Synthetic single-walled metal oxide (aluminosilicate) nanotubes (SWNTs) are emerging materials for a number of applications involving molecular transport and adsorption due to their unique pore structure, high surface reactivity, and controllable dimensions. In this thesis, I discuss the potential for employing SWNTs in next generation separation platforms based upon recent progress on synthesis, interior modification, molecular diffusion properties, transport modeling and composite membrane preparation of metal oxide SWNTs. First, I describe the structure, synthesis, and characterization of the SWNTs. Thereafter, chemical modification of the nanotube interior is described as a means for tuning the nanotube properties for molecular separations. Interior functionalization of SWNTs (e.g. carbon nanotubes and metal oxide nanotubes) is a long-standing challenge in nanomaterials science. After controlled dehydration and dehydroxylation of the SWNTs, I then demonstrate that the SWNT inner surface can be functionalized with various organic groups of practical interest via solid-liquid heterogeneous reactions. Finally, I describe a mass transport modeling and measurements for composite membranes composed of SWNTs as fillers. This work demonstrates the use of SWNTs for novel scalable separation units from both a nanoscale and a macroscale point of view.

No description available.

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Bibliography: leaves 232-250 / xv, 250 leaves : ill ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Thesis (Ph.D.)--University of Adelaide, Dept. of Chemical Engineering, 1993

Produced water presents economical and environmental challenges to oil producers. Downhole separation technology is able to separate oil or gas from produced fluid in downhole environment and injects waste water into deeper formations, thus saving energy and reducing waste emission. More than 120 downhole separation systems have been installed worldwide, but only about 60% of the installations achieved success. Most of the failures were due to the injectivity decline under the invasion of impurities in the injected water, such as suspended particles and oil droplets. A reliable model is needed to predict the reaction of reservoir permeability under the invasion of such impurities and serves as a tool to screen appropriate formations for downhole separator installations. / Previous experimental studies on particle-induced permeability damage reveal that high particle concentration, low fluid velocity, large particle size lead to more severe damage. The damage mechanisms are attributed to surface interception, bridging and size exclusion of particles in porous media. While for droplets, the resultant permeability decline is mostly due to surface interception. Empirical correlations with key parameters determined by core flooding data are widely applied to the simulation of permeability decline under invasion of particles and droplets. These correlations are developed based on characteristics of certain rocks and fluids, thus their applications are very restricted. / A more scientific method is to model the flow and capture of particulates at pore level. Reservoir rocks are porous media composed of pores of various sizes. Pore network models employ certain assumptions to imitate real porous media, and have been proved realistic in simulating fluid flow in porous media. In this study, a 2-dimensional square network model is used to simulate capture of particles and droplets in porous media. Pore bodies are represented by globes and pore throats are imitated with capillary tubes. The flow rates in the network are obtained by simultaneously solving mass balance equations at each pore body. The network model is tuned to match the porosity and permeability of a certain rock and serves as the infrastructure where the capture process takes place. / Particles are categorized as Brownian and non-Brownian particles according to size. For Brownian particles, diffusion is dominant and Fick’s law is applied to each pore inside the network to obtain deposition rate. For non-Brownian particles, their trajectories are mainly governed by gravity and drag force acting on them. Besides, the size of each particle is compared with the size of the pore where it is captured to determine the damage mechanism. For particles much smaller than the pore size, surface deposition is dominant and the permeability decline is gradual. For particles with sizes comparable to pore size, bridging and clogging are dominant and the permeability decline is much more severe. / Unlike particles, droplets can not be captured on top of each other. Accordingly, a captureequilibrium theory is proposed. Once the pore surface is covered by droplets, equilibrium is reached and droplets flow freely through porous media without being captured. The simulation on capture of oil droplets reveals that the surface wettability has significant influence on the resultant permeability damage. Most natural reservoirs are neutrally or oil wet. It is thus recommended to apply these surface conditions to future simulations. / The proposed model is validated with test data and reasonably good agreements are obtained. This new mechanistic model provides more insights into the capture process and greatly reduces the dependence on core flooding data.

Thesis (M. S.)--Mechanical Engineering, Georgia Institute of Technology, 2007. / Dr. Martha Gallivan, Committee Member ; Dr. Chris Paredis, Committee Member ; Dr. Janet K. Allen, Committee Member ; Dr. Peter Hesketh, Committee Co-Chair ; Dr. Farrokh Mistree, Committee Co-Chair.

Thesis (Ph.D.)--University of Waikato, 2006. / Includes bibliographical references (leaves [186]-203) Also available via the World Wide Web.

The need to reduce the cost of adsorption technology has led scientists to explore the use of many low cost adsorbents especially those from renewable resources. Lignocellulose and montmorillonite clay have been identified as potentially low cost and efficient adsorbent materials for the removal of toxic heavy metals and organic substances from contaminated water. Montmorillonite clay has good adsorption properties and the potential for ion exchange. Lignocellulose possesses many hydroxyl, carbonyl and phenyl groups and therefore, both montmorillonite and lignocellulose are good candidates for the development of effective and low cost adsorbents in water treatment and purification. The aim of this study was to prepare composite materials based on lignocellulose and montmorillonite clay and subsequently evaluate their efficacy as adsorbents for heavy metal species and organic pollutants in aqueous solution. It was also important to assess the adsorption properties of the modified individual (uncombined) lignocellulose and montmorillonite. Lignocellulose and sodium-exchanged montmorillonite (NaMMT) clay were each separately modified with methyl methacrylate (MMA), methacrylic acid (MAA) and methacryloxypropyl trimethoxysilane (MPS) and used as adsorbents for the removal of heavy metals and dyes from aqueous solution. The lignocellulose and NaMMT were modified with MMA, MAA and MPS through free radical graft polymerisation and/or condensation reactions. NaMMT was also modified through Al-pillaring to give AlpMMT. The materials were characterised by fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and small angle X-ray scattering (SAXS) and characterisation results showed that the modification of the montmorillonite with MAA, MMA and MPS was successful. The modified lignocellulose and montmorillonite materials were evaluated for the adsorption of heavy metal ions (Cd2+ and Pb2+) from aqueous solution by the batch method. The adsorption isotherms and kinetics of both Cd2+ and Pb2+ onto the NaMMT clay, AlpMMT and lignocellulose materials are presented. The Langmuir isotherm was found to be the best fit for the adsorption of both heavy metals onto all the adsorbents. AlpMMT showed very poor uptake for heavy metals (both Cd2+ and Pb2+). PMMAgMMT, PMAAgMMT, PMAAgLig and PMPSgLig showed improved adsorption for both heavy metals. The mechanism of heavy metal adsorption onto the adsorbents was best represented by the pseudo second-order kinetic model. PMPSgLig, NaMMT and AlpMMT showed relatively high adsorption capacities for methyl orange, while the adsorption of neutral red was comparable for almost all the adsorbents. Neither the Langmuir model nor the Freundlich model was found to v adequately describe the adsorption process of dyes onto all the adsorbents. The pseudo second-order model was found to be the best fit to describe the adsorption mechanism of both dyes onto all the adsorbents. The modification of lignocellulose and montmorillonite with suitable organic groups can potentially produce highly effective and efficient adsorbents for the removal of both heavy metals and dyes from contaminated water. Novel adsorbent composite materials based on lignocellulose and montmorillonite clay (NaMMT) were also prepared and evaluated for the removal of pollutants (dyes and heavy metals) from aqueous solution. The lignocellulose-montmorillonite composites were prepared by in situ intercalative polymerisation, using methyl methacrylate, methacrylic acid and methacryloxypropyl trimethoxysilane (MPS) as coupling agents. The composite materials were characterised by FTIR, TGA, TEM and SAXS. SAXS diffractograms showed intercalated nanocomposites of PMMAgLig-NaMMT and PMAAgLig-NaMMT, whereas PMPSgLig-NaMMT showed a phase-separated composite and the same results were confirmed by TEM. The lignocellulose-montmorillonite composites were assessed for their adsorption properties for heavy metal ions (Cd2+ and Pb2+) and dyes (methyl orange and neutral red) from aqueous solution. Among these composite materials, only PMAAgLig-NaMMT showed a marked increase in the uptake of both Cd2+ and Pb2+ relative to lignocellulose and montmorillonite when used independently. The adsorption data were fitted to the Langmuir and Freundlich isotherms, as well as to the pseudo first-order and pseudo second-order kinetic models. The data were best described by the Langmuir isotherm and the pseudo second-order kinetic model. On the adsorption of dyes, only PMPSgLig-NaMMT showed enhanced adsorption of methyl orange (MetO) compared with lignocellulose and montmorillonite separately. The enhanced adsorption was attributed to the synergistic adsorption due to the presence of MPS, lignocellulose and NaMMT. Competitive adsorption studies were carried out from binary mixtures of MetO and Cd2+ or Pb2+ in aqueous solution. The adsorption process of MetO onto the composite material was found to follow the Freundlich adsorption model, while the mechanism of adsorption followed both the pseudo first-order and pseudo second-order models. This particular composite can be used for the simultaneous adsorption of both heavy metals and organic dyes from contaminated water. The adsorption of neutral red to the composite materials was comparable and the pseudo second-order kinetic model best described the adsorption mechanism.

A valorização dos subprodutos como a glicerina e a torta de oleaginosas, originados no processo de produção de biodiesel, tem sido a principal alternativa para tornar esse biocombustível competitivo em relação ao diesel de petróleo. Essa alternativa pode estar associada a uma vantajosa integração de processos, como é o caso de utilização da glicerina como solvente para separação da mistura etanol-água em usinas de álcool. Para isso, estudou-se a utilização da glicerina em substituição ao etilenoglicol, esta última substância de origem fóssil. A glicerina elimina o azeótropo formado pela modificação do equilíbrio líquido-vapor da mistura etanol-água, aumentando a diferença de volatilidade entre esses componentes. Para verificação das condições operacionais adequadas ao processo de destilação extrativa de desidratação do etanol, foram realizados experimentos em escala de laboratório, com auxílio de um Delineamento Composto Central Rotacional (DCCR). As variáveis independentes foram a fração molar glicerina/água e o grau de vácuo, este último como forma de se evitar a decomposição térmica da glicerina em acroleína. A análise das superfícies de resposta mostrou que a fração molar glicerina/etanol torna-se adequada acima de 0,4 e que a pressão absoluta do sistema torna-se adequada em torno de 380 mm Hg. Com isto, obteve-se um modelo estatístico de simulação e a previsão de condições adequadas ao processo, para o desenvolvimento de uma tecnologia que privilegie as ações de preservação ao meio ambiente. / The recovery of by-products like glycerin and cake from oilseeds, resulting in the production of biodiesel, has been the main alternative to make this biofuel competitive compared to petroleum and diesel oil. This alternative can be associated with a beneficial integration of processes, such as use of glycerin as a solvent for separation of ethanol-water mixture in plants alcohol. Thus, the use of glycerin in place of ethylene glycol, a substance of fossil origin was tested. The glycerin eliminates the azeotrope formed by modification of the liquid-vapor equilibrium of ethanol-water mixture, increasing the difference in volatility between these components. To verify the operating conditions suitable for the process of extractive distillation for ethanol dehydration, experiments were performed in laboratory scale, using a central composite rotational design (CCRD). The independent variables were the molar fraction glycerol / water and the degree of vacuum, the latter as a way to avoid thermal decomposition of glycerol into acrolein. The analysis of the response surfaces showed that the molar fraction glycerin / ethanol becomes appropriate than 0.4 and the absolute pressure of the system is adequate around 380 mm Hg. In this way it was possible to obtain a statistical model for simulation and prediction of appropriate conditions to the process for developing a technology that prior actions to preserve the environment.

A contínua expansão da indústria de processamento de hidrocarbonetos e a extensa utilização de produtos relacionados com o petróleo aumentou a ameaça da poluição por esse tipo de produto no meio ambiente. Na indústria, em geral, há uma demanda muito grande por água de boa qualidade e grande parte do referido volume será eliminado para corpos receptores com uma alta carga de matéria orgânica e sólidos, motivo pelo qual águas residuárias geradas em todos os processos industriais devem passar por um tratamento específico. Com isso, alguns processos físico-químicos são largamente solicitados e entre eles a flotação por ar dissolvido (FAD), onde a produção de microbolhas é essencial para um eficiente tratamento do efluente contaminado. Nesta pesquisa foi proposta uma técnica inovadora para produção de microbolhas. A nova técnica induz um fluxo de ar na linha de aspiração de uma bomba centrífuga, em função da pressão negativa existente neste ponto da instalação. Como metodologia de identificação de condições de produção otimizada de microbolhas, foi aplicado um planejamento experimental do tipo delineamento composto central rotacional (DCCR). Dentro das condições de trabalho foram identificadas por variáveis independentes a razão entre as vazões de ar e água (X1) e a pressão na linha de descarga da bomba (X2). Quando testado em um protótipo piloto de flotação por ar dissolvido (FAD), a técnica possibilitou uma eficiência de separação água/óleo da ordem de 97 %. De acordo com os resultados obtidos, a referida metodologia mostrou-se vantajosa em comparação aos processos convencionais de saturação da água a ser tratada com ar comprimido, pela redução de equipamentos e custos com energia. / The continuous expansion of the hydrocarbon processing industry and the extensive use of petroleum-related products has increased the threat of pollution by this type of product in the environment. In the industries, in general, there is a great demand for good quality water and much of the volume of water will be eliminated for receiving bodies with a high load of organic matter and solids. Thus the wastewater generated in all industrial processes needs to have a specific treatment. Some physical-chemical processes are widely requested, including the dissolved air flotation (DAF), where the production of microbubbles is essential for an effective treatment of the contaminated effluent. In this research an innovative technique was proposed for producing microbubbles for the treatment of oily water. The new technique induces a flow of air in the suction of a centrifugal pump, depending on the negative pressure existing at this point in the installation line. A central composite rotational design was used to determine the efficiency of the method. Within the working conditions, independent variables were identified by the ratio between the air flow and water (X1) and the pressure in the pump discharge (X2) line. When tested in a dissolved air flotation prototype (DAF), the technique provided a separation efficiency of 97 % water/oil. According to the results obtained, the above method proved to be advantageous compared to to the conventional process of saturation of the effluent treated with compressed air, by reducing the number of equipment and the energy costs.