Thesis (MBA)--Stellenbosch University, 2011. / Petroleum fuels energy supply and its availability is an essential precondition for socio-economic development in any economy. Energy is required in meeting the basic human needs such as food, shelter, health, education and for economic activities such as transport, agriculture and mining. Botswana’s energy consumption is dominated by petroleum fuels. The country has no known petroleum reserves and it has to import all its petroleum requirements in refined form, from the neighbouring South Africa. The study focuses on the challenges of security of supply of petroleum products in Botswana. What is at stake is to identify alternative supply sources and routes of petroleum products to Botswana, thus reducing the risk of wholly dependence on South Africa for the supply. A major goal is to develop alternative sources and routes from neighbouring countries. This can be achieved by the Botswana Government taking advantage of regional cooperation with neighbouring countries. The study explores other approaches to reduce the high dependence on South Africa. One of the possible solutions is for Botswana Government to establish a state owned oil company which could play a catalytic role in the implementation of many of the steps considered in this study. This company could, for example, be charged with crude oil exploration in Botswana and with steps to assist locally owned Botswana companies to establish themselves in the marketing and distribution of petroleum. Much will, however, depend on the resources that can be mobilised by the Botswana Government for such a State Oil Company. The study is based on secondary data obtained mainly from the Division of Energy in the Ministry of Minerals, Energy and Water Resources. Feasibility studies conducted by consultants engaged by the Ministry played an important role in the literature underlying this report.

This paper describes a new technique for analyzing fire debris using nuclear magnetic resonance (NMR) spectroscopy. Petroleum distillates, which are commonly used accelerants, were weathered, burned, and steamdistilled. These, as well as virgin samples of the accelerants, were analyzed by gas chromatography and nuclear magnetic resonance spectroscopy. In addition, solvent studies and detectibility limit studies were conducted. The use of NMR is described as a valuable adjunct to the existing methods of analysis.

Neste trabalho foi desenvolvido um método empregando a microextração líquidolíquido dispersiva em fase reversa (RP-DLLME) para extração e pré-concentração de Al, Cd, Cu, Fe, Mn, Ni e Zn em amostras de óleo diesel. A determinação dos analitos foi feita por espectrometria de emissão óptica de plasma indutivamente acoplado (ICP-OES). Para a etapa de extração e pré-concentração, empregou-se uma mistura de solventes dispersor e extrator, a qual foi adicionada diretamente na amostra aquecida. Posteriormente, para separação das fases, as soluções foram centrifugadas e, foi retirada a fase sedimentada para determinação dos analitos por ICP-OES. Para o desenvolvimento do método foi utilizado o planejamento experimental e otimização de processos, onde inicialmente utilizou-se um planejamento fatorial fracionado e em seguida um delineamento composto central rotacional. As variáveis estudadas foram temperatura de extração (60, 70 e 80 oC), massa de amostra (5, 10 e 15 g), volume da solução extratora (0,5, 1 e 1,5 mL), concentração do extrator (1, 1,5 e 2 mol L-1) e proporção do dispersor na solução extratora (60, 70 e 80%). Resultados quantitativos foram obtidos empregando as seguintes condições: i) temperatura de extração: 70 oC, ii) massa de amostra: 8,5 g, iii) volume da solução extratora: 1 mL, iv) concentração de HNO3: 2 mol L-1 e v) proporção do dispersor: 70% (v/v). Todos os experimentos foram feitos usando a adição de 1,0 µg g-1 de Al, Cd, Cu, Fe, Mn, Ni e Zn diretamente nas amostras de diesel, para isso foi utilizado um padrão multielementar de óleo lubrificante Conostan® (100 mg L-1). Os resultados foram expressos como recuperação dos analitos (%). As soluções de calibração foram feitas em solução aquosa e os extratos foram diretamente determinados por ICP-OES. Os limites de quantificação (LQ) para Al, Cd, Cu, Fe, Mn, Ni e Zn foram 0,0492, 0,0031, 0,0031, 0,0140, 0,0008, 0,0049 e 0,0093 µg g-1, respectivamente. A exatidão do método foi avaliada por meio de ensaios com adição de analitos. Recuperações quantitativas foram obtidas para todos analitos e os desvios padrão relativos foram inferiores a 7%. Posteriormente, o método foi aplicado para 6 amostras de óleo diesel comercial, S-10 e S-500, e a concentração de Al, Fe e Zn foi na faixa de 0,026 até 0,150 µg g-1, os demais analitos ficaram abaixo do LQ do método. Então, o método desenvolvido empregando a RP-DLLME e posterior determinação por ICP-OES apresentou-se com precisão e exatidão adequados para determinação de Al, Cd, Cu, Fe, Mn, Ni, Zn em óleo diesel em baixas concentrações, minimizando o consumo de reagentes e, consequentemente a geração de resíduos, de forma rápida e de simples execução, mostrando-se adequado para análises de rotina. / This research developed a method for employing a reversed-phase dispersive liquidliquid microextraction (RP-DLLME) as sample preparation for the extraction and preconcentration of Al, Cd, Cu, Fe, Mn, Ni and Zn in biodiesel samples. The determination of analytes were executed through inductively coupled plasma optical emission spectrometry (ICP-OES). The extraction/pre-concentration step of the analytes was performed using a mixture of two solvents, a dispersing and an extractor, which were added directly to the heated sample. Subsequently, for separation of the phases, the solutions were centrifuged and the sedimented phase was withdrawn to determine the analytes by ICP-OES. For the development of the method was used the experimental planning and optimization of processes, where initially a fractional factorial design was used and then a central composite rotatable design. The variables studied were temperature of the extraction (60, 70 and 80 oC), sample mass (5, 10 and 15 g), volume of extraction phase (0.5, 1 and 1.5 mL), concentration of the extraction (1.5 and 2 mol L-1) and the proportion of the dispersant in the extractive solution (60, 70 and 80%). Quantitative results were obtained using the following conditions: i) temperature of the extraction: 70 oC, ii) sample mass: 8.5 g, iii) volume of extraction phase: 1 mL, iv) concentration of HNO3: 2 mol L-1, and v) proportion of dispersant: 70% (v / v). All experiments were performed using the addition of 1.0 μg g-1 of Al, Cd, Cu, Fe, Mn, Ni and Zn directly in the diesel samples, was used a standard multi-element Conostan® lubricant oil (100 mg L-1). The results were expressed as analyte recovery (%). The calibration solutions were made in aqueous solution and the extracts were directly determined by ICP-OES. The quantification limits (LQ) for Al, Cd, Cu, Fe, Mn, Ni and Zn were 0.0492, 0.0031, 0.0031, 0.0140, 0.0008, 0.0049 and 0.0093 μg g-1, respectively. Accuracy was assessed by addition of analytes. Quantitative recoveries were obtained for all analytes and the relative standard deviations were less than 6.4%. The method was applied to 6 samples of commercial diesel oil, S-10 and S-500, and Al, Fe and Zn were determined in the range of 0.026 to 0.150 μg g-1, the remaining analytes were below the LQ of the method. The method developed using RP-DLLME and determination by ICP-OES presented with adequate precision and accuracy for the determination of Al, Cd, Cu, Fe, Mn, Ni, Zn in diesel oil in low concentrations, minimizing reagent consumption and, consequently the generation of toxic wastes, in a fast and simple way, and is suitable for routine analysis.

Este trabalho desenvolve uma estrutura de otimização que auxilia a tarefa de escalonamento das atividades de transporte de derivados de petróleo em uma rede de dutos. A malha dutoviária em estudo é utilizada para o transporte de derivados leves de petróleo com alto valor agregrado, sendo composta por 9 áreas (3 refinarias, 1 porto e 5 terminais). dentro deste cenário, a busca por resultados práticos considerando uma carga computacional aceitável torna-se um grande desafio. A abordagem adotada baseia-se na decomposição do problema, onde é investigada a aplicação de um modelo de programação linear inteira mista (Mixed Integer Linear Programming - MILP) com domínio de tempo contínuo para determinar o escalonamento das operações de curto-prazo da rede de dutos. Em função da abordagem hierárquica proposta, a etapa de ordenação da lista de bateladas utilizada na fase de temporização foi inicialmente desenvolvida através de heur´siticas construtivas que falham em situações particulares. Neste sentido, o problema de ordenação é reformulado através do emprego de estruturas de alto nível presentes em técnicas de programação lógica por restrições (Constraint Logic Programming - CLP). Na forma como é apresentada, a estrutura desenvolvida vem sendo extensivamente testada em cenários reais envolvendo mais de 100 bateladas para o horizonte de aproximadamente um mês. A partir desta ferramenta, novas programações de curto-prazo serão propostas, programações existentes serão validadas e informações de diagnóstico da rede serão obtidas de forma a auxiliar o processo de tomada de decisão operacional. / This work addresses an optimisation structure to support the operational decision-making of scheduling activities in a real world pipeline network. The used scenario to transport petroleum derivaties involves 9 areas (3 refineries, 1 harbour, and 5 distribution centres). Thus, the computational burden for determining a short-term scheduling within the considered scenario is a relevant issue. A decomposition approach is proposed to address such real-world problem. A continuous-time mixed integer linear programming model (MILP) is studied and used to determine the operational short-term scheduling. In this context of multilevel hierarchical structure, sequencing of activities are carried out by a heuristic algorithm which can fail for some particular cases. Thus, we propose to reformulate the sequencing problem by using high-level constructs of Constraint Logic Programming (CLP). The optimisation structure has been extensively tested in typical operational scenarios which, involve in general more than 100 batches. The scheduling horizon is considered to be about 1 month. Many insights have been derived from the obtained solutions, and the proposed approach can support the decision-making process.

Durante as atividades de produção de petróleo offshore são utilizadas tubulações que transportam o petróleo bruto do fundo do poço até à plataforma ou até à costa marítima. No fundo mar as tubulações são submetidas a temperaturas da ordem de 4 oC. Nessas condições, quando a atividade de produção é interrompida para manutenções ou por paradas de emergência, o óleo bruto, com alto teor de parafinas, tende a se gelificar. Para reiniciar o escoamento são necessárias pressões acima da pressão usual de trabalho para promover a quebra do gel. A literatura mostra que não só o histórico de térmico, mas também o histórico de cisalhamento afetam a gelificação de óleos parafínicos e, portanto, a pressão de reinício do escoamento. O objetivo deste trabalho é avaliar experimentalmente as variáveis que influenciam o reinício do escoamento de petróleo parafínico. Para isso, uma unidade experimental foi construída de modo a reproduzir experimentalmente o reinício do escoamento de petróleo parafínico gelificado. A unidade permite o controle da temperatura, da taxa de resfriamento, da taxa de cisalhamento e do tempo de repouso na formação do gel. A pressão máxima necessária para o início do escoamento foi observada, os valores coletado e analisado. A investigação realizada mostra que todos os parâmetros testados apresentam alguma influência na pressão durante o reinício do escoamento de óleo parafínicos gelificados. / In offshore production, pipelines are used to transport crude oil from the well bore to the platform and from the plataform to the seacoast. When production is interrupted for maintenance or emergency, waxy crude oils tend to form gel at seabed low temperatures. At flow start-up, an increase in pressure above the usual operating pressure is required to break the gel. The literature has reported that not only the temperature but also the cooling rate, the shear rate during cooling and the material aging time affect the gelation of waxy crude oils, and, therefore, the start-up pressure. The objective of the current work is to evaluate experimentally the start-up flow of waxy crude oils in pipelines. In order to accomplish that, an experimental lab loop was build to reproduce the flow start-up of gelled waxy crude oils. The loop allows the control of temperature, cooling rate, shear rate and aging time in the gel formation. The pressure peaks measured during the flow restart were presented and analized as a function of the controlled parameters. The research shows that all parameters tested have some influence on the picks of pressure during the start up flow of paraffinic oil gelled.

Este trabalho desenvolve uma estrutura de otimização que auxilia a tarefa de escalonamento das atividades de transporte de derivados de petróleo em uma rede de dutos. A malha dutoviária em estudo é utilizada para o transporte de derivados leves de petróleo com alto valor agregrado, sendo composta por 9 áreas (3 refinarias, 1 porto e 5 terminais). dentro deste cenário, a busca por resultados práticos considerando uma carga computacional aceitável torna-se um grande desafio. A abordagem adotada baseia-se na decomposição do problema, onde é investigada a aplicação de um modelo de programação linear inteira mista (Mixed Integer Linear Programming - MILP) com domínio de tempo contínuo para determinar o escalonamento das operações de curto-prazo da rede de dutos. Em função da abordagem hierárquica proposta, a etapa de ordenação da lista de bateladas utilizada na fase de temporização foi inicialmente desenvolvida através de heur´siticas construtivas que falham em situações particulares. Neste sentido, o problema de ordenação é reformulado através do emprego de estruturas de alto nível presentes em técnicas de programação lógica por restrições (Constraint Logic Programming - CLP). Na forma como é apresentada, a estrutura desenvolvida vem sendo extensivamente testada em cenários reais envolvendo mais de 100 bateladas para o horizonte de aproximadamente um mês. A partir desta ferramenta, novas programações de curto-prazo serão propostas, programações existentes serão validadas e informações de diagnóstico da rede serão obtidas de forma a auxiliar o processo de tomada de decisão operacional. / This work addresses an optimisation structure to support the operational decision-making of scheduling activities in a real world pipeline network. The used scenario to transport petroleum derivaties involves 9 areas (3 refineries, 1 harbour, and 5 distribution centres). Thus, the computational burden for determining a short-term scheduling within the considered scenario is a relevant issue. A decomposition approach is proposed to address such real-world problem. A continuous-time mixed integer linear programming model (MILP) is studied and used to determine the operational short-term scheduling. In this context of multilevel hierarchical structure, sequencing of activities are carried out by a heuristic algorithm which can fail for some particular cases. Thus, we propose to reformulate the sequencing problem by using high-level constructs of Constraint Logic Programming (CLP). The optimisation structure has been extensively tested in typical operational scenarios which, involve in general more than 100 batches. The scheduling horizon is considered to be about 1 month. Many insights have been derived from the obtained solutions, and the proposed approach can support the decision-making process.

No description available.

In accordance with the main aim of the study, a widely accessible, modifiable tool was created for parties interested in maintaining the national electricity supply network and parties interested in informing policy on plug-in vehicle adoption schemes and recharging behaviour control. The Parry Tool enables the user to incorporate present limits to plug-in vehicle recharging demand scheduling as imposed by the state of present technology (no third party mechanism for monitoring and control of recharging), present human travel behaviour needs and existing patterns in electricity usage; into the investigation of the impacts of recharging demand impacts and the design of mitigation measures for deflecting (parrying) worst case scenarios. The second aim of the project was to demonstrate the application of the Parry Tool. The multidisciplinary/interdisciplinary information gathered by the Parry Tool was used to produce national demand profiles for plug-in vehicle recharging demand, calculated using socioeconomic and travel behaviour-estimated population sizes for plug-in eligible vehicles and vehicle usage patterns, which were added to existing national electricity demand for a chosen test week – this was the first scenario subsequently tested. The information gathered by the Parry Tool was then used to inform the design of two demand management methods for plug-in vehicle recharging: Recharging Regimes and weekly recharging load-shifting – these were the second and third scenarios subsequently tested. Unmitigated simultaneous recharging demand in scenario 1 (all vehicles assumed to recharge at home upon arrival home every day) severely exacerbated peak demand, raising it by 20% above the highest peak in existing demand for the year 2009 over half an hour from 58,554 MW to 70,012 MW – a challenge to the generation sector. This increased the difference between daily demand minima and maxima and made the new total demand have sharper peaks – a challenge for grid regulators. Recharging Regimes in scenario 2 split the estimated national plug-in vehicle populations into groups of different sizes that started recharging at different times of the day, with the word ‘regime’ being applied because the spread of start times changed over the course of the test week from workdays to weekend. This avoided exacerbation of the peak and reduced the difference between daily demand minima and maxima by raising minima, providing a load-levelling service. Scenario 3 embellished the Recharging Regimes with workday-to-weekend recharging load-shifting that therefore took better advantage of the often overlooked weekly pattern in existing demand (demand being higher on workdays than weekends), by allowing partial recharging of a segment of the plug-in vehicle population. Limited consideration of the impact of changing vehicle energy usage (for which distance travelled was assumed to proxy in this study) showed that the more vehicles used their batteries during the day, the better the levelling effect offered by Recharging Regimes. Greater utilisation of battery capacity each day, however, can also be assumed to lessen the potential for workday-to-weekend load levelling, because load-shifting depends upon vehicles being able to partially recharge or defer recharging to later days and still meet their travel needs plus keep a reserve State Of Charge (SOC) for emergency and other unplanned travel. Whilst altering vehicle energy usage did not change the finding that unmitigated simultaneous recharging exacerbated existing peak demand, it was noted that when limited mileage variation was considered this sharpened the profile of total demand – the rise and fall of the new peak far steeper than that of the original peak in existing demand. The Parry Tool combines a series of integrated methods, several of which are new contributions to the field that use UK data archives but may potentially be adapted by researchers looking at energy issues in other nations. It presents a novel fossil-fuel based justification for targeting road transport – acknowledging energy use of fossil fuel as the originator of many global and local problems, the importance of non-energy use of petroleum products and subsequent conflicts of interest for use, and a fossil fuel dependency based well-to-wheel assessment for UK road transport for the two energy pathways: electricity and petroleum products. It presents a method for the recalculation and ranking of top energy use/users using national energy use statistics that better highlights the importance of the electricity industry. It also presents the first publicly documented method for the direct consultation and extraction of vehicle-focused statistics from the people-focused National Travel Survey database, including a travel behaviour and household income-based assessment of plug-in vehicle eligibility, used to scale up to national estimates for battery electric and plug-in electric hybrid vehicle (BEV and PHEV) national population sizes. The work presented here is meant to allow the reader to perceive the potential benefits of using several resources in combination. It details the Parry Tool, a framework for doing so, and where necessary provides methods for data analysis to suit. It should however be noted that methods were kept as simple as possible so as to be easily followed by non-specialists and researchers entering the field from other disciplines. Methods are also predominantly data-exploratory in nature: strong conclusions therefore should not be drawn. Rather, the work here should be seen as a guideline for future work that may more rigorously study these combined topics and the impacts they may have upon plug-in vehicle ownership, usage behaviour, impacts of recharging upon the national network and the design of mitigation measures to cope with this new demand.

"The primary purpose of this research was to quantify fire suppression and fire intensification phenomena for water spray application to high flash point hydrocarbon oil pool fires. Test data and analyses of the phenomena include the drop size distribution and application and delivered densities of various water sprays, and spray-induced oil cooling and oil splattering for mineral seal oil and for cooking oil 30-cm diameter pool fires. Four different types of tests were conducted as described below. A Dantec Particle Dynamic, phase Doppler, Analyzer was used to measure the water drop sizes and velocities generated by 13 selected nozzles and sprinkler heads. Most measurements were made 0.91 m (3 ft) below the nozzles/sprinklers, since this was the location of the center of the hydrocarbon pool in later fire tests. The correlations for the volume-median drop diameter, dw, were of the form , where D is the nozzle orifice and is the spray Weber number based on D and the nozzle velocity. A ring burner was designed and constructed for uniformly heating oil pool surfaces from above and igniting them. The resulting oil temperatures while the oil was heated to its flash point satisfied the one-dimensional transient heat conduction model for a semi-infinitely thick solid with a shallow heated layer near the surface. Water sprays actuated when the oil surface temperature reached its flash point rapidly cooled the heated layer and caused mixing with the cooler oil below. Fire suppression tests were conducted to determine the relationship between required water spray density, drop size, and oil temperature in order to achieve suppression. A data correlation using non-dimensional parameters was developed to quantify the fire suppression criteria for the high flash point oil fires. Oil pool fires with the higher flash point oils, such as the 291oC flash point soybean oil, could be suppressed with much lower water densities than those of the lower flash point (137oC) mineral seal oil. However, if the water spray drop sizes are sufficiently small, the lower flash point oil fires can also be extinguished with lower spray densities. The NFPA 15 specified critical water density (0.30 gpm/ft2, 12 mm/min) to extinguish high flash point pool fires is only valid for mineral seal oil when the drop size is lower than about 300 µm. It is valid with larger drop sprays only when the flash point of the oil is higher than 190 according to the correlation developed here. Spray-induced pool fire intensification tests were conducted under a fire products calorimeter for measuring heat release rates. Supplemental oil vaporization rate tests were also conducted to determine the contributions of oil vaporization and oil splattering to the intensified fire. Results showed that vaporization could only account for between 1% and 1.7% of the heat release rate in intensified mineral seal oil fires, and less than 1% of the heat release rate in intensified soybean oil fires. The remainder is due to spray-induced oil splattering, which increased with increasing drop Weber number as well as increased oil temperature. The heat release rate is enhanced by factor from 2.12 to 5.55 compared to the heat release rate of free burning cooking oil. For mineral seal oil, this ratio is in the range 0.92 to 1.25 for the spray conditions tested. Correlations with the dimensionless factors of and the Weber number of the water spray were also developed to quantify the ratio of the splattered oil to applied spray density."

In Nigeria, almost every business enterprise relies on petroleum products for power or transportation. Shortages of petroleum products cripple business activities and undermine development of the Nigerian economy. The purpose of this multiple case study was to explore supply chain management strategies needed by petroleum business leaders to mitigate shortages and sustain business development in Nigeria. The sample for the study included 10 senior leaders from 2 private-sector Nigerian downstream petroleum supply companies located in the Niger Delta region, who had successfully implemented strategies for petroleum supply. The resource based view theory served as the conceptual framework for the study. Data collection included semistructured face-to-face interviews and review of operational and policy documents from the supply companies. Data were transcribed, analyzed, and validated through member checking and triangulation, resulting in the identification of 6 themes: appropriate allocation of resources to all segments of the supply value chain for efficiency, efficient banking and foreign exchange operations, engaging appropriate human capital for operational efficiency, technology application in both operational and nonoperational segments, maintaining good organization reputation in the industry, and investment in Nigerian crude oil refining and infrastructures. Findings may be used by petroleum business leaders and investors to create effective and efficient supply chain management, leading to product availability, employment opportunities, poverty reduction, and economic development.