Dissertations / Theses on the topic 'Metallurgy - Ion exchange processes'

This thesis explores the behaviour of metal cyanide complexes under oxidative acid conditions in ion exchange systems, with the objective of developing an ion exchange based process for the treatment of gold cyanidation tailings. The novel cyanide detoxification process developed from this study employs strong base ion exchange resins to extract cyanide from tailings. Variations in the stability of cyanide complexes are exploited to concentrate, recover, or destroy cyanide species loaded on the resin, through the use of an oxidative acid eluent containing H2O2 and H2SO4. This eluent removes all base metal cyanide complexes from strong base resins, while regenerating the resin. The spent eluent, containing the base metals recovered from the tailings, can be used as a source of such base metals. Copper can be recovered separately from other base metals if necessary. Low levels of precious metals present in the tailings are accumulated on the resin as the ion exchange bed is cycled between loading and elution stages. They can be recovered economically, so as to offset the cost of the tailings detoxification. Cyanide is initially concentrated as an alkaline solution, which can be detoxified within the process or recovered for recycling. This process was successfully tested at pilot scale by treating approximately 14,000 m3 of cyanide contaminated tailings solution, over 14 loading/elution cycles on a standard strong base ion exchange resin bed. This treatment reduced the total cyanide concentration of the contaminated solution from approximately 50 mg/L to an average of 1.5 mg/L. The reagent cost was approximately ADD 0.50 per m3 of treated liquor. When the resin was repeatedly loaded with mixed metal cyanide species and eluted with the oxidative acid eluent, a gradual deterioration of the ion exchange resin performance was noted. The reduction of net operating capacity of the columns due to resin deterioration was in the order of 1-3% per loading/elution cycle. The oxidation of resin catalysed by copper, the precipitation of metal hexacyanoferrates on the resin and the oxidation of Au(CN)2- to Au(CN)4- were identified as possible factors giving rise to the reduction of resin loading capacity.

Thesis (MTech (Chemical Engineering))--Cape Peninsula University of Technology, 2009.
Neuro-fuzzy computing techniques have been approached and evaluated in areas of process control; researchers have recently begun to evaluate its potential in pattern recognition. Multi-component ion exchange is a non-linear process, which is difficult to model and simulate as there are many factors influencing the chemical process which are not well understood. In the past, empirical isotherm equations were used but there were definite shortcomings resulting in unreliable simulations. In this work, the use of artificial intelligence has therefore been researched to test the effectiveness in simulating ion exchange processes. The branch of artificial intelligence used was the adaptive neuro fuzzy inference system. The objective of this research was to develop a neuro-fuzzy software package to simulate ion exchange processes. The first step towards building this system was to collect data from laboratory scale ion exchange experiments. Different combinations of inputs (e.g. solution concentration, resin loading, impeller speed), were tested to determine whether it was necessary to monitor all available parameters. The software was developed in MSEXCEL where tools like SOLVER could be utilised whilst the code was written in Visual Basic. In order to compare the neuro-fuzzy simulations to previously used empirical methods, the Fritz and Schluender isotherm was used to model and simulate the same data. The results have shown that both methods were adequate but the neuro-fuzzyapproach was the more appropriate method. After completion of this study, it could be concluded that a neuro-fuzzy system does not always have the ability to describe ion exchange processes adequately.

Ce travail porte sur l'amélioration de la sélectivité préférentielle d'une membrane cationique à base d’ETFE pour une utilisation en électrodialyse afin de traiter des effluents industriels contenant un mélange d’acides et de sels métalliques. Pour cela, nous avons fait appel à la méthode de la modification chimique de la surface d’une membrane cationique par la formation d’un film superficiel mince portant des charges positives afin de former une barrière de répulsion électrostatique pour des cations bivalents tout en permettant le passage de cations monovalents tels que les protons.

La synthèse de la membrane cationique de base a été réalisée en passant par différentes étapes à savoir :le greffage du styrène - divinylbenzène (DVB), la chlorosulfonation et l’hydrolyse.

Au cours de ce travail, nous avons mis au point un protocole de greffage du styrène-DVB dans le film d’ETFE qui permet l’obtention d’un film ayant un taux de greffage reproductible assurant à la membrane cationique finale une bonne conductivité électrique et une capacité d’échange acceptable pour une membrane d’électrodialyse. Une étude de la réaction de greffage en fonction de la concentration en réticulant a été réalisée.

Nous avons procédé par la suite à la modification de la surface du film d’ETFE greffé styrène-DVB par la formation d’une couche superficielle mince fixée par des liens covalents. Les membranes modifiées ont été obtenues par la réaction d’une seule face du film d’ETFE greffé chlorosulfoné avec la 3-diméthylaminopropylamine. La modification chimique de la surface du film ETFE greffé chlorosulfoné a été suivie par la technique FTIR-ATR. L’effet de la concentration de la diamine sur les propriétés électrochimiques des différentes membranes modifiées a été étudié. La résistance électrique des membranes modifiées équilibrées au contact de solutions de chlorure de sodium et d'acide sulfurique a été mesurée par la technique d’impédance. La détermination du nombre de transport du proton et de l’ion sodium a été réalisée à partir de mesures du potentiel de membrane. La densité de courant limite des membranes a été évaluée sur base des courbes courant-tension. Les mesures de chronopotentiométrie ont été également effectuées sur les différentes membranes synthétisées.

Les résultats de ces caractérisations montrent que la modification de la surface engendre des changements considérables au niveau des propriétés électrochimiques des membranes résultantes. La résistance électrique, la densité de courant limite ainsi que les propriétés de transport de la membrane dépendent d’une part de la concentration de la diamine utilisée et d’autre part de la solution dans laquelle la membrane modifiée est équilibrée.

La sélectivité préférentielle des différentes membranes vis-à-vis des protons par rapport aux ions bivalents a été testée en réalisant des électrodialyses d’un milieu mixte H2SO4-NiSO4. Nos résultats montrent que la modification chimique de la surface de la membrane affecte d’une manière significative le transport des ions nickel tout en respectant le passage des protons. Une meilleure séparation a été obtenue pour une membrane modifiée en utilisant la diamine pure.

Doctorat en Sciences
info:eu-repo/semantics/nonPublished

Biodiesel purification processes generate wastewater streams that require a large amount of energy when distillation is used as a treatment technology. Process simulation software was used to show that an alternative water treatment process involving ion exchange would require only 31% of the energy used by distillation. Experiments showed that multiple washing stages were required to meet the standard specification for sodium, an impurity present in crude biodiesel, when washing biodiesel made from used frying oil. A comparison was made between washing biodiesel in a cross-current washing configuration and a counter-current configuration. Both configurations met the specification for sodium within three washing stages; however, the counter-current configuration required less water, making it the more efficient process. Lastly, the removal of sodium from wastewater samples using an ion exchange resin was experimentally investigated. The results validated the use of ion exchange to reduce energy consumption in biodiesel purification.

The world population of the 21st century is facing an increasingly challenging energy landscape and declining water quality and availability, further compounded by a rapidly expanding global population against the backdrop of climate change. To meet the challenges of the water-energy nexus in a sustainable manner, existing methods need to be advanced and new technologies developed. Osmotically-driven and ion-exchange membrane processes are two classes of emerging technologies that can offer cost-effective and environmentally sensible solutions to alleviate the pressure on our water and energy demands. The objective of this thesis is to advance forward osmosis (FO), pressure retarded osmosis (PRO), and reverse electrodialysis (RED) for the sustainable production of water and energy.

A main hindrance restricting the progress of osmotically-driven membrane processes, FO and PRO, is the absence of adequate membranes. This work demonstrates the fabrication of thin-film composite polyamide FO membranes that can attain high water flux and PRO membranes capable of achieving power density of 10 W/m², twice the benchmark of 5 W/m² for PRO with natural salinity gradients to be cost-effective. A membrane fabrication platform based on mechanistic understanding of the influence of membrane transport and structural parameters on process performance was developed. The morphology and microstructure of the porous support layer, and hydraulic permeability and salt selectivity of the polyamide active layer were specifically tailored by thoughtful control of the fabrication and modification conditions.

The Gibbs free energy from the mixing of river water with seawater can potentially be harnessed for clean and renewable energy production. This work analyzed the thermodynamics of PRO power generation and determined that energy efficiencies of up to ∼91% can theoretically be attained. The intrinsic limitations and practical constraints in PRO were identified and discussed. Using a tenth of the annual global river water discharge of 37,000 km ³ for PRO could potentially produce electricity for over half a billion people, ascertaining natural salinity gradients to be a sizeable renewable source that can contribute to diversifying our energy portfolio.

However, fouling of the membrane support layer can diminish the PRO productivity by detrimentally increasing the hydraulic resistance. Analysis of the water flux behavior and methodical characterization of the membrane properties shed light on the fouling mechanism and revealed the active-support layer interface to play a crucial role during fouling. A brief osmotic backwash was shown to be effective in cleaning the membrane and achieving substantial performance recovery.

Reverse electrodialysis (RED) is an ion-exchange membrane process that can also extract useful work from salinity gradients. This dissertation research examined the energy efficiency and power density of RED and identified a tradeoff relation between the two performance parameters. Energy efficiency of ∼33-44% can be obtained with technologically-available membranes, but the low power densities of < 1 W/m² is likely to be impede the realization of the process. To further advance RED as a salinity energy conversion method, ion-exchange membrane technology and stack design need to be advanced beyond their current limitations.

When analyzed with simulated existing state-of-the-art membranes, PRO exhibited greater energy efficiencies (54-56%) and significantly higher power densities (2.4-38 W/m²) than RED (18-38% and 0.77-1.2 W/m ²). The drawback of RED is especially pronounced at large salinity gradients, where the high solution concentrations overwhelm the Donnan exclusion effect and detrimentally diminish the ion exchange membrane permselectivity. Additionally, the inherent different in driving force utilization (osmotic pressure difference for PRO and Nernst potential for RED) restricts RED from exploiting larger salinity gradients to enhance performance. Overall, PRO is found to be the more favorable membrane-based technology for accessing salinity energy.

This work presents pioneering advances for forward osmosis and pressure retarded osmosis membrane development. The fundamental studies of the osmotically-driven membrane processes and ion-exchange membrane processes yielded significant findings that enhanced our mechanistic and thermodynamic understanding of the technologies. The important insights can serve to inform the realization of the emerging membrane-based technologies for the sustainable production of water and energy. The implications of the thesis are potentially far-reaching and are anticipated to shape the discussion on FO, PRO, and RED.

The recovery of Carboxylic acids were based on two particular objective: the study of the efficiency of a cation exchange resin, used in order to reduce the pH of the actual effluent, considering it is necessary to have a low pH for the anion exchange resin to be able to adsorb the acids from the effluent, and the preliminary studies perfomerd on the anion exchange resin, at various flow rates and both mode of operation, expanded and packed bed mode, using a simulated effluent, were the carboxylic acids were represented by just acetic acid, as the target molecule.

Perfluorosulfonate ionomers, such as Nafion® have been shown to demonstrate a profound affinity for large cationic complexes, and the study of polymer-bound cations may provide insight regarding Nafion® morphology by contrasting molecular size with existing models. The trimetallic complex, [{(bpy)2Ru(dpp)}2RhBr2] 5+, is readily absorbed by ion exchange into Na+ -form Nafion® membranes under ambient conditions. The dimensions of three different isomers of the trimetallic complex are estimated to be: 23.6 Å × 13.3 Å × 10.8 Å, 18.9 Å × 18.0 Å × 13.7 Å, and 23.1 Å × 12.0 Å × 11.4 Å, yielding an average molecular volume of 1.2×103 Å3 . At equilibrium, the partition coefficient for the ion-exchange of the trimetallic complex into Nafion® from a DMF solution is 5.7 × 103 . Furthermore, the total cationic charge of the exchanged trimetallic complexes counterbalances 86 ± 2% of the anionic SO3 − sites in Nafion®. The characteristic dimensions of morphological models for the ionic domains in Nafion® are comparable to the molecular dimensions of the large mixedmetal complexes. Surprisingly, SAXS analysis indicates that the complexes absorb into the ionic domains of Nafion® without significantly changing the ionomer morphology. Given the profound affinity for absorption of these large cationic molecules, a more open-channel model for the morphology of perfluorosulfonate ionomers is more reasonable, in agreement with recent experimental findings. In contrast to smaller monometallic complexes, the time- v dependent uptake of the large trimetallic cations is biexponential. This behavior is attributed to a fast initial ion-exchange process on the surface of the membrane, accompanied by a slower, transport-limited ion-exchange for sites in the interior of the ionomer matrix. The development of Nafion®/[{(bpy)2Ru(dpp)}2RhBr2] 5+ modified electrodes is also described for both FTO electrodes and materials made from electrospun carbon mats. The [{(bpy)2Ru(dpp)}2RhBr2] 5+ complexes behave as photocatalytic hydrogen production catalysts in the Nafion® membrane. Furthermore, a second bulk photoelectrolysis experiment with the Nafion®/[{(bpy)2Ru(dpp)}2RhBr2] 5+/FTO electrodes shows an enhancement of catalytic activity compared to the first photoelectrolysis experiment. This enhancement is attributed to halide loss following the first reduction process. Lastly, electrospun carbon nanofiber mats behave as electron donor materials for [{(bpy)2Ru(dpp)}2RhBr2] 5+/Nafion® membranes.
Ph. D.

High nutrient loading into groundwater and surface water systems has deleterious impacts on the environment, such as eutrophication, decimation of fish populations, and oxygen depletion. Conventional onsite wastewater treatment systems (OWTS) and various waste streams with high ammonium (NH4+) concentrations present a challenge, due the inconsistent performance of environmental biotechnologies aimed at managing nutrients from these sources. Biological nitrogen removal (BNR) is commonly used in batch or packed-bed reactor configurations for nitrogen removal from various waste streams. In recognition of the need for resource recovery, algal photobioreactors are another type of environmental biotechnology with the potential for simultaneously treating wastewater while recovering energy. However, irrespective of the technology adopted, outstanding issues remain that affect the consistent performance of environmental biotechnologies for nitrogen removal and resource recovery. In OWTS, transient loading can lead to inconsistent nitrogen removal efficiency, while the presence of high free ammonia (FA) can exert inhibitory effects on microorganisms that mediate transformation of nitrogen species as well as microalgae that utilize nitrogen. Therefore, to overcome these challenges there have been experimental studies investigating the addition of adsorption and ion exchange (IX) media that can temporarily take up specific nitrogen ions. Bioreactors comprised of microorganisms and adsorption/IX media can attenuate transient loading as well as mitigate inhibitory effects on microorganisms and microalgae; however, the interplay between physicochemical and processes in these systems is not well understood. Therefore, the main objective of this dissertation was to develop theoretical and numerical models that elucidate the complex interactions that influence the fate of chemical species in the bioreactors. To achieve this objective and address the issues related to improving the understanding of the underlying mechanisms occurring within the environmental biotechnologies investigated, the following three research studies were done: (i) experimental and theoretical modeling studies of an IX-assisted nitrification process for treatment of high NH4+ strength wastewater (Chapter 3), (ii) theoretical and numerical modeling of a hybrid algal photosynthesis and ion exchange (HAPIX) process for NH4+ removal and resource recovery (Chapter 4), and (iii) mathematical and numerical modeling of a mixotrophic denitrification process for nitrate (NO3-) removal under transient inflow conditions (Chapter 5). The experimental results for the IX-assisted nitrification process showed that by amending the bioreactor with zeolite, there was a marked increase in the nitrification rate as evidenced by an increase in NO3– production from an initial concentration of 3.7 mg-N L-1 to 160 mg-N L-1. This increase is approximately an order of magnitude greater than the increase in the reactor without chabazite. Therefore, the experimental studies provided support for the hypothesis that IX enhances the nitrification process. To garner further support for the hypothesis and better understand the mechanisms in the bioreactor, a novel mathematical model was developed that mechanistically describes IX kinetics by surface diffusion coupled with a nitrification inhibition model described by the Andrews equation. The agreement between the model and data suggests that the mathematical model developed provides a theoretically sound conceptual understanding of IX-assisted nitrification. A model based on the physics of Fickian diffusion, IX chemistry, and algal growth with co-limiting factors including NH4+, light irradiance, and temperature was developed to describe a batch reactor comprised of microalgae and zeolite. The model can reproduce the temporal history of NH4+ in the reactor as well as the growth of microalgae biomass. The mathematical model developed for the HAPIX process balances between simplicity and accuracy to provide a sound theoretical framework for mechanisms involved. In OWTS, transient inflow conditions have an influence on the performance of environmental biotechnologies for nitrogen removal. Prior experiments have shown that for denitrification, a tire-sulfur hybrid adsorption and denitrification (T-SHAD) bioreactor consistently removes nitrogen under varying influent flow and concentration conditions. To enhance the understanding of the underlying mechanisms in the T-SHAD bioreactor, a mathematical model describing mass transport of NO3- and SO42- in the aqueous phase and mixotrophic denitrification was developed. Additionally, a numerical tool to solve the mathematical model was implemented and compared to previously conducted experiments. Results from the numerical simulations capture the trend of the experimental data showing approximately 90% NO3- -N removal under varying flow conditions. Moreover, the model describes the effluent characteristics of the process showing a transient response in correspondence the changes in fluid velocity. The new tools developed provide new insight into the underlying mechanisms of physical, chemical, and biological processes within these bioreactors. The tools developed in this dissertation have a potential broad impact in environmental biotechnology for wastewater treatment in on-site systems, for treatment of high strength wastewater, and can be extended easily for stormwater management systems aimed at mitigating high nutrient loading to the environment.

Thesis (PhD)--Stellenbosch University, 2013.
ENGLISH ABSTRACT: In this study an economical, environmentally friendly, selective and efficient process for the extraction and recovery of [AuCl4]- from aqueous acidic chloride-rich solutions, particularly those aqueous solutions having low concentrations of the precious metal complexes has been investigated. Functionalized poly(styrene-co-maleimide) (PSMI) nanoparticles were synthesized by thermal imidization of the poly(styrene-co-maleic anhydride) (PSMA) copolymer with 3-N,N-dimethylaminopropylamine. Stable water-based dispersions were obtained containing spherical, monodisperse PSMI nanoparticles with a narrow size-distribution and average diameters of 50 ± 5 nm. The specific surface area of the bulk PSMI nanoparticles is 88.1 ± 2.2 m2/g with an average pore diameter of 82.3 Å. 13C NMR, FTIR and elemental analyses confirmed the successful and complete conversion of PSMA into the PSMI derivative. The functionalized PSMI nanoparticles synthesized were investigated as a novel anion-exchange material for the extraction of [AuCl4]- ions from aqueous acidic solutions. Batch sorption studies were carried out as a function of various parameters, such as initial gold concentration, PSMI mass, contact time and agitation rate. The [AuCl4]- extraction occurred with extremely fast sorption kinetics and is dependent on the rate of agitation during the batch sorption process. The functionalized PSMI nanoparticles show a maximum gold loading capacity of 1.76 mmol/g (347.7 mg/g). Langmuir and Freundlich isotherm models were applied to analyze the experimental sorption data. The best model describing the sorption process is given by the Langmuir model. Desorption efficiencies of about 80 % and 93 % were obtained using acidified thiourea (0.25 M thiourea/2 M HCl) and a mixture of 10 M HNO3/0.5 HCl as elutant solutions, respectively. X-ray photoelectron spectroscopy (XPS) analysis unambiguously confirms that the immobilized gold species exists in several oxidation states of 0, +I and +III on the PSMI nanoparticles. This proves that the [AuCl4]- ions initially present in the gold feed solutions unfortunately are subject to a reduction phenomenon on the surface of the functionalized PSMI nanoparticles. The existence of the various gold species contributed significantly to poor desorption efficiencies. In addition to PSMI nanoparticles, micro- to millimeter size PSMI resin beads was prepared by an electrospray methodology. This allows for a wide range of PSMI spherical and quasi-spherical bead diameters of shape to be prepared by manipulation of the experimental conditions employed during the electrospray process, such as the concentration of the PSMI in solution, the capillary tip-to-collector distance, flow rate and the applied voltage. 13C NMR and FTIR spectroscopy analyses show that the electrospray methodology allows PSMI resin beads preparation without any change in chemical composition of the PSMI material. Surface area and porosity analysis shows that 450 μm and 1620 μm PSMI beads selected for use in the gold extraction experiments are microporous and have BET specific surface areas of 2.8 ± 0.4 m2/g and 2.0 ± 0.1 m2/g, respectively. Micro- to millimeter size PSMI resin beads of 450 μm and 1620 μm diameter were tested as potential anion-exchange resins for the extraction of [AuCl4]- from aqueous acidic solutions. The time-dependent studies reveal that the extent of gold uptake increases with an increase in contact time and is dependent on the gold concentration in the [AuCl4]- feed solutions. A maximum loading capacity of 120.7 mg/g and 98.16 mg/g was attained for the 450 μm and 1620 μm resin beads, respectively. The experimental sorption data followed a linear trend consistent with a Freundlich sorption model. This sorption trend for [AuCl4]- suggests that a multi-layer sorption process predominates. Desorption of immobilized gold species from the loaded PSMI resin beads was investigated using various elutants such as HCl, HNO3, thiourea, NaCN and NaOH solutions. The best results were obtained using a mixture of 10 M HNO3/0.5 M HCl as elutant with a desorption efficiency of about 97%. Finally, superparamagnetic magnetite (Fe3O4) nanoparticles with a high degree of crystallinity and phase purity were synthesized by a chemical co-precipitation of Fe2+ and Fe3+ salts. The average diameters of the obtained Fe3O4 nanoparticles were about 7 – 8 nm. The Fe3O4 nanoparticles were coated with oleic acid surfactant molecules and used as seed particles for the preparation of 50 nm diameter magnetic PSMI nanoparticles via an in situ imidization reaction. TEM analysis confirmed that the magnetically responsive PSMI nanoparticles consist of magnetite core-polymer shell structure, although more work is required to perfect such materials.
AFRIKAANSE OPSOMMING: In hierdie studie is ‘n ekonomiese, omgewings vriendelike, seleketiewe en effektiewe proses vir die ekstraksie en herwinning van [AuCl4]- uit suur chloried-ryke oplossings, spesifiek oplossings van lae konsentrasies van edel metal komplekse was bestudeer. Gefunksionaliseerde poli(stireen-ko-maleïmied) (PSMI) nanopartikels was gesintetiseer deur middel van termiese imidisasie van die poli(stireen-ko-maleïk anhidried) kopolimeer met 3-N,N-dimetielaminopropielamien. Stabiele dispersies in water was gevind wat soos sweriese mono-disperse PSMI nanopartikels met ‘n noue partikel-grootte verspreiding met ‘n gemiddelde deursnee van 50 ± 5 nm. Die spesifieke oppervlak area van die massa PSMI nanopartikels is 88.1 ± 2.2 m2/g met ‘n gemiddelde porie-grootte van 82.3 Å. 13C NMR, FTIR en elementêre analiese bevestig die suksesvolle en volledige omskakeling van PSMA na PSMI. Die gefunksionaliseerde PSMI nanopartikels was bestudeer as ‘n nuwe anion-uitruil material vir die ekstraksie van [AuCl4]- ione uit suur oplossings. Stel sorpsie studies was uitgevoer as ‘n funksie van verskeie parameters soos onder andere die goud konentrasie in oplossing, PSMI massa, kontak tyd en ‘n mengings tempo. Die [AuCl4]- ekstraksie gebeur met ‘n geweldige sorpsie kinetika en is afhanklik van die mengings tempo gedurende die stel sorpsie proses. Die gefunksionaliseerde PSMI nanopartikels het ‘n maksimum goud sorpsie kapsiteit van 1.76 mmol/g (347.7 mg/g). Langmuir en Freundlich isoterm modelle was gepas en geanaliseer op die experimentele sorpsie data waarvan die Langmuir isoterm model die data die beste gepas het. De-sorpsie effektiwiteit van ongeveer 80 % en 93% was vekry vir die aangesuurde thiourea (0.25 M thiourea/2 M HCl) en ‘n mengsel van 10 M HNO3/0.5 M HCl as elueer oplossings, onderskeidelik. X-straal foto-elektron spektroskopie (XPS) analiese bevestig ongetwydeld die geimmobileerde goud spesies in oksidasietoestande van 0, +I, en +III op die PSMI nanopartikels. Hierdie is bewyse dat die [AuCl4]- oorspronklik teenwoordig in die goud oplossings is onderhewe auto-reduksie fenomeen op die oppervlak van die gefunksionalieerde PSMI nanopartikels. Die bestaan van verskeie goud spesies dra by tot die power de-sorpsie effektiwiteit van ge-immobiliseerde goud. Bykomend tot die nanopartikels is mikro- tot millimeter grootte PSMI partikels voorberei met ‘n elektro-sproei proses. Hierdie metode stel ons instaat om ‘n wye reeks sferiese en quasi-sferiese PSMI partikel se deersnee voorteberei. Deur die manupulasie van die eksperimentele kondisies gedurende die elektro-sproei proses, soos die konsentrasie van die PSMI in oplossing, die kapilêre punt-tot-ontvanger afstant, vloeispoed en die toegepasde potensiaal. 13C KMR en FTIR spectroskopiese analiese wys dat die elektro-sproei proses die PSMI partikel bereiding toelaat sonder enige veranderinge in die chemiese samestelling van die PSMI materiaal. Oppervlak area en porie-grootte analise wys dat 450lksdfhld en dskl jmm partikels gebruik in die goud ekstraksie eksperimente is mikro-porieës en het spesifieke oppervlak-areas van 2.8 ± 0.4 m2/g en 2.0 ± 0.1 m2/g onderskeidelik. Mikro- tot millimeter grootte poli(stireen-ko-maleimied) (PSMI) partikels van 450 μm en 1620 μm deursnee was getoets as potensieele anion-uitruilings-hars vir die ekstraksie van [AuCl4]- vanuit suur oplossings. Die tyd afhanklike studies gee aanduiding dat die mate van goud opname toeneem met ‘n toename in kontak-tyd en is afhanklik van die goud konsentrasie in die [AuCl4]- oplossings. ‘n Maksimum opname-kapasiteit van 120.7 mg/g en 98.2 mg/g was verkry vir die 450 μm en 1620 μm hars partikels onderskeidelik. Die eksperimentele sorpsie-data volg ‘n lineêre neiging in ooreenstemming met die Freundlich model. Die sorpsie neiging van [AuCl4]- dui aan dat ‘n meervuldige laag sorpsie proses domineer. De-sorpsie van die geimobiliseerde goud spesies vanaf die PSMI hars partikels was bestudeer deur gebruik te maak van verskeie elueermiddels soos HCl, HNO3, thiourea, NaCN en NaOH oplossings. Die beste resultate is verkry deur ‘n mengsel te gebruik van 10M HNO3/0.5M HCl as elueermiddel met n de-sorpsie effektiviteit van ongeveer 97%. Superparamagnetiese magnetiet (Fe3O4) nanopartikels met ‘n hoë graad van kristaliniteit en fase-reinheid was voorberei deur ‘n chemiese ko-neerslagvorming van Fe2+ en Fe3+ soute. Die gemiddelde deursnee van die Fe3O4 nanopartikels was ongeveer 7 – 8 nm. Die Fe3O4 nanopartikels was omhul met oleic suur benatter molekules wat gebruik word as saadjies vir voorbereiding van 50 nm deursnee-magnetiese PSMI nanopartikels deur middel van ‘n imidisasie reaksie. TEM analiese bevestig dat die magnetiese PSMI partikels nanopartikels bestaan uit ‘n magnetiet-kern polimeer-skil struktuur.

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Tese (Doutoramento)
IPEN/T
Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

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Dissertacao (Mestrado)
IPEN/D
Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

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Tese (Doutoramento)
IPEN/T
Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

La presente Tesis Doctoral consiste en la determinación de las propiedades de transporte de diferentes especies catiónicas a través de membranas de intercambio catiónico. Las membranas de intercambio iónico son un componente clave de los reactores electroquímicos y de los sistemas de electrodiálisis, puesto que determinan el consumo energético y la eficiencia del proceso. La utilización de este tipo de membranas para el tratamiento de efluentes industriales no es muy extendida debido a los requisitos de elevada resistencia química y durabilidad que deben cumplir las membranas. Otro asunto importante radica en la eficiencia en el transporte de los iones que se quieren eliminar a través de la membrana. Normalmente, existe una competencia por el paso a través de las membranas entre diferentes especies debido al carácter multicomponente de los efluentes a tratar. Sin embargo, una mejora en las propiedades de las membranas de intercambio iónico permitiría la implantación del tratamiento mediante reactores electroquímicos de efluentes industriales con un contenido importante en compuestos metálicos, tales como los baños agotados de las industrias de cromado. La utilización de una tecnología limpia como la electrodiálisis conllevaría diferentes ventajas, entre las cuales destacan la recuperación de los efluentes para su reutilización en el proceso industrial, el ahorro en el consumo de agua y la disminución de la descarga de contaminantes al medio ambiente. La determinación de las condiciones de operación óptimas así como la mejora de las propiedades de transporte de las membranas constituye el principal tema de la presente investigación. Para ello, se emplearán diferentes tipos de membrana. En primer lugar, se estudiará el comportamiento de las membranas poliméricas comerciales que poseen unas propiedades de resistencia química elevadas, las cuales se tomarán como referencia. De forma paralela, se producirán membranas conductoras de iones a partir de materiales cerámicos económicos, ya que la resistencia de los materiales cerámicos a sustancias oxidantes y muy ácidas es mayor que la de los materiales poliméricos. Este punto constituye la parte más innovadora de la investigación, puesto que la mayoría de las membranas de intercambio iónico comerciales están basadas en materiales poliméricos que no pueden resistir las condiciones específicas de los efluentes industriales. Una vez determinadas las condiciones de operación óptimas, se realizarán ensayos en plantas piloto con el fin de confirmar los resultados obtenidos mediante las técnicas de caracterización y determinar el grado de recuperación y coste energético asociado a los procesos electrodialíticos de tratamiento de efluentes industriales.
Martí Calatayud, MC. (2014). STUDY OF THE TRANSPORT OF HEAVY METAL IONS THROUGH CATION-EXCHANGE MEMBRANES APPLIED TO THE TREATMENT OF INDUSTRIAL EFFLUENTS [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/46004
TESIS
Premiado

La séparation et la purification de biomolécules à partir de milieux bruts, végétaux ou biologiques, est un sujet vaste etcomplexe. De sa compréhension et de son développement dépendent des enjeux industriels, et notamment le completdéveloppement des procédés biotechnologiques, les procédés de séparation, ou downstream processes, constituant environ 80% des coûts totaux de ces procédés. Ce travail se veut une contribution à ces problématiques. Il a été motivé par des résultatsobtenus au préalable dans le laboratoire qui montraient qu’il est possible de récupérer une protéine de très grande taille àpartir d’un milieu réel végétal par l’application d’une seule opération chromatographique (Kerfai, 2011). Suite à ce résultat,des hypothèses ont été énoncées, auxquelles ce travail essaie de répondre : quel(s) mécanisme(s) peuvent expliquer cerésultat ? Existe-t-il une localisation spécifique pour la fixation de la molécule sur l’échangeur d’ions qui rend plus simple etefficace sa récupération lors de l’étape d’élution ? Ainsi, notre objectif a été de progresser dans la connaissance des aspectsfondamentaux de la chromatographie d’échange d’ions appliquée à la séparation des protéines à partir d’un milieu brut.Notamment, l’influence de la présence d’autres protéines dans le milieu a été analysée, et ce dans le cas particulier deprotéines de poids moléculaire très différents, comme c’était le cas dans le travail précédemment cité. Des approches variées,théoriques et expérimentales à différentes échelles sur des milieux réels ou synthétiques, ont été appliquées et parfoisdéveloppées, pour essayer de répondre à ces questions. A l’échelle du procédé, une méthode statistique d’analyse desdonnées (Analyse en Composantes Principales ou ACP) a été menée, dont l’exploitation reste délicate. A l’échelle dulaboratoire, l’étude de l’équilibre et de la cinétique d’échange d’ions a été menée sur des solutions synthétiques de deuxprotéines : la sérum albumine bovine (BSA) (en tant que protéine de référence, couramment étudiée) et la ferritine (protéinede stockage du fer) de point isoélectrique proche de celui de la BSA mais de masse molaire plus élevée. Les résultatsmontrent que des modèles relativement classiques peuvent être appliqués, y compris pour les protéines de très grandes tailles,pour expliquer les aspects cinétiques de l’échange. Le couplage des flux de matière des protéines à l’intérieur des particulesde l’échangeur est très probable, malgré des diffusivités très différentes. Interpréter les résultats d’équilibre reste bien plusardu. La concentration en sel ou la présence de la BSA n’ont que très peu d’effet sur la rétention de la ferritine à l’équilibre.En revanche, la présence de la ferritine affecte très fortement la rétention de la BSA (pourtant plus favorable). Parmi lesphénomènes suggérés dans la littérature, l’effet Vroman a été recherché, mais il n’a pas été constaté dans le système pour lesconditions de travail utilisées. Les isothermes d’adsorption en conditions compétitives n’ont pas pu être simulées par lesmodèles habituels (comme l’isotherme multi-constituants de Langmuir), alors que celles des protéines seules sont tout à faitclassiques. En outre, un blocage partiel des pores de la résine par la ferritine reste probable, empêchant la diffusion de laBSA. Afin de vérifier ce dernier point, une méthodologie a été développée afin d’observer à l’échelle microscopique lesprofils de concentration des éléments représentatifs du système (P, Fe, Cl…) dans les particules. Cette méthode qui se trouveà un stade très avancé de développement, n’a pas encore permis de conclure faute de sensibilité suffisante des sondes àdisposition
Bioseparations from crude media, vegetable or biological, is a large and complex subject. Future industrial issues depend ontheir understanding and development, namely for biotechnological processes as downstream processes represent up to 80 %of their total cost. This work hopes to contribute to these general questions. It is justified by previous results obtained in thelaboratory showing that it is possible to recover a high molecular weight (HMW) protein from a complex vegetal juice in justone chromatographic operation. Hypotheses have been formulated, to which this work tries to answer: what mechanism couldexplain this behaviour? Is-there a specific location inside particles for the uptake of such protein, facilitating the recoveryduring elution step? Our objective has been to progress on the knowledge of fundamental questions concerning ion-exchangechromatography and their applications for proteins recovery from complex media. The effect of the other proteins in solutionhas been analysed, specifically in the situation where both proteins have a very different molecular weight, as in the previouscited work. Theoretical and experimental approaches, at various scales, have been applied or developed on real or syntheticsystems in order to answer some of these questions. At the process scale, a statistical method for data analysis (PrincipalComponent Analysis or PCA) has been applied. The complete interpretation of its results remains very hard. At thelaboratory scale, equilibrium and kinetics of ion exchange have been studied for synthetic solutions of two proteins: bovineserum albumin (BSA) (as reference protein widely studied), and ferritin (iron storage protein) having similar isoelectric pointas BSA but with higher molecular weight. Classical models for ion-exchange kinetics can explain the experimental results,even for HMW proteins. Mass transfer fluxes seem to be coupled for both proteins, even if they have usually very differentdiffusivities. The interpretation of equilibrium results is much more difficult. Equilibrium uptake of ferritin is not, or lightly,influenced by salt concentration or BSA content. Nevertheless, the presence of ferritin in the medium affects strongly BSAequilibrium uptake (however more favourable). Among the phenomena suggested in the literature, the Vroman effect hasbeen researched but it does not take place under the experimental conditions applied. Simulation of multi-componentisotherms has not been possible by classical models (such as multi-component Langmuir isotherm), while protein isothermsin single solution are standard. Besides, a partial blockage of the resin pores by ferritin is possible, preventing BSA diffusion.Therefore, a methodology has been developed at the microscopic scale, with the aim to observe concentration profiles forrepresentatives elements (P, Fe, Cl …) inside particles. The method, well developed, does not allow to conclude for themoment, because the probes used were not sensible enough

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Tese (Doutoramento)
IPEN/T
Instituto de Pesquisas Energeticas e Nucleares, Sao Paulo

This diploma thesis is focused on the charge exchange processes between projectile and target studied by the Low Energy Ion Scattering (LEIS) technique. Basic premise to investigate charge exchange processes is correct cleaning processes and proper settings of experimental instrument Qtac 100 placed in the Central European Institute of Technology (CEITEC) in Brno. Ion fraction expresses neutralization rate of the projectile. The parametr is investigated for clean and oxidized polycrystalline copper. Oxygen presence performs a significant part of reionization of backscattered neutralized projectiles.

Les milieux biologiques bruts, provenant des opérations de transformation de biomasse sont souvent caractérisés à la fois par leur caractère polluant et par un potentiel de valorisation important. Le développement de procédés adaptés au traitement de tels milieux complexes présente ainsi beaucoup d’intérêt. Les jus verts générés par la déshydratation de la luzerne (Medicago Sativa) sont caractérisés par une forte teneur en protéines. Outre leur valeur nutritionnelle importante, ces protéines ont des applications potentielles dans plusieurs domaines, notamment environnemental de part leur teneur élevée en Ribulose 1,5 Bisphosphate Carboxylase Oxydase (Rubisco), enzyme responsable de la fixation du CO2 chez les plantes. Dans ce travail la séparation sélective de la Rubisco à partir du jus de luzerne industriel centrifugé par chromatographie d’échange d’ions a été étudiée. Dans un premier temps une méthode d’analyse qualitative et quantitative a été mise au point pour la détection et la quantification de la Rubisco en solution et ainsi le suivi du procédé de séparation. Dans un deuxième temps, le procédé de séparation a été étudié en colonne, en lit fixe et en lit expansé, en utilisant le support échangeur d’anions Q Hyper Z et l’effet de la dilution du milieu sur la capacité dynamique du procédé a été analysé dans les deux cas. Les résultats obtenus ont montré que les deux modes de contact permettent d’avoir des capacités dynamiques de rétention du même ordre de grandeur que celles de la littérature. Après élution, la Rubisco a été concentrée jusqu’à 21 fois et les fractions produites étaient caractérisées par un grand degré de pureté. Par ailleurs, des études d’équilibre et cinétique d’échange ont été initiées dans ce travail et ont démontré que malgré la taille importante de la protéine d’intérêt (560 kDa) les limitations stériques à son transfert ne sont pas plus importantes que dans le cas de protéines plus simples et plus petites et que le support Q Hyper Z présente effectivement une grande affinité pour la protéine. Enfin une première approche théorique a été conduite pour la compréhension des interactions entre la protéine et l’échangeur dans ce milieu complexe. Elle a permis de confirmer l’importance de la prise en compte de la présence d’autres biomolécules dans le milieu sur la rétention de la Rubisco, peut être même plus que celle des sels
Biological raw material derived from bio-refinery processes, is often considered a source of pollution but it seems also to be a promising alternative to potential material recovery. The development of suitable processes for handling such complex biological material has so many concerns. Green juice produced from mechanical dehydration of Alfalfa (Medicago sativa) is an excellent source of protein with high nutritional quality. Ribulose-1,5-bisphosphate carboxylase oxygenase (Rubisco) is the most abundant protein in the green juice, with potential applications in many fields, such as human nutrition, pharmaceuticals, environmental… The aim of this study is to isolate and recover Rubisco produced from an industrial alfalfa green juice, by ion exchange chromatography process. First of all, a qualitative and quantitative analytical method was developed to provide reliable information about Rubisco content monitoring in the separation process. In a second step, the separation process was performed in fixed and expanded bed, using the anion exchanger Q Hyper Z. In both cases, the effect of the dilution of the green juice on the dynamic capacity of the columns was studied. The results showed that the dynamic capacity retention was similar in both columns to those reported in literature. After elution step, Rubisco was concentrated 21 times and produced with high level of purity. Furthermore, kinetic of ion exchange study was initiated. Despite the large size of the protein (560 kDa), steric limitations to mass transfer were not very significant when compared to those of conventional small proteins. The support Q Hyper Z showed an excellent affinity for the protein recovery. Finally, a first theoretical investigation has been conducted for understanding the retention mechanism between the protein and the separation column. This study shows the importance of taking into account the presence of other bio-molecules in order to perform the retention of Rubisco, perhaps even more than that of salts

Dissertação de Mestrado Integrado em Engenharia Química apresentada à Faculdade de Ciências e Tecnologia
Olive mill wastewater and effluents containing contaminants of emerging concern are one of the most recalcitrant effluents to conventional methods. Thus, this study focus mainly on Fenton-like processes for the treatment of these type of effluents aiming at its release into the natural water bodies. Synthetic olive mill wastewater was submitted to heterogeneous Fenton, using red mud - an alumina residue -, being the source of iron(III). The adsorption of the lab-made effluent onto the catalyst had no significant effects in the pollutants' removal. By testing different amounts of both red mud and \ch{H2O2}, it was possible to achieve around 100\% of the pollutants' degradation and 25\% mineralization. The optimal parameters with which such results were made possible were pH = 3, [\ch{H2O2}] = 100 mg/L and a catalyst load of 1g/L. Toxicity tests made on \textit{Corbicula fluminea} and \textit{Viibrio fischeri} showed a rise in toxicity from the treated solutions, when compared to the original one. As for \textit{Lepidium sativum} the toxicity from the treated solutions proved to be less toxic than the original. The contaminants used were Carbamazepine, Sulphametoxazole and Lorazepam. The solution containing these three compounds was also subject to heterogeneous Fenton-derived processes. Under sunlight, at near-neutral pH, the degradation of the three compounds went over the 50\% degradation line, reaching 62\% for Lorazepam. Synthetic Olive mill waste water was later treated with homogeneous photo-Fenton, using iron sulphate as the source of iron. The optimal conditions were 1 g/L of iron (II), pH = 3 and 100 mg/L of initial load of \ch{H2O2}, reaching 70\% of mineralization, ending up with a residual amount of \ch{H2O2} of approximately 23 mg/L, halved by the 50 mg/L obtained by homogeneous Fenton. Regarding iron removal processes, both failed to meet the 2 mg/L limit of iron allowed to be disposed. However, more experimental test have to be made to support the results obtained.
Efluente sintético proveniente da indústria do azeite e efluentes com contaminantes de preocupação emergente são dos efluentes mais recalcitrantes aos métodos convencionais. Assim, este estudo foca-se principalmente nos processos do tipo Fenton para o tratamento destes tipos de efluentes, visando a sua libertação nos corpos aquáticos naturais.O primeiro foi submetido a Fenton heterogéneo, usando red mud - um resíduo da alumina - sendo esta a a fonte de ferro(III). A adsorção do efluente no catalisador não teve efeitos significativos na remoção dos poluentes. Testando diferentes quantidades de red mud e \ch{H2O2}, foi possível atingir cerca de 100\% da degradação dos poluentes e 25\% de mineralização. Os parâmetros óptimos a partir dos quais tais resultados foram possíveis foram pH = 3, [\ch{H2O2}] = 100 mg/L e uma concentração inicial de catalisador de 1g/L. Testes de toxicidade realizados em \textit {Corbicula fluminea} e \textit {Viibrio fischeri} mostraram um aumento na toxicidade das soluções tratadas, quando comparadas com a solução original. Quanto à \textit {Lepidium sativum}, a toxicidade das soluções tratadas mostrou-se menos tóxica do que a solução original. Os contaminantes utilizados foram Carbamazepina, Sulphametoxazole e Lorazepam. A solução, contendo estes três compostos, foi também sujeita a processos derivados de Fenton heterogéneos. Sob a luz do sol, a pH quase neutro, a degradação dos três compostos ultrapassou a linha de 50 \% de degradação, atingindo 62\% no caso referente ao Lorazepam.Efluente sintético proveniente da indústria do azeite foi, desta feita, tratado com foto-Fenton homogéneo, utilizando sulfato de ferro como fonte de ferro(II). As condições ótimas foram 1 g/L de ferro (II), pH = 3 e 100 mg/L de carga inicial de \ch{H2O2}, atingindo 70\% de mineralização, terminando com uma quantidade residual de \ch {H2O2} de aproximadamente 23 mg/L, sendo aproximadamente metade dos 50 mg/L obtida pelo Fenton homogéneo. Em relação à Permuta iónica, a resina Dowex provou ser a escolha mais adequada em comparação às resinas Purolite e Lewatit. Em relação aos processos de remoção de ferro, ambos falharam em atingir o limite de 2 mg / L de ferro que pode ser libertado para o meio. No entanto, mais testes experimentais devem ser feitos para sustentar os resultados obtidos.

碩士
大漢技術學院
土木工程與環境資源管理研究所
106
In the discussion, we will study the recycling and reuse of waste expendable polystyrene. We used three methods to sulfonate virgin polystyrene(VPS) and waste expendable polystyrene(WPS). To discuss the degree of the sulfonation, the ion exchange capacity and the rate of heavy metal removal. We used the 1,2-dichlorothane to be the solvent. First we melted VPS or WPS. Then we used different quantities of sulfonation agent in it. After 1hr, we put 7.5ml of methanol alcohol inside to stop the reaction of the sulfonation process. Using high temperature and pressure to remove the solvent. Then we put the product of sulfonation process inside the deionized water to separate the byproducts and used an oven to dry it over 24hrs. After that we get the sulfonation result we were hoping for. The result shows that acetyl acid was the best sulfated agent and the best degree of sulfonation were 36.67% . VPS was better than WPS. But we still can study further the reuse of waste expendable polystyrene. It has potential to remove the heavy metal elements and we can help to improve that.

The development of selective and effective hemicellulose recovery and upgrade processes is one of the current major hurdles preventing the full onset of economic and environmentally sustainable biorefineries. In this work, four ion exchange resins (IERs) were characterized and evaluated as alternative catalysts, in order to explore the advantages of the acid-catalyzed processes for the i) direct hydrolysis of raw biomass and ii) the hydrolysis of oligosaccharides, both into monomeric hemicellulose-derived sugars. The hemicellulose hydrolysis using IERs was compared to the use of dilute sulfuric acid for diverse model feedstocks. For H2SO4 processes, xylan conversion into xylose reached 83.9% for Eucalyptus residues (ER), and 98.6% for Miscanthus. When using IERs, a superior or equivalent performance, namely, xylose yields of 93.7% (ER), and 91.3% (Miscanthus) were achieved when using Amberlyst 15. This was further validated for Wheat Straw (WS) that presented a complete hydrolysis of xylan into xylose, showing that IERs usage is an effective alternative for biomass deconstruction. In the two-step process, autohydrolysis and organosolv were compared as means to produced Xylo-oligosaccharides (XOS) both from ER and WS. Autohydrolysis presented higher XOS yields for both materials and these could be effectively hydrolyzed by IERs, namely Amberlite IR120 and specially Amberlyst 15, enabling to reach efficiencies superior to the H2SO4 catalyzed process. Catalyst reutilization is possible, and typically higher in autohydrolysis when compared to organosolv derived streams. This process was demonstrated to be able to be further intensified by the use of a continuous system, using raffinose as model oligosaccharide, for which a 50% hydrolysis was achieved for a low residence time (5 min) at 140ºC. Finally, the performance of the IERs is discussed based on their structures and properties and the impact of the amount of ash present in the feedstock.
O desenvolvimento de processos seletivos e eficientes de recuperação de hemiceluloses é um dos principais obstáculos ao aparecimento de biorrefinarias sustentáveis a nível económico e ambiental. Neste trabalho, foram caracterizadas e avaliadas quatro resinas de troca iónica (IERs) como catalisadores ácidos alternativos, com o objetivo de explorar as vantagens dos processos ácidos para a i) hidrólise direta de biomassa e ii) hidrólise de oligossacáridos, ambas em monómeros de açúcares derivados de hemicelulose. A hidrólise da hemicelulose usando IERs foi comparada ao uso de ácido sulfúrico diluído para diversas matérias-primas. Nos processos catalisados por H2SO4, a conversão de xilano em xilose atingiu 83,9% para resíduos de eucalipto (ER) e 98,6%, para Miscanthus. As IERs, apresentaram um desempenho superior ou equivalente, com rendimentos de xilose de 93,7% (ER) e 91,3% (Miscanthus) usando Amberlyst 15. Isto foi posteriormente validado para a palha de trigo (WS) que apresentou hidrólise completa de xilano em xilose, demonstrando que as IERs são uma alternativa eficaz para desconstrução da biomassa. No processo de duas etapas, a auto-hidrólise e o organosolv foram comparados como processos de produção de Xilo-oligossacáridos (XOS) para ER e WS. A autohidrólise apresentou maiores rendimentos em XOS, para ambos os materiais. O XOS obtidos puderam ser eficazmente hidrolisados por IERs, nomeadamente Amberlite IR120 e principalmente Amberlyst 15, permitindo eficiências superiores ao processo catalisado por H2SO4. A reutilização do catalisador é possível, e normalmente é maior nos licores de auto-hidrólise em comparação com os licores organosolv. Este processo demonstrou poder ser ainda intensificado pelo uso de um sistema contínuo, utilizando rafinose como oligossacárido modelo, onde foi obtida uma hidrólise de 50% para um tempo de residência baixo (5 min) a 140ºC. Por fim, o desempenho das IERs é discutido com base nas suas estruturas e propriedades e no impacto da quantidade de cinza presente na matéria-prima.

Tracertests stellen heute einen integralen Bestandteil im Repertoire der hydro(geo)logischen Charakterisierungstechniken dar. Insbesondere konservative Stoffe werden zur Bestimmung von hydraulischen Reservoir- und Aquiferparametern eingesetzt. Diese Stoffe verhalten sich weitestgehend inert und unterliegen somit nur vernachlässigbaren physikochemischen Wechselwirkungen während ihrer Verweilzeit im untersuchten Geosystem. Im Gegensatz dazu stellt der Einsatz nicht-konservativer organischer Stoffe als Tracer einen relativ neuen Ansatz dar, welcher das Potential birgt, zusätzliche Informationen zu ablaufenden Untergrundprozessen zu gewinnen, sofern die Wechselwirkungsarten und somit das Tracerverhalten bekannt sind. Folglich ist die genaue Kenntnis potentieller Transportprozesse und deren Abhängigkeiten eine unabdingbare Voraussetzung für eine erfolgreiche Interpretation dieser Tracer. In diesem Zusammenhang ist die Sorption an Festphasen für zahlreiche gelöste organische Verbindungen der wohl bedeutendste physikochemische Transportprozess. Aus diesem Grund ist die systematische Untersuchung von Sorptionsprozessen und deren Abhängigkeiten von den Moleküleigenschaften bzw. Randbedingungen ein Hauptbestandteil der hier vorgestellten, kumulativen Dissertationsschrift. Die aus den Sorptions-untersuchungen abgeleiteten Schlussfolgerungen wurden in die Entwicklung eines neuen, reaktiven Reservoir-Tracers für die geologische Speicherung von CO2 mit einbezogen. Um einen Überblick über das Sorptionsverhalten organischer Verbindungen mit unterschiedlichen Funktionalitäten zu gewinnen, wurde zunächst der pH-abhängige Stofftransport mehrerer dissoziierbarer Arzneimittelwirkstoffe (Säuren, Basen, Zwitter) mit Hilfe von Sedimentsäulenexperimenten untersucht. Hierzu wurden die Sorptionskoeffizienten bestimmt und mit den vorausberechneten Ergebnissen zweier Korrelationsansätze verglichen. Eine starke pH-Abhängigkeit zeigte die Sorption für alle Moleküle mit einem pKS-Wert im oder nahe des untersuchten pH-Bereiches. Eine zufriedenstellende Vorhersage war nur für neutrale und anionsche (saure) Verbindungen möglich. Im Gegensatz dazu war die Sorption der kationischen (basischen) und zwitter-ionischen Verbindungen stärker als erwartet. Als Ursache dafür kann das Auftreten zusätzlicher, elektrostatischer Sorptionsmechanismen angesehen werden, welche in den konventionellen Korrelationsansätzen nicht berücksichtigt werden. Somit konnte unter anderem erwartet werden, dass auch Kationenaustausch einen signifikanten Prozess für die Retardation organischer Kationen im Untergrund darstellt. Mit zwei kationischen Beta-Blockern durchgeführte Säulenversuche belegen die dominierende Rolle von Kationenaustauschprozessen. Steigende Konzentrationen anorganischer Kationen führen aufgrund der verstärkten Konkurrenz um die Austauscherplätze des Sorbens zu einer geringeren Sorption der organischen Kationen. Der Beitrag nicht-hydrophober Wechselwirkungen zur Gesamtsorption konnte mit >99% abgeschätzt werden. Aufgrund der großen Bedeutung von Kationenaustauschprozessen sollten weitere Einflussfaktoren berücksichtigt werden, um den Transport organischer Kationen zuverlässig vorhersagen zu können. Daher wurde anschließend der Einfluss konkurrierender anorganischer Kationen auf die Sorption organischer Kationen in Wasser/Sediment-Batchtests systematisch untersucht. Die bei verschiedenen Hintergrundkonzentrationen an anorganischen Kationen aufgenommenen Sorptionsisothermen des kationischen Beta-Blockers Metoprolol zeigten eine deutlich stärkere Beeinflussung der Sorption durch Ca2+ als durch Na+. Durch die gefundene Korrelation zwischen dem Freundlich-Koeffizienten und der Konzentration anorganischer Kationen wird eine Vorhersage der Metoprolol-Sorption im Bereich der untersuchten Randbedingungen möglich. Zudem konnte der Beitrag sorptiver Wechselwirkungen zum organischen Kohlenstoff des Sediments als vernachlässigbar bestimmt werden. Insgesamt liefern die erzielten Ergebnisse einen weiteren wichtigen Beitrag zur Prozessbeschreibung der Sorption und helfen somit, die Vorhersage des Stofftransportes organischer Kationen im Untergrund zu verbessern. Im letzten Teil der Arbeit werden das Konzept und die Entwicklung eines neuen, reaktiven Tracers (KIS-Tracer) zur Charakterisierung von Grenzflächen während Injektionen von überkritischem CO2 in tiefe salinare Aquifere beschrieben. Durch eine Hydrolysereaktion an der CO2/Wasser-Grenzfläche mit bekannter Kinetik wird ein Zusammenhang zur zeitlichen Änderung der Grenzflächengröße geschaffen. Basierend auf den vorangegangenen Untersuchungen zur Sorption, wurde das konservative, organische Anion Naphthalinsulfonat als Basisstruktur für die Tracersynthese (Veresterung) und somit auch als gewünschtes Hydrolyseprodukt ausgewählt. Neben der Definition notwendiger Tracereigenschaften wurden bereits erste Verbindungen synthetisiert, im Labor getestet und mit einem neuentwickelten, makroskopischen Modell ausgewertet. Abschließend wurde das Tracerverhalten exemplarisch für verschiedene hypothetische Funktionen der zeitlichen Grenzflächenänderung numerisch modelliert. Die bisher erzielten Ergebnisse sind sehr vielversprechend und gewähren einen ersten Einblick in das Potential von KIS-Tracern.

In clay soils having low initial pH values, electrokinetic transport of heavy metals has proven to be effective. The transport of these metals is predicated on maintaining a low pH throughout the cell, which in turn keeps the metals in the pore water phase, where they are accessible to EK transport. Development of high pH gradients in the cathode region due to the formation of OH$\sp{-}$, from the dissociation of water, produces unfavorable conditions for the transport of heavy metals, namely precipitation. Standard electrokinetic methods have not been employed to a great extent in natural clayey soil. These soils tend to magnify the problems mentioned above and pose several unique problems related to remediation that currently used techniques cannot overcome. Most natural clayey soils have inherently high pH values. The use of EDTA, EK methodology and ion exchange textiles is a new hybrid technique for the enhanced solubilization, transport and localization of Pb and Ni respectively in natural clayey soils. A four-point examination of many of the important system properties related to this hybrid technique, and the effect of the textiles on these properties forms the subject of this thesis. Electrical parameters, system chemistry, enhanced solubilization and transport of EDTA and EK methods only, and the overall localization and removal efficiency of EDTA-EK-Textile experimentation. EDTA-EK methods, without textiles, produced enhanced solubility and transport of lead and nickel. Using all three techniques, solubility was enhanced and the localization and removal achieved was in the range of 90-95% of lead and nickel ions localized within 10% of the cell. This represents a significant improvement over standard EK methods (which typically have been applied only to low pH soil) and represents a viable remediation technique in natural clayey soil.

Tese de doutoramento em Engenharia Química e Biológica
A presente tese teve como objectivo principal a recuperação de fructo-oligossacarídeos (FOS) de misturas de açúcares obtidas por fermentação. Entre as técnicas de separação actualmente disponíveis, a cromatografia líquida foi o método escolhido. Duas fases estacionárias foram estudadas, nomeadamente o carvão activado e várias resinas de troca iónica. A adsorção/dessorção de FOS contidos numa mistura de caldo de fermentação, usando um gradiente de água/etanol, foi estudada numa coluna de carvão activado. Após optimização do método foi possível recuperar 74.5% (p/p) de FOS em relação aos FOS inicialmente contidos no meio de fermentação. Adicionalmente, obtiveram-se fracções com graus de pureza até 97% (p/p). Este método mostrou ser também foi eficiente na dessalinização do caldo fermentativo. O método de separação usando a coluna de carvão activado foi um bom ponto de partida para a obtenção de grandes quantidades de FOS puros de uma forma simples e pouco dispendiosa. No entanto, o principal objectivo desta tese consistia no desenvolvimento de um processo de separação para ser usado numa escala industrial, portanto, economicamente atractivo. Assim, a técnica de cromatografia de leito móvel simulado (SMB) foi seleccionada como sendo o método de separação mais adequado. A cromatografia de SMB tem a vantagem de trabalhar de um modo contínuo, usando água como eluente e fases estacionárias homogéneas, levando a resultados muito reprodutíveis. Como tal, estudaram-se várias resinas de troca iónica com potencial suficiente para serem utilizadas numa planta piloto de SMB. A adequação das resinas na separação de mono- e dissacarídeos foi avaliada através dos estudos de equilíbrio de adsorção, cinética e de resistência mecânica. A resina seleccionada foi uma Dowex Monosphere 99K/320, tipo gel, com 320 mm de diámetro das partículas, em forma de potássio. Estabeleceu-se um modelo matemático para descrever a eluição cromatográfica do caldo fermentativo em coluna e identificaram-se os parâmetros cinéticos e de adsorção. Os FOS foram purificados com sucesso de 37.1 a 62.9% (w/w), usando o SMB. Além disso, o rendimento e a produtividade obtidos para FOS no refinado atingiu 69.4% (w/w) e 82.1 g.L-1.h-1, respectivamente. Até agora, nenhum trabalho científico reportou a recuperação de FOS de caldos fermentativos utilizando o SMB. Com a grande expansão do mercado de FOS na última década, devido ao crescente interesse dos consumidores por alimentos saudáveis, os resultados obtidos nesta tese mostram-se muito promissores para a indústria alimentar, nomeadamente no desenvolvimento de novos processos para a recuperação de açúcares produzidos por processos fermentativos.

The concern with water quality problems worldwide has led to the improvement of water/wastewater treatment processes. In this PhD project, industrial water and drinking water treatments using membrane processes were investigated in three different case studies. The main aim of these works was the assessment, optimisation and validation of the process’s technologies for the respective case studies. These studies included in a laboratory stage followed by a pilot-scale stage. The first case study contemplates residual water from a rubber industry presenting high chemical oxygen demand (COD). The impact of retrofitting of the existent wastewater treatment process with the replacement of the previously used evaporator with an integrate system (nanofiltration+ evaporator), was evaluated. Two modes of operation were considered, batch and continuous, depending on the daily flowrate of water to be treated in this industry. The second case study addresses surface water treatment, for production of drinking water with a high chemical and microbiological quality, required by the current legislation. The research was focused on the validation of a multibarrier system incorporating nanofiltration and UV photolysis performed at three different locations of the surface drinking water production line. The third case study focuses on a novel treatment process dealing with groundwater contaminated by arsenic (in its inorganic arsenate form) with the purpose to be applied in rural areas located far from centralised drinking water supply infrastructures. It has been a challenge worldwide to treat arsenic contaminated drinking water in order to meet the current strict regulation standard for As. In this research, an ion exchange membrane process, integrating Donnan dialysis with precipitation of this target pollutant was proposed. This work explored the feasibility of arsenic removal from water streams containing sulphate, which strongly competes with arsenate and is preferentially transported through strong-base anion-exchange membranes. Subsequently, the optimisation of arsenic removal from drinking water by the process proposed was performed by using a response surface methodology (RSM). A systematic analysis of the three case studies was carried out and is presented in this thesis in order to provide a deeper insight into the treatment processes studied (theoretical and practical aspects), which makes the proposed solutions also applicable to other water/wastewater treatment cases, facing similar challenges.