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Microalga-based technologies are introduced to provide a new generation of biofuels. The cultivation of microalgae in wastewater as the growth medium may offer the dual benefit of wastewater treatment and sustainable biofuel production. The potential of microalgal biomass to be converted into biodiesel depends on the accumulation of lipids, mainly triacylglycerols. However, the presence of toxic contaminants in municipal or industrial wastewater could negatively affect the biomass growth and modify the pattern of lipid accumulation in algae cells. This research aims to evaluate the potential of cultivating microalgae in wastewater for the removal of selected contaminants and the production of biodiesel. The hypothesis underlying this work was that growing microalgae in the presence of contaminants, typically found in wastewater, may induce a stress response that potentially increases the lipid productivity and enhances the biofuel yield. This research explored the potential of microalgae to be used for the removal of wastewater pollutants while accumulating high concentrations of neutral lipid that can be converted into biodiesel. Physiological and transcriptional responses of two genera of green algae were observed in the presence of stresses induced by toxic metals in raw hydraulic fracturing flowback water and pharmaceuticals found in municipal wastewater. Two green algae, Dunaliella salina and Chlorella vulgaris, were selected based on the availability of genetic information, current trends in the alga industry, and specific growth requirement in hypersaline flowback water and municipal wastewater. The first part of this research focuses on the possibility of using the salt-tolerant green microalga, D. salina, for the removal of toxic metals from hydraulic fracturing flowback water. In the second part of this research, the freshwater green microalga, C. vulgaris, was exposed to a suite of pharmaceuticals, commonly found in municipal wastewater, and the effects on the biomass growth and lipid accumulation were evaluated. In Chapter 3, aqueous geochemical characteristics of hydraulic fracturing flowback water were determined. Metagenomic analysis was also used to characterize the microbial community structure of the water samples. This technique included DNA extraction, PCR amplification of genes for 16S and 18S ribosomal RNA, and pyrosequencing. Although the two flowback water samples were shown to have water property measures in the range of reported values in literature, they were significantly different from each other regarding water properties such as total dissolved solids and total organic carbon. They also had distinct microbial community structures. It was shown the flowback water samples contained mainly halophilic, anaerobic, and thermophilic species with a pattern that was expected to be seen in natural gas shale reservoirs. Chapter 4 covers the characterization of the effects of contaminants (toxic metals) in hydraulic fracturing flowback water on the biomass growth and cellular lipid accumulation in Dunaliella salina. Metals were analyzed using ICP-MS. Biomass accumulation was determined by spectrophotometry and gravimetric methods. Lipid accumulation and composition were determined by GC-MS after conversion into fatty acid methyl esters. D. salina was successfully cultivated in saline hydraulic fracturing flowback water, and algal biomass growth was associated with a significant reduction of several toxic metals in the samples. D. salina, grown in flowback water, accumulated high levels of cellular lipids. Also, the estimated biodiesel properties were comparable with other algal biodiesel and complied with the US and EU biodiesel standards. The last chapter of part one presents the effects of a collection of metals commonly found in hydraulic fracturing flowback water and other industrial wastewaters on growth and lipid accumulation of D. salina. The impacts of the nitrogen concentration in the growth medium were also observed. The Nile red assay (fluorescence measurement after Nile red staining) was used to assess lipid accumulation. A range of toxic effects on the algal growth was observed. However, the effects were lower at higher nitrogen level that may indicate to an improved toxicity resistance when nutrient stress is minimal. Even with a high dose-dependent toxicity on growth, some toxic metals increased lipid accumulation. Chapter 6 describes the microplate-based toxicity test conducted to characterize the effect of a range of emerging contaminants (pharmaceuticals) commonly found in municipal wastewater on the biomass growth and cellular lipid accumulation measured by Nile red staining assay. Similar to what was observed for metals in Chapter 5, some pharmaceuticals increased lipid accumulation, even with a high dose-dependent toxicity on algal growth. Most tested pharmaceuticals at municipal wastewater levels (low) did not have a significant effect on the algal growth and lipid accumulation. Toxicity data (EC50 of growth) were well in agreement with what was reported in literature and antibiotics were the most toxic compounds among the different pharmaceutical classes. Chapter 7 presents a further characterization of the effects of a few selected compound from the previous chapter. Changes in the algal lipid composition upon exposure to the selected compounds were determined by qualitative and quantitative analysis of the extracted lipids using GC-MS. FT-IR spectroscopy was used to detect changes in the cellular constituents. The transcriptional responses of the key genes involved in the lipid metabolism of C. vulgaris were also investigated upon exposure to tetracycline using reverse-transcription real-time PCR and the results were interpreted based on the measured levels of cellular lipids and other metabolites. Lipid accumulation was changed upon exposure of algae to pharmaceuticals; however, the FAMEs profile did not show a significant variation. FT-IR spectroscopy highlighted the subtle changes in the cellular basis, and FT-IR peak associated with lipids was strongly correlated with total FAMEs quantified by GC-MS (Pearson correlation coefficient = 0.89). Gene expression analysis showed a general down-regulation of genes involved in the lipid biosynthesis. Results from this research are expecting to help develop and optimize innovative algal-based technologies combining the benefits of wastewater treatment, sustainable biofuel production, and mitigation of carbon dioxide emissions. / Civil Engineering

Energy related geo-systems involve a wide range of engineering solutions from energy piles to energy geo-storage facilities and waste repositories (CO₂, nuclear). The analysis and design of these systems require proper understanding of geo-materials, their properties and their response to extreme temperature and high stress excitations, the implications of mixed-fluid conditions when contrasting fluid viscosities and densities are involved, the effect of static and cyclic coupled hydro-thermo-chemo-mechanical excitations, and rate effects on the response of long design-life facilities. This study places emphasis on thermal geo-systems and associated physical properties. Uncemented soils and rocks are considered. The research approach involves data compilation, experimental studies and analytical methods. Emphasis is also placed to engineer geomaterials in order to attain enhanced performance in energy geo-systems. The thermal conductivity and stiffness of most geomaterials decrease as temperature increases but increase with effective stress. This macroscale response is intimately related to contact-scale conduction and deformation processes at interparticle contacts. Pore-filling liquids play a critical role in heat conduction as liquids provide efficient conduction paths that can diminish the effects of thermal contact resistance. Conversely, grains and fluids can be selected to attain very low thermal conductivity in order to create mechanically sound thermal barriers. In the case of rock masses, heat (and gas) recovery can be enhanced by injecting fluids at high pressure to cause hydraulic fractures. Scaled experiments reveal the physical meaning of hydraulic fractures in pre-structured rocks (e.g., shale) and highlight the extensive self-propped dilational distortion the medium experiences. This result explains the higher production rate from shale gas and fractured geothermal reservoirs that is observed in the field, contrary to theoretical predictions.

Thesis (MEng)--Stellenbosch University, 2014. / ENGLISH ABSTRACT: Current numerical methods in the eld of hydraulic fracturing are based mainly on continuum methods, such as the Finite Element Method (FEM) and the Boundary Element Method (BEM). These methods are governed by Linear Elastic Fracture Mechanics (LEFM) criteria, which su er from the inherent aw of a non-physical stress representation at the fracture tip. In response to this, a non-local method is proposed, namely the peridynamic theory, to model sleeved hydraulic fracture. A 2D implicit quasi-static ordinary state based peridynamic formulation is implemented on various benchmark problems, to verify the ability to capture constitutive behaviour in a linear elastic solid, as well as, the quanti cation of adverse e ects on the accuracy of the displacement solution, due to the nature of the non-local theory. Benchmark tests consist of a plate in tension, where convergence to the classical displacement solution, non-uniform re nement and varying cell sizes are tested, as well as, a thick walled cylinder with internal pressure, where three di erent loading techniques are tested. The most accurate loading technique is applied to the sleeved fracture model, in order to simulate fracture initiation and propagation. This model is then veri ed and validated by using the Rummel & Winter hydraulic fracturing model and experimental results, respectively. Displacement error minimisation methods are implemented and as a result, the displacement solutions for a plate in tension converges to the analytical solution, while the thick walled cylinder solutions su er from inaccuracies due to an applied load on an irregularly discretized region. The fracture initiation test captures the fracture tip behaviour of the Rummel & Winter model and the fracture propagation test show good correlation with experimental results. This research shows that the peridynamic approach to sleeved hydraulic fracture can yield a realistic representation of fracture initiation and propagation, however, further research is needed in the area of a pressure load application on a solid using the peridynamic approach. / AFRIKAANSE OPSOMMING: Huidige numeriese metodes in die veld van hidrouliese breking is hoofsaaklik gebaseer op kontinuum metodes, soos die Eindige Element Metode (EEM) en die Rand Element Metode (REM). Hierdie metodes word beheer deur Linie^ere Elastiese Breukmeganika (LEB) kriteria, wat ly aan die inherente gebrek van 'n nie- siese voorstelling van die spanning by die fraktuur punt. Om hierdie probleme aan te spreek, word 'n nie-lokale metode voorgestel, naamlik die peridinamiese teorie, om gehulsde hidrouliese breking te modelleer. 'n 2D implisiete kwasi-statiese ordin^ere toestand gebaseerde peridinamika formulering word ge mplimenteer op verskeie norm probleme, om te veri eer of dit oor die vermo e beskik om die konstitutiewe gedrag van 'n linie^ere elastiese soliede materiaal te modeleer, asook die kwanti sering van nadelige e ekte op die verplasings oplossing as gevolg van die natuur van die nie-lokale teorie. Normtoetse bestaan uit 'n plaat in trek spanning, waar konvergensie na die klassieke verplasings oplossing, nie-uniforme verfyning en vari^eerende sel groottes getoets word, asook 'n dikwandige silinder onder interne druk, waar drie verskillende belasting aanwendingstegnieke getoets word. Die mees akkurate belasting aanwendingstegniek word dan gebruik in die gehulsde hidrouliese breking model, om fraktuur aanvangs en uitbreiding na te boots. Die model word dan geveri- eer deur die Rummel & Winter hidrouliese breking model en eksperimentele resultate, onderskeidelik. Fout minimering metodes word toegepas en as 'n resultaat, konvergeer die verplasing oplossing vir die plaat na die analitiese oplossing, terwyl die oplossing van die dikwandige silinder onakuraathede toon as gevolg van 'n toegepaste belasting op 'n onre elmatig gediskretiseerde gebied. Die modellering van die fraktuur inisi ering by die fraktuur punt, stem goed ooreen met die Rummel en Winter voorspelling en die fraktuur uitbreiding stem goed ooreen met eksperimentele resultate. Hierdie navorsing toon dat die peridinamiese benadering tot gehulsde hidrouliese breking wel die fraktuur inisi ering en uitbreiding realisties kan modelleer, maar nog navorsing word wel benodig in die area waar 'n druk belasting op 'n peridinamiese soliede model toegepas word.

Deep slurry injection is a process of solid waste disposal that involves grinding the solid waste to a relatively fine-grained consistency, mixing the ground waste with water and/or other liquids to form slurry, and disposing of the slurry by pumping it down a well at a high enough pressure that fractures are created within the target formation. This thesis describes the site assessment criteria involved in selecting a suitable target reservoir for deep slurry injection. The main goals of this study are the follows: <ul> <li>Identify the geological parameters important for a prospective injection site</li> <li>Recognize the role of each parameter</li> <li>Determine the relationships among different parameters</li> <li>Design and develop a model which can assemble all the parameters into a semi-quantitative evaluation process that could allow site ranking and elimination of sites that are not suitable</li> <li>Evaluate the model against several real slurry injection cases and several prospective cases where slurry injection may take place in future</li> </ul> The quantitative and qualitative parameters that are recognized as important for making a decision regarding a target reservoir for deep slurry injection operations are permeability, porosity, depth, areal extent, thickness, mechanical strength, and compressibility of a reservoir; thickness and flow properties of the cap rock; geographical distance between an injection well and a waste source or collection centre; and, regional and detailed structural and tectonic setup of an area. Additional factors affecting the security level of a site include the details of the lithostratigraphic column overlying the target reservoir and the presence of overlying fracture blunting horizons. Each parameter is discussed in detail to determine its role in site assessment and also its relationship with other parameters. A geological assessment model is developed and is divided into two components; a decision tree and a numerical calculation system. The decision tree deals with the most critical parameters, those that render a site unsuitable or suitable, but of unspecified quality. The numerical calculation gives a score to a prospective injection site based on the rank numbers and weighting factors for the various parameters. The score for a particular site shows its favourability for the injection operation, and allows a direct comparison with other available sites. Three categories have been defined for this purpose, i. e. average, below average, and above average. A score range of 85 to 99 of 125 places a site in the ?average? category; a site will be unsuitable for injection if it belongs to the ?below average? category, i. e. if the total score is less than 85, and the best sites will generally have scores that are in the ?above average? category, with a score of 100 or higher. One may assume that for sites that fall in the ?average? category there will have to be more detailed tests and assessments. The geological assessment model is evaluated using original geological data from North America and Indonesia for sites that already have undergone deep slurry injection operations and also for some possible prospective sites. The results obtained from the model are satisfactory as they are in agreement with the empirical observations. Areas for future work consist of the writing of a computer program for the geological model, and further evaluation of the model using original data from more areas representing more diverse geology from around the world.

Atualmente, os estudos envolvendo nanomateriais como aditivos em propantes são o foco das companhias e universidades norte-americanas para o desenvolvimento de propantes que possam sofrer alterações químicas e mecânicas dentro do reservatório ou para permitir a rastreabilidade e direcionamento. Este trabalho apresenta um desenvolvimento de grânulos de metacaulim capazes de incorporar nanomateriais em sua estrutura. O método adotado para sua produção foi a mistura intensiva da matéria-prima (MP) com nanomateriais dispersados e adicionados em resina para revestimento. A rota de produção tem potencial para produzir grânulos com grau de K&S variando entre 0,7 e 0,9 tanto para esfericidade como para o arredondamento. Os ensaios de resistência ao esmagamento resultaram em valores entre 3 K e 4 K (x 1.000 psi) para algumas das amostras sinterizadas a 1.300 ºC. As análises de MEV comprovam a incorporação dos nanomateriais de carbono, na estrutura interna dos propantes. / Today, studies on nanomaterials that are used as additives in proppants are the focus of North America\'s companies and universities in order to develop either proppants that can suffer mechanical and chemical changes inside the reservoir or that enable their traceability and direction. This work presents a development on the microspheres of metakaolin\'s capacity to incorporate nanomaterials to their structure. The production route has the potential to produce K & S grade microspheres ranging from 0.7 to 0.9 for both sphericity and rounding. Crush strength tests resulted in values between 3 K and 4 K (x 1,000 psi) for some of the samples sintered at 1300 °C. The SEM analyzes prove the integration of carbon nanomaterials into the proppant structures.

[pt] Um dos principais objetivos da engenharia de petróleo é desenvolver e aplicar técnicas capazes de aumentar a produtividade de poços de petróleo, incluindo a estimulação da formação através de operações que aumentem a permeabilidade da rocha-reservatório e facilitem o escoamento do fluido. Dentre as técnicas de estimulação, a mais utilizada é o fraturamento hidráulico, a qual tem viabilizado a exploração em cerca de 40 por cento dos poços produtores de petróleo em todo o mundo. Durante o fraturamento hidráulico, um material granular conhecido como material de sustentação ou propante, é injetado nas fraturas recém-criadas com o objetivo de mantê-las abertas e garantir-lhes condições de alta permeabilidade. A produção de material de sustentação (proppant flowback) é termo usado para descrever o refluxo do propante para o interior do poço, juntamente com o hidrocarboneto produzido. O controle do fluxo de propante representa um grave desafio para a indústria de petróleo, pois pode causar graves problemas operacionais e de segurança, relacionados com o desgaste dos equipamentos de produção, problemas econômicos associados ao custo de limpeza, paralisação das operações e intervenção no tratamento da fratura, problemas ambientais relacionados com a disposição de sólidos impregnados por hidrocarbonetos, etc. Neste contexto, a presente dissertação apresenta um estudo detalhado dos principais tipos de propante e de suas propriedades, bem como descreve os mecanismos que influem no refluxo do material de sustentação da fratura e analisa os principais modelos apresentados na literatura para previsão deste fenômeno. Uma retroanálise considerando os dados de campo em 22 poços da Petrobrás, localizados em Sergipe, permite uma comparação da eficiência entre quatro dos modelos, desenvolvidos com base em resultados de ensaios de laboratório, indicando suas vantagens e desvantagens para aplicação na prática da engenharia. / [en] One of the main objectives of petroleum engineering is to develop and to apply techniques aiming the productivity increase of oil fields, including the stimulation of the rock through operations that increase the permeability of the oil reservoir and makes the flow of the fluid toward the well more efficient. Among the stimulation techniques, the most used is the hydraulic fracturing, carried out in about 40 percent of the producing oil wells around the world. During hydraulic fracturing, a granular material known as proppant, is injected into the just created fractures with the objective to keep them open and in order to guarantee the designed conditions of high permeability. Proppant flowback is the technical terminology employed to describe the flow of proppant from the fracture to the interior of the oil well, together with the produced hydrocarbon. An efficient and reliable control of this problem is still a major challenge to the oil industry, given the serious operational and security problems that it may cause, including costs of interrupted operations, cleaning measures, environmental contamination risks associated with the disposal of residues impregnated by oil, etc. In this context, the present thesis presents a detailed description on the main proppant materials and their engineering properties and available treatments, as well as on the physical mechanisms that control the flowback phenomenon. Several simple models published in the literature, that permit the forecast of proppant flowback in a fast and easy way, are also presented and discussed. Finally, a back-analysis considering the actual conditions in 22 Petrobras oil wells located in Sergipe was also carried out, what permitted a comparison among the results calculated according 4 prediction models, putting in evidence their advantages, shortcomings and adequacy as a design or control tool in the design and exploration of oil fields stimulated by hydraulic fracturing.

[pt] A viabilidade da exploração de um campo petrolífero está associada às características produtivas da formação, obtidas mediante o desenvolvimento e a aplicação de técnicas capazes de aumentar a economicidade dos poços. A técnica de estimulação mais utilizada atualmente é o fraturamento hidráulico, que tem como uma das etapas principais a injeção de um material granular, denominado de propante, para a manutenção da abertura da fratura. Tal técnica tem como obstáculo o refluxo do propante para o interior do poço (proppant flowback), ocasionando diversos problemas que podem levar à interrupção da produção do mesmo. Alguns modelos teóricos e empíricos foram desenvolvidos para a previsão desse fenômeno, mas os mecanismos que o governam não são ainda claramente explicados. Alguns fatores que influenciam na produção de propante são largura da fratura, tensão de fechamento, gradiente hidráulico e características do propante. O refluxo de propante não é considerado nos procedimentos atuais de projeto de fraturamento hidráulico. Nessa dissertação de mestrado foi desenvolvida uma ferramenta computacional com uma arquitetura orientada a objeto, em linguagem de programação Java, para a análise de estabilidade do propante no interior da fratura com base em modelos empíricos e teóricos. Além disso, foi investigada a influência da inclusão de restrições no projeto de fraturamento de modo a prevenir o fenômeno. Busca-se, desse modo, a obtenção de melhores projetos de fraturamento hidráulicos com prevenção do refluxo de propante, garantindo a produtividade do poço e prolongando sua vida útil. / [en] The viability of the exploration of an oil field is associated with the productive characteristics of the formation, guaranteed by means of the development and application of techniques capable of increasing the productivity and the economy of the oil fields. The currently most used stimulation technique is hydraulic fracturing, by which one of the main stages is the injection of a granular material called proppant to keep the fracture open and enhance fracture permeability. This technique presents as a drawback the phenomenon known as proppant flowback. The proppant is carried to the inside of the well causing many problems which can lead to production interruption. Some empirical and theoretical models for its prediction have been developed, however the mechanisms that govern it are still not clearly explained. Parameters that are related to proppant flowback are fracture width, closure pressure, drag force and proppant characteristics. Proppant flowback prediction is not included in today s procedures of the hydraulic fracturing project. In the present work a computational tool for proppant stability analysis was developed based on empirical and theoretical prediction models. This tool has an object oriented architecture written in Java language. The influence of the introduction of restrictions to prevent proppant production in the hydraulic fracture design procedure was also investigated. In this way, it is aimed to obtain hydraulic fracturing projects by which proppant flowback is prevented in field situations assuring well productivity and extending its activity period.

Deep slurry injection is a process of solid waste disposal that involves grinding the solid waste to a relatively fine-grained consistency, mixing the ground waste with water and/or other liquids to form slurry, and disposing of the slurry by pumping it down a well at a high enough pressure that fractures are created within the target formation. This thesis describes the site assessment criteria involved in selecting a suitable target reservoir for deep slurry injection. The main goals of this study are the follows: <ul> <li>Identify the geological parameters important for a prospective injection site</li> <li>Recognize the role of each parameter</li> <li>Determine the relationships among different parameters</li> <li>Design and develop a model which can assemble all the parameters into a semi-quantitative evaluation process that could allow site ranking and elimination of sites that are not suitable</li> <li>Evaluate the model against several real slurry injection cases and several prospective cases where slurry injection may take place in future</li> </ul> The quantitative and qualitative parameters that are recognized as important for making a decision regarding a target reservoir for deep slurry injection operations are permeability, porosity, depth, areal extent, thickness, mechanical strength, and compressibility of a reservoir; thickness and flow properties of the cap rock; geographical distance between an injection well and a waste source or collection centre; and, regional and detailed structural and tectonic setup of an area. Additional factors affecting the security level of a site include the details of the lithostratigraphic column overlying the target reservoir and the presence of overlying fracture blunting horizons. Each parameter is discussed in detail to determine its role in site assessment and also its relationship with other parameters. A geological assessment model is developed and is divided into two components; a decision tree and a numerical calculation system. The decision tree deals with the most critical parameters, those that render a site unsuitable or suitable, but of unspecified quality. The numerical calculation gives a score to a prospective injection site based on the rank numbers and weighting factors for the various parameters. The score for a particular site shows its favourability for the injection operation, and allows a direct comparison with other available sites. Three categories have been defined for this purpose, i. e. average, below average, and above average. A score range of 85 to 99 of 125 places a site in the ?average? category; a site will be unsuitable for injection if it belongs to the ?below average? category, i. e. if the total score is less than 85, and the best sites will generally have scores that are in the ?above average? category, with a score of 100 or higher. One may assume that for sites that fall in the ?average? category there will have to be more detailed tests and assessments. The geological assessment model is evaluated using original geological data from North America and Indonesia for sites that already have undergone deep slurry injection operations and also for some possible prospective sites. The results obtained from the model are satisfactory as they are in agreement with the empirical observations. Areas for future work consist of the writing of a computer program for the geological model, and further evaluation of the model using original data from more areas representing more diverse geology from around the world.

For more than five decades, hydraulic fracturing has been widely used to enhance oil and gas production. Hydraulic fracturing in solid materials (e.g., rock) has been studied extensively. The main goal of this thesis is a comprehensive study of the physical mechanisms of hydraulic fracturing in cohesionless sediments. For this purpose, experimental techniques are developed to quantify the initiation and propagation of hydraulic fractures in dry particulate materials. We have conducted a comprehensive experimental series by varying such controlling parameters as the properties of particulate materials and fracturing fluids, boundary conditions, initial stress states, and injection volumes and rates. In this work, we suggest principle fundamental mechanisms of hydraulic fracturing in particulate materials and determine relevant scaling relationships (e.g., the interplay between elastic and plastic processes). The main conclusion of this work is that hydraulic fracturing in particulate materials is not only possible, but even probable if the fluid leak-off is minimized (e.g., high flow rate, high viscosity, low permeability). Another important conclusion of this work is that all parts of the particulate material are likely to be in compression. Also, the scale effect (within the range of the laboratory scales) appears to be relatively insignificant, that is, the observed features of fractures of different sizes are similar. Based on the observed fracture geometries, and injection pressures we suggested three models of hydraulic fracturing in particulate materials. In the cavity expansion or ??e driving model, the fracturing fluid is viewed as a sheet pile (blade) that disjoints the host material, and the cavity expansion occurs at the fracture (blade) front. The shear banding model is also consistent with a compressive stress state everywhere in the particulate material and explains the commonly observed beveled fracture front. The model of induced cohesion is based on the fluid leak-off ahead of the fracture front. The induced cohesion may be caused by the tensile strain near the fracture tip (where the stress state is also compressive), which, in turn, induces the cavitation of the leaked-off fluid and hence capillary forces.