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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
161

Captage du CO2 par des amines en milieu aqueux et non aqueux (solvant eutectique profond) / CO2 capture by amines in aqueous and non-aqueous media (deep eutectic solvent)

Mahi, Mohammed Ridha 09 July 2019 (has links)
Ce travail porte sur l'étude de la capacité d'absorption du CO2 par différents types d'amines dissoutes en milieux aqueux et non aqueux. Ce dernier est constitué d'un mélange de chlorure de choline et d'éthylène glycol dans une proportion molaire respectivement de 1 pour 2. Ce solvant, communément appelé "Ethaline", appartient à la catégorie dite des « Solvants à Eutectique Profond » ainsi désignés car leur composition eutectique permet d'obtenir des mélanges généralement liquides à température ambiante. Pour ce faire un appareil d'équilibre liquide-vapeur avec analyse en ligne de la phase vapeur par GC a été réalisé et son fonctionnement validé. Les isothermes d'absorption du CO2 ainsi que la volatilité (composition de la phase vapeur) des mélanges étudiés, avec et sans CO2, ont été déterminées à différentes températures et pour différentes compositions en amines. Le domaine de pression exploré est particulièrement large : du Pascal à 800 kPa. L'étude a montré que la substitution de l'eau par "l'Ethaline" conduit à une capacité d'absorption du CO2 presque identique à celle de la MEA et DEA en solution aqueuse. Par contre dans le cas de la MDEA on observe une capacité d'absorption plus faible en milieu « Ethaline » qu'en milieu aqueux. Les isothermes d'absorption du CO2 des trois classes d'amines en milieu aqueux et non aqueux ont été corrélés par les modèles semi empiriques de (Gabrielsen et al., 2005) initialement établis par ces auteurs pour les solutions aqueuses (un modèle pour les amines primaires et secondaires conduisant à la formation de carbamates en présence de CO2, un modèle pour les amines tertiaires donnant des sels d'ammonium avec le CO2). Nous avons montré que ces deux modèles représentent avec succès les isothermes d'absorption en milieu non aqueux. Les constantes d'équilibre et les enthalpies de réaction qui s'en déduisent montrent que ces dernières sont plus faibles (en valeur absolue) pour la MEA et TMDEA en solution éthaline qu'en solution aqueuse. Dans le cas de la MDEA la nature du solvant n'a qu'une influence minime sur l'enthalpie de réaction. Les valeurs expérimentales des volatilités des amines dans les différents mélanges Amine- CO2 en milieu aqueux ont été corrélées par différents modèles semi-empiriques. Trois modèles thermodynamiques de coefficients d'activité ; le modèle de Wilson, NRTL et UNIQUAC ont été utilisés afin de restituer les données expérimentales de l'équilibre liquide-vapeur des systèmes aqueux d'amines (sans CO2). Une représentation satisfaisante des résultats expérimentaux par les trois modèles a été obtenue / This work focuses on the study of the absorption capacity of CO2 by different types of dissolved amines in aqueous and non-aqueous media. The latter consists of a mixture of choline chloride and ethylene glycol in a molar proportion of 1 to 2 respectively. This solvent, commonly called "Ethaline", belongs to the category called "Deep Eutectic Solvents" so designated because their eutectic composition makes it possible to obtain mixtures that are generally liquid at room temperature. With this aim, a liquid-vapor equilibrium apparatus with on-line analysis of the vapor phase by GC was performed and its operation validated. The CO2 absorption isotherms and the volatility (composition of the vapor phase) of the studied mixtures, with and without CO2, were determined at different temperatures and for different amine compositions. The explored pressure range is particularly large: from 1 Pa to 800 kPa. The study showed that the substitution of water by "Ethaline" leads to a CO2 absorption capacity almost identical to that of MEA and DEA in aqueous solution. On the other hand, in the case of MDEA, a lower absorption capacity is observed in Ethaline than in aqueous medium. In the hypothesis of a use of the DES+amine solvent for CO2 capture in post-combustion process, a decrease of the vapor pressure of the solvent (comparing to that of water+amine) has an advantage because of the low solvent loss due to vaporization in the absorber. The second advantage is most likely a lower effect of equipment corrosion, the third positive point is a lower enthalpy of absorption of MEA and MDEA in (1 ChCl : 2 EG) comparing to aqueous medium, resulting in a possible saving of energy in the regenerator of almost 40%. The disadvantage of the use of amines in "Ethaline" solution is the high viscosity of this solvent which decreases the kinetics of material transfer and reaction with CO2. The CO2 absorption isotherms and the experimental values of the amine volatilities in the different Amine-H2O-CO2 mixtures were well correlated by different semi-empirical models. Three thermodynamic models based on the activity coefficients; the Wilson model, NRTL and UNIQUAC were used to restitute experimental data for the liquid-vapor equilibrium of aqueous amine systems (without CO2). A satisfactory representation of the experimental results by the three models was obtained
162

Aqueous humor flow rate in normal cats and the effect of topical 2% dorzolamide on aqueous humor flow and intraocular pressure

Crumley, William R. January 1900 (has links)
Master of Science / Department of Clinical Sciences / Amy Rankin / Objective - To establish the aqueous humor flow rate in normal cats via fluorophotometry, utilizing a noninvasive method previously established in other species and to evaluate the effect of topical 2% dorzolamide on aqueous humor flow rate and intraocular pressure (IOP) in normal cats. Animals - 20 clinically normal domestic shorthair cats. Procedures – Topical administration of 10% sodium fluorescein was performed using a 3-drop protocol to establish its use in this species. Aqueous flow was measured using fluorophotometry in the right and left eyes. The subjects were then divided into 2 groups: the first received topical 2% dorzolamide (Trusopt®) and the second received topical artificial tear solution (control). The study was divided into two phases: a 3 day acclimation phase (no treatments given) and a 5 day treatment phase (treatments given three times daily). IOP measurements were taken at 7am, 10am, 1pm, 5pm, and 9pm throughout all phases of the study. Fluorophotometry was performed to measure the aqueous flow rate just prior to and at the end of the treatment phase (days 3 and 9 respectively). Results - The calculated aqueous humor flow rate for normal cats in the right, left, and both eyes was 5.94 ± 2.30 μl/min, 5.05 ± 2.06 μl/min, and 5.51 ± 2.21 μl/min, respectively. No significant differences were noted between the right and left eyes. In the dorzolamide group, the average flow rate during treatment (3.47 + 1.50 μl/min ) was significantly lower than prior to treatment (5.9 + 2.20 μl/min)(P < 0.001). The mean IOP during treatment (11 + 3 mmHg) was significantly lower than the mean IOP prior to treatment (15 + 3 mmHg)(P < 0.001). In the control group, there were no significant differences in aqueous humor flow or IOP values before or during treatment. Conclusions - The technique utilized for this study met the standard for accurate fluorophotometric calculation of aqueous humor flow. The average aqueous humor flow rate for normal cats calculated in this study was 5.51 ± 2.21 μl/min. Topical 2% dorzolamide significantly lowers aqueous humor flow (a 41% reduction) and IOP (a 26% reduction) in normal cats.
163

Cu- and Fe-mediated Atom-Transfer Radical Polymerization in Aqueous Solution

Smolne, Sebastian 06 June 2016 (has links)
No description available.
164

Enhanced adsorptive removal of p-nitrophenol from water by aluminum metal–organic framework/reduced graphene oxide composite

Wu, Zhibin, Yuan, Xingzhong, Zhong, Hua, Wang, Hou, Zeng, Guangming, Chen, Xiaohong, Wang, Hui, zhang, Lei, Shao, Jianguang 16 May 2016 (has links)
In this study, the composite of aluminum metal-organic framework MIL-68(Al) and reduced graphene oxide (MA/RG) was synthesized via a one-step solvothermal method, and their performances for pnitrophenol (PNP) adsorption from aqueous solution were systematically investigated. The introduction of reduced graphene oxide (RG) into MIL-68(Al) (MA) significantly changes the morphologies of the MA and increases the surface area. The MA/RG-15% prepared at RG-to-MA mass ratio of 15% shows a PNP uptake rate 64% and 123% higher than MIL-68(Al) and reduced graphene oxide (RG), respectively. The hydrogen bond and pi-pi dispersion were considered to be the major driving force for the spontaneous and endothermic adsorption process for PNP removal. The adsorption kinetics, which was controlled by film-diffusion and intra-particle diffusion, was greatly influenced by solution pH, ionic strength, temperature and initial PNP concentration. The adsorption kinetics and isotherms can be well delineated using pseudo-second-order and Langmuir equations, respectively. The presence of phenol or isomeric nitrophenols in the solution had minimal influence on PNP adsorption by reusable MA/RG composite.
165

Developing Environmentally Friendly Dye-sensitized Solar Cells

Ellis, Hanna January 2016 (has links)
Due to climate change and its effects, alternative renewable energy sources are needed in the future human society. In the work of this thesis, the Dye-sensitized Solar Cell (DSC) has been investigated and characterized. DSCs are appealing as energy conversion devices, since they have high potential to provide low cost solar light to electricity conversion. The DSC is built up by a working electrode consisting of a conductive glass substrate with a dye-sensitized mesoporous TiO2 film, a counter electrode with a catalyst and, in between, the electrolyte which performs the charge transport by means of a redox mediator. The aim of this thesis was to develop and evaluate cheap and environmentally friendly materials for the DSC. An alternative polymer-based counter electrode catalyst was fabricated and evaluated, showing that the PEDOT catalyst counter electrode outperformed the platinum catalyst counter electrode. Different organic dyes were evaluated and it was found that the dye architecture affected the performance of the assembled DSCs. A partly hydrophilic organic triphenylamine dye was developed and applied in water-based electrolyte DSCs. The partly hydrophilic dye outperformed the reference hydrophobic dye. Small changes in dye architecture were evaluated for two similar dyes, both by spectroscopic and electrochemical techniques. A change in the length of the dialkoxyphenyl units on a triphenylamine dye, affected the recombination and the regeneration electron transfer kinetics in the DSC system. Finally, three water soluble cobalt redox couples were developed and applied in water-based electrolyte DSCs. An average efficiency of 5.5% (record efficiency of 5.7%) for a 100% water-based electrolyte DSC was achieved with the polymer-based catalyst counter electrode and an organic dye with short dimethoxyphenyl units, improving the wetting and the regeneration process.
166

The development of vesiculated beads

Terblanche, Johannes C. 04 1900 (has links)
Thesis (MScIng)--University of Stellenbosch, 2003. / ENGLISH ABSTRACT: Vesiculated beads consist of aerated microvoids encapsulated in a solid spherical continuous polymeric shell. The difference in refractive index between the voids and polymer granules causes effective scattering of incident light on the particles, presenting it with a white appearance. The size of these beads generally range in the region of 0.5 – 40 μm, making it suitable for use as pigment extender in the surface coatings or paint industry. Currently, titanium dioxide pigment is predominantly used as opacifying agent in paint formulations, but due to the high cost associated in purchasing this pigment, as well as fluctuation in import prices, paint manufacturers are looking for alternative products to replace or at least partially replace this pigment. As an alternative, opaque vesiculated polymer particles can be produced locally at a cheaper price and in existing vessels available in the paint industry. Approximately five years ago a paint company in Mexico and member of the Nova Club, started research in developing vesiculated beads for production in their factories. However, it was found extremely difficult to scale-up the production to industrial size, since the system was very sensitive to process variables. A local paint company and member of the Nova Club acquired this technology and continued further research in developing vesiculated beads on large scale in existing Cowles disperser systems found in the paint industry. The beads consist mainly of an organic phase comprising of unsaturated carboxylated polyester and styrene. A polyamine is also added to assist the formation of vesicles in the organic phase. This phase is slowly added under agitation to an aqueous phase consisting of deionised water, a thickener and colloid stabilisers to form an oil-inwater emulsion. Agitation is continued for a specified period of time, also known as the emulsification period, to allow sufficient time for the organic globules to break-up to smaller particle sizes. These globules are subsequently catalysed with a freeradical initiator and redox activator and left static overnight to allow formation of the solid beads. To determine the most important process parameters during production of vesiculated beads, a fully integrated laboratory scale Cowles reactor system was designed and constructed, geometrically analogous to the vessels found in the paint industry. The system measures and controls production temperature, mixing speed and component addition rates. Production runs were performed where various process parameters were varied to investigate the effect on properties, which include average particle size and particle size distribution, pH, viscosity and opacity. The most important process parameters that were found to play a significant role include production temperature, organic phase addition rate, emulsification time, the Cowles impeller diameter and mixing speed. Production runs were performed in geometrically similar 5l and 20l vessels on the laboratory-scale system to investigate the effect of scale-up. A model presented by Klein et al. (1996) was used as basis for describing the average particle size as a function of mixing speed, impeller diameter, vessel diameter and emulsification time. The applicability of this model was tested on average particle size data obtained from industrial scale runs performed on the plants and proved to be reasonably accurate. / AFRIKAANSE OPSOMMING: Sferiese polimeerpartikels met klein lugholtes vasgevang in ‘n harde omhulsel word al jare in die verf industrie aangewend as pigment. Weens die verskil in brekingsindeks tussen die soliede polimeerpartikel en die vasgevange lugholtes, word invallende lig versprei op so ‘n manier dat die partikels ondeursigtig (of wit) voorkom. Hierdie partikels kan geproduseer word met deursneë wat strek van 0.5 – 40 μm, wat dit geskik maak vir gebruik in verf formulasies. Tans word titaandioksied poeier hoofsaaklik gebruik in verf as pigment, maar weens die hoë koste van die invoer en aankoop van hierdie produk, het verfmaatskappye begin soek na goedkoper alternatiewe. Aangesien hierdie ondeursigtige polimeerpartikels plaaslik goedkoper vervaardig kan word in bestaande mengvate beskikbaar in verf aanlegte, dien dit as moontlike plaasvervanger. Ongeveer vyf jaar gelede het ‘n Mexikaanse verfmaatskappy, wat lid is van die Nova Klub, navorsing begin doen om hierdie polimeerpartikels in hul fabrieke te produseer. Dit was egter vir hulle onmoontlik om die produksie op te skaal na industriële vervaardiging aangesien die proses baie sensitief was vir produksieveranderlikes. Sekere eienskappe soos die gemiddelde partikelgrootte, partikelverspreiding, pH, viskositeit en deursigtigheid van die partikels kon nie van lot tot lot herhaal word nie en verdere navorsing is gestaak. ‘n Plaaslike verfmaatskappy (ook lid van die Nova Klub) het die tegnologie oorgeneem en die proses verder ontwikkel. Die proses is aangepas sodat “Cowles” mengers, wat wydverspreid in die verf industrie beskikbaar is, gebruik kan word om dit te vervaardig. Die partikels bestaan hoofsaaklik uit ‘n organiese fase wat ‘n onversadigde gekarboksileerde poliëster en stireen insluit. ‘n Poli-amien word ook bygevoeg en is verantwoordelik vir die vorming van die lugholtes in die partikels. Hierdie fase word stadig onder menging by ‘n tweede water fase, bestaande uit gedeïoniseerde water, ‘n verdikker en kolloïdale stabiliseerders gevoeg om ‘n olie-in-water emulsie te vorm. Menging word voortgesit vir ‘n bepaalde emulsifiseringsperiode om die oliedruppels verder op te breek. Gevolglik word hierdie druppels gekataliseer met ‘n vry-radikaal inisieerder en redoksaktiveerder en oornag staties gelos om vorming van die soliede partikels toe te laat. Aangesien eienskappe van die polimeerpartikels so sensitief is vir prosesveranderlikes, is besluit om aanvanklik ‘n ten volle geïntegreerde laboratorium skaal “Cowles” reaktorsisteem te ontwerp en bou. Hierdie sisteem is geometries gelykvormig aan die mengvate wat in verffabrieke gevind word. Die produksietemperatuur, stuwergrootte, mengspoed en materiaal toevoertempo kan effektief gemeet, verstel en beheer word. Eksperimentele lopies is gedoen en die effek van verskeie produksieveranderlikes op eienskappe is ondersoek. Die belangrikste veranderlikes wat die proses beïnvloed, is die emulsifiseringstemperatuur, die toevoertempo van die organiese fase, emulsifiseringsperiode, stuwerdeursnit en mengspoed. Eksperimentele lopies is gedoen op twee geometriese gelykvormige mengvate (5l en 20l kapasiteit) om die effek van opskaling op eienskappe te ondersoek. ‘n Model wat deur Klein et al. (1996) voorgestel is, is as basis gebruik om die gemiddelde partikelgrootte te bepaal as ‘n funksie van mengspoed, stuwerdeursnit, mengvat deursnit en emulsifiseringstyd. Hierdie model is getoets op partikelgrootte data wat verkry is van groot industriële skaal lopies uitgevoer in die fabrieke onder bekende produksie kondisies en daar is gevind dat hierdie model bevredigend gebruik kan word om die gemiddelde partikelgrootte te voorspel.
167

Thermal degradation of aqueous amines used for carbon dioxide capture

Davis, Jason Daniel 21 October 2009 (has links)
Aqueous amine solutions loaded with CO2 were degraded in stainless steel sealed containers in forced convection ovens. Amine loss and degradation products were measured as a function of time by cation chromatography (IC), HPLC, and IC/mass spectrometry. A full kinetic model was developed for 15-40 wt% MEA (monoethanolamine) with 0.2 – 0.5 mol CO2/mol MEA at 100°C to 150°C. Experiments using amines blended with MEA demonstrate that oxazolidone formation is the rate-limiting step in the carbamate polymerization pathway. With 30 wt% MEA at 0.4 mol CO2/mol MEA and 120°C for 16 weeks there is a 29% loss of MEA with 13% as hydroxyethylimidazolidone (HEIA), 9% as hydroxyethylethylenediamine (HEEDA), 4% as the cyclic urea of the MEA trimer, 1-[2-[(2-hydroxyethyl)amino]ethyl]-2-imidazolidone, 3% as the MEA trimer, 1-(2-hydroxyethyl)diethylenetriamine, and less than 1% as larger polymeric products. In the isothermal experiments, thermal degradation was slightly more than first order with amine concentration and first order with CO2 concentration with an activation energy of 33 kcal/mol. In a modeled isobaric system, the amount of thermal degradation increased with stripper pressure, but decreased with an increase in amine concentration and CO2 concentration due to a reduction in reboiler temperature from the changing partial pressure of CO2. Three-fourths of thermal degradation in the stripper occurred in the reboiler due to the elevated temperature and long residence time which offset the decrease in CO2 concentration compared to the packing. The amount of degradation for other amines tested starting with the least degraded include; cyclic amines with no side chains < long chain alkanolamines < alkanolamines with steric hindrance < tertiary amines < MEA < straight chain di- and triamines. Piperazine and morpholine had no measurable thermal degradation under the conditions of this experiment and were the most resistant to thermal degradation. Diethyelenetriamine and HEEDA had the largest amount of degradation with over 90% loss at 135°C for 8 weeks. / text
168

Carbon dioxide absorption, desorption, and diffusion in aqueous piperazine and monoethanolamine

Dugas, Ross Edward 02 June 2010 (has links)
This work includes wetted wall column experiments that measure the CO₂ equilibrium partial pressure and liquid film mass transfer coefficient (kg') in 7, 9, 11, and 13 m MEA and 2, 5, 8, and 12 m PZ solutions. A 7 m MEA/2 m PZ blend was also examined. Absorption and desorption experiments were performed at 40, 60, 80, and 100°C over a range of CO₂ loading. Diaphragm diffusion cell experiments were performed with CO₂ loaded MEA and PZ solutions to characterize diffusion behavior. All experimental results have been compared to available literature data and match well. MEA and PZ spreadsheet models were created to explain observed rate behavior using the wetted wall column rate data and available literature data. The resulting liquid film mass transfer coefficient expressions use termolecular (base catalysis) kinetics and activity-based rate expressions. The kg' expressions accurately represent rate behavior over the very wide range of experimental conditions. The models fully explain rate effects with changes in amine concentration, temperature, and CO₂ loading. These models allow for rate behavior to be predicted at any set of conditions as long as the parameters in the kg' expressions can be accurately estimated. An Aspen Plus® RateSep™ model for MEA was created to model CO₂ flux in the wetted wall column. The model accurately calculated CO₂ flux over the wide range of experimental conditions but included a systematic error with MEA concentration. The systematic error resulted from an inability to represent the activity coefficient of MEA properly. Due to this limitation, the RateSep™ model will be most accurate when finetuned to one specific amine concentration. This Aspen Plus® RateSep™ model allows for scale up to industrial conditions to examine absorber or stripper performance. / text
169

Structural studies of aqueous solutions at high temperatures : critical opalescence and hydration

Sullivan, Darius M. January 2000 (has links)
No description available.
170

Aqueous Phase Tracers of Chemical Weathering in a Semi-arid Mountain Critical Zone

Jardine, Angela Beth January 2011 (has links)
Chemical weathering reactions are important for the physical, chemical, and biological development of the critical zone. We present findings from aqueous phase chemical analyses of surface and soil pore waters during a 15 month study in a small semi-arid mountain catchment of the Santa Catalina Mountain Critical Zone Observatory. Stream water geochemical solutes are sourced to two distinct locations - fractured bedrock baseflow stores and soil quickflow stores. Solid phase observations of albite, anorthite, and K-feldspar transformation to Ca-montmorillonite and kaolinite are supported by stream water saturation states calculated via a PHREEQC geochemical model. While differences in mineral assemblages, soil depths, and horizonation suggest greater weathering in schist versus granite lithologies and in hillslope divergent versus convergent zones, soil pore water solute ratio analysis does not readily distinguish these differences. However, preliminary investigation of aqueous rare earth elements suggests detectable lithologic and landscape positional differences warranting focus for future research efforts.

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