Tesi sul tema "Membrane separation"

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.

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

The overall aim of this research is to develop unique conducting polyaniline (PANI) membranes that can be electrically tuned to achieve different fluxes and selectivity. The target application is in a tuneable membrane reactor, where these membranes allow the fouling layer to be pushed off/through membranes by application of external potential. To achieve this, several different types of PANI membranes were examined. The permeation properties of HCl-doped PANI membranes can be modified electrically to produce in-situ tuneable separations. However, acid dopant leaching and membrane brittleness limit the further application of these membranes. Polymer acid doped PANI membranes using poly(2-acrylamido-2-methyl-1-propanesulfonic acid) or PAMPSA were investigated as a solution. These PAMPSA doped PANI membranes displayed improved mechanical strength and filtration stability. However, the membranes showed decreased electrical conductivity, leading to a limited tuneable permeance and selectivity under applied potential. To overcome this new challenge, expanded graphite and a large acid (dodecylbenzene sulfonic acid or DBSA) were incorporated into the PAMPSA doped PANI membranes to increase the conductivity. Despite increasing both conductivity and electrical tuneability, the resulting membranes were more porous with looser molecular weight cut-off (outside of the desired NF/low UF MWCO range) than without modification. Efforts to tighten PAMPSA doped membranes to the same MWCO as HCl doped membranes using volatile co-solvents (THF and acetone) were unsuccessful: porosity was due to the large acid dopants. Membranes were examined for their potential for in-situ fouling removal of model foulant bovine serum albumin under applied voltage. This was successful and defouling extent was found to be closely related to membranes with higher conductivity and greater acid stability. Overall, it has been demonstrated that the conducting polyaniline composite membranes can be made to be stable to acid leaching and be more mechanically robust, whilst also being externally electrically tuned to different molecular selectivities with the potential for in-situ fouling control.

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.

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

Thesis (Ph.D)--Chemical Engineering, Georgia Institute of Technology, 2008.
Committee Chair: Koros, William; Committee Member: Beckham, Haskell; Committee Member: Eckert, Charles; Committee Member: Henderson, Cliff; Committee Member: Meredith, Carson. Part of the SMARTech Electronic Thesis and Dissertation Collection.

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.

Membrane materials for gas separations span a wide range including polymers, metals, ceramics and composites. Our aim is to create economical hydrothermally stable membranes that can provide high H₂-CO₂ separation at a temperature of 300 degree Celsius, for application in the water-gas shift reactor process. The present work describes the development of novel silica and silica-titania membranes from the controlled oxidative thermolysis of polydimethylsiloxane. The scope of this thesis is fabrication of membranes, material characterization and preliminary gas permeation tests (35-80 degree Celsius) on PDMS derived silica membrane films. The developed membranes can withstand up to 350 degree C in air. High permeabilties of small gas penetrants like He, H₂ and CO₂ have been observed and fairly high separation factors of O₂/N₂=3, H₂/N₂= 14 and H₂/CH₄=11 have been obtained. As the temperature of operation increases, the permeability of hydrogen increases and the separation factor of H₂ from CO₂ increases. The silica membranes exhibit gas separation factors higher than the respective Knudsen values. Additionally, design and construction of a new high temperature gas permeation testing system is described, which will cater to gas permeation tests at temperatures up to 300 degree Celsius for future work. The thesis also includes a detailed plan for future studies on this topic of research.

Orientadores: Teresa Massako Kakuta Ravagnani, Leila Peres
Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química
Made available in DSpace on 2018-08-18T23:18:07Z (GMT). No. of bitstreams: 1 Araujo_PauloJardelPereira_D.pdf: 15740528 bytes, checksum: bd5969744efcacfde55b69c10f951f33 (MD5) Previous issue date: 2011
Resumo: O biodiesel além de ser biodegradável e obtido de fontes renováveis, apresenta propriedades físico-químicas muito semelhantes ao diesel de petróleo, não necessitando de um novo motor para utilização do mesmo. A rota química mais comumente usada para obtenção do biodiesel é a transesterificação. Nesta, pela reação de um álcool com os triacilgliceróis (TAG) presentes principalmente em óleos vegetais e gordura animal, são produzidos o biodiesel e, como produto secundário, o glicerol em grandes quantidades. A presença deste glicerol é indesejada, pois além de diminuir a produtividade do biodiesel pelo equilíbrio termodinâmico estabelecido no processo, também aumenta seu custo pelo alto tempo de decantação e/ou uso de centrífugas para remover o glicerol do biodiesel. Devido a este inconveniente, o presente trabalho propõe rota alternativa para separação do glicerol, utilizando membrana de microfiltração (TiO2/Al2O3). Vários sistemas foram analisados, focando a separação do glicerol, o aumento do fluxo permeado e da conversão de TAG na catálise heterogênea. Inicialmente estudou-se a permeabilidade e seletividade dos reagentes e produtos obtidos na síntese do biodiesel com a membrana, através de experimentos binários. A partir destes resultados, estabeleceu-se uma nova configuração do sistema para então analisar estes fatores em misturas compostas pelos quatro constituintes do processo através de um planejamento fatorial. Os resultados apresentados geraram modelos que descrevem com 95% de confiabilidade o coeficiente de rejeição ao glicerol e o fluxo permeado frente aos fatores analisados (nível de emulsificação, razão molar óleo/etanol e conversão de TAG). Selecionou-se então, uma melhor faixa destes fatores que resultem em um máximo de rejeição ao glicerol com máximo fluxo permeado, obtendo um resultado bastante representativo do processo que apresentou um bom fluxo permeado (90,11kg/h.m2) com alta rejeição de glicerol (98,69%). Posteriormente propôs-se um estudo do processo simultâneo de reação e separação (leito fixo catalítico envolto em membrana), sendo selecionado para a reação de síntese um catalisador heterogêneo (SrO suportado em alumina), visando facilitar o processo de separação e reduzir significativamente o número de etapas de purificação dos produtos. Os resultados de conversão do TAG foram baixos, impossibilitando uma análise completa do sistema com esta configuração do ponto de vista de reação e separação concomitante
Abstract: In addition to being biodegradable and renewable, Biodiesel presents physicochemical properties very similar to those of petroleum-based diesel, so a new engine is not required for its use. The most commonly used chemical process for obtaining biodiesel is transesterification. In this process, through the reaction of an alcohol with triacylglycerols (TAG) present mainly in vegetable oils and animal fat, biodiesel is formed with large quantities of glycerol as a byproduct. The presence of glycerol is unwanted because besides reducing the productivity of biodiesel through the thermodynamic equilibrium established in the process, it also increases the cost due to the long time for settling and/or use of centrifuges for removing the glycerol from biodiesel. Taking into account this inconvenience, this paper proposes an alternative process for the separation of glycerol, using TiO2/Al2O3 membranes. Various systems were analyzed, focusing on the separation of glycerol, the increase of the permeate flux, and the increase in the TAG productivity in heterogeneous catalysis. At first we studied the permeability and selectivity of reagents and products obtained in the biodiesel synthesis with a membrane through binary experiments. From these results a new configuration of the system was established, with subsequent analysis of the new interaction in mixtures of the four components of the process (oil, Ethanol, Biodiesel, glycerol) using a factorial design as tool. Results presented in the factorial design generated models that describe with 95% reliability the glycerol rejection coefficient and the permeate flux compared to the analyzed factors (level of emulsification, molar ratio of oil/ethanol and TAG conversion). A best range of factors that result in a maximum glycerol rejection with maximum permeate flux was selected, obtaining a fairly representative result of the process showing a good permeate flux (90.11 kg/h.m2) with high glycerol rejection rate (98.69%). Subsequently, the study of the reaction and separation simultaneous process was proposed (fixed catalytic bed involved in a membrane) selecting an heterogeneous catalyst (SrO on alumina) to facilitate the separation process and significantly reduce the number of purification steps of products. Results of biodiesel conversion were low, preventing a full assessment of the system with this configuration considering simultaneous reaction and separation
Doutorado
Sistema de Processos Quimicos e Informatica
Doutor em Engenharia Química

Thesis (MTech (Chemical Engineering))--Peninsula Technikon, 2000.
Oxygen transport across biofilms and membranes may be a limiting factor in the operation of a membrane bio-reactor. A Gradostat fungal membrane bio-reactor is one in which fungi are immobilized within the wall of a porous polysulphone capillary membrane. In this study the mass transfer rates of gases (oxygen and carbon dioxide) were investigated in a bare membrane (without a biofilm being present). The work provides a basis for further transport study in membranes where biomass is present. The diaphragm-cell method can be employed to study mass transfer of gases in flat-sheet membranes. The diaphragm-cell method employs two well-stirred compartments separated by the desired membrane to be tested. The membrane is maintained horizontally. -The gas (solute) concentration in the lower compartment is measured versus time, while the concentration in the upper liquid-containing compartment is maintained at a value near zero by a chemical reaction. The resistances-in-series model can be used to explain the transfer rate in the system. The two compartments are well stirred; this agitation reduces the resistances in the liquid boundary layers. Therefore it can be assumed that in this work the resistance in the membrane will be dominating. The method was evaluated using oxygen as a test. The following factors were found to influence mass transfer coefficient: i) the agitation in the two compartments; ii) the concentration of the reactive solution and iii) the thickness of the membrane.

Thesis (PhD)--University of Stellenbosch, 2005.
ENGLISH ABSTRACT: A new membrane based affinity separation system that is bio-specific, biocompatible, well characterised and capable of being regenerated or re-used is described. The amphiphilic non-ionic surfactant Pluronic® F108, was covalently derivatised to form two novel bioligands (Pluronic-Biotin and Pluronic-DMDDO) for the bio-specific immobilisation of avidin conjugated proteins and histidine tagged proteins respectively. Pluronic was also used to non-covalently functionalise nonporous membranes for ligand attachment and to simultaneously shield the surfaces from non-specific protein adsorption. Each component of this bioaffinity system (from the membrane matrix to the elution/desorption of the ligate/ligand system) was studied with the aim of producing a well characterised system and key quantitative data for the development of a robust, reliable, re-usable and scalable technology. Specifically, this study describes: 1. The fabrication and partial characterisation of nonporous planar and capillary membranes as model affinity matrices. 2. The development and evaluation of a robust protocol for solvent desorption and accurate colorimetric quantification of Pluronic® F108 and its derivatives. 3. Interfacial analysis of Pluronic adsorption onto nonporous affinity membranes, including the direct solid-state analysis of model, halogenated Pluronic derivatives using nuclear microprobe analysis. 4. Development of a surfactant based protocol for affinity membrane regeneration and re-use. 5. Specific bioaffinity immobilisation of avidin conjugated peroxidase onto biotinylated membranes in the presence of model protein foulants. 6. Cloning and expression of C-terminal hex-histidine tagged human cytochrome b5 into the bacterial expression system E. coli BL-21 DE3. 7. Development and characterisation of an immobilised metal affinity membrane system for metal chelation (Ni2+, Cu2+ and Zn2+) using a new chelator Pluronic- N,N-dicarboxymethyl-3,6-diazaoctanedioate and the bio-specific immobilisation of N-terminal hex-histidine tagged pantothenate kinase.
AFRIKAANSE OPSOMMING: 'n Nuwe membraan-gebaseerde affiniteitskeidingsisteem word beskryf wat biospesifiek, bioversoenbaar en goed gekarakteriseer is, en geregenereer of hergebruik kan word. Die amfifiliese nie-ioniese surfaktant Pluronic is kovalent gederivatiseer om twee nuwe bioligande (Pluronic-Biotien en Pluronic-DMDDO) te vorm vir biospesifieke immobilisering van proteïnligate. Pluronic is ook gebruik om nie-poreuse membrane niekovalent te funksionaliseer vir ligandaanhegting en om hulle oppervlaktes teen niespesifieke proteïen-adsorbsie af te skerm. Elke komponent van hierdie bioaffiniteitsisteem (van die membraanmatriks tot die uitwas/desorpsie van die ligaat/ligand sisteem) is ondersoek met die doel om 'n goed-gekarakteriseerde sisteem te produseer en om kwantitatiewe data te genereer vir die ontwikkeling van 'n robuuste, betroubare, herbruikbare en opskaleerbare tegnologie. Hierdie studie beskryf spesifiek: 1. Die fabrisering en gedeeltelike karakterisering van nie-poreuse planêre en kapillêre membrane as model affiniteitsmatrikse. 2. Die ontwikkeling en evaluering van 'n robuuste protokol vir oplosmiddel desorpsie en akkurate kolorimetriese kwantifikasie van Pluronic® F108 en afgeleides daarvan. 3. Intervlakanalises van Pluronic adsorpsie op nie-poreuse affiniteitsmembrane, insluitend die direkte vastetoestand analise van model ligand-gemodifiseerde Pluronic deur die gebruik van kern-mikrosonde analise. 4. Ontwikkeling van 'n surfaktant-gebaseerde protokol vir affiniteitsmembraan regenerering en hergebruik. 5. Spesifieke bioaffiniteitsimmobilisering van avidien-gekonjugeerde peroksidase op gebiotinileerde membrane in die teenwoordigheid van model bevuilende proteïne. 6. Klonering en uitdrukking van C-terminaal hex-histidien geëtiketeerde menslike sitochroom b5 in die bakteriële uitdrukkingsisteem E. coli BL-21 DE3. 7. Ontwikkeling en karakterisering van 'n geïmmobiliseerde metaalaffiniteitsmembraansisteem vir metaalchelering (Ni2+, Cu2+ en Zn2+) met behulp van die nuwe cheleerder Pluronic-N,N-dikarboksimetiel-3,6- diasaoktaandioaat en die bio-spesifieke immobilisering van N-terminaal hexhistidiengeëtiketerde pantotenaatkinase.

Whey protein fractionation is an important industrial process that requires effective large-scale processes. Although packed bed chromatography has been used extensively, it suffers from low processing rates due to high back-pressures generated at high flow rates. Batch chromatography has been applied but generally has a low efficiency. More recently, adsorptive membranes have shown great promise for large-scale protein purification, particularly from large-volume dilute feedstocks. A new method for producing versatile adsorptive membranes by combining membrane and chromatographic resin matrices has been developed but not previously applied to whey protein fractionation. In this work, a series of mixed matrix membranes (MMMs) were developed for membrane chromatography using ethylene vinyl alcohol (EVAL) based membranes and various types of adsorbent resin. The feasibility of MMM was tested in bovine whey protein fractionation processes. Flat sheet anion exchange MMMs were cast using EVAL and crushed Lewatit® MP500 (Lanxess, Leverkusen, Germany) anion resin, expected to bind the acidic whey proteins β-lactoglobulin (β-Lac), α-lactalbumin (α-Lac) and bovine serum albumin (BSA). The MMM showed a static binding capacity of 120 mg β-Lac g⁻¹ membrane (36 mg β-Lac mL⁻¹ membrane) and 90 mg α-Lac g⁻¹ membrane (27 mg α-Lac mL⁻¹ membrane). It had a selective binding towards β-Lac in whey with a binding preference order of β-Lac > BSA > α-Lac. In batch whey fractionation, average binding capacities of 75.6 mg β-Lac g⁻¹ membrane, 3.5 mg α-Lac g⁻¹ membrane and 0.5 mg BSA g⁻¹ membrane were achieved with a β-Lac elution recovery of around 80%. Crushed SP Sepharose™ Fast Flow (GE Healthcare Technologies, Uppsala, Sweden) resin was used as an adsorbent particle in preparing cation exchange MMMs for lactoferrin (LF) recovery from whey. The static binding capacity of the cationic MMM was 384 mg LF g⁻¹membrane or 155 mg LF mL⁻¹ membrane, exceeding the capacity of several commercial adsorptive membranes. Adsorption of lysozyme onto the embedded ion exchange resin was visualized by confocal laser scanning microscopy. In LF isolation from whey, cross-flow operation was used to minimize membrane fouling and to enhance the protein binding capacity. LF recovery as high as of 91% with a high purity (as judged by the presence of a single band in gel electrophoresis) was achieved from 150 mL feed whey. The MMM preparation concept was extended, for the first time, to produce a hydrophobic interaction membrane using crushed Phenyl Sepharose™ (GE Healthcare Technologies, Uppsala, Sweden) resin and tested for the feasibility in whey protein fractionation. Phenyl Sepharose MMM showed binding capacities of 20.54 mg mL⁻¹ of β-Lac, 45.58 mg mL⁻¹ of α-Lac, 38.65 mg mL⁻¹ of BSA and 42.05 mg mL⁻¹ of LF for a pure protein solution (binding capacity values given on a membrane volume basis). In flow through whey fractionation, the adsorption performance of the Phenyl Sepharose MMM was similar to the HiTrap™ Phenyl hydrophobic interaction chromatography column. However, in terms of processing speed and low pressure drop across the column, the benefits of using MMM over a packed bed column were clear. A novel mixed mode interaction membrane was synthesized in a single membrane by incorporating a certain ratio of SP Sepharose cation resin and Lewatit MP500 anion resin into an EVAL base polymer solution. The mixed mode cation and anion membrane chromatography developed was able to bind basic and acidic proteins simultaneously from a solution. Furthermore, the ratio of the different types of adsorptive resin incorporated into the membrane matrix could be customised for protein recovery from a specific feedstream. The customized mixed mode MMM consisting of 42.5 wt% of MP500 anionic resin and 7.5 wt% SP Sepharose cationic resin showed a binding capacity of 7.16 mg α-Lac g⁻¹ membrane, 11.40 mg LF g⁻¹ membrane, 59.21 mg β-Lac g⁻¹ membrane and 6.79 mg IgG g⁻¹ membrane from batch fractionation of 1 mL LF-spiked whey. A tangential flow process using this membrane was predicted to be able to produce 125 g total whey protein per L membrane per h.

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.

Compared to the conventional amine adsorption process to separate CO₂ from natural gas, the membrane separation technology has exhibited advantages in easy operation and lower capital cost. However, the high CO₂ partial pressure in natural gas can plasticize the membranes, which can lead to the loss of CH₄ and low CO₂/CH₄ separation efficiency. Crosslinking of polymer membranes have been proven effective to increase the CO₂ induced plasticization resistance by controlling the degree of swelling and segmental chain mobility in the polymer. This thesis focuses on extending the success of crosslinking to more productive asymmetric hollow fibers. In this work, the productivity of asymmetric hollow fibers was optimized by reducing the effective selective skin layer thickness. Thermal crosslinking and catalyst assisted crosslinking were performed on the defect-free thin skin hollow fibers to stabilize the fibers against plasticization. The natural gas separation performance of hollow fibers was evaluated by feeding CO₂/CH₄ gas mixture with high CO₂ content and pressure.

Thesis (MTech (Chemical Engineering))--Cape Peninsula University of Technology, Cape Town, 2006
During recent years, the use of liquid membranes has gained general interest in the treatment of effiuents where solute concentrations are low and large volumes of solutions should be processed, and, if possible, without generating any secondary waste. Liquid membrane processes have been proposed as a clean technology, owing to their characteristics, i.e. high specificity, low energy and utilization. Two liquid membrane processes have been used in metal recovery, which are the liquid surfactant membrane (LSM), which corresponds to double water-in-oil emulsion and solid . supported liquid membranes (SLM), which are made by dispersing or impregnating the extractant within the pores of in.ert solid support. Previously, the recovery of eu (IT) in a SLM system was conducted by other membrane models such as hollow fibre, spiral and flat sheet. Only a small measure of success on scale-up and industrialization of these models has been attained. One of the disadvantages of the hollow fibre system was the small lumen size through which the feed needed to pass. Pores became clogged by suspended particles because the pressure drop over the small diameter augments lower flow rates and therefore, pre-filtering is necessary (Rathore, et al., 2001). In this study the behaviour of a tubular SLM reactor with an inner diameter of the lumen approximately fifty times bigger than that of the hollow fibre are used in order to solve the problem of clogging. This tubular reactor was incorporated in to a bench scale plant and proved successful in copper extraction. By observing transient data, mass transport coefficients were determined and compared to published values.

[ES] La presente tesis doctoral se centra en el desarrollo de nuevas membranas de separación de gases, así como su empleo in-situ en reactores catalíticos de membrana para la intensificación de procesos. Para este propósito, se han sintetizado varios materiales, como polímeros para la fabricación de membranas, catalizadores tanto para la metanación del CO2 como para la reacción de síntesis de Fischer-Tropsch, y diversas partículas inorgánicas nanométricas para su uso en membranas de matriz mixta. En lo referente a la fabricación de las membranas, la tesis aborda principalmente dos tipos: orgánicas e inorgánicas. Con respecto a las membranas orgánicas, se han considerado diferentes materiales poliméricos, tanto para la capa selectiva de la membrana, así como soporte de la misma. Se ha trabajado con poliimidas, puesto que son materiales con temperaturas de transición vítrea muy alta, para su posterior uso en reacciones industriales que tienen lugar entre 250-300 ºC. Para conseguir membranas muy permeables, manteniendo una buena selectividad, es necesario obtener capas selectivas de menos de una micra. Usando como material de soporte otro tipo de polímero, no es necesario estudiar la compatibilidad entre ellos, siendo menos compleja la obtención de capas finas. En cambio, si el soporte es de tipo inorgánico, un exhaustivo estudio de la relación entre la concentración y la viscosidad de la solución polimérica es altamente necesario. Diversas partículas inorgánicas nanométricas se estudiaron para favorecer la permeación de agua a través de los materiales poliméricos. En segundo lugar, en cuanto a membranas inorgánicas, se realizó la funcionalización de una membrana de paladio para favorecer la permeación de hidrógeno y evitar así la contaminación por monóxido de carbono. El motivo por el cual se dopó con otro metal la capa selectiva de la membrana metálica fue para poder emplearla en un reactor de Fischer-Tropsch. Con relación al diseño y fabricación de los reactores, durante esta tesis, se desarrolló el prototipo de un microreactor para la metanación de CO2, donde una membrana polimérica de capa fina selectiva al agua se integró para evitar la desactivación del catalizador, y a su vez desplazar el equilibrio y aumentar la conversión de CO2. Por otro lado, se rediseñó un reactor de Fischer-Tropsch para poder introducir una membrana metálica selectiva a hidrogeno y poder inyectarlo de manera controlada. De esta manera, y siguiendo estudios previos, el objetivo fue mejorar la selectividad a los productos deseados mediante el hidrocraqueo y la hidroisomerización de olefinas y parafinas con la ayuda de la alta presión parcial de hidrógeno.
[CAT] La present tesi doctoral es centra en el desenvolupament de noves membranes de separació de gasos, així com el seu ús in-situ en reactors catalítics de membrana per a la intensificació de processos. Per a aquest propòsit, s'han sintetitzat diversos materials, com a polímers per a la fabricació de membranes, catalitzadors tant per a la metanació del CO2 com per a la reacció de síntesi de Fischer-Tropsch, i diverses partícules inorgàniques nanomètriques per al seu ús en membranes de matriu mixta. Referent a la fabricació de les membranes, la tesi aborda principalment dos tipus: orgàniques i inorgàniques. Respecte a les membranes orgàniques, diferents materials polimèrics s'ha considerat com a candidats prometedors, tant per a la capa selectiva de la membrana, així com com a suport d'aquesta. S'ha treballat amb poliimides, ja que són materials amb temperatures de transició vítria molt alta, per al seu posterior ús en reaccions industrials que tenen lloc entre 250-300 °C. Per a aconseguir membranes molt permeables, mantenint una bona selectivitat, és necessari obtindre capes selectives de menys d'una micra. Emprant com a material de suport altre tipus de polímer, no és necessari estudiar la compatibilitat entre ells, sent menys complexa l'obtenció de capes fines. En canvi, si el suport és de tipus inorgànic, un exhaustiu estudi de la relació entre la concentració i la viscositat de la solució polimèrica és altament necessari. Diverses partícules inorgàniques nanomètriques es van estudiar per a afavorir la permeació d'aigua a través dels materials polimèrics. En segon lloc, quant a membranes inorgàniques, es va realitzar la funcionalització d'una membrana de pal¿ladi per a afavorir la permeació d'hidrogen i evitar la contaminació per monòxid de carboni. El motiu pel qual es va dopar amb un altre metall la capa selectiva de la membrana metàl¿lica va ser per a poder emprar-la en un reactor de Fischer-Tropsch. En relació amb el disseny i fabricació dels reactors, durant aquesta tesi, es va desenvolupar el prototip d'un microreactor per a la metanació de CO2, on una membrana polimèrica de capa fina selectiva a l'aigua es va integrar per a així evitar la desactivació del catalitzador i al seu torn desplaçar l'equilibri i augmentar la conversió de CO2. D'altra banda, un reactor de Fischer-Tropsch va ser redissenyat per a poder introduir una membrana metàl¿lica selectiva a l'hidrogen i poder injectar-lo de manera controlada. D'aquesta manera, i seguint estudis previs, el objectiu va ser millorar la selectivitat als productes desitjats mitjançant el hidrocraqueix i la hidroisomerització d'olefines i parafines amb l'ajuda de l'alta pressió parcial d'hidrogen.
[EN] The present thesis is focused on the development of new gas-separation membranes, as well as their in-situ integration on catalytic membrane reactors for process intensification. For this purpose, several materials have been synthesized such as polymers for membrane manufacture, catalysts for CO2 methanation and Fischer-Tropsch synthesis reaction, and inorganic materials in form of nanometer-sized particles for their use in mixed matrix membranes. Regarding membranes manufacture, this thesis deals mainly with two types: organic and inorganic. With regards to the organic membranes, different polymeric materials have been considered as promising candidates, both for the selective layer of the membrane, as well as a support thereof. Polyimides have been selected since they are materials with very high glass transition temperatures, in order to be used in industrial reactions which take place at temperatures around 250-300 ºC. To obtain highly permeable membranes, while maintaining a good selectivity, it is necessary to develop selective layers of less than one micron. Using another type of polymer as support material, it is not necessary to study the compatibility between membrane and support. On the other hand, if the support is inorganic, an exhaustive study of the relation between the concentration and the viscosity of the polymer solution is highly necessary. In addition, various inorganic particles were studied to favor the permeation of water through polymeric materials. Secondly, as regards to inorganic membranes, the functionalization of a palladium membrane to favor the permeation of hydrogen and avoid carbon monoxide contamination was carried out. The membrane selective layer was doped with another metal in order to be used in a Fischer-Tropsch reactor. Regarding the design and manufacture of the reactors used during this thesis, a prototype of a microreactor for CO2 methanation was carried out, where a thin-film polymer membrane selective to water was integrated to avoid the deactivation of the catalyst and to displace the equilibrium and increase the CO2 conversion. On the other hand, a Fischer-Tropsch reactor was redesigned to introduce a hydrogen-selective metal membrane and to be able to inject it in a controlled manner. In this way, and following previous studies, the aim is to enhance the selectivity to the target products by hydrocracking and hydroisomerization the olefins and paraffins assisted by the presence of an elevated partial pressure of hydrogen.
I would like to acknowledge the Spanish Government, for funding my research with the Severo Ochoa scholarship.
Escorihuela Roca, S. (2019). Novel gas-separation membranes for intensified catalytic reactors [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/121139
TESIS

Olefin/paraffin separation is a large potential market for membrane applications. Carbon molecular sieve membranes (CMS) are promising for this application due to the intrinsically high separation performance and the viability for practical scale-up. Intrinsically high separation performance of CMS membranes for olefin/paraffin separations was demonstrated. The translation of intrinsic CMS transport properties into the hollow fiber configuration is considered in detail. Substructure collapse of asymmetric hollow fibers was found during Matrimidﾮ CMS hollow fiber formation. To overcome the permeance loss due to the increased separation layer thickness, 6FDA-DAM and 6FDA/BPDA-DAM polyimides with higher rigidity were employed as alternative precursors, and significant improvement has been achieved. Besides the macroscopic morphology control of asymmetric hollow fibers, the micro-structure was tuned by optimizing pyrolysis temperature protocol and pyrolysis atmosphere. In addition, unexpected physical aging was observed in CMS membranes, which is analogous to the aging phenomenon in glassy polymers. For performance evaluation, multiple "proof-of-concept" tests validated the viability of CMS membranes under realistic conditions. The scope of this work was expanded from binary ethylene/ethane and propylene/propane separations for the debottlenecking purpose to mixed carbon number hydrocarbon processing. CMS membranes were found to be olefins-selective over corresponding paraffins; moreover, CMS membranes are able to effectively fractionate the complex cracked gas stream in a preferable way. Reconfiguration of the hydrocarbon processing in ethylene plants is possible based on the unique CMS membranes.

We examined the effect of the pore dimension of zeolites on the separation of gas mixtures using atomistic simulation methods. We studied two categories of the zeolites with small pores: pore modified silicalite for H₂/CH₄separation and small pore silica zeolites for CO₂/CH₄separation. The effect of pore modification of silicalite on the H₂/CH₄separation was examined. Under some degrees of surface modification, the CH₄flux was reduced much more than the H₂flux, resulting in high ideal selectivities. The use of small pore zeolites for CO₂/CH₄separations was studied. In DDR, we showed that CO₂diffusion rates are only weakly affected by the presence of CH₄, even though the latter molecules diffuse very slowly. Consequently, therefore, the permeance of CO₂in the equimolar mixtures is similar to the permeance for pure CO₂, while the CH₄permeance in the mixture is greatly reduced relatively to the pure component permeance. The calculated CO₂/CH₄separation selectivities are higher than 100 for a wide range of feed pressure, indicating excellent separation capabilities of DDR based membranes. Inspired by the observation in DDR we also examined the separation capabilities of 10 additional pure silica small pore zeolites for CO₂/CH₄separations. From these considerations, we predict that SAS, MTF and RWR will exhibit high separation selectivities because of their very high adsorption selectivities for CO₂over CH₄. CHA and IHW, which have similar pore structures to DDR, showed comparable separation selectivities to DDR because of large differences in the diffusion rates of CO₂and 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.

Efficient separation of hydrogen from gas mixtures is a truly enabling technology for hydrogen as an energy carrier. Palladium(Pd)-based membranes are 100% selective to hydrogen, but need to be made thin, yet without defects in order for the technology to be applicable. The motivation for this work has been to examine solubility properties and surface topography for Pd-based membranes, and further elucidate the influence these parameters have on the overall hydrogen permeation capabilities. Extremely thin, defect-free Pd-alloy membranes supplied by SINTEF Materials and Chemistry were investigated in this study.Thin Pd/Ag23wt.% free standing films of thickness 4 &#956;m and 8 &#956;m were inves- tigated before and after heat treatment in air at 300 C. A revealing trend of increased flux resulting from this heat treatment was observed. Surface topogra- phy studies by atomic force microscopy (AFM) showed a correlating increase in surface roughness as a result of the heat treatment. In addition, surface topogra- phy investigation was performed on a hydrogen stabilized 8 &#956;m thick Pd/Ag23wt.% membrane. High increase in roughness was detected on feed side whereas minimal roughness alteration was observed on permeate side of the membrane. Equilibrium sorption measurements of H2 in Pd/Ag23wt.% films of various thick- nesses (2.2-10 &#956;m) were performed at 300 C, 350 C and 400 C to the measure the film’s solubility properties. A pronounced temperature dependence was observed for all membranes, that is, high solubility at low temperatures and vice versa for high temperatures. This is consistent with theory and previously reported solu- bility results. A thickness dependence for the H2 solubility was observed in the equilibrium sorption results. Thinner membranes showed better solubility capa- bilities than the thicker ones. Surface characterization showed increasing surface roughness on growth side on these as-grown films in correspondence with augmen- tation in film thickness. The correlative surface roughness and solubility alterations related to thickness indicate a plausible membrane bulk structural dependence of the solubility.Finally, sorption equlibrium measurements on very thin Pd alloy films, &#8764;2 &#956;m, of Pd/Ag23wt.%, Pd/Au5at.% and Pd/Y5at.% were carried out at 300 C, 350 C and 400 C. All three palladium-alloys showed decreasing solubility properties for in- creasing temperature. The Pd/Ag23wt.% membrane showed the highest solubility capabilities, succeeded closely by the Pd/Y5at.% membrane, while the Pd/Au5at.% membrane was not comparably capable to ad-/absorb H2 gas. This is concluded as a result of unequal lattice expansion effects the different alloying elements exert in a pure Pd lattice.The hydrogen permeation is a complex function of many parameters. In this work parameters such as, hydrogen pressure, temperature, material composition, mem- brane thickness and surface structure have demonstrated their influence on the membranes solubility and/or permeation abilities.

A theoretical explanation of the existence of lipid rafts in cell membranes remains a topic of lively debate. Large, micrometer sized rafts are readily observed in artificial membranes and can be explained using thermodynamic models for phase separation and coarsening. In live cells such domains are not observed and various models are proposed to describe why the systems do not coarsen. We review these attempts critically and show within a phase field approach that membrane bound proteins have the potential to explain the different behaviour observed in vitro and in vivo. Large scale simulations are performed to compute scaling laws and size distribution functions under the influence of membrane bound proteins and to observe a significant slow down of the domain coarsening at longer times and a breakdown of the self-similarity of the size-distribution function
Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich

A theoretical explanation of the existence of lipid rafts in cell membranes remains a topic of lively debate. Large, micrometer sized rafts are readily observed in artificial membranes and can be explained using thermodynamic models for phase separation and coarsening. In live cells such domains are not observed and various models are proposed to describe why the systems do not coarsen. We review these attempts critically and show within a phase field approach that membrane bound proteins have the potential to explain the different behaviour observed in vitro and in vivo. Large scale simulations are performed to compute scaling laws and size distribution functions under the influence of membrane bound proteins and to observe a significant slow down of the domain coarsening at longer times and a breakdown of the self-similarity of the size-distribution function.
Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.

Metal membranes are useful for hydrogen separation from mixed gas streams. They can exhibit perfect selectivity for hydrogen. However, in order to be commercially viable, in addition to providing high hydrogen fluxes, they must also be resistant to poisoning, possess long operating lifetimes and be cost effective. Many types of metal membranes such as pure metals, disordered alloys and amorphous metals have been studied for this application. In this work, we aim to identify intermetallic stoichiometric compounds of two or more metals that could be used as potential membrane materials for hydrogen separation. In the past, first principle calculations combined with Monte Carlo methods have been developed that can accurately predict H₂ fluxes through metal membranes at different hydrogen pressures and temperatures. Although these models are accurate, they are computationally intensive. In this work, we use these methods and develop screening criteria based on calculated properties that enable us to perform detailed calculations on a diminishing set of materials and rapidly identify the favorable candidates for hydrogen separation. We screened 1059 intermetallics at this high level of theory, which is the largest set of materials studied for this application. We divided the intermetallics into Pd-based and non-Pd based materials using additional screening algorithms to reduce the number of calculations required to identify potential candidate materials. 8 intermetallics were identified that had permeabilities that was comparable or higher to that of pure Pd. MgZn₂ and MnTi were found to have the highest H permeabilities among all the intermetallics studied. In addition to ground state structures, metastable structures were also found to be stabilized in the presence of hydrogen. Our work demonstrates the ability of these computational methods to identify potential novel materials for specific applications from large sets of materials that would not be possible experimentally. In the models for hydrogen permeability developed above, H-induced metal lattice rearrangements were not considered. Experimental evidence suggests that hydrogen heat treated (HHT) Pd-Au alloys undergo lattice rearrangement that results in an ordered structure which has a higher solubility than the non-HHT alloys. Using a combination of cluster expansion methods developed for predicting hydrogen permeability of disordered alloys and Monte Carlo methods, we predicted the extent of H induced lattice rearrangement in Pd₉₆Au₄ and Pd₈₅Au₁₅ alloys. We also predicted the solubility, diffusivity and permeability of these rearranged phases and found that their H permeability is higher than the non-rearranged phases. Our models capture the H-induced lattice rearrangement and provide useful insight of the conditions where this phenomenon is significant. Using the tools developed in this work, similar alloys that have a tendency to undergo lattice rearrangement that results in enhanced H permeability can be identified.

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.

Polyimide membranes containing nickel dithiolenes were investigated for the separation of propylene and propane. Permeation and sorption experiments were conducted as well thermal property analyses. Results indicate that the dithiolene has an antiplasticizing effect on the polymers studied. Upon addition of the dithiolene there is a subsequent reduction in the permeability coefficient and the permeability selectivity remains relatively unchanged. There is some evidence of increases in solubility selectivity, but a larger decrease in diffusivity selectivity results in a decrease in the permeability selectivity. Investigation of the thermal and mechanical properties of dithiolene-containing films indicates a reduction in fractional free volume as well as the glass transition temperature when compared to the pure polymer. There is also an increase in the modulus of the films upon addition of the dithiolene. The implications of these results and their correlation with antiplasticization are discussed.

Le comportement plastifiant de polymères purs a été bien étudié dans la littérature. Toutefois, il n'y a eu que peu d'études concernant les membranes à matrices mixtes (MMM). Dans le chapitre 2 de cette thèse, le comportement plastifiant de MMM préparés à partir de nanoparticules mésoporeuses Fe(BTC) et du polymère Matrimid® est étudié avec un gaz pur ou en mélange. Les réseaux métaux-organiques (MOF) sous forme particulaires ont présenté une relativement bonne compatibilité avec le polymère. L'incorporation de Fe(BTC) dans du Matrimid® a permis d'augmenter la perméabilité et la sélectivité des membranes. Pour de faibles pressions de 5 bars, les MMM ont une perméabilité au CO2 de 60% plus grande ainsi qu'une sélectivité de 29% plus grande à comparer à la sélectivité idéale de membranes Matrimid®. Il a été observé que la présence de particules Fe(BTC) retardait l'effet plastifiant vers de plus grandes pressions. De plus, cette pression augmente avec le taux de MOF au sein du matériau. Ce retard est attribué à la mobilité réduite des chaînes polymères dans l'entourage des particules Fe(BTC). Egalement, pour des concentrations en MOF plus élevées, les membranes présentent une sélectivité plus ou moins constante sur toute la gamme de pression étudiée. Le chapitre 3 présente ensuite la préparation et le caractère plastifiant des MMMs basées sur trois types de MOFs (MIL-53(Al) (MOF « repirant »), ZIF-8 (MOF « flexible ») and Cu3(BTC)2 (MOF « rigide »)) dispersés dans le Matrimid®. Les performances en gaz pur ou en mélange ont été étudiées en fonction de la quantité de MOF introduite. Parmi les trois systèmes MOF-MMM, les membranes avec le Cu3(BTC)2 ont présenté la plus haute sélectivité alors que les membranes avec du ZIF-8 ont montré une plus grande perméabilité. Ces améliorations sont essentiellement le fait de la structure cristalline du MOF et de son interaction avec les molécules de CO2. Le chapitre 4 décrit la préparation de membranes à base de mélange Matrimid® polyimide (PI)/polysulfone (PSF) contenant des particules de ZIF-8 pour la séparation gazeuse à haute pression. Un mélange optimisé avec un rapport PI/PSF de 3:1 a été utilisé pour une étude sur la stabilité et la performance de ces MMMs incorporant différentes concentration de ZIF-8. PI et PSF étant miscibles, une bonne compatibilité avec les particules de ZIF-8 est observée. Les MMMs PI/PSF-ZIF-8 ont démontré une amélioration significative de la perméabilité en CO2 lors de l'augmentation de la concentration en ZIF-8, ce qui a été attribué à une augmentation modérée de la capacité de sorption et à une diffusion plus rapide au travers des particules de ZIF-8. Lors des mesures en gaz purs, les membranes PI/PSF (3:1) ont présenté une plastification vers 18 bars alors que l'introduction de ZIF-8 repousse cette valeur à 25 bars. En mélange de gaz, les MMMs PI/PSF-ZIF-8 ont abouti à une suppression de la plastification comme l'a confirmé une mesure constante de la perméabilité et de la sélectivité du CH4, et cet effet est plus accentué avec l'augmentation de la concentration en ZIF-8. Les résultats en séparation des gaz avec les MMMs PI/PSF-ZIF-8 montrent une performance supérieure à celle du Matrimid® ce qui laisse augurer un élargissement du spectre d'application de ces membranes, particulièrement pour la séparation du CO2 à haute pression. Dans le chapitre 5, une nouvelle voie de préparation des MMMs via la fusion contrôlée de particules a été introduite. La modification du Matrimid® par du 1-(3-aminopropyl)-imidazole a permis d'améliorer considérablement la compatibilité avec les particules de ZIF-8. Il a ainsi été possible de préparer des MMMs contenant 30% de MOF sans perte de sélectivité. En augmentant la concentration en ZIF-8, les MMMs ont de meilleures performances dans la séparation de mélange CO2/CH4 à comparer au polymère initial. La perméabilité a augmenté de plus de 200% avec une augmentation de 65% de sélectivité pour le mélange CO2/CH4
The plasticization behavior of pure polymers is well studied in literature. However, there are only few studies on the plasticization behavior of mixed matrix membranes. In Chapter 2 of this thesis, pure and mixed gas plasticization behavior of MMMs prepared from mesoporous Fe(BTC) nanoparticles and the polymer Matrimid® is investigated. All experiments were carried with solution casted dense membranes. Mesoporous Fe(BTC) MOF particles showed reasonably good compatibility with the polymer. Incorporation of Fe(BTC) in Matrimid® resulted in membranes with increased permeability and selectivity. At low pressures of 5 bar the MMMs showed an increase of 60 % in CO2 permeability and a corresponding increase of 29 % in ideal selectivity over pure Matrimid® membranes. It was observed that the presence of Fe(BTC) particles increases the plasticization pressure of Matrimid® based MMMs. Furthermore, this pressure increases more with increasing MOF loading. This delay in plasticization is attributed to the reduced mobility of the polymer chains in the vicinity of the Fe(BTC) particles. Also, at higher Fe(BTC) loadings, the membranes showed more or less constant selectivity over the whole pressure range investigated. Chapter 3 subsequently presented the preparation and plasticization behavior of MMMs based on three distinctively different MOFs (MIL-53(Al) (breathing MOF), ZIF-8 (flexible MOF) and Cu3(BTC)2 (rigid MOF)) dispersed in Matrimid®. The ideal and mixed gas performance of the prepared MMMs was determined and the effect of MOF structure on the plasticization behavior of MMMs was investigated. Among the three MOF-MMMs, membranes based on Cu3(BTC)2 showed highest selectivity while ZIF-8 based membranes showed highest permeability. The respective increase in performance of the MMMs is very much dependent on the MOF crystal structure and its interactions with CO2 molecules. Chapter 4 described the preparation of Matrimid® polyimide (PI)/polysulfone (PSF)-blend membranes containing ZIF-8 particles for high pressure gas separation. An optimized PI/PSF blend ratio (3:1) was used and performance and stability of PI/PSF mixed matrix membranes filled with different concentrations of ZIF-8 were investigated. PI and PSF were miscible and provided good compatibility with the ZIF-8 particles, even at high loadings. The PI/PSF-ZIF-8 MMMs showed significant enhancement in CO2 permeability with increased ZIF-8 loading, which was attributed to a moderate increase in sorption capacity and faster diffusion through the ZIF-8 particles. In pure gas measurements, pure PI/PSF blend (3:1) membranes showed a plasticization pressure of ~18 bar while the ZIF-8 MMMs showed a higher plasticization pressures of ~25 bar. Mixed gas measurements of PI/PSF-ZIF-8 MMMs showed suppression of plasticization as confirmed by a constant mixed gas CH4 permeability and a nearly constant selectivity with pressure but the effect was stronger at high ZIF-8 loadings. Gas separation results of the prepared PI/PSF-ZIF-8 MMMs show an increased commercial viability of Matrimid® based membranes and broadened their applicability, especially for high-pressure CO2 gas separations. In Chapter 5, a novel route for the preparation of mixed matrix membranes via a particle fusion approach was introduced. Surface modification of the polymer with 1-(3-aminopropyl)-imidazole led to an excellent ZIF-8-Matrimid® interfacial compatibility. It was possible to successfully prepare MMMs with MOF loadings as high as 30 wt.% without any non-selective defects. Upon increasing the ZIF-8 loading, MMMs showed significantly better performance in the separation of CO2/CH4 mixtures as compared to the native polymer. The CO2 permeability increased up to 200 % combined with a 65 % increase in CO2/CH4 selectivity, compared to the native Matrimid®. Chapter 6 finally discussed the conclusions and directions for future research based on the findings presented in this thesis

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.

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