L’activité scientifique du sujet porte sur l’acquisition de données expérimentales et la modélisation de la composition des clathrates hydrates de gaz. Les domaines d’application concernent la séparation et le stockage de gaz, la purification de l’eau, et le stockage d’énergie par matériaux à changement de phase.L’équipe a mis en évidence il y a quelques années que la composition des hydrates de gaz était sensible aux conditions de cristallisation, et que le phénomène de formation se produisait en dehors de l’équilibre thermodynamique.Le travail de thèse a permis d’explorer plusieurs modes de cristallisation à partir de solutions de même composition initiale pour observer les différences concernant l’état final, compositions notamment, et les relier à la vitesse de cristallisation. Suivant le mode de cristallisation, lent ou rapide, l’acquisition des données expérimentales peut prendre de quelques jours à plusieurs semaines. Les expériences sont réalisées en réacteur pressurisé dans lequel nous mesurons en ligne la composition de la phase gaz et de la phase liquide, pour calculer par bilan de matière la composition de la phase hydrate.Nous avons bien mis en évidence des variations dans la composition de la phase hydrate suivant le mode de cristallisation. Nous avons dû établir un modèle thermodynamique donnant la composition de la phase hydrate à l’équilibre pour des mélanges de gaz qui n’avaient jamais été traité par la littérature, et qui ont donc nécessité des campagnes de mesure extrêmement lentes et donc longues pour être sûr de l’état thermodynamique à l’équilibre.Nous sommes en cours d’établir un modèle cinétique pour modéliser les écarts à cet état d’équilibre de référence pour nos expériences réalisées à vitesse de cristallisation rapide. / The scientific goal of this thesis is based on the acquisition of experimental data and the modeling of the composition of clathrates gas hydrate. The domains of application concern the gas separation and storage, water purification, and energy storage using change phase materials (PCMs).Our research team has recently demonstrated that the composition of gas hydrates was sensitive to the crystallization conditions, and that the phenomenon of formation was out of thermodynamic equilibrium. During this thesis, we have investigated several types of crystallization, which are based on the same initial states. The goal is to point out the differences between the initial solution composition and the final solution composition, and to establish a link between the final state and the crystallization rate.Depending on the rate of crystallization (slow or fast), the acquisition time of experimental data lasted from a few days to several weeks. The experimental tests were performed inside a stirred batch reactor (autoclave, 2.44 or 2.36 L) cooled with a double jacket. Real-time measurements of the composition of the gas and the liquid phases have been performed, in order to calculate the composition of the hydrate phase using mass balance calculations. Depending on the crystallization mode, we have identified several variations of the composition of the hydrate phase and final hydrate volume.We have established a successful thermodynamic model, which indicates the composition of the hydrate phase and hydrate volume in thermodynamic equilibrium state using a gas mixture which had never been used before in the literature. So this thermodynamic model has required an extremely slow experimental test. These tests were also long in order to be sure of the thermodynamic equilibrium state.We are currently establishing a kinetics model in order to model the deviations from the reference point of equilibrium of our experimental tests which were carried out at a high crystallization rate.

Dans le cadre de l’entreposage et du stockage des colis de déchets nucléaires et du transport de combustibles usés, nous nous sommes intéressés par l’étude de la production d’hydrogène de deux produits de corrosion de l’aluminium : l’hydroxyde d’aluminium (Al(OH)3) et l’oxyhydroxyde d’aluminium (AlO(OH)).La production du dihydrogène par irradiation de ces matériaux a été étudiée en fonction de la taille et de la structure que ce soit à température ambiante ou après. Afin d’avoir une meilleur compréhension des mécanismes de production de ce gaz, les défauts créés par irradiation ont été caractérisés en utilisant la Résonnance Paramagnétique Electronique (RPE). Différentes sources d’irradiation ont été utilisées comme le rayonnement Gamma, les électrons accélérés et les ions lourds. Dans un second temps, l’effet de l’hydratation de surface des matériaux a été également étudié. Enfin, l’effet de la présence d’impuretés sur la production de H2 a été brièvement étudié. / Dihydrogen production is a critical issue for the current management of nuclear wastes. One potential source of hydrogen generation is the radiolysis of hydrated mineral phases encountered in the nuclear waste transportation and storage casks. We chose to study aluminum hydroxide (Al(OH)3) (Bayerite) and oxyhydroxides (AlOOH) (Boehmite) as model compounds. The determination of molecular hydrogen production was evaluated with respect to structure and particle size at room temperature and after annealing. In order to have a better understanding of the mechanisms and to identify the precursors of molecular hydrogen, we studied the irradiation defects and their stabilities using Electron Paramagnetic Resonance (EPR). The effect of adsorbed water and structural water on the molecular hydrogen production was studied. Different radiation sources were used such as Gamma radiation, electron beam radiations and heavy ions. In the last part, preliminary results related to the impact of impurities on hydrogen production are presented.

Gegenstand der vorliegenden Arbeit war es, die Grundlagen für ein mögliches technisches Verfahren zur Aromatennitrierung mit Salzhydratschmelzen (M(NO3)3 · n H2O, M = Fe, Cr, Bi, In, Al; n = 4 - 9) zu untersuchen. Es sollte geklärt werden, ob Toluol quantitativ zu Dinitrotoluol bzw. Benzol zu Nitrobenzol umgesetzt werden kann. In Screening-Versuchen wurden geeignete, nitrierend wirkende Salzhydrate ermittelt, sowie Wege untersucht, die Reaktivität der eingesetzten Salzhydratschmelzen durch Variation von Wasser- bzw. Säuregehalt, Durchmischung, verschiedenen Schmelzenzusätzen bzw. Reaktionstemperatur zu steigern. Das entstehende Verhältnis der Isomeren der Mono- und Dinitrierung wurde hinsichtlich einer möglichen Beeinflussung untersucht. Das Spektrum an Nebenprodukten wurde bestimmt, sowie Möglichkeiten aufgezeigt, diese zu vermeiden. Dabei konnte gezeigt werden, dass im Gegensatz zum etablierten Mischsäureverfahren beim Einsatz von Salzhydratschmelzen keine kresolischen Nebenprodukte gebildet werden. Weiterhin wurden Möglichkeiten zur Präparation wasserarmer Salzhydratschmelzen durch thermische Entwässerung bzw. Reaktion mit flüssigem N2O4 untersucht, die Löslichkeit der isomeren Zwischen- und Endprodukte in der Salzhydratschmelze bestimmt sowie das thermische Verhalten von Dinitrotoluol in Gegenwart der Salze betrachtet.

Thesis (MSc)--Stellenbosch University, 2014. / ENGLISH ABSTRACT: A theoretical and experimental study was performed in order to identify factors that influence the propensity of compounds containing anionic functional groups that are commonly found on pharmaceutical drug compounds to form hydrates. A Cambridge Structural Database (CSD) survey was initially undertaken to determine the propensity of different pharmaceutically acceptable anions to form hydrates. The results showed that hydrate formation will take place more regularly when the polarity of the functional group increases. Furthermore, if the charge distribution is very concentrated over the polar groups, hydrate formation will occur more readily. This observation was further investigated by performing a series of potential energy surface (PES) scans for the hydrogen bond (H-bond) in the structure of N-(aminoiminomethyl)-N-methylglycine monohydrate (creatine monohydrate) with various Density Functional Theory (DFT) and Wave Functional Theory (WFT) methods. WFT is often also referred to as ab initio, which refers to the construction of the wave function from first principles when this theory is applied. The scans revealed that several strong and directional H-bonds with different geometrical parameters between the carboxylate group and the water molecule are possible, which suggests that the H-bond plays an important role in driving the formation of pharmaceutical hydrates. A total of 44 hydrate structures were identified that have pharmaceutically acceptable functional groups. Optimisations in the gas phase and in an implicit solvent polarisable continuum solvent model with a variety of solvents showed that there is a significant dependence of the H-bond interaction energy on the anionic group as well as the steric density of surrounding substituents. It was found that the M06-2X method utilising the 6-311++G(d,p) basis set outperformed the other methods that were tested when compared to optimisations performed with the benchmark MP2/aug-cc-pVTZ level of theory. Furthermore, the strength of the H-bond was measured in the 44 experimentally determined structures by using a total of five generalized gradient approximation (GGA) methods, of which two methods contained the DFT-D3 correction. The results of these DFT methods were subsequently compared to results obtained at the benchmark MP2/aug-cc-pVTZ level of theory. The M06-2X method was identified as the most economical method to calculate H-bond energies. It was also found that the H-bond interaction energy shows a substantial dependence on the electrostatic environment. This was observed by a significant decrease in H-bond strength as the relative permittivity of the solvent increases. The effect of steric density on the H-bond interaction energy was investigated by performing hydrogen bond propensity calculations. These values were then compared to the interaction energies of each structure and the results showed that the presence of large bulky substituents can lead to an increase in bond energy by forcing the anionic functional group closer to the water molecule. Contrastingly, the bulky group can also push the anionic group away from the water molecule and result in a decrease in bond energy. Approximate values for the amount of stabilisation offered to the H-bonding system by the surrounding crystalline environment were calculated by optimising the H-bond geometrical parameters of selected compounds with a combination of the M06-2X and MP2 methods utilising the 6-311++G(d,p) basis set. The H-bond interaction energies were then calculated at the M06-2X/6-311++G(d,p) level of theory and compared to the H-bond interaction energies in geometries that have been fully optimised. After these energies were compared and the crystal packing of each structure was investigated, it was found that the packing of some structures within the crystalline environment limits the number of H-bonds that can be formed between the water and the compound of interest. Full optimisation calculations result in structures with cooperative stabilisation, such that more than one H-bond is found between the two fragments. The effect of substituents on H-bond interaction energy was investigated by the addition of six electron-donating and electron-withdrawing groups on four aromatic compounds with different anionic functional groups, namely carboxylate, nitrogen dioxide, sulfonate and phosphonate. It should also be mentioned that the nitrogen dioxide is not an anionic functional group, but it was included as it is a neutral radical that often forms hydrogen bonds. A total of 80 structures were optimised with a combination of the M06-2X and MP2 methods utilising the 6-311++G(d,p) basis set. This was followed by counterpoise corrected single point calculations at the M06-2X/6-311++G(d,p) level of theory. The results showed that the H-bond interaction energy bears no relationship to the inductive strength or the inductive ability of the substituents, but rather the ability of these substituents to rotate the anionic functional group and allow cooperative stabilisation of the H-bond. Furthermore, AIM analysis was performed for the substituted H-bonded aromatic structure. The results showed that electron-donating groups that are placed at the para position yield stronger H-bonds, which is once again accompanied by cooperative stabilisation. Electron-withdrawing groups with sufficient inductive effects can result in a weaker H-bond when placed at the meta position. The effect of water activity (aw) on the hydrate crystal formation was investigated experimentally by performing a series of crystallisations in various solvent mixtures. These mixtures consisted of water mixed with acetone, ethanol and ethyl acetate. A total of three organic acids were used in crystal formation, namely pyridine-4-carboxylic acid (isonicotinic acid), N-amino-iminomethyl-N-methylglycine (creatine) and benzene-1,3,5-tricarboxylic acid. It was found that water activity affects the formation of the hydrate as well as the anhydrous product. Additionally, nucleation and super saturation plays a large role in crystal formation and can serve as an effective technique when the formation of crystals of an appropriate shape and size is required for further analysis. / AFRIKAANSE OPSOMMING: 'n Teoretiese en eksperimentele studie was uitgevoer om faktore te identifiseer wat die geneigdheid van verbindings met anioniese funksionele groepe wat algemeen gevind word op farmaseutiese dwelm verbindings om die hidraat produk te vorm, affekteer. 'n Opname van strukture in die Cambridge Strukturele Databasis (CSD) is onderneem om die geneigdheid van verskillende farmaseutiese aanvaarbare anione om hidrate te vorm te bepaal. Die resultate het getoon dat hidraatvorming meer gereeld plaasvind indien die polariteit van die funksionele groepe toeneem. Verder is daar ook opgemerk dat 'n gekonsentreerde ladingsverspreiding op die polêre groepe ook tot 'n toename in hidraat vorming sal lei. Hierdie waarneming is verder ondersoek deur 'n reeks potensiële energie oppervlak (PES) skanderings van die waterstof binding (H-binding) vir die struktuur van N-amino-iminometiel-N-metielglisien monohidraat (kreatien monohidraat) met verskeie Digtheids-Funksionele Teorie (DFT) en Golffunksie Teorie (WFT) metodes uit te voer. Die skanderings het getoon dat verskeie sterk, gerigte H-bindings met verskillende geometriese parameters tussen die karboksilaatgroep en die watermolekule kan vorm. Hierdie bevindinge lê klem op die belangrike rol wat H-bindings in die vorming van farmaseutiese koolhidrate speel. 'n Totaal van 44 hidraat strukture met farmaseutiese aanvaarbare funksionele groepe was geïdentifiseer. Optimaliserings is in die gas fase asook in 'n implisiete kontinuum polariseerbare oplosmiddel model met 'n verskeidenheid oplosmiddels uitgevoer. Die resultate het 'n beduidende afhanklikheid van die H-binding interaksie-energie op die anioniese groep asook die steriese afkskerming van omringende groepe getoon. Daar is bepaal dat die M06-2X metode wat saam met die 6-311++G(d,p) basisstel die mees akkuraatste resultate gelewer het in vergelyking met die ander DFT metodes asook die MP2/aug-cc-pVTZ maatstaf. Die H-binding se sterkte is vir hierdie strukture bereken deur vyf GGA metodes te gebruik, waarvan twee metodes van die DFT-D3 korreksie gebruik maak. Die resultate van die berekeninge met hierdie DFT metodes is daarna vergelyk met resultate verkry met die MP2/aug-cc-pVTZ maatstaf. Daar is gevolglik bepaal dat die M06-2X metode die mees ekonomiese metode is om H-binding energië te bereken. Die H-binding interaksie energie toon 'n aansienlike afhanklikheid op die diëlektriese konstante van die oplosmiddel aan. Hierdie waarneming is op grond van 'n beduidende afname in die H-binding interaksie-energie indien die relatiewe permittiwiteit van die oplosmiddel verhoog word gemaak. Die effek van steriese digtheid is ondersoek deur waterstofbindinggeneigdheid waardes te bereken. Hierdie waardes is met die interaksie-energië van elke struktuur vergelyk. Die resultate dui daarop dat steries digte groepe tot 'n toename in interaksie energie kan lei wanneer die anioniese funksionele groep nader aan die water molekule gestoot word. Verder is dit ook moontlik vir hierdie steries digte groepe om die anioniese groep weg van die water molekule te stoot en gevolglik 'n afname in interaksie energie te veroorsaak. Benaderde waardes vir die hoeveelheid stabilisering wat die omringende kristallyne omgewing aan die H-binding bied is bereken deur die H-binding geometriese parameters van geselekteerde verbindings met die M06-2X en MP2 metodes en die 6-311++G (d,p) basisstel te optimaliseer. Die H-binding interaksie-energië is gevolglik by die M06-2X/6-311++G(d,p) vlak van teorie bereken en met die H-binding energië in strukture wat volledige optimaliseer is vergelyk. Nadat hierdie waardes vergelyk is, is daar gevind dat die pakking van strukture in the kristallyne omgewing verhoed dat sekere H-bindings tussen die water molekule en die verbinding van belang kan vorm. Strukture wat volledig optimaliseer is, lei tot strukture wat in staat is om koöperatiewe stabilisering te ondergaan. Koöperatiewe stabilisering word gekenmerk deur die vorming van meer as een H-binding tussen twee fragmente. Die effek van substituente op die H-binding interaksie energie is ondersoek deur die bevoeging van ses elektrondonor- en elektronontrekkendegroepe op vier aromatiese verbindings, naamlike die karboksilaatgroep , stikstofdioksied , sulfonaat en fosfonaat. Dit moet ook genoem word dat stikstofdioksied nie 'n anioniese funksionele groep is nie, maar dit was wel ingesluit omdat dit ‘n neutrale radikaal groep is wat dikwels waterstofbindings vorm. 'n Totaal van 80 strukture optimiserings was uitgevoer met 'n kombinasie van die M06-2X en MP2 metodes wat gebruik maak van die 6-311++G(d,p) basisstel. Dit is gevolg deur interaksie-energie berekeninge op die M06-2X/6-311++G(d,p) vlak van teorie. Die resultate het getoon dat daar geen verband tussen die induktiewe vermoë van die substituente en die sterkte van die H-binding is nie, dit is eerder die vermoë van hierdie substituente om die anioniese funksionele groep te laat roteer wat toelaat dat koöperatiewe stabilisering van die H-binding kan geskied. Die AIM analise is op 'n gesubstitueerde H-binding struktuur toegepas. Die resultate het getoon dat elektrondonorgroepe wat by die para posisie geplaas word tot sterker H-bindings sal lei, wat weereens met koöperatiewe stabilisering vergesel word. Elektrononttrekkendegroepe met sterk induktiewe effekte kan tot 'n swakker H-binding lei indien hulle by die meta posisie geplaas word. Die effek van water aktiwiteit (𝑎w) op hidraatkristalvorming is deur die uitvoering van 'n reeks kristallisasies in verskeie oplosmiddelmengsels ondersoek. Hierdie oplosmiddel mengsels bestaan uit water met asetoon, etanol of etielasetaat gemeng. Kristallisasies is vir drie organiese sure, naamlik piridien-4-karboksielsuur, N-amino-iminometiel-N-metielglisien monohidraat en 1,3,5-benseen tri-karboksielsuur uitgevoer. Daar is gevind dat water aktiwiteit 'n invloed op die vorming van die hidraat en watervrye produkte kan hê. Daarbenewens, speel water aktiwiteit 'n belangrike rol in die nukleasie fase van kristalvorming en kan as 'n effektiewe tegniek dien om kristalle van 'n toepaslike vorm en grootte vir verdere analise te verkry.

Les coulis d'hydrates de gaz sont une alternative intéressante en tant que fluides frigoporteurs utilisables dans les boucles de réfrigération secondaire. La génération du coulis par injection directe d'un gaz comme le CO2 au sein d'un fluide refroidi permet de surmonter les problèmes techniques liés aux méthodes de génération mécaniques. L'objectif de la thèse est d'étudier l'effet d'additifs sur l'amélioration des conditions d'écoulement du coulis ainsi que sur les modifications de leurs conditions de formation. Dans ce travail de thèse nous nous sommes donc attachés à caractériser l'effet de l'addition d'un promoteur d'hydrates, le tetrahydrofurane (THF) sur les conditions de formation de l'hydrate mixte THF+CO2 dans les systèmes eau-CO2-THF. La calorimétrie différentielle programmée, DSC, sous pression contrôlée de gaz a été employée comme technique expérimentale .Les résultats obtenus (conditions de température de formation, enthalpie et capacité calorifique de dissociation pour diverses pressions de CO2 et concentrations de THF) ont été comparés avec les prédictions d'un modèle thermodynamique combinant l'expression de van der Waals et Platteeuw et l'équation d'état RKS associée à la loi de mélange MHV2 et au modèle UNIFAC. Une autre partie de la thèse a été consacrée à l'étude des conditions de formation et d'écoulement d'un coulis d'hydrates à base de CO2 en présence d'additifs. Pour cela, un dispositif expérimental capable de mesurer le débit et les pertes de charges a été employé. Après une étude phénoménologique des conditions de formation et d'écoulement des coulis, une sélection d'additifs permettant d'améliorer ces conditions a été réalisée. Une caractérisation rhéologique du coulis en présence de l'additif le plus performant complète ce travail.

Salts in solution should be removed by desalination techniques to prevent equipment fouling and corrosion. Common desalination technologies are energy intensive such as Multi Stage Flash (MSF) distillation which requires 14.5 J/m3 (Ribeiro. J, 1996) of energy. Desalination technologies produce purified water and a concentrated salt solution, where the salt concentration is dependent on the desalination technology used. This work investigates gas hydrate technology as a possible desalination technology. Hydrates are composed of guest molecules and host molecules. Guest molecules may be in the form of a liquid or gas. During hydrate formation, host molecules, water, form a cage enclosing the guest molecule. Common hydrate formers or guest molecules such as; methane, ethane, propane and carbon dioxide are currently being investigated in literature, for use in gas hydrate desalination technology. Common hydrate formers form hydrates at low temperatures; below 288 K and high pressures; above 2 MPa. To increase the temperature and reduce the pressure at which gas hydrates form, commercially available hydrofluorocarbon hydrate formers such as R14, R32, R116, R134a, R152a, R218, R404a, R407c, R410a and R507 are preliminarily investigated in this work. The criteria for choosing the most suitable fluorine-based formers require the former to be: environmentally acceptable where it is approved by the Montreal Protocol; non-toxic where it has a low acute toxicity; non-flammable; chemically stable; a structure II hydrate to simplify the washing process; available in commercial quantities; low cost in comparison to other hydrate formers; compatible with standard materials and contain a high critical point for a large heat of vaporisation (McCormack and Andersen, 1995). Taking all these criteria into account, R134a was chosen for further investigation as a possible hydrate former. In this work, hydrate-liquid-vapour phase equilibrium measurements are conducted using the isochoric method with a static high pressure stainless steel equilibrium cell. The Combined Standard Uncertainty for the 0-1 MPa pressure transducer, 0-10 MPa pressure transducer and the Pt100 temperature probes are ±0.64 MPa, ±5.00 MPa and ±0.09 K respectively. Vapour pressure measurements for Hydrofluoropropyleneoxide, CO2, R22 and R134a were measured to verify the pressure and temperature calibrations. Hydrate test systems for R22 (1) + water (2) and R134a (1) + water (2) were measured to verify calibrations, equipment and procedures. New systems measured included R134a (1) + water (2) + {5wt%, 10wt% or 15wt%} NaCl (3). For the system R134 (1) + water (2) at 281 K the dissociation pressure is 0.269 MPa. However, addition of NaCl to the system resulted in a shift of the HVL equilibrium phase boundary to lower temperatures or higher pressures. The average shift in temperature between the system R134a (1) + water (2) containing no salt and the systems containing {5, 10 and 15} wt% NaCl are -1.9K, -4.8K and -8.1K respectively. In this work, the measured systems were modelled using two methods of approach. The first method is where hydrofluorocarbon hydrate former solubility is included, (Parrish et al., 1972) and the second is where hydrofluorocarbon hydrate former solubility is ignored, (Eslamimanesh et al., 2011). From these models, it is found that hydrofluorocarbon solubility could not be neglected. In this work, the hydrate phase was modelled using modifications of the van der Waals and Platteeuw model, (Parrish et al., 1972). The liquid and vapour phases are modelled using the Peng- Robinson equation of state with classical mixing rules (Peng, 1976). The electrolyte component is modelled using the Aasberg-Peterson model (Aasberg-Petersen et al., 1991) modified by Tohidi (Tohidi et al., 1995). The percent absolute average deviation (%AAD) for the systems, which includes solubility, is 0.41 for R22 (1) + water (2) and 0.33 for R134a (1) + water (2). For the system R134a (1) + water (2) + {5 wt%, 10 wt% or 15 wt%} NaCl (3) the % AAD is 5.14. Using the hydrate former, R134a, is insufficient to ensure gas hydrate technology is competitive with other desalination technologies. Hydrate dissociation temperature should be increased and pressure decreased further to ambient conditions. As evident in literature, promoters, such as cyclopentane, are recommended to be added to the system to shift the HLV equilibrium phase boundary as close to ambient conditions as possible. / Thesis (M.Sc.Eng.)-University of KwaZulu-Natal, Durban, 2011.

The first project in this work used classical molecular dynamics to study the ice recrystallization inhibition potential of a series of carbohydrates and alcochols, using the hydration index, partial molar volumes and isothermal compressibilities as parameters for measuring their cryogenic efficacy. Unfortunately, after 8 months of testing, this work demonstrates that the accuracy and precision of the density extracted from simulations is not sufficient in providing accurate partial molar volumes. As a result, this work clearly demonstrates that current classical molecular dynamics technology cannot probe the volumetric properties of interest with sufficient accuracy to aid in the research and development of novel cryoprotectants.The second project in this work used molecular dynamics simulations to evaluate the Gibbs free energy change of substituting CO2 in sI clathrate hydrates by N2,CH4, SO2 and H2S flue gas impurities under conditions proposed for CO2 capture (273 K, 10 bar). Our results demonstrate that CO2 substitutions by N2 in the small sI cages were thermodynamically favored. This substitution is problematic in terms of efficient CO2 capture, since the small cages make up 25% of the sI clathrate cages, therefore a significant amount of energy could be spent on removing N2 from the flue gas rather than CO2. The thermodynamics of CO2 substitution by CH4, SO2 and H2S in sI clathrate hydrates was also examined. The substitution of CO2 by these gases in both the small and large cages were determined to be favorable. This suggests that these gases may also disrupt the CO2 capture by sI clathrate hydrates if they are present in large concentrations in the combustion flue stream. Similar substitution thermodynamics at 200 K and 10 bar were also studied. With one exception, we found that the substitution free energies do not significantly change and do not alter the sign of thermodynamics. Thus, using a lower capture temperature does not significantly change the substitution free energies and their implications for CO2 capture by sI clathrate hydrates.

No description available.

[pt] Os hidratos de gás natural são sólidos cristalinos, semelhantes ao gelo, formados pela associação de moléculas de água e de gás numa determinada estrutura organizada. Sua ocorrência é uma preocupação inegável para a Indústria de Petróleo e Gás, dado o risco potencial de garantia de escoamento, podendo ocasionar paradas não programadas em operações como a perfuração e produção. Portanto, grandes investimentos são feitos a fim de prevenir a formação de hidratos. No entanto, os cenários cada vez mais desafiadores de produção de petróleo estão incentivando a busca de metodologias de avaliação de risco, procurando identificar as condições para a formação de hidratos, mas com pouca possibilidade de entupimento. Neste contexto, o entendimento de reologia de hidratos é um elemento chave, pois permite detectar a formação do hidrato a partir de variações das propriedades reológicas. Entretanto, uma dificuldade desta abordagem ocorre devido à condição necessária para a formação de hidrato, a combinação de alta pressão e baixa temperatura. Este trabalho se insere neste contexto: para avaliar o processo de formação de hidrato em condições mais favoráveis utiliza-se em geral um fluido modelo que forma hidratos à pressão atmosférica. Este trabalho visa analisar os efeitos dos cortes de água e de tensoativos na viscosidade, nos módulos de armazenagem e dissipação de um fluido modelo, uma emulsão de água-em-óleo. A formação de hidrato ocorre com a adição de ciclopentano a este modelo de emulsão. / [en] Natural gas hydrates are solid crystalline, similar to the ice, formed by the association of water molecules and gas of a given organized structure. Its occurrence is an undeniable concern for Oil and Gas, given the potential risk of flow assurance and may cause unscheduled downtime in operations, such as drilling and production. Therefore, large investments are made in order to prevent the formation of hydrates. However, the increasingly challenging scenarios of oil production are encouraging the pursuit of new methodologies for risk assessment, seeking to identify the conditions hydrates will form, but with little chance of clogging. In this context, the understanding of rheology of hydrate is a key element, it allows detecting the formation of hydrate as of changes in rheological properties. However, a difficulty of this approach occurs due to need for hydrate formation conditions, the combination of high pressure and low temperature. This work fits in this context: to evaluate the process of hydrate formation on conditions more favorable is used usually a fluid model that form hydrates at atmospheric pressure. This work aims to analyze the effects of the water cuts and surfactants on viscosity, in storage and dissipation modules of model fluid water emulsion in oil. The hydrate formation occurs adding on this model fluid cyclopentane.

Hidratos de gás são importantes em questões que vão desde o bloqueio de tubulações na indústria de produção de óleo e gás, até o sequestro de dióxido de carbono, transporte de gás natural, dessalinização de água salgada e purificação de água contaminada. A fim de investigar estes campos e aplicações, necessita-se determinar inicialmente a temperatura e pressão nas quais os hidratos se formam. Isto pode ser feito por meio de experimentos de formação e/ou dissociação de hidratos, bem como utilizando-se de modelos termodinâmicos, correlações empíricas e métodos computacionais. Estudou-se nesse trabalho o desempenho da PC-SAFT na modelagem da fase fluida no equilíbrio da formação de hidratos, comparando seus resultados com a equação de Peng-Robinson e o modelo proposto por Klauda e Sandler. Para a molécula de água, em especial, avaliaram-se as configurações possíveis para o esquema de associação. Para a fase hidrato, avaliou-se a equação de van der Waals e Platteuw (vdWP), e levou-se em conta o efeito das cascas adicionais na estimativa da constante de Langmuir. Por fim, foram propostas duas equações com termos ajustáveis para a fugacidade da água na fase hidrato em função da temperatura, uma linear e outra quadrática, para utilização conjunta com a equação PC-SAFT. Para comparação, quando possível os sistemas foram avaliados com auxílio do software CSMGem. A utilização da equação PC-SAFT em conjunto com as expressões propostas resultou na melhor predição da pressão de equilíbrio em temperaturas determinadas. / Gas hydrates are important for issues that include flow assurance in oil and gas industries, carbon sequestration, natural gas transport, seawater desalinization, and purification of contaminated water. To investigate those fields and applications, temperature and pressure in which hydrates are formed must be determined. This can be done through hydrate formation and/or dissociation experiments, as well as through thermodynamic models, empirical correlations, and computational methods. In this work, the performance of the PC-SAFT in modeling the fluid phase in hydrate phase equilibrium was investigated. Its results were compared to the Peng-Robinson equation of state and to the model proposed by Klauda and Sandler. For the water molecule, different association schemes were considered. For the hydrate phase, the van der Waals and Platteuw (vdWP) equation was used. The effect of additional shells in the estimation of the Langmuir constant was assessed. Finally, equations for water fugacity in hydrate phase, as a function of temperature, were proposed. These equations were intended to be used with the PC-SAFT equation of state, and both linear or quadratic equations were considered. For comparison, when possible the software CSMGem was used to compute the equilibrium conditions. The use of the PC-SAFT EOS, along with the proposed equations, resulted in a better prediction of the equilibrium pressure as a function of temperature.