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Competitive Adsorption of Iron and Natural Organic Matter in Groundwater Using Granular Activated CarbonAl-Attas, Omar 01 October 2012 (has links)
The treatment of potable water in Vars, ON is accomplished by filtering the colored, iron-laden groundwater through granular activated carbon (GAC) filters. When first installed, these filters unexpectedly experienced chromatographic displacements of iron into the produced water which resulted in orange-brown water at consumers’ taps. The treatment plant was later modified by adding potassium permanganate oxidation and a greensand filter prior to the GAC adsorption columns. Consequently, iron was almost completely removed and no longer caused operational problems. The main objective of this dissertation is to study the interactions between natural organic matter (NOM) and iron that caused the observed chromatographic effect. This study was divided into three main stages: a) characterization study on Vars groundwater and its treatment system; b) study of the competitive adsorption of iron with NOM in Vars groundwater; and c) evaluation of the rapid small-scale column test (RSSCT) for predicting the full-scale GAC column breakthroughs. The characterization of Vars groundwater showed that ferrous iron was found to be the dominant iron species, representing 90% of the total iron, and that 15 - 35% of the iron was complexed with NOM. It was hypothesized that the chromatographic displacement of iron from the GAC columns was caused by NOM-iron complexes; however, field mini-column experiments showed this was not the case. Thus, competitive adsorption between iron and NOM was seen as the more likely cause of the chromatographic effect. The adsorption capacity of ferrous iron in Vars raw water was less than that in organic-free water by a factor of 7 due to the competition with NOM over the GAC adsorbing sites. However, the NOM adsorption capacity was not reduced due to the presence of ferrous iron. It was hypothesized that ideal adsorption solution theory (IAST) models, which have been successful in describing competitive adsorption between target organic compounds and NOM, could model the competition between an inorganic compound such as ferrous iron and NOM. The hypothesis was proved to be correct, and the adsorption isotherm of iron in competition with NOM in Vars groundwater was simulated very well by several versions of the IAST model. However, none of the models were capable of simulating the competitive adsorption of NOM and ferrous iron simultaneously. Since the presence of iron did not significantly reduce the adsorption capacity of NOM, a simplified approach of using the single-solute NOM isotherm to represent the competitive NOM isotherm was recommended. The performance of the rapid small-scale column test (RSSCT) was evaluated in order to simulate the iron chromatographic effect observed at Vars’ full-scale GAC column. The RSSCT was not capable of predicting the iron phenomenon and the test proved to be problematic due to the oxidation and precipitation of iron within the small voids between the small-scale column’s GAC particles. The RSSCT, using constant and linear diffusivities, were applied to simulate the NOM adsorption after greensand treatment. Integrating both diffusivities, the tests predicted the onset and slope of the NOM breakthrough up to 10-L water treated/g GAC, which is equivalent to 250 days of operation time for the full-scale column. However, the NOM breakthroughs deviated beyond that point and the RSSCT using constant diffusivity underestimated the column performance greatly. On the other hand, the linear diffusivity RSSCT underestimated the performance to a lesser degree and its NOM breakthrough was quite parallel to the full-scale performance with lower NOM removals of 15%. The higher long-term NOM removal in the full-scale system may be explained by biodegradation, a phenomenon that was not considered by the short duration of RSSCT.
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Competitive Adsorption of Iron and Natural Organic Matter in Groundwater Using Granular Activated CarbonAl-Attas, Omar 01 October 2012 (has links)
The treatment of potable water in Vars, ON is accomplished by filtering the colored, iron-laden groundwater through granular activated carbon (GAC) filters. When first installed, these filters unexpectedly experienced chromatographic displacements of iron into the produced water which resulted in orange-brown water at consumers’ taps. The treatment plant was later modified by adding potassium permanganate oxidation and a greensand filter prior to the GAC adsorption columns. Consequently, iron was almost completely removed and no longer caused operational problems. The main objective of this dissertation is to study the interactions between natural organic matter (NOM) and iron that caused the observed chromatographic effect. This study was divided into three main stages: a) characterization study on Vars groundwater and its treatment system; b) study of the competitive adsorption of iron with NOM in Vars groundwater; and c) evaluation of the rapid small-scale column test (RSSCT) for predicting the full-scale GAC column breakthroughs. The characterization of Vars groundwater showed that ferrous iron was found to be the dominant iron species, representing 90% of the total iron, and that 15 - 35% of the iron was complexed with NOM. It was hypothesized that the chromatographic displacement of iron from the GAC columns was caused by NOM-iron complexes; however, field mini-column experiments showed this was not the case. Thus, competitive adsorption between iron and NOM was seen as the more likely cause of the chromatographic effect. The adsorption capacity of ferrous iron in Vars raw water was less than that in organic-free water by a factor of 7 due to the competition with NOM over the GAC adsorbing sites. However, the NOM adsorption capacity was not reduced due to the presence of ferrous iron. It was hypothesized that ideal adsorption solution theory (IAST) models, which have been successful in describing competitive adsorption between target organic compounds and NOM, could model the competition between an inorganic compound such as ferrous iron and NOM. The hypothesis was proved to be correct, and the adsorption isotherm of iron in competition with NOM in Vars groundwater was simulated very well by several versions of the IAST model. However, none of the models were capable of simulating the competitive adsorption of NOM and ferrous iron simultaneously. Since the presence of iron did not significantly reduce the adsorption capacity of NOM, a simplified approach of using the single-solute NOM isotherm to represent the competitive NOM isotherm was recommended. The performance of the rapid small-scale column test (RSSCT) was evaluated in order to simulate the iron chromatographic effect observed at Vars’ full-scale GAC column. The RSSCT was not capable of predicting the iron phenomenon and the test proved to be problematic due to the oxidation and precipitation of iron within the small voids between the small-scale column’s GAC particles. The RSSCT, using constant and linear diffusivities, were applied to simulate the NOM adsorption after greensand treatment. Integrating both diffusivities, the tests predicted the onset and slope of the NOM breakthrough up to 10-L water treated/g GAC, which is equivalent to 250 days of operation time for the full-scale column. However, the NOM breakthroughs deviated beyond that point and the RSSCT using constant diffusivity underestimated the column performance greatly. On the other hand, the linear diffusivity RSSCT underestimated the performance to a lesser degree and its NOM breakthrough was quite parallel to the full-scale performance with lower NOM removals of 15%. The higher long-term NOM removal in the full-scale system may be explained by biodegradation, a phenomenon that was not considered by the short duration of RSSCT.
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Competitive Adsorption of Iron and Natural Organic Matter in Groundwater Using Granular Activated CarbonAl-Attas, Omar January 2012 (has links)
The treatment of potable water in Vars, ON is accomplished by filtering the colored, iron-laden groundwater through granular activated carbon (GAC) filters. When first installed, these filters unexpectedly experienced chromatographic displacements of iron into the produced water which resulted in orange-brown water at consumers’ taps. The treatment plant was later modified by adding potassium permanganate oxidation and a greensand filter prior to the GAC adsorption columns. Consequently, iron was almost completely removed and no longer caused operational problems. The main objective of this dissertation is to study the interactions between natural organic matter (NOM) and iron that caused the observed chromatographic effect. This study was divided into three main stages: a) characterization study on Vars groundwater and its treatment system; b) study of the competitive adsorption of iron with NOM in Vars groundwater; and c) evaluation of the rapid small-scale column test (RSSCT) for predicting the full-scale GAC column breakthroughs. The characterization of Vars groundwater showed that ferrous iron was found to be the dominant iron species, representing 90% of the total iron, and that 15 - 35% of the iron was complexed with NOM. It was hypothesized that the chromatographic displacement of iron from the GAC columns was caused by NOM-iron complexes; however, field mini-column experiments showed this was not the case. Thus, competitive adsorption between iron and NOM was seen as the more likely cause of the chromatographic effect. The adsorption capacity of ferrous iron in Vars raw water was less than that in organic-free water by a factor of 7 due to the competition with NOM over the GAC adsorbing sites. However, the NOM adsorption capacity was not reduced due to the presence of ferrous iron. It was hypothesized that ideal adsorption solution theory (IAST) models, which have been successful in describing competitive adsorption between target organic compounds and NOM, could model the competition between an inorganic compound such as ferrous iron and NOM. The hypothesis was proved to be correct, and the adsorption isotherm of iron in competition with NOM in Vars groundwater was simulated very well by several versions of the IAST model. However, none of the models were capable of simulating the competitive adsorption of NOM and ferrous iron simultaneously. Since the presence of iron did not significantly reduce the adsorption capacity of NOM, a simplified approach of using the single-solute NOM isotherm to represent the competitive NOM isotherm was recommended. The performance of the rapid small-scale column test (RSSCT) was evaluated in order to simulate the iron chromatographic effect observed at Vars’ full-scale GAC column. The RSSCT was not capable of predicting the iron phenomenon and the test proved to be problematic due to the oxidation and precipitation of iron within the small voids between the small-scale column’s GAC particles. The RSSCT, using constant and linear diffusivities, were applied to simulate the NOM adsorption after greensand treatment. Integrating both diffusivities, the tests predicted the onset and slope of the NOM breakthrough up to 10-L water treated/g GAC, which is equivalent to 250 days of operation time for the full-scale column. However, the NOM breakthroughs deviated beyond that point and the RSSCT using constant diffusivity underestimated the column performance greatly. On the other hand, the linear diffusivity RSSCT underestimated the performance to a lesser degree and its NOM breakthrough was quite parallel to the full-scale performance with lower NOM removals of 15%. The higher long-term NOM removal in the full-scale system may be explained by biodegradation, a phenomenon that was not considered by the short duration of RSSCT.
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Synthetic porous materials : a study of adsorption selectivity and structure-property relationshipsDe Villiers, Dawie 12 1900 (has links)
Thesis (MSc)--Stellenbosch University, 2015. / ENGLISH ABSTRACT: The aim of this thesis was to study structure-property relationships in porous materials using various adapted analytical techniques and in-house instruments. The thesis is divided into two sections, and the first section of work constitutes the majority of the thesis.
The first section of work deals with the theoretical versus experimental classification of sorption selectivity in porous compounds. A transiently porous metallocycle that can adsorb acetylene and carbon dioxide served as a model host for this experiment. A volumetric sorption instrument had to be constructed to carry out sorption with acetylene. Even though the metallocycle should theoretically be selective for acetylene over carbon dioxide based on single-gas sorption isotherms, this was not the case during the sorption of a mixture of the two gases. Furthermore, high-pressure single-crystal diffraction was carried out utilising an in-house environmental gas cell, and structural elucidation indicated that both acetylene and carbon dioxide coexist in a single cavity of the host. Additional complementary techniques are discussed that were used to confirm that both gases are present in a single host cavity. The techniques included infrared spectroscopy as well as high-pressure florescence and Raman spectroscopy, which had to be conducted with a specially designed pressure vessel and with adapted instrumentation. Finally, density functional theory calculations were employed to explain how host-guest and guest-guest interactions lead to the change in adsorption selectivity. It is concluded that researchers need to show experimentally that a compound is selective for the adsorption of a specific gas, because theoretical models are not always accurate.
The second part of this work focuses on a fundamental study of the structure-property relationships in a porous hydrogen-bonded organic framework. The section starts off by exploring the activation conditions and thermal stability of the framework. This is followed by an exploration of a possible phase transformation or thermal expansion in the framework, but neither of these occurred. Thereafter, an extended study of the framework’s sorption behaviour with various gases is discussed. Then, a structural study of its solvated phase is used to explain the framework’s stability. Finally, a novel analytical method is introduced, and two examples are used to demonstrate why the instrument is useful in the field of supramolecular chemistry. The chapter is concluded by stating the importance these fundamental studies, as well the development of new analytical techniques. / AFRIKAANSE OPSOMMING: Die doel van hierdie tesis was om die struktuur-afhanklike eienskappe van poreuse materiale te ondersoek. Die studie het gebruik gemaak van verskeie aangepasde analitiese metodes asook instrumente wat spesifiek vir die studie gebou was. Die werk word in twee dele verdeel, en die meerderheid van die tesis word in die eerste deel bevat.
In die eerste deel van die tesis word die validiteit van teoretiese- teen eksperimentele adsorpsie selektiwiteit opgeweeg. ʼn Gasheer wat bestaan uit ringvormige koördinasie-verbindings en wat asetileen asook koolstof dioksied kan adsorbeer, dien as ʼn model gasheer vir die studie. ʼn Volumetriese sorpsie instrument was spesiaal vir die studie gebou sodat asetileen sorpsie gedoen kon word. Volgens asetileen en koolstof dioksied se enkel-gas adsorpsie isoterme moet asetileen teoreties met voorkeur geadsorbeer word gedurende ʼn adsorpsie eksperiment waarin beide gasse teenwoordig is, maar eksperimenteel was dit bepaal dat dit nie so is nie, dus is daar ʼn verandering in die gasheer se adsorpsie selektiwiteit. Hierna word strukturele data van die gasheer, onder ʼn hoë druk van die gas mengsel, versamel deur gebruik te maak van enkel-kristal diffraksie en ʼn spesiaal-gemaakde gas sel. Die strukturele data toon dat beide asetileen en koolstof dioksied teenwoordig is binne elke porie van die gasheer. Daar word dan van addisionele analitiese metodes gebruik te maak om die observasie te bevestig. Die analitiese metodes sluit in infrarooi spektroskopie asook hoë-druk fluoressensie en Raman spektroskopie wat geëis het dat ʼn spesiale druk-bestande monster houer gebou moes word en dat analitiese instrumente gemodifiseer moet word. Ten slotte was daar van “density functional theory” gebruik gemaak om te verduidelik dat die interaksie tussen die gasheer en gas sowel as die interaksie tussen twee gasse lei tot die verandering in adsorpsie selektiwiteit. Uit hierdie bevinding word die gevolgtrekking gemaak dat navorsers met meer eksperimentele data vorendag sal moet kom voordat ʼn gevolgtrekking gemaak kan word dat ʼn raamwerk selektief een gas adsorbeer. Die tweede afdeling van die werk fokus op ʼn fundamentele studie van die struktuur-afhanklike eienskappe van ʼn poreuse waterstof-verbinde organies raamwerk. Die afdeling begin deur ʼn ondersoek van die aktivering kondisies sowel as die temperatuur-afhanklike stabiliteit van die raamwerk. Dit word gevolg deur te soek na moontlike fase veranderings of temperatuur-afhanklike uitsetting van die raamwerk, maar nie een van die twee eienskappe word waargeneem nie. Daarna word die deeglike ondersoek van die raamwerk se adsorpsie vermoë met verskeie gasse bespreek. Dit word gevolg deur ʼn strukturele studie van die solvaat van die raamwerk, wat dan gebruik word om die stabiliteit van die raamwerk te verduidelik. Ten slotte word ʼn analitiese metode bekend gestel, en twee voorbeelde word gebruik om te wys hoe nuttig die metode is om ʼn kombinasie van resultate te bekom. Die hoofstuk word saamgevat deur te verduidelik hoekom dit belangrik is om hierdie tipe fundamentele studies te doen asook waarom nuwe analitiese metodes ontwerp moet word.
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Empleo de zeolitas en procesos de adsorción y separación de hidrocarburos de cadena cortaSánchez, Ledys Yelitza 10 September 2018 (has links)
Los procesos de separación de mezclas de hidrocarburos y gases ligeros mediante adsorción selectiva empleando sólidos microporosos son de interés en numerosas aplicaciones industriales. El objetivo de este trabajo se centra en la purificación de productos gaseosos de interés en la industria petroquímica y la separación de mezclas de CH4/CO2 para la valorización de gas natural. Se pretende evaluar diferentes métodos sencillos que permitan determinar de forma experimental las isotermas de los gases puros a partir de mezclas, y por tanto evaluar la termodinámica de los procesos de adsorción competitiva de forma rigurosa. También se utiliza el método de cálculo de la teoría de la solución ideal adsorbida (IAST Ideal adsorbed Solution Theory) para estimar la adsorción binaria de los compuestos en una mezcla de gases a partir de las isotermas de los compuestos puros y se compara con los valores experimentales de adsorción competitiva.
En primer lugar, se evalúa la capacidad de diferentes zeolitas de poro medio, ZSM-5, IM-5 y TNU-9, en procesos de separación de mezclas de hidrocarburos ligeros lineales y ramificados (propano, isobutano, n-pentano y neopentano). Se establecen los modelos de ajuste de las isotermas de adsorción, así como las ecuaciones que permiten calcular el calor isostérico de adsorción y el cálculo de la predicción IAST.
En un segundo apartado se ha desarrollado un método que, combinando isotermas gravimétricas y volumétricas de mezclas de dos gases de diferente peso molecular, permite obtener las isotermas de cada uno de los adsorbatos por separado. Para ello, se han utilizado mezclas de CO2 y CH4 en distintas proporciones y las zeolitas Beta, ITQ-29 y B-DDR como adsorbentes. Se debe tener en cuenta que la zeolita Beta se utiliza como modelo de adsorbente no selectivo y como punto de comparación para las otras zeolitas. La combinación de isotermas volumétricas y gravimétricas permitió calcular la isoterma completa de cada gas en una mezcla binaria durante un proceso de adsorción competitiva. Por otro lado, se ha aplicado el método de cálculo IAST a este mismo caso de estudio. Los resultados obtenidos por ambos métodos no coinciden, especialmente para el caso de la zeolita B-DDR que presenta una adsorción muy preferencial por el CO2. Sin embargo, la estimación termodinámica IAST se acerca mucho a los resultados experimentales obtenidos por la zeolita Beta, lo que indica que este método no es adecuado para la determinación de la selectividad en procesos de separación sobre sólidos microporosos en los que hay adsorción preferencial.
En un tercer apartado se presenta el estudio de la adsorción dinámica de mezclas CO2/CH4 en condiciones variables de presión y composición a temperatura constante, sobre diferentes zeolitas. Como primera etapa, se llevó a cabo la adsorción dinámica de CO2 y N2 sobre la zeolita 13X con el objeto de poner a punto un nuevo equipo de curvas de ruptura diseñado en el Instituto de Tecnología Química (ITQ), logrando encontrar resultados que están de acuerdo con los publicados en la literatura para esta separación. Adicionalmente, se han evaluado las propiedades de separación de mezclas de gases CO2/CH4 por métodos dinámicos sobre las zeolitas Beta e ITQ-29, encontrando que los valores obtenidos para los gases puros CO2 y CH4 por métodos dinámicos y estáticos son muy similares para estas zeolitas y que, efectivamente, éstas son capaces de separar mezclas de CO2 y CH4. Sin embargo, en el caso de las curvas de ruptura para las mezclas CO2/CH4 sobre la zeolita Beta, se encuentran zonas de transferencia de masa menos abruptas que en el caso de la zeolita ITQ-29, confirmando que la zeolita Beta es un adsorbente menos eficiente para la separación de esta mezcla. / The separation processes of hydrocarbons and light gas mixtures by selective adsorption using microporous solids are interesting in numerous industrial applications. The objective of this work focuses on the purification of gaseous products of interest in the petrochemical industry and the separation of CH4/CO2 mixtures in order to increase the natural gas' value. The aim is to evaluate different simple methods that allow to determine experimentally the isotherms of pure gases from mixtures, and therefore to evaluate the thermodynamics of competitive adsorption processes in a rigorous way. The Ideal Adsorbed Solution Theory (IAST) calculation method is also used to estimate the binary adsorption of the compounds in a mixture of gases from the isotherms of the pure compounds and it is compared to the values of competitive adsorption experiments.
Firstly, the capacity of different medium pore zeolites, ZSM-5, IM-5 and TNU-9, is evaluated in separation processes of linear and branched light hydrocarbon mixtures (propane, isobutane, n-pentane and neopentane). The adjustment models of the adsorption isotherms are established, as well as the equations that allow to calculate the isoteric heat of adsorption and the calculation of the IAST prediction.
In a second section, a method has been developed that, combining gravimetric and volumetric isotherms of mixtures of two gases of different molecular weight, allows to obtain the isotherms of each of the adsorbates separately. For this, mixtures of CO2 and CH4 have been used in different proportions and zeolites Beta, ITQ-29 and B-DDR as adsorbents. It must be taken into account that zeolite Beta is used as a model of a non-selective adsorbent and as a point of comparison for the other zeolites. The combination of volumetric and gravimetric isotherms allowed to calculate the complete isotherm of each gas in a binary mixture during a competitive adsorption process. On the other hand, the IAST calculation method has been applied to this same case study. The results obtained by both methods do not coincide, especially for the case of zeolite B-DDR which presents a very preferential adsorption by CO2. However, the thermodynamic estimation with IAST is very close to the experimental results obtained by the zeolite Beta, which indicates that this method is not suitable for the determination of the selectivity in separation processes on microporous solids in which there is preferential adsorption.
In a third section we present the study of the dynamic adsorption of CO2/CH4 mixtures under variable conditions of pressure and composition at constant temperature, on different zeolites. As a first step, the dynamic adsorption of CO2 and N2 was carried out on the 13X zeolite in order to fine-tune the breakthrough curve equipment designed by the Chemical Technology Institute (ITQ), achieving results that are in accordance with the published results in the literature for this separation. Additionally, the separation properties of CO2/CH4 gas mixtures were evaluated by dynamic methods on Beta and ITQ-29 zeolites, finding that the values obtained for pure CO2 and CH4 gases by dynamic and static methods are very similar for these zeolites and that, indeed, they are capable of separating mixtures of CO2 and CH4. However, in the case of the breakthrough curves for the CO2/CH4 mixtures on the Beta zeolite, less abrupt mass transfer zones are found than in the case of the ITQ-29 zeolite, confirming that the Beta zeolite is an adsorbent less efficient for the separation of this mixture. / Els processos de separació de mescles d'hidrocarburs i gasos lleugers mitjançant adsorció selectiva emprant sòlids microporosos són d'interès en nombroses aplicacions industrials. L'objectiu d'aquest treball se centra en la purificació de productes gasosos d'interès en la indústria petroquímica i la separació de mescles de CH4/CO2 per a la valorització de gas natural. Es pretén avaluar diferents mètodes senzills que permeten determinar de forma experimental les isotermes dels gasos purs a partir de mescles, i per tant avaluar la termodinàmica dels processos d'adsorció competitiva de forma rigorosa. També s'utilitza el mètode de càlcul de la teoria de la solució ideal adsorbida (IAST Ideal Adsorbed Solution Theory) per a estimar l'adsorció binària dels compostos en una mescla de gasos a partir de les isotermes dels compostos purs i es compara amb els valors experimentals d'adsorció competitiva.
En primer lloc, s'avalua la capacitat de diferents zeolites de porus mitjà, ZSM-5, IM-5 i TNU-9, en processos de separació de mescles d'hidrocarburs lleugers lineals i ramificats (propà, isobutano, n-pentà i neopentano). S'estableixen els models d'ajust de les isotermes d'adsorció, així com les equacions que permeten calcular la calor isostérico d'adsorció i el càlcul de la predicció IAST.
En un segon apartat s'ha desenvolupat un mètode que, combinant isotermes gravimètriques i volumètriques de mescles de dos gasos de diferent pes molecular, permet obtenir les isotermes de cadasqun dels adsorbats per separat. Per a açò, s'han utilitzat mescles de CO2 i CH4 en diferents proporcions i les zeolites Beta, ITQ-29 i B-DDR com a adsorbents. S'ha de tenir en compte que la zeolita Beta s'utilitza com a model d'adsorbent no selectiu i com a punt de comparació per a les altres zeolites. La combinació d'isotermes volumètriques i gravimètriques va permetre calcular la isoterma completa de cada gas en una mescla binària durant un procés d'adsorció competitiva. D'altra banda, s'ha aplicat el mètode de càlcul IAST a aquest mateix cas d'estudi. Els resultats obtinguts per tots dos mètodes no coincideixen, especialment per al cas de la zeolita B-DDR que presenta una adsorció molt preferencial pel CO2. No obstant açò, l'estimació termodinàmica IAST s'acosta molt als resultats experimentals obtinguts per la zeolita Beta, la qual cosa indica que aquest mètode no és adequat per a la determinació de la selectivitat en processos de separació sobre sòlids microporosos en els quals hi ha adsorció preferencial.
En un tercer apartat es presenta l'estudi de l'adsorció dinàmica de mescles CO2/CH4 en condicions variables de pressió i composició a temperatura constant, sobre diferents zeolites. Com a primera etapa, es va dur a terme l'adsorció dinàmica de CO2 i N2 sobre la zeolita 13X amb l'objecte de posar a punt un nou equip de corbes de ruptura dissenyat en l'Institut de Tecnologia Química (ITQ), aconseguint trobar resultats que estan d'acord amb els publicats en la literatura per a aquesta separació. Addicionalment, s'han avaluat les propietats de separació de mescles de gasos CO2/CH4 per mètodes dinàmics sobre les zeolites Beta i ITQ-29, trobant que els valors obtinguts per als gasos purs CO2 i CH4 per mètodes dinàmics i estàtics són molt similars per a aquestes zeolites i que, efectivament, aquestes són capaces de separar mescles de CO2 i CH4. No obstant açò, en el cas de les corbes de ruptura per a les barreges CO2/CH4 sobre la zeolita Beta, es troben zones de transferència de massa menys abruptes que en el cas de la zeolita ITQ-29, confirmant que la zeolita Beta és un adsorbent menys eficient per a la separació d'aquesta mescla. / Sánchez, LY. (2018). Empleo de zeolitas en procesos de adsorción y separación de hidrocarburos de cadena corta [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/107362 / TESIS
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MODELING BICOMPONENT ADSORPTION OF AROMATIC COMPOUNDS ONTO NONPOLAR POLYMERIC RESIN MN200Wang, Shubo January 2015 (has links)
A large number of organic contaminants are commonly found in industrial and municipal wastewaters. Aromatic compounds, such as phenol, aniline and their derivatives, are contaminants of high priority and usually coexist in waste streams from industries of, for example, aromatic amine compounds and ammonolysis of phenols. Thus, for proper unit design to remove contaminant mixtures by adsorption, multi-component adsorption models are necessary. The present work was aimed at examining the applicability of Ideal Adsorbed Solution Theory (IAST), a prevailing thermodynamic model, and its derivative i.e. Segregated IAST (SIAST) and Real Adsorbed Solution Theory (RAST) to multi-solute adsorption from the aqueous phase, specifically, bi-solute adsorption of phenols, anilines and nitrobenzene onto a hyper-crosslinked polystyrene resin, MN200. Based on the experimental bi-solute adsorption isotherms, we have successfully developed methods for modeling with RAST incorporated with Wilson equation, Nonrandom two-liquid (NRTL) model, and an empirical four-parameter equation developed in this work. It turns out that our proposed four-parameter equation can fit the activity coefficients, γ_(i ), better than the other two equations and thus enhanced the accuracy of RAST in predicting bi-solute adsorption equilibrium. Besides successfully developing methods for properly designing binary-solute batch experiments and accurately modeling with RAST, two empirical linear relationships have been developed for the adsorption of a number of infinite dilute solutes in the presence of a major contaminant (either 4-methylphenol or nitrobenzene). Results show that polyparameter linear free energy relationships have a great potential in predicting adsorbed phase activity coefficients of solutes when the adsorbed amounts are dominated by the major contaminant and the adsorbed mixture resembles infinite dilute solution. Activity coefficients under such conditions were represented by〖 γ〗_i^∞ and were successfully extrapolated to γ_(i )at non-infinite conditions by γ_(i )models i.e. Wilson equation. To the best of our knowledge, this is the first systematic study predicting adsorbed phase activity coefficients for bi-solute adsorption. In addition, our tri- and tetra-solute adsorption data showed that the predominating solute, NB in this case, solely contributed to the competitive effect while the dilute solutes tend not to interact with each other. This indicates that for each solute, the competitive effects can be independently considered and a multi-component system with n components but only one component dominating can be treated as (n-1) bi-solute systems separately. This will significantly simplify the calculation for modeling multi-component adsorption while it is also close to many real systems where there is one major contaminant or a large amount of NOM in present. Our findings have proved a major step forward to accurately modeling multi-solute adsorption for proper unit design of adsorption processes. / Civil Engineering
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Elimination de pesticides sur lit de charbon actif en grain en présence de matière organique naturelle : Elaboration d'un protocole couplant expériences et calculs numériques afin de simuler les équilibres et les cinétiques compétitifs d'adsorption.Baup, Stéphane 27 November 2000 (has links) (PDF)
Face à la pollution persistante des eaux naturelles par les pesticides, le charbon actif en grain (CAG) représente une réelle possibilité de traitement, de plus en plus souvent mis en œuvre en potabilisation. L'efficacité de ce traitement dépend des équilibres et des cinétiques d'adsorption, de l'hydrodynamique du réacteur et de la compétition avec la matière organique naturelle contenue dans les eaux brutes destinées à la potabilisation. Dans ce cadre, l'objectif de cette recherche est double : élaborer un protocole d'acquisition des paramètres d'équilibre et de cinétique d'adsorption compétitive et concevoir un logiciel de simulation de l'adsorption sur lit de CAG. L'approche théorique s'appuie sur : (1) le modèle de la diffusion de surface homogène (HSDM) qui prend en compte le coefficient de transfert de masse externe (kf) et le coefficient de diffusion superficielle (Ds) pour modéliser la cinétique d'adsorption, (2) la théorie de la solution adsorbée idéale (IAST) pour modéliser la compétition et (3) l'introduction d'un composé fictif (EBC) qui représente la matière organique naturelle. Le travail expérimental consiste d'une part à réaliser des isothermes d'adsorption sur l'eau ultra pure, l'eau réelle et l'eau réelle diluée par de l'eau ultra pure afin d'obtenir les paramètres d'équilibre. D'autre part, des cinétiques d'adsorption, effectuées sur colonne différentielle d'adsorption (DCBR), permettent d'acquérir les coefficients de diffusion superficielle. Les programmes de simulation ont été conçus, écrits et validés sur plusieurs résultats issus de la littérature. Ces programmes ont ensuite été impliqués dans le protocole global de simulation du filtre de charbon actif en grain réel. Pour une eau naturelle, ce protocole a été mis en œuvre sur trois pesticides et deux charbons actifs en grain.
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