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Thesis (MSc)--Stellenbosch University, 2001. / ENGLISH ABSTRACT: At the Mondi Kraft paper mill in Piet Retief, paper machine effluent is pre-treated by means of dissolved air flotation (DAF) and a mierostrainer prior to ultrafiltration (UF). Despite the rigorous pre-treatment of the effluent, severe fouling of the UF membranes still persisted, resulting in a sharp decrease in operational flux. In an attempt to improve the flux performance of the UF membranes an investigation was launched into the possible causes of membrane fouling. The study yielded the following results: Ultraviolet-visible (UV-Vis) spectrophotometric analyses of varIOUS effluent samples collected from different locations at the mill indicated the presence of aromatic compounds. Lignosulphonate appeared to be the main constituent in all the samples analysed. UV-Vis spectrophotometry was also performed on fouling extracted from membranes In order to evaluate the different approaches attempted to reduce membrane fouling. Most of the UV-Vis spectra obtained did not show the absorbance maxima below 210 nm that were seen for the paper machine effluent, DAF product, lignosulphonate and mierostrainer product. This indicated that the compounds with absorbance at lower wavelengths did not foul the membranes to the same extent as the aromatic substances with absorbance maxima between 230 and 400 nm. The influence of pH on the absorption of the various effluent samples was also investigated. An increase in pH resulted in (1) a "shift" in the wavelength scans from a lower to a higher wavelength, suggesting ionisation (deprotonation) with a subsequent delocalization of electrons and (2) an increase in the turbidity. The increase in turbidity which accompanied the Increase in pH could be explained by complex formation between the carboxylate ions, phenolic groups and divalent metal ions present in the effluent. Inductively coupled plasma analyses of several effluent samples with pH values 7 and 13 indicated the presence of significant amounts of Ca2+ ions in the effluent. There was a significant decrease in the Ca2+ levels with an increase in pH, which supported the hypothesis that Ca2+ might contribute to complex formation. This resulted in a decrease in solubility and an increase in turbidity. The addition of a chelating agent (ethylenediaminetetra-acetic acid disodium salt) to an effluent solution at pH 13 redissolved the precipitate and considerably reduced the turbidity. The subsequent addition of CaCh again induced precipitation and increased turbidity, confirming the role of Ca2+ in complex formation. Gel permeation chromatographic analyses of mierostrainer product at pH 13 showed the formation of high molecular mass organo-calcium complexes. The exact molecular mass of the complexes present in the mierostrainer product could not be determined by electro spray mass spectrometry because of their poor ionisation ability. Atomic force microscopy and scanning electron microscopy (SEM) showed distinct differences in the membrane surface texture before and after fouling. Furthermore, SEM images of the UF membranes exposed the limited ability of the 30 urn microstrainer, installed downstream from the DAF unit, to remove residual fibres from the DAF product. Static fouling experiments performed on all the flocculants and coagulants used In the paper-making process at the mill showed that none of these substances fouled the UF membranes. Cleaning of the UF membranes with Triton XIOO®, a nOn-IOnIC surfactant, caused a temporary increase in the operating flux to values higher than that of the initial flux. Mechanical cleaning of the UF membrane surface with spongebalIs proved to be one of the most effective and successful methods to prevent flux loss caused by fouling. Pre-coating of the UF membranes with Plutonic" FI08, another non-ionic surfactant, did not promote membrane productivity. Evaluation of various types of membranes indicated that hydrophilic or negatively charged membranes withstood membrane fouling more effectively than hydrophobic UF membranes under the same operating conditions. / AFRIKAANSE OPSOMMING: By Mondi Kraft se papier meule in Piet Retief word afloopwater vanaf die papiermasjiene vir hergebruik met behulp van ultrafiltrasie (UF) behandel. Opgeloste lugflotasie (OLF) en mikrosiwwing word as voorbehandeling vir die UF membraanproses ingespan. Ondanks die intensiewe voorafbehandeling wat toegepas word, vind daar geweldige aanvuiling van die UF membrane plaas wat tot die vinnige verlaging in bedryfsfluks aanleiding gee. 'n Ondersoek na die moontlike oorsake van membraan-aanvuiling het die volgende bevindinge opgelewer: Ultraviolet-sigbare (UV-Vis) spektroskopie van water monsters wat by die meule versamel is, het die teenwoordigheid van aromatiese komponente aangetoon, met lignosulfonaat die hoofkomponent in al die monsters wat ontleed is. Ekstrakte afkomstig van aangevuilde membrane is ook met behulp van UV-Vis-spektroskopie geanaliseer om verskeie benaderings te evalueer om 'n afname in membraan-aanvuiling te bewerkstellig. Die oorgrootte meerderheid spektra het nie die absorpsie maksima onder 210 nm aangetoon wat teenwoordig was in monsters van die papier masjien afloopwater, OLF uitvloeisel, lignosulfonaat en mikrosif produkwater nie. Dit het aangedui dat die komponente wat by laer golflengte absorbeer nie die UF membrane in dieselfde mate aanvuil as daardie komponente wat by hoër golflengtes (tussen 230 en 400 nm) absorbeer nie. Die invloed wat pH op die absorpsie van komponente teenwoordig in die onderskeie afloopwatermonsters het, is ook ondersoek. 'n Toename in pH het bygedra tot (1) 'n verskuiwing in die spektra vanaf 'n lae na 'n hoër golflengte vanweë ionisasie (deprotonering) met gevolglike delokalisasie van elektrone en (2) 'n toename in turbiditeit. Die toename in turbiditeit wat verband hou met die toename in pH was verduidelik aan die hand van kompleksvorming tussen die karboksilaat ione, fenoliese groepe en divalente metaal ione in die afloopwater. Induktief gekoppelde plasma analise van verskeie water monsters by pH 7 en 13 het die teenwoordigheid van 'n groot hoeveelheid Ca2+ aangetoon. 'n Verlaging in die vlakke van opgeloste Ca2+ het met die toename in pH verband gehou. Dit het die moontlike verbintenis tussen Ca2+ en kompleksvorming ondersteun wat bygedra het tot die afname in oplosbaarheid en toename in turbiditeit. Die byvoeging van etileendiamientetra-asynsuur-dinatriumsout, 'n kelerings reagens by afloopwater (pH 13) het die presipitaat weer in oplossing gebring en die turbiditeit merkwaardig verlaag. Die byvoeging van CaCh het weer presipitasie geïnduseer, met 'n gevolglike toename in turbiditeit. Hiermee is Ca2+ se rol in kompleksvorming bevestig. Gelpermeasie-chromatografiese analise van die mikrosif produk (pH 13) het die vorming van hoë molekulêre massa organo-kalsium komplekse bevestig. Dit was egter nie moontlik om met behulp van massaspektrometrie die korrekte molekulêre massa van die komplekse te bepaal nie vanweë hul onvermoë om te ioniseer. Atomiese krag mikroskopie en skandeer elektron mikroskopie (SEM) het duidelik die voor en na verskil getoon wat aanvuiling op die membraantekstuur gehad het. 'n SEM foto van die aangevuilde UF membraan het die onvermoë van die mikrosif blootgelê om oorblywende vesels vanuit die OLF produkwater te verwyder. Resultate bekom gedurende passiewe aanvuilingseksperimente het aangetoon dat al die in-proses flokkulante en koagulante wat gebruik word by die papier meule geen bydrae tot die aanvuiling van die UF membrane maak nie. Skoonmaak van die UF membrane met Triton XIOO® bring 'n verhoging in bedryfsvloed teweeg, maar die verhoging, wat hoër as die oorspronklike vloed is, is kortstondig. Meganiese skoonmaak van die buismembrane met behulp van sponsballe blyk die mees effektiewe skoonmaakmetode te wees. Voorafbehandeling van die UF membrane met Plutonic" F 108 het nie die membraanproduktiwiteit verhoog nie. Daar is ook bevind dat hidrofiliese of negatief gelaaide membrane groter weerstand bied teen aanvuiling in vergelyking met hidrofobiese UF membrane onder dieselfde bedryfstoestande.

The goal of this research was to identify and fabricate zeolitic membranes that can separate radioisotope krypton-85 (half-life 10.72 years) and xenon gas released during spent nuclear fuel reprocessing. In spent nuclear fuel reprocessing, fissionable plutonium and uranium are recovered from spent nuclear fuel and recycled. During the process, krypton-85 and xenon are released from the spent nuclear fuel as process off-gas. The off-gas also contains NO, NO2, 129I, 85Kr, 14CO2, tritium (as 3H2O), and air and is usually vented to the atmosphere as waste without removing many of the radioactive components, such as 85Kr. Currently, the US does not reprocess spent nuclear fuel. However, as a member of the International Framework for Nuclear Energy Cooperation (IFNEC, formerly the Global Nuclear Energy Partnership), the United States has partnered with the international nuclear community to develop a “closed” nuclear fuel cycle that efficiently recycles all used nuclear fuel and safely disposes all radioactive waste byproducts. This research supports this initiative through the development of zeolitic membranes that can separate 85Kr from nuclear reprocessing off-gas for capture and long-term storage as nuclear waste. The implementation of an 85Kr/Xe separation step in the nuclear fuel cycle yields two main advantages. The primary advantage is reducing the volume of 85Kr contaminated gas that must be stored as radioactive waste. A secondary advantage is possible revenue generated from the sale of purified Xe. This research proposed to use a zeolitic membrane-based separation because of their molecular sieving properties, resistance to radiation degradation, and lower energy requirements compared to distillation-based separations. Currently, the only commercial process used to separate Kr and Xe is cryogenic distillation. However, cryogenic distillation is very energy intensive because the boiling points of Kr and Xe are -153 °C and -108 °C, respectively. The 85Kr/Xe separation step was envisioned to run as a continuous cross-flow filtration process (at room temperature using a transmembrane pressure of about 1 bar) with a zeolite membrane separating krypton-85 into the filtrate stream and concentrating xenon into the retentate stream. To measure process feasibility, zeolite membranes were synthesized on porous α-alumina support discs and permeation tested in dead-end filtration mode to measure single-gas permeance and selectivity of CO2, CH4, N2, H2, He, Ar, Xe, Kr, and SF6. Since the kinetic diameter of krypton is 3.6 Å and xenon is 3.96 Å, zeolites SAPO-34 (pore size 3.8 Å) and DDR (pore size 3.6 Å) were studied because their pore sizes are between or equal to the kinetic diameters of krypton and xenon; therefore, Kr and Xe could be separated by size-exclusion. Also, zeolite MFI (average pore size 5.5 Å) permeance and selectivity were evaluated to produce a baseline for comparison, and amorphous carbon membranes (pore size < 5 Å) were evaluated for Kr/Xe separation as well. After permeation testing, MFI, DDR, and amorphous carbon membranes did not separate Kr and Xe with high selectivity and high Kr permeance. However, SAPO-34 zeolite membranes were able to separate Kr and Xe with an average Kr/Xe ideal selectivity of 11.8 and an average Kr permeance of 19.4 GPU at ambient temperature and a 1 atm feed pressure. Also, an analysis of the SAPO-34 membrane defect permeance determined that the average Kr/Xe selectivity decreased by 53% at room temperature due to unselective defect permeance by Knudsen diffusion. However, sealing the membrane defects with polydimethylsiloxane increased Kr/Xe selectivity by 32.8% to 16.2 and retained a high Kr membrane permeance of 10.2 GPU at ambient temperature. Overall, this research has shown that high quality SAPO-34 membranes can be consistently fabricated to achieve a Kr/Xe ideal selectivity >10 and Kr permeance >10 GPU at ambient temperature and 1 atm feed pressure. Furthermore, a scale-up analysis based on the experimental results determined that a cross-flow SAPO-34 membrane with a Kr/Xe selectivity of 11.8 and an area of 4.2 m2 would recover 99.5% of the Kr from a 1 L/min feed stream containing 0.09% Kr and 0.91% Xe at ambient temperature and 1 atm feed pressure. Also, the membrane would produce a retentate stream containing 99.9% Xe. Based on the SAPO-34 membrane analysis results, further research is warranted to develop SAPO-34 membranes for separating 85Kr and Xe.

This paper presents the results of the spike tests performed in the alternative water supply pilot testing program for the City of Pembroke Pines. It establishes the effectiveness of a protocol that can be used to gain further insight on the rejection capacities of RO membranes. An in-depth study of the molecular descriptors affecting rejection by RO membranes is presented and used in the development of a discriminant function analysis. This analysis proved to be an effective way to predict the passage of Emerging Substances of Concern (ESOCs) through RO membrane. Further, a principal component (PC) analysis was performed to determine which factors accounted the largest variation in RO permeability. Additionally, this paper defines the groundwork for a discriminant analysis model that, if further developed, could serve as an important tool to predict the rejection capabilities of RO treatment when handling with ESOCs. / by Fernando J. Pleitez Herrera. / Thesis (M.S.C.S.)--Florida Atlantic University, 2012. / Includes bibliography. / Mode of access: World Wide Web. / System requirements: Adobe Reader.

Robust industrially relevant membranes for CO₂ removal from aggressive natural gas feed streams were developed and characterized. Asymmetric hollow fiber membranes with defect-free selective skin layers on an optimized porous support substructure were successfully spun and subsequently stabilized by covalent crosslinking within the economical membrane formation process. Thermal treatment conditions, which promote sufficient crosslinking without introducing defects or undesired substructure resistance, were identified. It was found that crosslinking improves membrane efficiency and plasticization resistance as well as mechanical strength of fibers. The capability to maintain attractive separation performance under realistic operating conditions and durability against deleterious impurities suggests that the crosslinked fibers have great potential for use in diverse aggressive applications, even beyond the CO₂/CH₄ example explored in this work.

It has been postulated that the control of thrombus formation on molecularly engineered surfaces is an important step in developing clinically durable small-diameter vascular prostheses. This has led to designing a membrane-mimetic assembly that contains physiological regulators of blood coagulation, thrombomodulin (TM) and heparin, to provide strategies for generating actively antithrombogenic surfaces. The membrane-mimetic construct contains polymeric phospholipid monolayer on an alkylated polyelectrolyte multilayer supported by planar substrate such as glass or silicone. When incorporated with TM, the model platform exhibited the biological function by catalyzing activation of protein C. Surface TM activity was extensively investigated at physiologic shear rates (50 sec-1 and 500 sec-1). Significantly, reaction rates become saturated at TM surface densities greater than or equal to ~ 800 fmole/cm2 due to due to a transport limitation. Based on the similar membrane-mimetic construct, a functional heparinized surface was designed as an alternative anticoagulant system. Immobilization of heparin onto membrane-mimetic surfaces was achieved through biotin-streptavidin binding specificity. Activity of surface heparin to facilitate thrombin inactivation was investigated at shear rates of 50 and 500 sec-1. Significantly, rate of thrombin decay becomes saturated when the surface coverage of heparin is higher than 4.4 pmole of heparin per cm2. We further investigated the effects of surface bound TM and heparin on tissue factor (TF) -induced thrombin generation in a flow model. Specifically, TF positioned over a 2 x 6 mm2 upstream region as a trigger for thrombin generation and TM and/or heparin positioned over the remaining downstream (34 x 6 mm2) portion of the test film. Compared to TF alone surface, thrombin generation was profoundly reduced in the presence of surface bound TM and/or heparin. Significantly, thrombin production was maximally inhibited more than 85% in the presence of TM and heparin, possibly due to anticoagulant synergism of both anticoagulants. We believe that current membrane-mimetic systems can potentially create actively antithrombogenic surfaces.

Energy efficient purification of hydrogen is an important technological challenge with broad applications in the chemical, petrochemical, metallurgical, pharmaceutical, textile and energy industries. Palladium-alloy membranes are particularly suited to this problem due to their high hydrogen permeability, thermal stability, and virtually infinite selectivity. In current systems hydrogen flux is observed to be inversely proportional to membrane thickness which is indicative of the interstitial diffusion mechanism of hydrogen permeation. This observation, along with the high cost of palladium, has motivated continuous efforts to decrease membrane thickness. Theoretical modeling of membrane performance predicts that as membrane thickness continues to decrease, eventually the permeation rate will no longer be limited by diffusion through the bulk Pd but will become limited by desorption from the permeate surface. If it exists, this is a vital transition to pinpoint due to the fact that below this thickness membrane operating conditions will have a drastically different effect on hydrogen permeation behavior and no additional performance enhancements will result from further decreasing thickness. A handful of experimental results in the open literature contradict these modeling predictions. A new model is developed in this work to explain these contradictions by considering the non-ideal behavior of hydrogen solution into metals which has been neglected in previous models. Additionally, it has been demonstrated that hydrogen permeation through bulk Pd depends on membrane microstructure, making deposition conditions and post-deposition thermal treatment important issues for repeatable performance. The interplay of these issues on the performance of ultra-thin, Pd-Ag alloy hydrogen separating membranes is experimentally investigated. It is demonstrated that the hydrogen permeation behavior of sub-micrometer thick Pd-Ag alloy membranes exhibits diffusion-limited behavior in the context of the new model. The microstructure evolution during annealing is characterized and a correlation is drawn with the observed transient hydrogen permeation behavior during initial testing of a new membrane. In addition, two distinct failure modes of the microfabricated membranes are observed and the implications for future Pd-based membrane research are discussed.

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.

Mixed-matrix hollow fiber membranes are being developed to offer more efficient gas separations applications than what the current technologies allow. Mixed-matrix membranes (MMMs) are membranes in which molecular sieves incorporated in a polymer matrix do separation between gas mixtures based on the molecular size difference and/or adsorption properties of the component gases vis-à-vis the porous structure and the nature of adsorption sites in the molecular sieve. The development of MMMs to deliver on its promises has however been slow. The major challenges encountered in the efficient development of MMMs are associated with some of the paradigm shifts involved in their processing. For instance, mixed-matrix hollow fiber membranes are prepared by a dry-wet jet spinning method. For an efficient large scale processing of hollow fibers the rheology and kinetics of phase separation of the MMM dopes are important control variables in the process design. Therefore, this research thesis aims to study the rheology and phase separation kinetics of mixed-matrix membrane dopes. In research efforts to develop predictive models for the shear rheology of suspensions of zeolite particles in polymer solutions it was found that MFI zeolite suspensions have relative viscosities that dramatically exceed the Krieger-Dougherty predictions for hard sphere suspensions. Our investigations show that the major origin of this discrepancy is the selective absorption of solvent molecules from the suspending polymer solution into the zeolite pores. Consequently, both the viscosity of the polymer solution and the particle contribution to the suspension viscosity are greatly increased. A predictive model for the viscosity of porous zeolite suspensions incorporating a solvent absorption parameter, α, into the Krieger-Dougherty model was developed. We experimentally determined the solvent absorption parameter and our results are in good agreement with the theoretical pore volume of MFI particles. In addition, fundamental studies were conducted with spherical nonporous silica suspensions to elucidate the role of colloidal and hydrodynamic forces on the rheology of mixed-matrix membrane dopes. Also in this thesis, details of a novel microfluidic device that enables measurements of the phase separation kinetics via video-microscopy are presented. Our device provides a well-defined sample geometry and controlled atmosphere for in situ tracking of the phase separation process. We have used this technique to quantify the phase separation kinetics (PSK) of polymer solutions and MMM dopes upon contact with an array of relevant nonsolvent. For the polymer solution, we found that PSK is governed by the micro-rheological and thermodynamic properties of the polymer solution and nonsolvent. For the MMM dopes, we found that the PSK is increased by increased particles surface area as a result of surface diffusion enhancement. In addition, it was found that the dispersed particles alter the thermodynamic quality of the dope based on the hydrophilic and porous nature of suspended particles.