMD) modul, utvecklad av Scarab Development AB. Värmen från TES.POD och omgivningstemperaturen utgör, i AGMD-modulen, en temperaturdifferens vilken i sin tur skapar en partielltryckskillnad över membranet. Denna partielltryckskillnad låter en del av det förorenade vattnet som flödar i AGMD-modulen att förångas och passera genom membranet. Föroreningarna stannar kvar i det strömmande vattnet och ångan kondenserar som renat vatten.  Arbetet visar att de 26kW som finns att tillgå i form av spillvärme är tillräckligt för att driva två AGMD-moduler att producera 7,1 l/h destillerat vatten per modul. Detta är under förutsättningar att det förorenade vattnet är 50°C och kylvattnet är 25°C. I rapporten återfinns också ett samband mellan mängden spillvärme och produktionen av destillerat vatten, eftersom TES.POD kan konfigureras till att producera spillvärme vid en högre temperatur. Sambandet visade på att 9% ökning av spillvärmens temperatur motsvarar 30% ökning i produktionen av destillerat vatten och en minskad elektricitetsproduktion på 33%.  Resultatet visar på att integrationen av dessa två produkter bildar ett system som både producerar rent vatten och elektricitet när så önskas. Detta system har till synes en stor efterfrågan, speciellt i områden utanför fast el- och vattennätverk men med goda förnyelsebara energikällor. Dessutom, eftersom vattendestillationen sker med spillvärme, kan produktionskostnaderna vara lägre än då konventionella energikällor används. Den potentiella inkomsten från produktionen estimeras till 673 790 SEK/year med en inköpskostnad om 93 861 SEK samt årliga omkostnader om 14 080 SEK/year.

See file / Se bif. fil

Despite the country's rural electrification programme, kerosene is the predominant source for lighting, and unsustainable and polluting woody biomass is virtually the only option available for cooking. The rural population also struggles with unsafe drinking water in terms of widespread arsenic contamination of well water. The present work has taken an integrated approach in an attempt to mitigate problems through small-scale polygeneration, a concept linking renewable energy sources to these energy needs via novel energy conversion systems. Anaerobic digesters (AD) for biogas production are promising in the rural setting, and field surveys have identified problems in the construction, maintenance and operation of existing AD, particularly in overall performance of household digesters. Based on these results, a number of operational and technological improvements are suggested for employing digesters in polygeneration units. This study also examines one approach for small-scale, low cost arsenic removal in groundwater through air gap membrane distillation, a thermally-driven water purification technology. Integration of biogas production with power generation and water purification is an innovative concept that lies at the core of feasibility analyses conducted in this work. One of the case studies presents a new concept for integrated biogas based polygeneration and analyzes the techno-economic performance of the scheme for meeting the demand of electricity, cooking energy and safe drinking water of 30 households in a rural village of Bangladesh. The specific technologies chosen for the key energy conversion steps are as follows: plug-flow digester; internal combustion engine; and membrane distillation. One major concern is local feedstock availability for the digester, since a single feedstock is impractical to serve both cooking, lighting and water purification systems. In this circumstance solar PV could be a potential option for integrated hybrid systems. / Bangladesh har varit föremål för en svår energikris (bristande el- och gasnät) de senaste tre decennierna. Landsbygden, som innefattar 75 % av befolkningen, har varit särskilt drabbad. Trots landets elektrifieringsprogram av landsbygden är fotogenlampor den företrädande ljuskällan, medan förorenande och ohållbar träbaserad biomassa är praktiskt taget det enda alternativet för matlagning. Landsbygden kämpar samtidigt mot osäkert dricksvatten, på grund av utbredd arsenikförgiftning av brunnsvatten, med negativa hälsoeffekter som följd. Tillgång till ren energi och säkert dricksvatten är verkliga behov bland de fattiga på landsbygden, för ökad välfärd. Detta arbete antar ett integrerat tillvägagångssätt för att försöka lösa dessa problem genom småskalig polygenerering. Detta koncept länkar samman förnyelsebara energikällor av biomassa och sol med energibehoven, genom nya energiomvandlingssystem. Anaerobiska rötkammare för biogasproduktion är lovande för landsbygdsmiljö, även om det för närvarande råder en betydande klyfta mellan den tekniska och kostandseffektiva potentialen och faktisk implementering på grund av bristande tekniskt kunnande och tillgång på råmaterial, höga installations- och driftkostnader, och begränsade användartillämpningar. Intervjuundersökningar visar på problem i konstruktion, underhåll och drift av befintliga anaerobiska rötkammare. Särskilt den generella prestandan hos hushållsrötkammare identifieras som bristfällig. Utifrån dessa resultat föreslås en rad drift- och teknikförbättringar för att utnyttja rötkammare i polygenereringssystem.   Denna studie undersöker även en metod för småskalig och kostnadseffektiv arsenikrening av grundvatten genom membrandestillation med luftspalt (Air Gap Membrane Distillation, AGMD), vilket är en termiskt driven vattenreningsteknik. Resultat från en experimentell undersökning visar att den undersökta AGMD-prototypen är kapabel att uppnå utmärkt separationseffektivitet med hänsyn till arsenikrening. Parametriska studier med fokus på varierande kylvattentemperatur illustrerar möjligheten att integrera AGMD-teknik i diverse termiska system. Integrering av biogasproduktion med kraftproduktion och vattenrening är ett innovativt koncept som utgör kärnan av förstudierna utförda i detta arbete. En av studierna visar ett nytt koncept för biogasbaserad polygenerering och analyserar den techno-ekonomiska prestandan av metoden för att möta efterfrågan av elektricitet, matlagningsvärme och säkert dricksvatten för 30 hushåll i en Bangladeshisk by på landsbygden. De specifika tekniker som valts för energiomvandlingsstegen är följande: plugg-flödesrötkammare, förbränningsmotor och en AGMD-enhet. Termodynamisk utvärdering inklusive mass- och energibalans av systemet undersöktes tillsammans med produktionskostnaden för elektricitet, matlagningsgas, och säkert dricksvatten. Även återbetalningsperiod och internräntan undersöktes. För att bemöta energi- och arsenikproblemen i Bangladesh, indikerar resultaten att detta polygenereringssystem är mycket mer konkurrenskraftigt och lovande (med avseende på produktionskostnaderna) jämfört med andra tillgängliga tekniker. Ett viktigt problem för rötkammaren är tillgången till lokalt råmaterial, eftersom en ensam källa till råmaterial är opraktiskt för att tillgodose efterfrågan från både matlagning, belysning och vattenrening. I detta fall kan solceller vara ett potentiellt alternativ för integrerade hybridsystem. Teknisk värdering och optimering har genomförts för elektricitet med verktyget HOMER (Hybrid Optimization of Multiple Energy Resources), för ett polygenereringssystem beläget i byn Panipara i Faridpur. Resultaten visar att systement kan tillgodoses det dagliga elektricitetsbehovet och samtidigt producera 0.4 m3 matlagningsbränsle och 2-3 L/person rent dricksvatten. Kostnadsuppskattningar visar att denna metod är högst gynnsam jämfört med andra förnyelsebara alternativ (t ex vind-, vatten-, biobränslebaserad- eller geotermisk energi). / <p>QC 20170419</p> / SIDA – the Swedish International Development Cooperation Agency, Department for Research Cooperation, SAREC- project no. SWE-2011-135 / STEM-Fjärrsyn project 2014

Cette thèse présente une approche originale du procédé de distillation membranaire avec balayage gazeux pour la concentration des solutions thermosensibles (SGMD). Pour ce faire, un nouveau contacteur membranaire avec des fibres creuses métalliques a été conçu afin réaliser le procédé de distillation à basse température. La chaleur nécessaire au procédé est produite au niveau des fibres par effet Joule, plutôt qu'à partir de chaleur latente de la phase aqueuse. La génération localisée de la chaleur a comme conséquence une réduction du phénomène de polarisation de la température. Des fibres creuses en acier inoxydable ont été synthétisées avec les propriétés structurales appropriées et une bonne résistance mécanique. La surface des pores des fibres a été rendue hydrophobe par le dépôt d'une fine couche d'un élastomère. En outre, une nouvelle méthode « verte » a été développée pour fabriquer des fibres creuses en alumine et acier inoxydable. Cette méthode est basée sur la gélification ionique des bio-polymères et ne n'utilise pas des solvants nocifs. L'étude expérimentale détaillée du SGMD a permis de déterminer l'influence de différents paramètres opérationnels sur les performances du procédé. Il a été démontré que l'effet Joule permet d'améliorer le flux et l'efficacité de la séparation non seulement pour le SGMD mais aussi pour la pervaporation. / This thesis presents an original approach for the concentration of thermo-sensitive solutions: the Sweep Gas Membrane Distillation (SGMD) process. A new membrane contactor with metallic hollow fibers has been designed and allows the distillation process to be operational at low temperature. Heat is generated in the fibers by the Joule effect, rather than being supplied as latent heat in the liquid bulk. The localized generation of heat results in a reduction of temperature polarization phenomena. The stainless-steel hollow fiber membranes have been synthetized with appropriate structural properties and sufficient mechanical strength. The pore surface of the fibers has been made hydrophobic by the deposition of a thin layer of an elastomer. Moreover, a novel and green method is presented to fabricate alumina and stainless-steel hollow fibers. This method is based on ionic gelation of a biopolymer and completely avoids the use of harmful solvents. By a detailed experimental study of the SGMD the influence of different operational parameters on the process performance has been investigated. The improvements in the flux and the separation efficiency using Joule effect have been successfully demonstrated, even in the case of pervaporation.

A cristalização assistida por destilação com membranas (membrane distillation crystallization, MDC) se destaca como uma alternativa aos processos convencionais de cristalização evaporativa com múltiplos estágios e/ou recompressão mecânica de vapor para dessalinização de soluções aquosas concentradas com descarga zero de líquido (zero liquid discharge, ZLD) no meio ambiente. Os principais atrativos da MDC são as condições operacionais mais brandas de temperatura e pressão, o que possibilita o emprego de fontes de calor de baixa entalpia e instalações menos requisitadas mecanicamente. Entretanto, por ser um processo de separação que envolve membranas, a formação de incrustação se destaca como inconveniente. Assim sendo, grande parte dos estudos em MDC têm sido voltados para essa questão, com foco na operação de destilação com membranas (membrane distillation, MD), quando o produto de interesse é a água recuperada. Nesse contexto, esta tese amplia o conhecimento na área, sendo estudados os fundamentos de cristalização e a sua relação com parâmetros selecionados do processo. Dessa forma, estudos teórico-experimentais foram conduzidos investigando os mecanismos de cristalização predominantes nesse, de maneira a ampliar a abrangência das teorias clássicas de cristalização. No primeiro capítulo, realizou-se uma revisão bibliográfica a fim de apresentar os fundamentos tecnológicos, bem como as características, limitações e desafios para consolidação em escala industrial da MDC. No segundo capítulo, foi definido o conhecimento científico produzido através da especificação de objetivos. No terceiro capítulo, a operação MD na configuração DCMD (direct contact membrane distillation) foi caracterizada utilizando equações matemáticas para o cálculo do fluxo de vapor. Os valores calculados foram validados com experimentos em escala de bancada. Foi possível identificar que a difusão ordinária molecular é o mecanismo de transporte de massa dominante nos poros da membrana, e quantificar os fenômenos de polarizações de temperatura e de concentração adjacentes à superfície da membrana. No quarto capítulo, a cristalização foi integrada com a DCMD e explorada em uma unidade de bancada. Os processos elementares e acessórios de cristalização predominantes foram esclarecidos como sendo nucleação primária heterogênea (incrustação por cristalização), nucleação secundária (abrasão de cristais) e crescimento cristalino molecular (aumento de tamanho). O quinto capítulo versou sobre uma estratégia proposta para reduzir a nucleação primária heterogênea, força motriz da incrustação por cristalização na membrana. Com base nos processos elementares e acessórios de cristalização identificados, foi avaliada uma modificação na MDC, a submersão de membranas em cristalizador, a qual foi implementada em escala de bancada. Essa modificação se mostrou mais sensível à formação de incrustação, com possibilidade de se encontrar condições favoráveis, uma vez que foi possível operar o processo durante três horas sem desenvolvimento de incrustação na membrana (tempo máximo investigado), mas precisa ser melhor investigada. Por último, no sexto capítulo abordou-se a nucleação primária heterogênea, relacionando esta com a queda de fluxo de vapor e com a distribuição de sólidos formados. O equacionamento do sistema validado no terceiro capítulo foi aplicado para quantificação da supersaturação local na membrana e respectiva associação com os mecanismos de cristalização. Observou-se que o aumento de fluxo aumenta a supersaturação local, que aumenta a nucleação primária heterogênea, sendo essa responsável pela formação de cristais que permaneceram aderidos na membrana (incrustação por cristalização) e que foram soltos em solução (suspensão). Os cristais soltos em solução são predominantes. A fluidodinâmica de escoamento (geometria dos módulos de membranas) associada à supersaturação local (fluxo de vapor) impactam no desprendimento de cristais na membrana originados por nucleação primária heterogênea. Com o aumento de supersaturação local, o desprendimento de cristais em suspensão é favorecido em módulo de membranas do tipo fibras ocas, enquanto não afeta o módulo do tipo tubular. Em seu conjunto, esta tese contribui para a melhoria do entendimento de aspectos fundamentais selecionados do processo MDC e para o emprego deste conhecimento em situações de interesse prático. / Membrane distillation crystallization (MDC) stand as an alternative to conventional evaporative crystallization processes with multiple-stage evaporator and/or mechanical vapor recompression towards concentrated brine desalination aiming at zero liquid discharge (ZLD) in the environment. The major advantages of MDC are the moderate temperature and pressure conditions, which allow the use of low enthalpy heat sources and facilities less mechanically required. However, as in membrane separation processes, membrane fouling plays an important role in MDC. Therefore, most MDC studies have been focused on that, with emphasis on membrane distillation (MD) operation, when the product of interest is the recovered water. In this context, this thesis extends the knowledge in the field, wherein the crystallization fundamentals and its relation with selected process parameters were studied. Thus, theoretical and experimental approaches were carried out in order to investigate the prevailing crystallization mechanisms in the process, so the range of the current crystallization theories could be extended. In the first chapter, a literature review was carried out in order to introduce selected fundamental concepts, as well as the process characteristics, limitations and challenges for industrial consolidation. In the second chapter, the scientific knowledge produced by this work was defined in its objectives. In the third chapter, the MD operation in direct contact configuration (DCMD) was characterized using mathematical equations for the calculation of vapor flux and validated with experimental data in a bench scale unit. The dominant mechanism of mass transport in porous media was found to be the ordinary molecular diffusion and the temperature and concentration polarization effects were quantified in the vicinity of membrane surface. In the fourth chapter, the crystallization operation was integrated with DCMD and investigated in a bench scale unit. The elementary and accessory crystallization mechanisms were highlighted as heterogeneous primary nucleation (crystallization fouling), secondary nucleation (crystal abrasion) and crystalline molecular growth (increase in size). The fifth chapter describes a strategy proposed in order to reduce heterogeneous primary nucleation, the driving force of membrane crystallization fouling. Based on the featured crystallization mechanisms, a modification in the conventional MDC operation was evaluated, the submersion of membranes into the crystallizer vessel, which was implemented in a bench scale unit. The preliminary results showed that this modification is more sensitive to crystallization fouling, with possibility to find promising conditions, once it was possible to operate during three hours without development of crystallization fouling (maximum period of time investigated), but further investigation is needed. Lastly, in the sixth chapter, the primary heterogeneous nucleation mechanism was explored, associating it to flux decay and solid distribution in the unit. The system equations validated in the third chapter were applied in order to quantify the supersaturation ratio generated in the vicinity of membrane surface and respective association with crystallization mechanisms. It was observed that increasing the vapor flux, the local supersaturation ratio also increase and, as consequence, the primary heterogeneous nucleation as well. This mechanism is responsible for the formation of crystals that remained adhered on membrane surface (crystallization fouling) and released in solution (suspension). The portion of crystals loose in solution was predominantly formed. The fluid dynamic of flow (geometry of membrane module) associated with the local supersaturation ratio (vapor flux) impact in the detachment of crystals in the membrane surface, originated by heterogeneous primary nucleation. With an increase in the local supersaturation ratio, the detachment of crystals is increased in the hollow fiber membrane module, while in the tubular module the detachment of crystals does not change. As a whole, this thesis contributes to a better understanding of MDC selected fundamental aspects and to the use of this knowledge in practical situations.