Dissertations / Theses on the topic 'Membrane and separation technologies'

Ce travail traite une investigation systématique des performances du procédé membranaire cyclique par séparation gazeuse. Premièrement, l'état de l'art du procédé membranaire cyclique, les problèmes techniques et la modélisation du transfert à travers la membrane ont été exposés. Deuxièmement, les études théoriques et expérimentales existantes sur le procédé cyclique sont passées en revue. Selon la durée de pression haute et sa fraction dans un cycle, ce genre d'opération est divisé en deux classes: classes courte et longue. D'après cette classification, une analyse systématique de l'intérêt potentiel de la classe courte par rapport aux performances d'une opération en régime permanent a été accomplie par des simulations et optimisations numériques. Par ailleurs, afin d'améliorer la performance, l'usage du MMM dans un tel procédé a été discuté. En parallèle à l'étude sur la classe courte, une nouvelle conception du procédé cyclique de classe longue a été proposée. Les avantages spectaculaires par rapport aux procédés membranaires classiques ont été mis en évidence à l'aide de nos simulations et optimisations. Finalement, une validation expérimentale a été effectuée afin de fournir un support solide à cette nouvelle conception
This study deals with a systematic investigation of the performance of cyclic membrane gas separation processes. First, a state of the art of membrane separation processes, including material challenges and mass transfer modeling issues is proposed. In a second step, a review of the different theoretical and experimental studies performed on cyclic processes is reported. With respect to the length of the high pressure stage and its fraction in one cycle, these operations are classified into short and long classes. Based on this classification, a systematic analysis of the potential interest of short class compared to steady-state operation performances has been achieved by means of numerical simulation and optimization. In order to improve the performance, the use of MMM in such a process has been further discussed. In parallel with the short class study, a design of novel long class has been proposed. Spectacular advantages with respect to classical membrane-based processes have been highlighted by means of our simulation and optimization studies. Finally, an experimental verification has been performed in order to provide a solid support to this novel process

La chromatographie membranaire est une alternative à la chromatographie classique sur résine basée sur le transport convectif des solutés à travers une membrane microporeuse plutôt que par le transport diffusif des solutés dans les particules de résines. Cette technique présente les avantages de diminuer les phénomènes de diffusion, de réduire les temps de séjour et les pertes de charge, et de permettre la purification rapide de quantités importantes de molécules. La chromatographie membranaire connaît un fort succès commercial. Une gamme importante de membranes chromatographiques mettant en jeu différents mécanismes de rétention (échange d’ions, affinité, etc.) et différentes géométries (feuille, spirale, etc.) est actuellement commercialisée. Malgré ce succès, différents aspects relatifs à la chromatographie membranaire restent mal connus. Cette thèse de doctorat se propose de répondre à certaines questions relatives à cette technique
Membrane chromatography (MC) is an alternative to traditional resin packed columns chromatography. The solute mass transport in the membrane occurs in convective through-pores rather than in stagnant fluid inside the pores of the resins particles, which is limited by the slow diffusive transport. MC offers the main advantage of reducing diffusion phenomena, shorter residence time and lowered pressures drops, and thus, facilitates rapid purification of large quantities of molecules. A wide range of chromatographic membranes involving different molecules retention mechanisms (ion exchange, affinity, etc...) is now commercialized. Despite their success, the influence of the geometry of the membrane chromatography devices remains relatively unexplored from a theoretical point of view. This doctoral thesis is aimed to clarify some ambiguous points related to this technique

Cette thèse décrit comment la morphologie et le polymorphisme de membranes en fluorure de poly(vinylidène) (PVDF) préparées par séparation de phase induite par la vapeur d'eau (VIPS) et par un non-solvant liquide peuvent être ajustés par la température à laquelle le PVDF est dissous (Tdis) pour former la solution de coulée. Les résultats montrent que Tdis présente une transition, notée comme la température de dissolution critique (Tcri), à partir de laquelle la morphologie et le polymorphisme des membranes changent radicalement. Ce phénomène observé pour les trois solvants, N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAc), and N,M-dimethylformamide (DMF), et les non-solvants (eau et une série d'alcools) utilisés dans cette étude peut être considéré comme général. La cristallisation a lieu avant la démixtion L-L quelle que soit Tdis. Pour une Tdis supérieure à Tcri, les membranes se présentent sous forme de nodules (cristallite forme beta) dont la taille décroît lorsque Tdis diminue. Ce domaine a été dénommé "à grossissement libre" car les chaînes de polymère peuvent cristalliser librement pendant la séparation de phase. Pour une Tdis inférieure à Tcri, des membranes avec une structure bi-continue (cristallite forme alpha) sont obtenues. Ce domaine a été appelé "à grossissement empêché" dans la mesure où la séparation de phase s'accompagne d'une gélification. Nous avons démontré que la morphologie et le polymorphisme cristallin des membranes de PVDF peuvent ainsi être contrôlés par la Tdis et la vitesse d'échange avec le non-solvant. Ces résultats sont interprétés en termes d'auto germination et de compétition entre gélification, cristallisation et démixtion L-L
This dissertation shows how the morphology and polymorphism of poly(vinylidene fluoride) (PVDF) membranes prepared by using vapor-induced phase separation (VIPS) and liquid-induced phase separation (LIPS) were tuned by varying the dissolution temperature at which PVDF was dissolved (Tdis) to form the casting solution. We observed a transition temperature denoted by critical dissolution temperature, Tcri, across which the morphology and polymorphism of membranes (obtained by VIPS) drastically changed. The phenomenon was considered as general, as a Tcri was observed for all the three solvents N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAc), and N,N-dimethylformamide (DMF) and the non-solvents, water and a series of alcohols, used in the present study. No matter which Tdis we used, polymer crystallization occurred prior to the L-L demixing. With Tdis above Tcri, the prepared membranes were composed of nodules (mainly in beta crystalline form) and the size of polymer domains decreased as the Tdis decreased. Because the polymer chains could freely coarsen to a large domain during the phase separation, we called the system free coarsening. With Tdis below Tcri, membranes with lacy (bi-continuous) structure (mainly in alpha crystalline form) were obtained. Because the polymer solution gelled during the phase separation, we called the system hindered coarsening. It was proven that PVDF membrane morphology and crystalline polymorphs can be monitored by Tdis and the solvent-nonsolvent exchange rate. These results were discussed in terms of self-seeding effect and competition between the gelation, crystallisation and L-L demixing

La séparation de phase au sein d'un système polymère/solvant est la méthode la plus couramment utilisée pour élaborer une membrane polymère poreuse. Les principales méthodes d'inversion de phase nécessitent l'usage de solvants organiques qui génèrent des problèmes environnementaux (traitement des bains de coagulation) et sanitaires (sécurité des installations industrielles). Cette étude porte sur le développement d'une nouvelle membrane polymère poreuse à partir d'un polymère biosourcé et hydrosoluble, l'hydroxypropylcellulose (HPC), permettant de s'affranchir de l'usage de solvants organiques. La propriété de thermosensibilité de l'HPC, caractérisé par une température critique basse en solution dans l'eau (LCST) de l'ordre de 40 °C, a par ailleurs permis de développer un procédé original d'élaboration de membranes HPC par séparation de phase induite par augmentation de la température au-delà de la LCST. Ce travail vise un triple objectif : (i) déterminer la formulation idoine permettant de former une membrane poreuse insoluble dans l'eau à partir d'HPC, (ii) appréhender et comprendre les mécanismes de structuration de la matrice polymère à travers l'interaction des mécanismes interdépendants de séparation de phase par décomposition spinodale, de réticulation chimique et d'extraction du solvant par évaporation et enfin (iii) caractériser l'aptitude des membranes à la filtration d'une solution aqueuse sous pression. Le suivi en ligne de la dynamique de séparation de phase d'un système HPC/eau/réticulant ± porogène (PEG200) par microscopie optique en contraste de phase, de la réticulation par rhéologie et de l'évaporation de l'eau par thermogravimétrie a ainsi permis de mettre en évidence l'impact de la formulation et des paramètres de conduite du procédé d'inversion de phase sur les propriétés morphologiques et d'usage des membranes. La porosité membranaire et le caractère symétrique de la morphologie ont notamment été corrélés à la vitesse des phénomènes concomitants de réticulation et d'évaporation de l'eau, donc à la vitesse de montée en température du procédé TIPS-LCST. La caractérisation de la perméabilité à l'eau des membranes HPC a confirmé l'efficacité de la réticulation et la résistance structurale des membranes au cours de plusieurs filtrations continues à l'eau. En raison du caractère thermosensible de l'HPC, ces membranes ont montré une aptitude remarquable à la filtration de solutions aqueuses à température élevée (60 °C). Par ailleurs, il a été montré que la perméabilité des membranes pouvait être en partie contrôlée par la température et la pression transmembranaire appliquée
Phase separation of polyer/solvent system is the most widespread industrial process to manufacture membranes. Large solvent quantity is usually used whatever the process, hence leading to environmental (coagulation and washing baths treatment) and health (industrial and plant safety) problems.This study focuses on the development of new porous membranes made from hydroxypropylcellulose (HPC), a water soluble polymer, avoiding the use of any organic solvent. Moreover, the thermo-sensitive character of this polymer, characterized by a Lower Critical Solution Temperature (LCST) in water of about 40 °C, enabled to design an original thermally induced phase separation process by temperature increase above the LCST. This study aims (i) to find the ideal polymer solution composition to produce insoluble HPC membrane, (ii) to approach and understand the link between phase separation mechanism by spinodal decomposition, crosslinkig reaction and water extraction by evaporation, (iii) characterize pure water permeability under pressure. On-line monitoring of phase sepration dynamics by phase contrast optical microscopy, crosslinking reaction by rheology and water evaporation by thermogravimetric analysis of the system HPC/water/cross-linking agent ± porogen (PEG200) allowed an understanding of simultaneous and related mechanisms occurring during elaboration (phase separation / cross-linking / water evaporation) and a correlation with HPC membrane morphologies and characteristics in relation with phase separation process parametres. Pure water permeability characterization demonstrated the efficiency of cross-linking and structural strength during several filtration cycles. Furthermore, it has been shown that water permeability of HPC membranes could be controlled in part by the temperature and the applied pressure

This diploma thesis is focused on the topic of membrane technologies used in wastewater treatment. The research part of the thesis deals with membrane separation of activated sludge, and the focus is on the submerged membrane modules. The thesis contains basic principles of MBR systems, an overview of used membrane modules, modes of operation, advantages and disadvantages of using this process. The practical part of the thesis proposes the intensification of WWTP Perná with using MBR technology. This part includes the technical-economic assessment of the activation WWTP with the third stage of treatment and activation WWTP with MBR.

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.

Les procédés de séparation membranaire sont une technologie bien connue et déjà largement utilisée dans le domaine de la purification des gaz. Ces procédés sont applicables à de nombreux secteurs d’activités industriels. Selon les performances de séparation recherchées, elles peuvent constituer une alternative intéressante aux technologies existantes de traitement des gaz (adsorption, cryogénie, contacteurs gaz/liquide). Pour exploiter au mieux cette technologie, le développement d'outils d’aide à la décision permettant d’identifier les procédés et les conditions opératoires économiquement avantageux est absolument nécessaire. Bien que les approches expérimentales d'optimisation appliquées à différentes études de cas conservent un intérêt certain, une approche générale et sa validation dans le cadre de différentes études de cas font toujours défaut. L’objectif principal de cette thèse est de développer un outil numérique le plus générique possible d’optimisation de procédés de séparation membranaire. Dans ce travail, la synthèse du procédé membranaire est traitée et modélisée comme un problème d'optimisation mathématique non linéaire et non convexe basé sur un paradigme de superstructure couvrant une combinatoire d'unités (modules membranaires, compresseurs, pompes à vide) et de connexions la plus exhaustive possible. Des fonctions de coûts réalistes et détaillées sont utilisées comme fonction objectif dans l'optimisation. Une stratégie d'optimisation globale continue, qui peut se considérer comme la composition de deux algorithmes : Multistart et Monotonic Basin Hopping (MBH) ; est présentée pour résoudre le problème d'optimisation susmentionné. L'efficacité de cette démarche d'optimisation est dans un premier temps validée en comparant sa solution à celles présentées dans la littérature. La méthode proposée est ensuite appliquée à l'optimisation de plusieurs cas emblématiques de la séparation de gaz (CO2 de gaz de haut fourneaux, séparation O2/N2 de l’air, traitement du biogaz et du gaz naturel). Différents degrés de liberté du système sont permis et analysés selon les cas (pressions variables, type de membrane variable). L'analyse détaillée des résultats est discutée en termes d’architecture de procédés et de distribution des coûts (CAPEX, OPEX)
Membrane separation is a well-known technology in gas purification, which is applicable in different aspects of the industry. Over the last decades, depending on the required separation performances, it became a viable alternative to several gas separation technologies (adsorption, cryogenics, gas /liquid contactors). To exploit at best this technology, nevertheless, tools to find cost-effective designs and operating conditions are necessary. While experimental optimization approaches applied to different case studies have been investigated extensively, a more generic optimization approach and its validation along different case studies are still missing. The work of this thesis starts with this key observation and tries to fill this gap. The membrane process synthesis is modelled as a nonlinear and non-convex mathematical optimization problem based on a superstructure paradigm covering a wide range of possible units (membrane modules, compressors, and vacuum pumps) and connections as exhaustive as possible. Realistic and detailed cost functions are used as the objective in the optimization. A continues global optimization strategy, that can be considered as the composition of two algorithms: Multistart and Monotonic Basin Hopping (MBH); is presented to solve the aforementioned optimization problem. The efficiency of this overall optimization approach is, first, validated by comparing its solution with the ones presented in the literature. Then, the proposed method is applied to the optimization of several important gas separation cases (CO2 recovery from blast furnace gas, O2/N2 air separation, and biogas and natural gas purification) by increasing the membrane system degree of freedom step by step. Detailed analysis of the results is discussed in terms of process architecture and cost distribution (CAPEX, OPEX)

Des membranes supports en polymère ont été photo-greffées par des poly(liquide ionique)s (polyLIs) à base d'imidazolium. Les polyLIs permettent de séparer le CO2 d'autres gaz et de stabiliser des nanoparticules. Dans le cas du captage de CO2, les expériences montrent qu'une couche fine homogène de gel réticulé en polyLI gonflé par du liquid ionique (LI) est obtenue sur la surface de fibres creuses. Les fibres ainsi obtenues ont montré des perméances au CO2 plus élevées (600-700 GPU) que des membranes commerciales et des sélectivités de CO2/N2 comparables (13 et 17). Dans le cas de membranes catalytiques, des nanoparticules de palladium (NPPd) servant de catalyseur ont été immobilisées en forte concentration locale au sein d'une couche de polyLI greffée à la surface de membranes. La réactivité des membranes catalytiques a été testée en configuration de contacteur traversé sur différentes réactions (couplage croisé C-C, hydrogénation, etc). Une conversion totale est obtenue pour des temps de séjours de quelques secondes, sans aucun sous-produit formé. Comparée aux NPPd colloïdaux dans un réacteur en batch, la membrane catalytique accélère les réactions d'environ 2000 fois en terme de temps de réaction sans perte de NPPd; la sélectivité est aussi accrue. Le réacteur membranaire catalytique a été modélisé afin d'obtenir les profils de concentration et de température et une meilleure compréhension des performances obtenues. Les membranes catalytiques se révèlent isothermes et les constantes cinétiques sont calculées. Enfin, les capacités de production de ces membranes catalytiques à une échelle industrielle sont estimées à environ 3 t/(hm3) pour le couplage de Suzuki
Polymeric support membranes were modified via photo-grafting by poly(ionic liquid)s (polyILs), featuring in the capability to separate CO2 from other gases and to stabilize metallic nanoparticles (MNPs). For CO2 capture, a thin polyIL-IL gel layer was homogenously coated on support hollow fibers. The composite fibers show high CO2 permeance and reasonable CO2/N2 selectivity. For the catalytic membrane, palladium NPs were generated inside a grafted polyLI layer. Compared to colloidal palladium system in a batch reactor, the catalytic membrane, as a contactor membrane reactor, is more efficient in terms of reaction time (ca. 2000 times faster), selectivity and MNP retainability. Theoretical study on reactor modeling, concentration & temperature profiles, and production capacity was done for an overall understanding of the catalytic membrane

A variety of methods exist to remove volatile organic compound (VOC) air pollutants from contaminated gas streams. As regulatory and public opinion pressures increase, companies are searching for more effective methods to control these emissions. This document is intended as a guide to help determine if existing systems are adequate and to provide additional information to improve the efficiency of the systems. It explores conventional methods of controlling VOC emissions, as well as innovative technologies including membrane separation, plasma destruction, and ozone catalytic oxidation. The conventional technologies covered include condensation, adsorption, absorption (or scrubbing), thermal incineration, flaring, catalytic incineration, and biofiltration. Each chapter includes a description of the technology, a discussion of the types of systems available, notes on the design of the system, economic estimates, an explanation of potential problems, and a list of considerations for installation and maintenance concerns. The final chapter is dedicated to the preparation and characterization of metal catalysts which were developed to improve the reaction rate of VOCs using ozone as an oxidant.
Ph. D.

Etude, sur plus de 20 membranes, performances de l'unite d'ultrafiltration pour la fabrication du surimi. Recherche des conditions optimales et application en site industriel. Etude de la concentration du phytoplancton par microfiltration, en conservant la viabilite des cellules. Essais sur site aquacole, mise au point des conditions operatoires: point de coupure et configuration de la membrane, vitesses tangentielles et pressions transmembranaires

Le présent travail est dédié à l’étude d’un procédé hybride couplant l’électrodialyse à membrane bipolaire et l’échange d’ions. Cette étude est appliquée au traitement de solutions diluées d’acide acétique. L’objectif est double : acquérir une compréhension théorique des processus de transfert et des mécanismes qui impactent la consommation énergétique de ce système hybride et, de façon plus appliquée, proposer une configuration de cellule qui permette d’éliminer l’acide de la solution traitée en la transférant vers un compartiment de concentration. Cette configuration doit permettre d’obtenir le taux de purification le plus élevé possible tout en minimisant la consommation d’énergie. Des critères visant à optimiser le choix des résines échangeuses d’ions (fortes ou faibles) dans les compartiments de dilution sont proposés. L’intérêt de l’utilisation d’une résine cationique forte sous forme H+ dans le compartiment de concentration est par ailleurs mise en évidence, conduisant à une diminution de la résistance du compartiment et de ce fait de la consommation d’énergie. Une étude réalisée sur des systèmes « couplés » et « découplés » a permis d’identifier les contributions résistives des différents éléments de l’empilement. Cette approche a conduit à la détermination des paramètres d’un modèle qui permet de prévoir la résistance électrique d’un lit de résine dans une solution donnée. Les consommations spécifiques d’énergie (kWh/kg d’acide transféré) ont été évaluées en fonction du taux de purification souhaité. L’ensemble de l’étude a permis d’établir des recommandations pour la conception de la cellule et pour le choix des paramètres opératoires
This work is dedicated to the study of a hybrid separation process involving bipolar membrane electrodialysis and ion exchange. This study is applied to the treatment of diluted effluents. The aim is first to acquire a theoretical understanding of transfer processes and mechanisms that affect energy consumption of this hybrid system. Then, in a more applied way, the objective is to be able to propose a cell configuration that allows to remove the acid from the treated solution by transferring it to a concentration compartment. This configuration must allow to obtain the highest purification rates as possible while minimizing energy consumption. Criteria aiming at optimizing ion exchange resins (strong or weak) in dilution compartment are proposed. The interest of the introduction of strong cationic resin under H+ form in the concentrated compartment is highlighted, as it enables reducing compartment resistance and hence energy consumption. Furthermore, experimental measurements successively conducted with “decoupled” and “coupled” systems identified resistive contributions of the different elements of the stack. This approach led to the determination of parameters of a model which predicts the resin bed electrical resistance in a given solution. Specific energy consumption (kWh/Kg transferred acid) was evaluated as a function of the desired purification rate. All the work led to recommendations for the cell design and for the choice of operating parameters

La présente étude a été consacrée à l'étude du potentiel du PDMS pour l'élaboration d'un procédé de séparation membranaire à sélectivité variable et contrôlée. La nanofiltration se base une théorie relativement jeune. Les mécanismes impliqués dans les performances des membranes sont encore sujet à controverse au vu des données de la littérature. La caractérisation du gonflement solvo-dépendant du polymère, ainsi que de ses propriétés de compressibilité à l'état gonflé, ont permis de relier directement les propriétés de perméation et de tamisage moléculaire d'une membrane de PDMS à son état physico-chimique. L'étude de l'influence des paramètres opératoires a dans un premier temps permis d'apporter des éléments de compréhension significatifs concernant les propriétés de perméation résultant de la variabilité de l'agencement structural et géométrique du réseau polymérique. Degré de gonflement, compressibilité de la membrane lorsque soumise à la pression transmembranaire, affinités solvant/membrane et viscosité du solvant ont été mise en avant pour décrire le flux de solvant à travers la membrane. Au vu des résultats, ce dernier résulterait davantage d'un transport de type hydraulique à travers les interstices du PDMS gonflé, qui se comporte analogiquement à un système poreux dans cet état. Les mécanismes de transport impliqués ont pu être confirmés et agrémentés au cours d'une étude de la rétention de molécules modèles : les polyéthylèneglycols. Il a alors été montré, via l'étude de leur rétention individuelle, la faisabilité d'un procédé membranaire dont les performances sont variables et peuvent être ciblés par un choix adéquat des conditions opératoires. Deux types majeures d'influences ont alors pu être soulignée : celles liées à la structure du système solvant/PDMS et celles attribuées aux propriétés physico-chimique de la solution à traiter, présentant des effets synergique pour certains d'entre eux. Après avoir démontré la flexibilité contrôlée des performances de filtration, l'application du système de NF a été concrétisée par l'étude de la purification et du fractionnement de peptides : une purification d'un milieu issu d'une synthèse par voie chimique (un hydrazynopeptide) et le fractionnement ciblé d'un hydrolysat de protéines en provenance de ressources agroalimentaires. Cette étude prospective a alors permis de conclure à de prometteuses capacités du système de NF pour la mise en oeuvre de séparations membranaire dont la sélectivité et la productivité peut être appréhendée et ciblée par des conditions opératoires adaptées
The present study aimed to study the ability to build an adaptative and controlled separation process using PDMS membranes for organic solvent nanofiltration (OSN). Despite the well understanding of mechanisms implied in the performances of nanofiltration in aqueous media, the ones conditioning OSN productivity and sieving properties remains unclear. The characterization of the PDMS swelling when put in contact with several solvent and submitted under pressure allowed for correlating the structural conformation of the PDMS membrane to its permeation properties. The study of the influence of different operating parameters on the solvent fluxes has brought significant insights in the understanding of permeation mechanisms. Swelling degree (SL), membrane compressibility under transmembrane pressure (TMP), solvent/membrane affinity and solvent viscosity were pointed out as major parameters governing the filtration through PDMS membranes. The results concluded on a molecular transport attributed to hydraulic transport through the swollen PDMS, which behavior in this state was similar to a porous material. The transport mechanisms were confirmed and deepened with a study of solute retention using homologous series of polyethylenglycols as « model » molecules. The results have shown the ability to build a separation process with targeted performances when using the appropriate operating conditions (TMP, SL, temperature...). Two main categories of impact were shown to condition the selectivity and the productivity of the membrane: the ones attributed to the polymer/solvent layout and the ones concerning the physico-chemical properties of the filtrated solution. Both categories have in addition presented synergetic effects on the process performances. After the demonstration of the ability to vary and control the sieving properties of the PDMS membranes, the nanofiltration system was applied to two concrete case studies: a purification of a hydrazynopeptide after its production via a chemical synthesis and a fractionation of a protein hydrolyzate originating from renewable resources. In both cases, the prospection of the PDMS ability in terms of targeted selectivity and productivity showed interesting results that confirmed a promising development of a separation process among the sieving properties can be regulated by the application of suitable operating conditions

The energy consumption of separation processes accounts for a large part of the total energy consumption in chemical industry. Membrane separation processes require much less energy than the currently used thermally driven separation processes and could therefore reduce energy consumption in industry considerably. Today, most commercially available membranes are organic polymeric membranes. Inorganic zeolite membranes have several superiorities over polymeric membranes, e.g., higher flux and selectivity, higher chemical and thermal stability, and thus have great potential for a variety of gas and liquid separations. Whereas there have been extensive studies on zeolite membrane separation at high temperature during the past decades, scientific reports on the low temperature applications of zeolite membranes is extremely scarce and there are no reports at cryogenic temperature. This work is pioneering research on investigation of the performance of zeolite membranes for separation of various gas mixtures at unprecedentedly low temperature, down to cryogenic temperature. In the present work, zeolite membranes were, for the first time, evaluated for gas separation at cryogenic temperature. Air separation by ultra-thin MFI membranes was carried out at a feed pressure ranging from 100 mbar to 5 bar over the temperature range of 62–110 K. The membranes were found to be oxygen selective at all the conditions investigated. The observed results were well above the upper bound in the 2008 Robeson selectivity-permeability plot when the feed pressure was less than or equal to 1 bar. The O2/N2 separation factor reached 5.0 at 67 K and 100 mbar, with a high O2 permeance of 8.6 × 10-7 mol m-2 s-1 Pa-1. The performance of our membranes (in terms of selectivity) was comparable to that recently reported for promising polymeric membranes, but 100 times higher in terms of permeance and flux. The membrane selectivity was found to increase with decreasing temperature and feed pressure. The present work has therefore indicated the optimum conditions for air separation using MFI membranes, namely low feed pressures and cryogenic temperatures. A mathematical model showed that the selectivity to O2 emanated from O2/N2 adsorption selectivity. N2/He separation is essential for helium recovery from natural gas and helium reclamation for airships and submarines. Zeolite membranes were evaluated for this separation over the temperature range of 85–260 K, possessing high N2-selectivity at all the conditions investigated. When the feed pressure was 5 bar and the permeate pressure was 0.5 bar, a highest N2/He separation factor of 62 was observed at 124 K. The N2 permeance was rather high, up to 39 ×10−7 mol m−2 s−1 Pa−1. The separation was attributed to adsorption selectivity of the membranes to N2, effectively suppressing the transport of He in the zeolite pores and this effect was more significant at cryogenic temperature. A mathematical model showed that the largest difference of adsorbed loading over the film at ca. 120 K was probably the main reason for the observed maximum selectivity at this temperature. The model also indicated that the selectivity could even be increased by 2–3 times if the membrane was totally defect-free. This work demonstrates that a zeolite membrane process could be rather competitive for N2/He separation. Synthesis gas generated from biomass is a valuable, renewable resource that can be used for production of clean energy and various chemicals. It is mainly a mixture of CO, CO2, and H2. CO2 is an undesired component in the syngas and should, therefore, be removed. In this work, CO2 separation from H2 and CO using zeolite membranes was studied for at low temperatures, down to 235 K and at a feed pressure of 9 bar. The membrane performance in terms of both selectivity and flux was superior to that reported for the state-of-the-art polymeric and inorganic membranes. The highest separation factor was 202 for CO2/H2 separation at 235 K and 21 for CO2/CO separation at 258 K, significantly higher than that at room temperature. The observed CO2 flux was very high, i.e., 300-420 kg m-2 h-1, in the entire temperature range of 235–310 K. Initial cost estimation revealed that high flux zeolite membranes were economically competitive with the present commercial polymeric membranes. Moreover, the process relying on our zeolite membranes was shown to be appreciably more space-efficient. Efficient light olefins/N2 separation technologies are of great interest to recover monomers from N2 purge gas in polymer plants. C3H6/N2 and C2H4/ N2 separation were investigated using zeolite membranes in a temperature range of 258–356 K. The membranes were rather selective towards the hydrocarbons. For C3H6/N2 separation, a maximum separation factor of 43 was observed at room temperature with a C3H6 permeance of 22×10-7 mol m-2 s-1 Pa-1. For C2H4/N2 separation, the maximum separation factor was 6 at 277 K with a C2H4 permeance of 57×10-7 mol m-2 s-1 Pa-1. The findings reveal that zeolite membranes are promising candidates for light olefins/N2 separation in petrochemical processes. The adsorption properties dominate separation performance for systems studied in the present work. The high selectivity emanates from competitive adsorption, e.g., the strongly adsorbing components hinder the permeances of the weakly adsorbing ones and the effect was stronger at low temperature. In addition, gas permeances through zeolite membranes tend to decrease at low temperature most likely due to decreasing diffusivity, especially at cryogenic temperature. However, the permeances of our membranes even at low temperature were still one to two orders of magnitude higher than those reported for inorganic and polymeric membranes. Thus, the high-flux membranes have great superiority in this case. The fairly high permeance even at low temperatures was ascribed to the ultra-thin (< 1µm) film and highly permeable support used. We provide here a promising candidate, ultra-thin zeolite membranes, with high permeance and excellent selectivity for gas separation application at low temperature.

Godkänd; 2016; 20160215 (penyex); Nedanstående person kommer att disputera för avläggande av teknologie doktorsexamen. Namn: Pengcheng Ye Ämne: Kemisk teknologi/Chemical Technology Avhandling: Zeolite Membrane Separation at Low Temperature Opponent: Professor Anne Julbe, European Institute of membranes (IEM), Frankrike. Ordförande: Professor Jonas Hedlund, Avd för kemiteknik, Institutionen för samhällsbyggnad och naturresurser, Luleå tekniska universitet. Tid: Fredag 22 april 2016, kl 10.00 Plats: C305, Luleå tekniska universitet

The aim of this work was to synthesise a series of hydrophilic derivatives of cis-1,2-dihydroxy-3,5-cyclohexadiene (cis-DHCD) and copolymerise them with 2-hydroxyethyl methacrylate (HEMA), to produce a completely new range of hydrogel materials. It is theorised that hydrogels incorporating such derivatives of cis-DHCD will exhibit good strength and elasticity in addition to good water binding ability. The synthesis of derivatives was attempted by both enzymatic and chemical methods. Enzyme synthesis involved the transesterification of cis-DHCD with a number of trichloro and trifluoroethyl esters using the enzyme lipase porcine pancreas to catalyse the reaction in organic solvent. Cyclohexanol was used in initial studies to assess the viability of enzyme catalysed reactions. Chemical synthesis involved the epoxidation of a number of unsaturated carboxylic acids and the subsequent reaction of these epoxy acids with cis-DHCD in DCC/DMAP catalysed esterifications. The silylation of cis-DHCD using TBDCS and BSA was also studied. The rate of aromatisation of cis-DHCD at room temperature was studied in order to assess its stability and 1H NMR studies were also undertaken to determine the conformations adopted by derivatives of cis-DHCD. The copolymerisation of diepoxybutanoate, diepoxyundecanoate, dibutenoate and silyl protected derivatives of cis-DHCD with HEMA, to produce a new group of hydrogels was investigated. The EWC and mechanical properties of these hydrogels were measured and DSC was used to determine the amount of freezing and non-freezing water in the membranes. The effect on EWC of opening the epoxide rings of the comonomers was also investigated

In the production of biodiesel via the transesterification of vegetable oils, purification to international standards is challenging. A key measure of biodiesel quality is the level of free glycerol in the biodiesel. In order to remove glycerol from fatty acid methyl ester (FAME or biodiesel), a membrane separation setup was tested. The main objective of this thesis was to develop a membrane process for the separation of free glycerol dispersed in FAME after completion of the transesterification reaction and to investigate the effect of different factors on glycerol removal. These factors included membrane pore size, pressure, temperature, and methanol, soap and water content. First, a study of the effect of different materials present in the transesterification reaction, such as water, soap, and methanol, on the final free glycerol separation was performed using a modified polyacrylonitrile (PAN) membrane, with 100 kD (ultrafiltration) molecular weight cut off for all runs at 25°C. Results showed low concentrations of water had a considerable effect in removing glycerol from the FAME. The mechanism of separation of free glycerol from FAME was due to the removal of an ultrafine dispersed glycerol-rich phase present in the untreated (or raw) FAME. The size of the droplets and the free glycerol separation both increased with increasing water content of the FAME. Next, three types of polymeric membranes in the ultrafiltration range with different molecular weight cut off, were tested at three fixed operating pressures and three operating temperatures (0, 5 and 25oC) to remove the free glycerol from a biodiesel reactor effluent. The ASTM standard for free glycerol concentration was met for the experiments performed at 25°C. The results of this study indicate that glycerol could be separated from raw FAME to meet ASTM and EN standards at methanol feed concentrations of up to 3 mass%. The process was demonstrated to rely on the formation of a dynamic polar layer on the membrane surface. Ceramic membranes of different pore sizes (0.05 µm (ultrafiltration (UF) range) and 0.2 µm (microfiltration (MF) range)) were used to treat raw FAME directly using the membrane separation set up at temperatures of 0, 5 and 25°C. The results were encouraging for the 0.05 µm pore size membrane at the highest temperature (25°C). The effect of temperature on glycerol removal was evident from its relation with the concentration factor (CF). Higher temperatures promoted the achievement of the appropriate CF value sooner for faster separation. Membrane pore size was also found to affect separation performance. A subsequent study revealed the effect of different variables on the size of the glycerol droplets using dynamic light scattering (DLS). A key parameter in the use of membrane separation technology is the size of the glycerol droplets and the influence of other components such as water, methanol and soaps on that droplet size. The effect of water, methanol, soap and glycerol on the size of suspended glycerol droplets in FAME was studied using a 3-level Box-Behnken experimental design technique. Standard statistical analysis techniques revealed the significant effect of water and glycerol on increasing droplet size while methanol and soap served to reduce the droplet size. Finally, a study on the effect of trans-membrane pressure (TMP) at different water concentrations in the FAME phase on glycerol removal using UF (0.03 µm pore size, polyethersulfone (PES)) and MF (0.1 and 0.22 µm pore sizes, PES) membranes at 25, 40 and 60°C was performed. Results showed that running at 25°C for the two membrane types produced the best results for glycerol removal and exceeded the ASTM and EN standards. An enhancement of glycerol removal was found by adding small amounts of water up to the maximum solubility limit in biodiesel. An increase in temperature resulted in an increase in the solubility of water in the FAME and less effective glycerol removal. Application of cake filtration theory and a gel layer model showed that the gel layer on the membrane surface is not compressible and the specific cake resistance and gel layer concentration decrease with increasing temperature. An approximate value for the limiting (steady-state) flux was reported and it was found that the highest fluxes were obtained at the lowest initial water concentrations at fixed temperatures. In conclusion, dispersed glycerol can be successfully removed from raw FAME (untreated FAME) using a membrane separation system to meet the ASTM biodiesel fuel standards. The addition of water close to the solubility limit to the FAME mixture enables the formation of larger glycerol droplets and makes the separation of these droplets straightforward.

Thesis: Ph. D., Massachusetts Institute of Technology, Department of Mechanical Engineering, 2017.
Cataloged from student-submitted PDF version of thesis.
Includes bibliographical references (pages 117-124).
Oil is a widespread pollutant from oil spills to industrial oily wastewater in the oil and gas, metalworking, textile and paper, food processing, cosmetics, and pharmaceutical industries. A wastewater of particular concern is produced water, an oily waste stream from hydrocarbon extraction activities. Worldwide, over 2.4 billion US gallons of produced water is generated every day. Membrane technologies have emerged as the preferred method for treating these wastewaters; this has allowed operators to reclaim and reuse fresh water for potable, industrial, and agricultural use and to meet waste discharge regulations. Yet, despite their technological predominance, membranes can become severely fouled and irreversibly damaged when bulk and small stabilized oil droplets, emulsions, are present in intake streams. In this thesis, we seek to mitigate these deleterious effects through several means. First we seek to better understand fouling by oil-in-water emulsions on conventional polymeric ultrafiltration membranes. We investigate the decrease in water production over time using model and actual produced water samples with varying solution zeta potentials and make meaningful recommendations to operators based on our observations. Next, we develop a robust multifunctional membrane which can in one step degrade organic pollutants and separate bulk and surfactant-stabilized oil/water mixtures while achieving high fluxes, high oil rejection, and high degradation efficiencies. Finally, we investigate the potential of novel in-air hydrophilic/oleophobic microfiltration and reverse osmosis membranes for their anti-oil fouling performance relative to conventional hydrophilic/oleophilic membranes. Contrary to claims in literature of superior performance, we find that in-air oleophobicity does not aid in underwater anti-fouling due to surface reconstruction of mobile perfluoroalkyl chains in the presence of water. Based on these observations, we discuss opportunities for future research on oil anti-fouling membranes using fluorinated moieties.
by Leonardo David Banchik.
Ph. D.

Gas separations are often required in chemical processes, e.g. air separation, ethylene production, etc. These are often challenging and costly processes because of the low temperature and high pressure needed if vapour-liquid phase separations are involved. This thesis focuses on hybrid membrane-distillation separations as an opportunity to develop more energy-efficient separation processes. In a typical ethylene plant, recovery, the separation and purification of the cracked product are economically important. The focus of this thesis is on the ‘C2splitter’ which separates the desired product, ethylene, from ethane. Cryogenic distillation, which is currently used to separate the binary ethylene-ethane mixture, is extremely expensive in terms of both capital and operating costs, especially because of refrigerated cooling requirements. Hybrid membrane-distillation processes are able to effectively separate low-boiling compounds and close-boiling mixtures and to reduce energy consumption, relative to cryogenic distillation. However, hybrid membrane-distillation processes present challenges for process modelling, design and operation. There are two major challenges associated with the modelling of hybrid processes for low temperature separations: i) the complex interaction between the process and the refrigeration system and ii) the large number of structural options, e.g. conventional column, membrane unit or hybrid membrane-distillation separation, where the distillation column can be integrated with the membrane unit to form a sequential, parallel, ‘top’or ‘bottom’ hybrid scheme. This thesis develops a systematic methodology to design, screen, evaluate and optimise various design alternatives. Schemes are evaluated with respect to energy consumption, i.e. power consumption of process and refrigeration compressors, or energy costs. In the methodology, process options are screened first for feasibility, based on numerous simulations and sensitivity analyses. Then, the feasible options are evaluated in terms of energy consumption and compared to the performance of a conventional distillation column. Finally, economically viable schemes are optimised to identify the most cost-effective heat-integrated structure and operating conditions. The methodology applies models for multi-feed and multi-product distillation columns, the membrane, compressor and refrigeration system; heat recovery opportunities are systematically captured and exploited. For the separation of relatively ideal mixtures, modified shortcut design methods, based on the Fenske-Underwood-Gilliland method are appropriate because they allow fast evaluation without needing detailed specification of column design parameters (i.e. number of stages, feed and side draw stage locations and reflux ratio). The modifications proposed by Suphanit (1999) for simple column design are extended to consider multi-feed and/or multi-product columns. The complex column designs based on the approximate calculations method are validated by comparison with more rigorous simulations using Aspen HYSYS. To design the hybrid system, a reliable and robust membrane model is also needed. To predict the performance of the module model, this work applies and modifies detailed membrane model (Shindo et al., 1985) and approximate method (Naylor and Backer, 1955) to avoid the need for initial estimates of permeate purities and to facilitate convergence. Heat integration opportunities are considered to reduce the energy consumption of the system, considering interactions within the separation process and with the refrigeration system. A matrix-based approach (Farrokhpanah, 2009) is modified to assess opportunities for heat integration. The modified heat recovery model eliminates the need to design the refrigeration cycle and uses a new simple, linear model that correlates the ideal (Carnot) and a more accurately predicted coefficient of performance. This work develops a framework for optimising important degrees of freedom in the hybrid separation system, e.g. permeate pressure, stage cut, side draw molar flow rate and purity, column feed and side draw locations. Heat recovery options between: i) column feeds and products; ii) the membrane feed and products and iii) the associated refrigeration system are considered. A deterministic and a stochastic optimisation algorithm are applied and compared for their efficiency of solving the resulting nonlinear optimisation problem. The new approach is demonstrated for the design and optimisation of heat-integrated sequential and parallel hybrid membrane-distillation flowsheets. Case study results show that hybrid scheme can reduce energy cost by 11%, compared to distillation, and that parallel schemes have around 8% lower energy costs than sequential hybrid schemes. These results suggest hybrid membrane-distillation processes may be competitive with distillation when applied for ethylene-ethane separations, but that further development of suitable membranes may still be needed.

Over the past 40 years, research pertaining to membrane technology has lead to the development of a wide range of applications including beverage production, water purification and the separation of dairy products. For the separation of gases, membrane technology is not as widely applied since the production of suitable gas separation membranes is far more challenging than the production of membranes for eg. water purification. Hydrogen is currently produced by recovery technologies incorporated in various chemical processes. Hydrogen is mainly sourced from fossil fuels via steam reformation and coal gasification. Special attention will be given to Underground Coal Gasification since it may be of great importance for the future of South Africa. The main aim of this study was to develop low temperature CsHSO4/SiO2 composite membranes that show significant Idea selectivity towards H2:CO2 and H2:CH4.

Nowadays, the need and interest for renewable sources of energy has increased. Biogas is a renewable source of energy that can be considered as a sustainable substitute for natural gas. Biogas is mainly composed of CH4 and CO2, and normally the CO2 content of the gas has to be reduced as it decreases the calorific value of the gas and it may also cause corrosion in pipes and other equipment. Most today’s technologies used for upgrading biogas have been adapted from upgrading of natural gas. However, these technologies are best suited for large scale operation; whereas, production of biogas is typically several orders of magnitude smaller. This leads to high costs for removal of CO2 from biogas and consequently, new efficient technologies for upgrading biogas should be developed. Membrane-based separations are generally considered as energy efficient and are suitable for a wide range in scale of production due to their modular design. Zeolite membranes have been singled out as especially attractive membranes for gas separations. In this work, we therefore study separation of CO2 from CH4 and H2 using zeolite MFI membranes.  The performance of a high-silica (Si/Al ca. 139) MFI membrane for CO2/CH4 separation was investigated in a wide temperature range i.e. 245 K to 300 K. The separation factor increased with decreasing temperatures as is typically the case for adsorption governed separations. The highest separation factor observed was about 10 at 245 K. The CO2 permeance was very high in the whole temperature studied, varying from ca. 60 × 10-7 mol s-1 m -2 Pa-1 at the lowest temperature to about 90 × 10-7 mol s-1 m -2 Pa-1 at the highest temperature studied. The CO2 permeance was higher than that reported previously in the open literature for this separation. Modeling of the experimental data revealed that the membrane performance was adversely affected by pressure drop over the support, whereas the effect of concentration polarization was small. Removing the former effect would improve both the permeance and selectivity of the membrane.  In order to investigate the impact of the aluminum content on the performance of MFI membranes for the CO2/CH4 separation, MFI membranes with different Si/Al ratios were prepared. Increasing the aluminum content makes the zeolite II more polar which should increase the CO2/CH4 adsorption selectivity. Again the effect of temperature on the performance was investigated by varying the temperature in a range almost similar as above. Altering the Si/Al ratio in MFI zeolite membranes indeed changed the separation performances. At the lower temperatures the separation performance increased with increasing aluminum content in the zeolite as a result of larger adsorption selectivity. However, as the temperature was decreased, the selectivity of the membrane with the highest aluminum content went through a maximum, whereas for the other membranes the selectivity continued to increase with decreasing temperature under the conditions studied. At the same time, the CO2 permeances were high for all membranes studied and for the membrane with the highest selectivity, the CO2 permeance increased from 65 × 10-7 to 100 × 10-7 mol s-1 m -2 Pa-1 with increasing temperature.  High-silica MFI membranes were also evaluated for CO2/H2 separation, which is critical for syngas purification and H2 production. The highest CO2 permeance at the feed pressure of 9 bar was about 78 × 10-7 mol s-1 m -2 Pa-1 at around 300 K, which is one or two order of magnitude higher than those reported previously in the literature. By decreasing the temperature, separation factor reached its highest value of 165 at 235 K.  In summary, zeolite membranes show great potential for CO2 separation from industrial gases, in particular for CO2 removal from synthesis gas. For the CO2/CH4 separation the selectivity of the MFI membranes should be improved or other frameworks relying on molecular sieving e.g. the CHA framework should be explored.

The aim of this work was to develop a viable solvent-extraction based system for the separation of rhodium (Rh) from aqueous chloride solutions. Ultimately, two different systems were developed. Kelex 100, a commercially available derivative of 8-hydroxyquinoline, was used as the extractant reagent in both of these systems. One of the systems involved the supported liquid membrane (SLM) extraction of Rh. In this system a very thin microporous "Gore-Tex" polymer sheet, impregnated with an organic solution of Kelex 100, served as the SLM. The other system involved the conversion of the chlorocomplexes of Rh to bromocomplexes prior to their solvent extraction with Kelex 100.
The results of the lab-scale experiments using a SLM of Kelex 100 having a surface area of 44 cm2 are reported. The optimum conditions for Rh permeation were found as a feed solution of 2.5 M HCl and a strip solution of 0.1 M HCl. The SLM was quite stable at the optimum conditions with no sign of organic loss or membrane deterioration after 72 hours of operation. It was determined that the HCl activity gradient across the membrane acts as the driving force that "pumps" the non-aquated Rh chlorocomplexes against their concentration gradient. The mechanism of Rh permeation was the ion-pair formation between the protonated Kelex 100 and RhCl6 3- complexes. The rate of Rh permeation was in the order of 10-6 mol.m-2.s-1. The mechanism of HCl and H2O permeation, which were co-extracted along with Rh chlorocomplexes, were found to be the hydration of protons at the low feed acid region and the formation of microemulsions at the high feed acid region. The permeated acid and water were separated from the SLM receiving phase by contacting the latter phase with an organic solution of trioctylamine (TOA). The chlorocomplexes of Rh(III) and acid are readily extracted to the TOA organic phase and subsequently subjected to differential stripping with a concentrated solution of Cl- and a mild NaOH solution, respectively. By interfacing the TOA solvent extraction with the SLM of Kelex 100 highly concentrated solutions of Rh (at least 10 times the initial concentration) and raffinates essentially free of rhodium were produced.
The UV-Visible investigations revealed that the bromocomplexes of Rh undergo aquation to a much lesser extent than that of the chlorocomplexes. The chlorocomplexes of Rh were converted to bromocomplexes by precipitating first the Na(NH4)2Rh(NO2)6 salt and subsequently dissolving that in an HBr solution. The newly formed bromocomplexes of Rh(III) responded very favorably to extraction with Kelex 100. Relatively high distribution coefficients, about 20, and very steep extraction isotherms were generated. The freshly loaded Kelex 100 organic was efficiently stripped upon contact with a strip solution of 6--8 M HCl and a contact time of 10--12 hours. The developed system shows high promise from a practical implementation point of view.

The world is facing a serious water crisis due to rapid population growth, industrialization and climate change. Water purification using membrane technologies provides a promising solution to address this problem. This thesis investigated the feasibility of membrane technologies in a wide range of applications covering drinking water purification and wastewater treatment. Target contaminants included fluoride, natural organic matter (NOM), emerging contaminants bisphenol A (BPA) and cimetidine, and the waterborne parasite Cryptosporidium. The first part of the thesis explored the solute-solute interactions of fluoride and humic substances (HS) in order to understand the behaviour of fluoride in natural water and during membrane filtration processes. It is shown that, at low pH and high ionic strength, fluoride ions are temporarily trapped inside the structure of HS aggregates. The second part of the thesis examined the feasibility of nanofiltration (NF) and reverse osmosis (RO) in treating challenging natural waters in Tanzania containing high fluoride and NOM concentrations, with the aim to increase the availability of drinking water sources. Fluoride retention was found to be dependent on ionic strength and recovery, which was predominantly due to a solution-diffusion mechanism. NOM retention was independent of water matrices but was governed by a size exclusion mechanism. NOM was observed to have a positive impact on fluoride removal. The third part of this work evaluated the on-site performance of a pilot-scale renewable energy powered membrane system in remote areas under varying solar conditions. While the technology is well established, the adaptation to remote areas is far from achieved. The system used in this study reliably produced high-quality drinking water despite of solar fluctuations. This area requires further work in terms of integration, technology adaptation and operation and maintenance schemes. The last part of the thesis reported the development of a series of novel photocatalytic polymers and tested their capabilities in removing wastewater contaminants. The photoactive polymers were highly capable of degrading BPA and cimetidine, as well as inactivating Cryptosporidium. These are very promising materials for simultaneous decontamination and disinfection of wastewater. The results obtained from this thesis provide new insights into solute-solute interactions, solute transport mechanisms, decentralized membrane system and novel membrane materials, which are hoped to contribute to advancements in current membrane technologies.

El procesado de alimentos conlleva, en mayoría de los casos, la generación de subproductos o residuos que pueden ser reutilizados o revalorizados mediante la utilización de técnicas de separación por membrana. Estas técnicas ofrecen la posibilidad de tratar las soluciones en condiciones de operación muy suaves, y no comportan en mayoría de las ocasiones, una alteración de los componentes a recuperar. Actualmente, las técnicas de separación por membrana, debido a su alta calidad y relativamente bajos costes, se encuentran completamente integradas en la mayoría de procesos productivos que requieren de una etapa de separación. Sin embargo, la investigación en el área de las técnicas de separación por membrana sigue abriendo nuevos campos de aplicación, que surgen con la mejora de las condiciones tecnológicas de los equipos y la posibilidad de obtener nuevas membranas adaptables a necesidades específicas.

En concreto, en este proyecto se utilizaron técnicas de separación por membranas para concentrar soluciones de azúcar procedentes de deshidratación osmótica (en adelante OD). El principal objetivo fue estudiar el potencial de varias técnicas de separación, haciendo hincapié en los flujos obtenidos durante la reconcentración y en la calidad de la solución reconcentrada.

La deshidratación osmótica es un tratamiento que permite una eliminación parcial del agua en un alimento y/o la incorporación de solutos de una manera controlada, respetando la calidad inicial del producto. El proceso consiste en introducir los alimentos en una solución hipertónica, controlando las condiciones de operación para favorecer, en mayor o menor grado la incorporación de solutos y la deshidratación del alimento. La aplicación de OD puede resultar en la mejora de las propiedades nutricionales y funcionales de los alimentos y en la reducción de la energía requerida para la deshidratación. El principal problema de la aplicación industrial de la OD radica en la gestión de la solución procedente del proceso. La reutilización de esta solución plantea una doble ventaja: primero desde el punto de vista ambiental, ya que se elimina un efluente del proceso que a menudo no puede ser vertido directamente, y segundo el ahorro económico que representa la recuperación de las materias primas que muchas veces contienen solutos de importante valor económico.

Los métodos de separación por membrana utilizados para recuperar las soluciones de OD fueron los siguientes: nanofiltración, osmosis directa y destilación osmótica por membranas. La nanofiltración (NF) presenta altos niveles de retención y un menor gasto de energía que la osmosis inversa, y en la industria azucarera se aplica como uno de los pasos en la clarificación y concentración de jarabes. En los procesos de contactores de membranas: osmosis directa (DO) y destilación osmótica por membranas (OMD), a diferencia de los procesos basados en el tamizaje, el flujo depende solamente de la diferencia de potencial osmótico. Las únicas presiones hidráulicas requeridas son las necesarias para bombear la solución de azúcar y la solución osmótica hasta la superficie de la membrana. Estas características hacen que estos procesos presenten como muy prometedores para la reconcentración de soluciones de azúcar de concentraciones elevadas.

Los experimentos de filtración se llevaron a cabo utilizando plantas piloto diseñadas y construidas expresamente para el presente proyecto. Durante todos los procesos de separación por membranas, se empleó como solución modelo una solución de sacarosa a diferentes concentraciones (5-60 ºBrix), debido a que las soluciones aplicadas en la deshidratación osmótica de frutas son habitualmente soluciones de azucares (sacarosa, glucosa o jarabes).

Durante los experimentos de NF se evaluó el funcionamiento de las membranas planas: Desal5 DK (GE- Osmonics), MPF-34 (Koch Membrane), NFT-50 (DSS) y tubulares: MPT-34 (Koch Membrane) y AFC 80 (PCIMembranes). Además de la solución de azúcar de diferentes concentraciones (5-20 ºBrix), se concentraron zumos de pera y manzana.


La reconcentración mediante osmosis directa se realizó utilizando dos modos de operación: off-site e on-site. En el modo off-site, la reconcentración por ósmosis directa se llevó a cabo en una planta de filtración provista de un módulo plano o tubular, dependiendo de la membrana. En el módulo se llevó a cabo la concentración. En el modo on-site, la deshidratación se realizaba conjuntamente con la reconcentración de la solución osmótica. La solución de reconcentración de la osmosis directa en off-site (offsiteDO) fue NaCl, mientras la solución de reconcentración de la osmosis directa on-site (on-site DO) fue una solución de sacarosa más concentrada que la solución osmótica (60 para una solución osmótica de 40 y 68 para una solución de 50 ºBrix). Para garantizar el flujo de agua entre las dos soluciones y altas retenciones de azúcar durante la off-site DO, se utilizaron membranas de NF planas (Desal5-DK y MPF-34) y tubulares (MPT-34 y AFC80). La reconcentración por osmosis directa on-site se levó a cabo empleando una membrana de microfiltración (Durapore, Millipore), ya que la solución de reconcentración (SS) es la misma que la solución osmótica y la alta viscosidad de la SS restringe mucho el flujo de agua si se utiliza una membrana más densa.

En la deshidratación por membranas (OMD) se utilizaron membranas hidrófobas (11806, Sartorius) que presentan una retención teórica del 100 %. Se comparó el rendimiento de dos soluciones de reconcentración: NaCl y CaCl2.

Con el fin de obtener información referente a la influencia de las propiedades de las membranas sobre el desarrollo del proceso de concentración de las soluciones procedentes de la deshidratación osmótica, se realizó un estudio detallado de las propiedades de las membranas aplicadas mediante AFM, SEM, FTIR, ángulo de contacto y medidas de potencial zeta. Con la finalidad de generar soluciones osmóticas para someterlas a reconcentración, y también para disponer de productos procedentes de deshidratación osmótica con soluciones frescas que pudieran compararse con aquellas procedentes de OD con solución reconcentrada, se deshidrataron diferentes lotes de manzana (Granny Smith) con soluciones de sacarosa de 40, 50 y 60 ºBrix. Estas pruebas permitieron determinar también el tímelo de operación para una máxima pérdida de agua con relativamente poca impregnación de las manzanas. Después de cada experimento se analizaron los siguientes parámetros: concentración de azúcar, pH, absorbancia a 420 nm de las soluciones y humedad de las manzanas.

La nanofiltración, aplicada en la primera fase del presente estudio, resultó ser viable solamente para la reconcentración de soluciones de concentraciones hasta 24 ºBrix. El aumento de la temperatura de 25 hasta 35 ºC para las dos membranas tubulares ocasionó un incremento del flujo de permeado, y el mismo efecto tuvo el aumento de presión transmembranaria de 8 a 12 bar.

Se comprobó que el factor más importante para la eficacia del proceso es disponer de una membrana que combine altos flujos y retenciones durante el proceso. La deposición de las partículas de sacarosa y/o los zumos se caracterizó mediante SEM y la topología de la capa filtrante de la membrana se identificó usando AFM. La topología de la capa filtrante de las membranas era diferente para cada una de ellas, a pesar de que todas estaban preparadas con el mismo material (poliamida). En las imágenes de los cortes transversales de las membranas realizados con SEM, se observaron los cambios en la estructura de las membranas producidos por la aplicación de presión durante los experimentos y las altas temperaturas empleadas durante su acondicionamiento. Gracias a las imágenes de SEM se pudo verificar también la eficacia del proceso de acondicionamiento de membranas.

A diferencia de NF, tanto la ósmosis directa como la destilación osmótica por membrana permiten la reconcentración de soluciones concentradas de sacarosa (hasta60 ºBrix). La eficacia de estas dos últimas técnicas se evaluó en unción de los flujos de agua obtenidos.

El sistema de ósmosis directa on-site propuesto para la reconcentración de las soluciones de OD permitió reutilizar las soluciones osmóticas como mínimo cuatro veces. Para la solución osmótica de 40 ºBrix la humedad de las manzanas fue similar utilizando solución fresca o reconcentrada. En cambio, una solución osmótica de 50 ºBrix, la pérdida de agua de las manzanas fue mayor cuando la deshidratación osmótica se llevó a cabo con reconcentración on-site de la solución osmótica. Los análisis de concentración de azúcar de las soluciones osmóticas y de la solución de reconcentración indican que la membrana elegida para los experimentos facilita el transporte óptimo de solutos y agua entre las dos soluciones. Además, el sistema de reconcentración por membrana propuesto es muy sencillo y de bajo coste porque no requiere presurización.

La osmosis directa en off-site proporcionó flujos mucho mayores que los obtenidos con el sistema on-site (1.3 kg/m2h para la solución osmótica de 50 ºBrix respecto a 0.0023 kg/m2h durante on-site DO para la misma solución). Sin embargo, el transporte de solutos de la solución de reconcentración hacía la solución osmótica puede ser considerado un obstáculo para su aplicación a escala industrial.

Los flujos de agua más elevados fueron obtenidos utilizando la OMD (2.01 kg/m2h para la solución osmótica de 50 ºBrix y con CaCl2 con la solución de reconcentración). Otra gran ventaja de este proceso es la retención de solutos que proporciona, hecho confirmado por los análisis realizados.

El estudio sobre el transporte durante los procesos de contactores de membranas indicó que la viscosidad es la propiedad limitante para la solución osmótica y la actividad de agua/alta presión osmótica como la propiedad más importante a la hora de elegir una solución de reconcentración. Para todos los procesos de separación aplicados, el aumento de la concentración de azúcar de la solución osmótica comporta una disminución notable del flujo de agua.

El desarrollo de un posible proceso de deshidratación osmótica con una etapa de reconcentración de la solución osmótica mediante procesos con contactores de membrana ha permitido calcular el área requerida para realizar la reconcentración: 3.6,9.7, 1608 m2 para OMD, off-site DO e on-site DO, respectivamente.

Las conclusiones del trabajo confirman la posibilidad de utilizar procesos por membrana para realizar la reconcentración de soluciones osmóticas. No obstante se ha constatado que técnicas más tradicionales basadas en diferencias de presión (NF) no son

Gas absorption in hollow fibre contactors is being increasingly used due to their enormous surface area/volume ratio. The capability of the hollow fibre membrane modules for the removal of CO 2 and SO2 from a binary gas mixture has been investigated experimentally. Four different modules were used in this study. The membranes in modules one and two were made of microporous polypropylene. The third module was made of non-porous silicone rubber (polydimethylsiloxane) while the latter one was a polyvinylidenefluoride (PVDF) asymmetric hollow fibre membrane. The gas mixtures used in the experiments were composed of 9.5% CO2 and 1% SO2 in N 2 , which was introduced into the hollow fibre lumen, while the absorbent liquid was fed into the shell side of module. The absorbent liquids used were water, aqueous solutions of diethanolamine (DBA) and ammonia at different concentrations (5, 10 and 20 wt%). The effects of different operating conditions on the permeation process have been investigated for co-current and counter-current flow patterns. In addition, to improve the silicone rubber hollow fibre membrane performance, baffles were installed within the shell of the permeator to increase liquid fibre contact. The results obtained showed that the use of baffles within the shell of the permeator improved the separation performance of the non-porous membrane module without any substantial increase in the physical size of the contacting device. Studies also showed that improved performance was observed when the system was operated under a counter-current flow pattern. The results showed that the use of an absorbent liquid in the permeate side of the fibres increased the selectivity of the membranes used, and reduced the need to maintain a high pressure ratio across the membrane. A decrease in the feed gas flow rate or increase in liquid flow rate generally improved the removal of gases. The results showed that the use of aqueous reactive solutions as an absorbing medium in the permeate side of the hollow fibre permeator can significantly improve CO2 removal from the gas mixture. However, the main problem when using a microporous membrane coupled with aqueous solutions of diethanolamine as absorbent was wetting of the microporous membrane by amine solutions. For 862 separation, the highest removal was attained using the microporous membrane coupled with water as absorbent liquid. This demonstrates that a hollow fibre based device can be a very efficient gas liquid contactor. The separation process was simulated with a numerical model based on the effective permeabilities of gases and compared with the experimental results. The model simulations showed good agreement with the experimental observations.

The search for alternatives to traditional energy intensive separation methods such as distillation has led to the introduction of processes based on membranes. In this research, the use of detailed mathematical models for the optimal design of membrane systems is investigated. Mathematical models of hollow-fibre and spiral-wound membrane modules are presented in this thesis. The models are developed from rigorous mass, momentum and energy balances and can be used to describe a generic membrane separation. This is in contrast to most existing models which are typically process specific and are only valid within a limited operating range. The generality of the new approach is demonstrated by application to gas separation, pervaporation, and reverse osmosis case studies. Simulation results for these systems show excellent agreement with published experimental data. The thesis also introduces an optimal design strategy for membrane separation systems. This strategy is characterised by two main features: firstly, detailed models are used. This is essential if sub-optimal and inaccurate solutions are to be avoided. Secondly, an optimisation technique based on genetic algorithms is implemented. This provides multiple solutions, allowing the user to interpret the results and make a more informed decision. The feasibility of the optimal design strategy is investigated using two realistic case studies. In the first study, the optimal design of reverse osmosis desalination plants is considered and the use of both hollow-fibre and spiral-wound modules is examined. The results of this study compare favourably with work published in the open literature and highlight the importance of using detailed models to describe membrane separation systems. In the second study, the use of pervaporation for ethanol dehydration is investigated. An existing pervaporation plant is evaluated and a significantly improved design is found.

The major innovation of this work is an establishment of a novel chiral separation process using preferential crystallization coupled with a membrane barrier. This hybrid process was proved to be promising from a significant increase in product yield and purity compared to existing chiral separation processes. This work sets up a process design platform to extend the use of this hybrid process to a separation of other mixtures. This novel process especially is a promising alternative for chiral separation of pharmaceutical compounds which include more than fifty percent of approved drugs world-wide. A better performance chiral separation technique contributes to cut the operating cost and to reduce the price of chiral drugs.

Thesis (MTech (Chemical Engineering))--Cape Peninsula University of Technology, 2006
A protocol already exists for fabrication of a capillary membrane having an internal ultrafiltration skin supported by a finger-like pore structure in the external capillary wall (Jacobs and Leukes, 1996; Jacobs and Sanderson, 1997). These membranes have been produced at the Institute of Polymer Science, University of Stellenbosch, South Africa. Two major applications emerged from the development of these internally skinned membranes. One application was in the production of potable water by Ultra-filtration (UF) from sources containing coloured water. A second application was in the immobilization of a white rot fungus in a ."gradostat" membrane bioreactor. Here a nutrient gradient through the membrane wall and fungal mat can be established and manipulated in order to stimulate continuous production of secondary metabolites (extra-cellular enzymes). These enzymes are useful in the degradation of polycyclic aromatic compounds, notably PCB species in contaminated water and soils (Jacobs and Sanderson, 1997). Two objectives emerged from experiences with the above applications. The first objective was to improve membrane performance in UF applications. In this case a reduction was sought in trans-membrane pressure differential required to attain a desired flux without sacrificing rejection. The pressure required for a given desired flux across a membrane depends on the resistance of the membrane skin layer and of its supporting sub-layer which together comprises the capillary wall and defmes its overall structure. If any of these resistances could be reduced, the overall resistance to transport of water would be reduced. Then it would be possible to operate the membrane at lower trans-membrane pressure differences. On the other hand, operation with higher pressure would also increase flux but require a thicker capillary wall to resist this pressure. In the attempt to optimise these properties of the capillary membrane, capillary membranes produced in the study reported here were tested to find the relationship of flux performance with the structures that resulted from varying key parameters affecting structure and integrity. The objective in the case of immobilizing fungi in membrane bioreactor applications was to attain thicker walls thus providing better support for the fungal mass. The internally skinned capillary membrane has finger-like microvoids that start next to the UF skin layer and extend across the capillary membrane wall and open at the external membrane periphery, giving an ideal structure for retaining the fungal biomass. The idea of a membrane with this type of morphology to immobilize white rot fungi was to anchor the growing fungus within these microvoids which imitate the natural environment in which these organisms live, that is, in the fibrous structure of decaying wood. The requirement to inoculate the microvoids with fungal spores (reproductive cells), implies that they need to be accessible from the outside, requiring a membrane wall that is externally unskinned. In the formation ofthe capillary membrane the processes of formation of the porous UP skin and the finger-like microvoids are mainly governed by diffusion of solvent out of a polymer dope (gel phase) and of non-solvent into the dope phase. Such exchanges are of primary importance between the bore fluid (containing non-solvent) and dope (containing solvent) or between the external spinning bath (high in solvent content) and dope. Diffusion effects also occur between the nascent pore voids and the precipitating polymer matrix. There are also expected to be some convection effects due to shear between the bore fluid and the moving dope gel phase and due to shrinkage ofthe gel phase. The variables selected for experimentation m the study reported here were: the dope extrusion rate (DER); dope composition (viscosity effects); bore fluid flow rate (BFF); bore fluid composition and wall thickness and diameter effects (determined largely by spinneret dimensions). Each of these has an expected effect on membrane structure and its resulting performance. Most were varied over narrow ranges indicated in the literature and by experience to be effective and critical. In addition, the effects of altering the walI thickness were investigated by using two different spinneret sizes. The external spinning bath composition (solvent content) was reported in the literature to be a particularly important parameter in the formation of externally unskinned membranes. Maintaining a high content of solvent in the external spinning bath could prevent skin formation. Too high a solvent content could, however, prevent phase transition and lead to later precipitation ofa dense skin on contact with the non-solvent in the later (humidification and rinsing) steps in the fmishing of the capillary membrane product. The external bath composition was therefore varied so as to find the bath composition that would match the cloud point for the polymer dope employed. As expected, the thickness of the membranes increased with DER increase. However, it was found that there is a critical wall thickness where an external skin layer is formed as a result of increasing the DER. A certain volumetric ratio ofDER to BFF (1,5:1 for this study) was therefore maintained in order to produce externally unskinned membranes. This shows that although the final membrane structure is detennined by the casting dope formulation, the fabrication protocol plays an equally important role in controlling structural properties and perfonnance. There was no significant change with the membrane thickness as a result of changing BFF but the voids became longer and more in number as the BFF was increased. Too high solvent content (99% NMP in this study) resulted in an external skin layer being formed. According to Smolders et.al. (1992), when the solvent content in the external spinning bath is too high, the polymer at the surface of the newly fonned membrane slowly dissolves in the external spinning bath re-forming a dope-like solution. When the newly formed membrane passes through the humidifier, the dope-like solution solidifies to form an external skin. At the same instance, too low solvent (93% for this study) resulted in external skin being fonned. Externally unskinned membranes were formed at 94 and 96% NMP bath composition. The use of a small spinneret resulted in very thin walled externally unskinned membranes.

Thesis (M. Phil.)--Hong Kong University of Science and Technology, 2004.
Includes bibliographical references (leaves 93-102). Also available in electronic version. Access restricted to campus users.

Mixed matrix hollow fiber membranes maintain the ease of processing polymers while enhancing the separation performance of the pure polymer due to inclusion of molecular sieve filler particles. This work shows the development process of high loading mixed matrix hollow fiber membranes for butane isomer separation, from material selection and engineering of polymer-sieve interfacial adhesion to mixed matrix hollow fiber spinning. The matching of gas transport properties in polymer and zeolite is critical for forming successful mixed matrix membranes. The nC4 permeability in glassy commercial polymers such as Ultem® and Matrimid® is too low (< 0.1 Barrer) for commercial application. A group of fluorinated (6FDA) polyimides, with high nC4 permeability and nC4/iC4 selectivity, are selected as the polymer matrix. No glassy polymers can possibly match the high permeable MFI to make mixed matrix membranes with selectivity enhancement for C4s separation. Zeolite 5A, which has a nC4 permeability (~3 Barrer) and nC4/iC4 selectivity (essentially ∞), matches well with the 6FDA polymers. A 24% nC4/iC4 selectivity enhancement was achieved in mixed matrix membranes containing 6FDA-DAM and 25 wt% treated 5A particles. A more promising mixed matrix membrane contains 6FDA-DAM-DABA matrix and 5A, because of a better match of gas transport properties in polymer and zeolite. Dual layer hollow fibers, with cellulose acetate core layer and sheath layers of 6FDA polyimides, were successfully fabricated. Successive engineering of the 6FDA sheath layer and the dense skin is needed for the challenging C4s separation, which is extremely sensitive to the integrity of the dense skin layer. The delamination-free, macrovoid-free dual layer hollow fiber membranes provide the solution for the expensive 6FDA polyimides spinning. Mixed matrix hollow fiber membranes are spun base on the platform of 6FDA/Cellulose acetate dual layer hollow fibers. Preliminary results suggest that high loading mixed matrix hollow fiber membranes for C4s is feasible. Following research is needed on the fiber spinning with well treated zeolite 5A nanoparticles. The key aspect of this research is elucidating the three-step (sol-gel-precipitation) mechanism of sol-gel-Grignard treatment, based on which further controlling of Mg(OH)2 whisker morphologies is possible. A Mg(OH)2 nucleation process promoted by acid species is proposed to explain the heterogeneous Mg(OH)2 growing process. Different acid species were tried: 1) HCl solution, 2) AlClx species generated by dealumination process and 3) AlCl3 supported on zeolite surfaces. Acids introduced through HCl solution and dealumination are effective on commercial 5A particles to generate Mg(OH)2 whiskers in the sol-gel-Grignard treatment. Supported AlCl3 is effective on both commercial and synthesized 5A particles (150 nm-1 µm) during the sol-gel-Grignard treatment, in terms of promoting heterogeneous Mg(OH)2 whiskers formation. But the byproduct of Al(OH)3 layer separates the Mg(OH)2 whiskers from zeolite surface, and leads to undesirable morphologies for polymer-zeolite interfacial adhesion. The elucidation of sol-gel-Grignard mechanism and importance of zeolite surface acidity on Mg(OH)2 formation, builds a solid foundation for future development towards ''universal'' method of growing Mg(OH)2 whiskers on zeolite surfaces.

Proteins exist in a variety of isoforms with minor differences, mostly due to their glycosylation patterns, which can modulate their biological functions. It seems to be of clinical relevance to measure the isoform-distribution.

Thesis describes a novel technology named Membrane-Assisted Isoform ImmunoAssay (MAIIA). This technique allows rapid (< 15 min.) isoform determination. It is based on a chromatographic separation combined with immunoassay detection. These steps are performed along a thin, disposable micro-porous chip in which capillary forces maintain the flow. By using anion-exchange as a chromatographic principle the technology has been utilized for the determination of transferrin isoforms in ten minutes. In one variant (the one-dimensional), selected isoforms (carbohydrate-deficient transferrin) are quantified. In a more elaborate variant (the two-dimensional) it was possible to determine the entire isoform profile of transferrin. Isoforms differing by only 0.1 pH unit in isoelectric point could be distinguished.

The chromatography along the microporous bed of nitrocellulose showed very good separation performance with plate heights of 10-20 µm and only minor flow rate variations between individual devices.

The quantitative determination of antibody-captured molecules was performed by using antibodies labelled with carbon black particles. Combined with a detection procedure by means of a flatbed scanner, a highly sensitive and specific immunoassay with a detection limit of 0.13 pM was obtained upon using IgE as a model analyte.

This technology can thus be used to rapidly distinguish proteins with minor structure differences and specifically determine protein isoforms in complex environments, e.g., blood, down in the pM (10^-12 M) concentration range.

An emulsion liquid membrane (ELM) containing Cyanex 302 has been successfully used for the recovery of cadmium from synthetic phosphoric acid solutions containing 30% wt. P205. The ELM formulation was optimised for high extraction rate and stability. Cyanex 302, and a mixture of NaC1 (3M) and HC1 (1M), were selected from a set of possible reagents and stripping phases, following equilibrium and kinetic experiments in two-phase systems. Under chemical control the rate of Cd2 extraction was pseudo first order with respect to Cd2 and Cyanex 302 concentration. Arlacel C was found to be the most suitable surfactant for emulsion stability. The dependence of the ELM rate of Cd 2 extraction on the concentrations of cadmium, Cyanex 302, and surfactant, as well as on phase and treat ratio, and homogeniser and stirrer speed, was investigated. Cadmium extraction levels were found to be above 90% for most conditions. The influence of operating variables on emulsion swelling and rupture was also evaluated as a function of time. Swelling of the internal phase of the emulsion reached values greater than 50%, whilst emulsion rupture was below 2%. Emulsion globule size distributions in the stirred tank were measured for different impeller speeds and diameters, reagent concentrations, and emulsion hold-up, using an endoscope attached to a high-speed video camera. A correlation for globule size, accounting for swelling and rupture phenomena, changes in viscosity and hold-up, was proposed and found to be in good agreement with experimental results. This allowed the effect of the stirring speed on the specific interfacial area and the mass transfer coefficient to be decoupled, and led to the conclusion that the overall rate of Cd 2 recovery was controlled by diffusional resistances in the continuous phase. A time- dependent model, and a quasi-steady state model were proposed for the extraction of cadmium with the ELM. Simulations with both models were found to be in good agreement with experimental results.