Gas-to-liquid (GTL) process involves the chemical conversion of natural gas (or other gas sources) into synthetic crude that can be upgraded and separated into different useful hydrocarbon fractions including liquid transportation fuels. A leading GTL technology is the Fischer Tropsch process. The objective of this work is to provide a techno-economic analysis of the GTL process and to identify optimization and integration opportunities for cost saving and reduction of energy usage and environmental impact. First, a basecase flowsheet is synthesized to include the key processing steps of the plant. Then, computer-aided process simulation is carried out to determine the key mass and energy flows, performance criteria, and equipment specifications. Next, energy and mass integration studies are performed to address the following items: (a) heating and cooling utilities, (b) combined heat and power (process cogeneration), (c) management of process water, (c) optimization of tail-gas allocation, and (d) recovery of catalystsupporting hydrocarbon solvents. Finally, an economic analysis is undertaken to determine the plant capacity needed to achieve the break-even point and to estimate the return on investment for the base-case study. After integration, 884 million $/yr is saved from heat integration, 246 million $/yr from heat cogeneration, and 22 million $/yr from water management. Based on 128,000 barrels per day (BPD) of products, at least 68,000 BPD capacity is needed to keep the process profitable, with the return on investment (ROI) of 5.1%. Compared to 8 $/1000 SCF natural gas, 5 $/1000 SCF price can increase the ROI to 16.2%.

This dissertation intends to provide new tuning techniques for several simple cubic equations of state (EOS) to improve their accuracy in calculating fluid phase equilibrium. It also provides graphical tools to predict some phase equilibrium phenomena from activity coefficient models. Finally, it presents simulation results for a new gas-to-liquids process. Saturation Properties for Fluids: By deriving a new identity linking the heat of vaporization for pure components to the EOS, we are able to find new expressions for the two constants a & b in the EOS. These new expressions then allow tuning of both constants a and b to experimental saturation properties at subcritical temperatures. These new tuning procedures prove effective to the point where the simpler Redlich-Kwong EOS provides better results with our procedure than does the usually superior Peng-Robinson EOS with conventional procedures. Activity Coefficient Models: This dissertation shows the flexibility of four activity coefficient models in the prediction of three fluid phase equilibrium phenomena. From these models we successfully developed new graphs that allow one to identify the presence of any of the three phenomena by visual inspection without performing a complex calculation as seen in current texts. Remote Natural Gas: This dissertation presents simulation results of a new gas-to-liquids process which converts natural gas to liquid transportation fuels. Based on the assumption of adiabatic reactions, our simulation results show that methane conversion increases with higher reaction temperature and longer residence times. Hydrogen can both inhibit methane decomposition and reduce coke formation. The rich components in the natural gas are found to decompose very fast and they have a vast quenching effect on the whole reactions. Recycling of unreacted methane also increases overall methane conversion. Finally, our simulator provides very close prediction of the experimental results from a pilot plant. Thus, we conclude that the simulation work is basically successful in fulfilling the goal of this research.

Fisher-Tropsch Synthesis is a primary pathway for gas-to-liquid technology. In order to overcome commercial problems associated with reaction and transport phenomena, the use of supercritical solvents has been proposed to increase chemical conversion and improve temperature control. One of the major challenges in designing the supercritical FTS systems is the solvent selection. Numerous alternatives exist and should be screened based on relevant criteria. The main aim of the thesis was to develop a safety metric that can be incorporated in the selection of an optimal supercritical solvent or a mixture of solvents. The objective was to minimize the cost while satisfying safety constraints or to establish tradeoffs between cost and safety. Hydrocarbons from C3 to C9 were identified as feasible solvents for FTS purposes. The choice of these solvents is dependent on their mixture critical temperature and pressure requirements that need to be satisfied upon entry into the FTS reactor. A safety metric system was developed in order to compare the risk issues associated with using the aforementioned solvents. In addition, an economic analysis of using the different solvents was performed. Finally, a case study was solved to illustrate the use of the proposed metrics and the selection of solvents based on safety and techno-economic criteria.

A descoberta de uma nova província petrolífera, conhecida como pré-sal, localizada no litoral brasileiro, representa um novo marco na produção de petróleo mundial. Dentre os vários desafios encontrados para exploração e produção dessa região, a presença de CO2 em grandes concentrações nos fluidos de alguns desses reservatórios tem sido um dos desafios de maior relevância para as empresas que exploram e produzem nessa área (FORMIGLI, 2007). Uma forma alternativa de sequestro do CO2 retirado do gás natural é a sua utilização como matéria prima ou co-alimentação para a síntese de produtos químicos, em especial aqueles com grande demanda de mercado. Um dos produtos que podem ser obtidos indiretamente a partir do CO2 é o petróleo sintético, produzido pelo processo conhecido como Gas-to-Liquids, ou GTL. Neste trabalho foi analisada a viabilidade técnica, econômica e potencial de captura de CO2, da produção de petróleo sintético, pelo processo GTL, offshore, a partir de dióxido de carbono (CO2) e metano (CH4), presentes na corrente de rejeito do tratamento do gás processado em uma plataforma de produção de petróleo e gás, através das reformas seca e a vapor, seguida da síntese Fischer-Tropsch. A partir de dados de literatura e com uso de simulador comercial de processos, a simulação do processo foi desenvolvida e diferentes alternativas para reaproveitamento das correntes residuais do processo foram analisadas, incluindo o reciclo e a queima dos efluentes combustíveis, assim como foram aplicadas técnicas de integração energética, otimização e análise econômica de processos. Os resultados indicaram que o processo, mássica e energeticamente integrado, na condição de menor emissão de CO2 e maior retorno financeiro, produziu petróleo sintético de forma técnica e economicamente viável. Os resultados indicaram ainda que o processo GTL, com as tecnologias utilizadas, não é indicado como método de captura de CO2 devido o fato de a geração desse componente para a produção de petróleo sintético ser duas vezes maior que a quantidade alimentada. / The discovery of a new oil province known as pre-salt, located in the Brazilian coast, represents a new frontier in the world\'s oil production. Among other challenges involved in the exploration and production in that region, the CO2 concentration at high levels in the fluids of some of those reservoirs has been the most relevant challenge for the companies that explore and produce in that area (FORMIGLI, 2007). An alternative to sequestering the CO2 extracted from natural gas is using it as a supply of raw material or as an input to the synthesis of chemical products, especially those with great market demand. One of the products that can be obtained indirectly from CO2 is synthetic fuel, produced by the process known as Gas-to- Liquids, or GTL. In this work the technical, economical and potential feasibility of CO2 capture is analyzed, as well as the production of synthetic fuel using the GTL process, offshore, from carbon dioxide (CO2) and methane (CH4), found in the waste chain of the gas treatment in an oil and gas production platform, through dry and steam reforming, followed by Fischer-Tropsch synthesis. Thus, based on literature data and on the use of a commercial process simulator, the simulation of the suggested process was developed and different alternatives to the reutilization of the waste chains were analyzed, including the recycling and burning of some effluent streams. Techniques of energetic integration, optimization and economic analysis of process have also been applied. The results indicated that the process, mass and energy integrated in the condition of lower CO2 emissions and greater financial return, produced synthetic oil in a technically and economically feasible way. The results also indicated that the GTL process, with the technologies used, is not suitable as a method for CO2 capture due to the fact that the generation of this component for the production of synthetic oil is two times greater than the amount fed.

A descoberta de uma nova província petrolífera, conhecida como pré-sal, localizada no litoral brasileiro, representa um novo marco na produção de petróleo mundial. Dentre os vários desafios encontrados para exploração e produção dessa região, a presença de CO2 em grandes concentrações nos fluidos de alguns desses reservatórios tem sido um dos desafios de maior relevância para as empresas que exploram e produzem nessa área (FORMIGLI, 2007). Uma forma alternativa de sequestro do CO2 retirado do gás natural é a sua utilização como matéria prima ou co-alimentação para a síntese de produtos químicos, em especial aqueles com grande demanda de mercado. Um dos produtos que podem ser obtidos indiretamente a partir do CO2 é o petróleo sintético, produzido pelo processo conhecido como Gas-to-Liquids, ou GTL. Neste trabalho foi analisada a viabilidade técnica, econômica e potencial de captura de CO2, da produção de petróleo sintético, pelo processo GTL, offshore, a partir de dióxido de carbono (CO2) e metano (CH4), presentes na corrente de rejeito do tratamento do gás processado em uma plataforma de produção de petróleo e gás, através das reformas seca e a vapor, seguida da síntese Fischer-Tropsch. A partir de dados de literatura e com uso de simulador comercial de processos, a simulação do processo foi desenvolvida e diferentes alternativas para reaproveitamento das correntes residuais do processo foram analisadas, incluindo o reciclo e a queima dos efluentes combustíveis, assim como foram aplicadas técnicas de integração energética, otimização e análise econômica de processos. Os resultados indicaram que o processo, mássica e energeticamente integrado, na condição de menor emissão de CO2 e maior retorno financeiro, produziu petróleo sintético de forma técnica e economicamente viável. Os resultados indicaram ainda que o processo GTL, com as tecnologias utilizadas, não é indicado como método de captura de CO2 devido o fato de a geração desse componente para a produção de petróleo sintético ser duas vezes maior que a quantidade alimentada. / The discovery of a new oil province known as pre-salt, located in the Brazilian coast, represents a new frontier in the world\'s oil production. Among other challenges involved in the exploration and production in that region, the CO2 concentration at high levels in the fluids of some of those reservoirs has been the most relevant challenge for the companies that explore and produce in that area (FORMIGLI, 2007). An alternative to sequestering the CO2 extracted from natural gas is using it as a supply of raw material or as an input to the synthesis of chemical products, especially those with great market demand. One of the products that can be obtained indirectly from CO2 is synthetic fuel, produced by the process known as Gas-to- Liquids, or GTL. In this work the technical, economical and potential feasibility of CO2 capture is analyzed, as well as the production of synthetic fuel using the GTL process, offshore, from carbon dioxide (CO2) and methane (CH4), found in the waste chain of the gas treatment in an oil and gas production platform, through dry and steam reforming, followed by Fischer-Tropsch synthesis. Thus, based on literature data and on the use of a commercial process simulator, the simulation of the suggested process was developed and different alternatives to the reutilization of the waste chains were analyzed, including the recycling and burning of some effluent streams. Techniques of energetic integration, optimization and economic analysis of process have also been applied. The results indicated that the process, mass and energy integrated in the condition of lower CO2 emissions and greater financial return, produced synthetic oil in a technically and economically feasible way. The results also indicated that the GTL process, with the technologies used, is not suitable as a method for CO2 capture due to the fact that the generation of this component for the production of synthetic oil is two times greater than the amount fed.

No description available.

Esta tesis se inscribe en el marco del Programa para el De-sarrollo y Utilización del Recurso Gasífero de la Provincia de Santa Cruz cuyo principal objetivo es identificar y examinar alternativas de incorporación de valor agregado al gas natu-ral. En particular en la presente se estudia, a nivel prefac-tibilidad privada y social, la viabilidad de la radicación de una planta localizada el Puerto Punta Loyola, destinada a la pro-ducción de combustibles Gas to Liquids (GTL) mediante el pro-ceso FischerTropsch. Para la evaluación privada se utiliza la metodología propuesta por UNIDO, mientras que para el aná-lisis social la de OCDE. Debido a que los procesos FischerTropsch permiten valorizar reservas de gas natural localizadas en regiones alejadas de los centros de consumo y permiten alcanzar las especificaciones de calidad de los combustibles, estas tecnologías pueden jugar un rol fundamental en los pró-ximos años. En Argentina, luego de la recuperación de la eco-nomía tras la crisis de los años 1999-2003 y del año 2009, la demanda de gas oil ha mostrado una tendencia creciente. Sin embargo, la capacidad de refinación local no ha sufrido varia-ciones significativas en los últimos años, teniendo por tanto que recurrirse a la importación para garantizar su provisión. Este problema de abastecimiento junto con las normas relati-vas a la calidad de los combustibles representan un nicho de mercado para el proyecto. Desde el punto de vista técnico es factible transformar el gas natural en combustibles líquidos ya que la tecnología ha sido probada por muchos años. Sin embargo, cabe mencionar que el costo de capital de la planta bajo estudio se duplicaría respecto de los proyectos mundiales. Los productos a comercializar se valúan según sus precios internos regulados por la Resolución N 394/2007 haciendo que el proyecto no sea aceptable. Por lo tanto, se plantean algunos escenarios alternativos -amortización acelerada o la posibilidad de financiar la inversión inicial- que si bien mejoran la rentabilidad del proyecto no resulta suficientes para reco-mendar su realización. El proyecto solo es aceptable cuando se supone que la producción se coloca a precios internacio-nales. Sin embargo, se demuestra que leves cambios desfavo-rables en las variables críticas tornarían el proyecto inacepta-ble. Los indicadores de rentabilidad se calcularon a partir de la tasa de descuento informada por la industria petroquímica (18%). A pesar de considerarlo alto, se respeta este dato aunque, dado que se trata de una tasa de rentabilidad real habría que tomar como referencia la estimación realizada por Weston y Copeland (1995). Respecto de la evaluación social solo se realiza el análisis de eficiencia, sin tener en cuenta la distribución del ingreso. En este marco, dado que el proyecto es intensivo en el uso de un recurso escaso en el país, no re-sulta aceptable. En un análisis posterior sería interesante estudiar un proceso alternativo de producción (Synfuels) para comparar los resultados. Además resultaría provechoso incor-porar los efectos de multiplicación de empleo que se origina-rán a partir de la instalación de la planta y de las externalida-des del proyecto. / This thesis was elaborated in the framework of the Programa para el Desarrollo y Utilización del Recurso Gasífero de la Pro-vincia de Santa Cruz whose main objective is to identify and examine alternatives to add value to natural gas. The work was focused on the study of the viability of a plant for the production of fuels Gas to Liquids (GTL) using Fischer-Tropsch process, to be located in Puerto Punta Loyola. For the private evaluation the methodology proposed by UNIDO was used, while the one proposed by the OECD guided the social analy-sis. Since Fischer-Tropsch processes can both add value to natural gas reserves located in regions far from consumption centers and reach the quality specifications for fuels, these technologies can play a fundamental role in the near future. In Argentina, after the 1999-2003 and 2009 crisis, demand for gas oil has shown an increasing trend. However, the local refi-ning capacity has not changed significantly in recent years, inducing increased imports to ensure supply. Shortages of supply problems together with quality standards of fuel provi-de a market niche for the project.From a technical point of view it is possible to transform natural gas into liquid fuels since the technology has been proven for many years. Howe-ver, it is noteworthy that the capital cost of the plant under study would double the cost of similar projects over the world. Products manufactured in the plant to be traded in the market have to be valued according to their domestic prices regulated by Resolution No. 394/2007 and because of this fact the project becomes unacceptable. Some alternative scenarios - accelerated depreciation or the possibility of finan-cing the initial investment- were then presented. Though able to improve the profitability of the projects they are not enough to recommend its implementation. The project beco-mes acceptable only when it is assumed that the production is valued at international prices. Besides, it is shown that sli-ght adverse changes in critical variables would make it un-acceptable. The profitability indicators were calculated using the discount rate reported by the petrochemical industry (18%). Although considered high, this value was respected. However, since this is a real rate of return, estimates by Wes-ton and Copeland (1995) should be taken as a reference. With respect to social evaluation only the analysis of effi-ciency was performed, regardless of income distribution. In this context, since the project is intensive in the use of a scarce resource in the country, it becomes not acceptable. In a future research it would be interesting to study an alter-native process of production (Synfuels) in order to compare the results. Moreover, it would be helpful to incorporate the employment multiplier effects induced by the installation of the plant as well as the externalities of the project.

Made available in DSpace on 2014-12-17T15:01:51Z (GMT). No. of bitstreams: 1 JoseRS_TESE.pdf: 2480554 bytes, checksum: 063a0cad7c7f0aba30894e5fdff5f4a7 (MD5) Previous issue date: 2010-07-30 / The current natural gas production of 52 Mm3d-1 and the large projects for its expansion has been setting new boundaries for the Brazilian industry of oil and gas. So far, one of the biggest challenges regards to the logistics for gas transportation from offshore fields. Therefore, the transformation of natural gas into gasoline, diesel and/or olefins via Fischer-Tropsch synthesis would be an alternative to this matter. In this work, the production of hydrocarbons by Fischer-Tropsch synthesis in a slurry reactor was investigated and a perovskite-type catalyst (LayCu0,4Fe0,6O3 ? d) was used with y varying from 0 to 1 on a molar basis. In addition, Nb2O5 support was also applied in order to observe the selectivity of the produced hydrocarbons by the Fischer-Tropsch process. It is shown that the hydrogen conversion was influenced by the support as well as the different phases of the samples. The kinetic results for the CO2 production suffered great influence with the introduction of the Nb2O5 support throughout the series of samples studied. The catalysts allowed obtaining welldefined cuts of hydrocarbons in the range of C1-C6 and C17-C28, and these results were clearly influenced by the support and the lanthanum content. The higher olefin/paraffin ratio obtained was 1.8 when using a non-supported perovskite with y equal to 0.8. This would indicate the suitability of using this material for the production of olefins / A produ??o atual de 52 milh?es m?dia-1 de g?s natural e os grandes projetos para esta expans?o vem estabelecendo novas fronteiras para a ind?stria nacional de petr?leo e g?s, sendo um dos maiores desafios a log?stica para o transporte do g?s oriundo de campos offshore. Uma alternativa seria usar o g?s natural para a produ??o de gasolina, diesel e/ou olefinas atrav?s da s?ntese de Fischer-Tropsch. No desenvolvimento deste trabalho foi investigado a produ??o de hidrocarbonetos via s?ntese de Fischer-Tropsch em um reator slurry mediante uso de catalisadores do tipo perovskita, LayCu0,4Fe0,6O3?d, onde y sofreu varia??o de 0 at? 1 em base molar. A s?ntese dos catalisadores levou em considera??o o estudo da influ?ncia do teor de lant?nio e do suporte (Nb2O5) na atividade e seletividade da rea??o de Fischer-Tropsch, objetivando a produ??o de hidrocarbonetos. As convers?es de H2 foram sensivelmente influ?nciadas pela presen?a de fases existentes em cada amostra, assim como pelo suporte. Os resultados da cin?tica de produ??o de CO2 sofreram grandes influ?ncias com a introdu??o do suporte em toda a s?rie das amostras produzidas. Os catalisadores empregados permitiram a obten??o de cortes bem definidos de hidrocarbonetos na faixa de C1-C6 e C17-C28, sendo estes resultados claramente influenciados pelo suporte e pela varia??o do teor de lant?nio. A maior rela??o olefina/parafina obtida foi de 1,8 para a perovskita com y igual a 0,8 na amostra n?o suportada, viabilizando o uso deste material na produ??o de olefinas

Today, a large proportion of the world's plenteous offshore natural gas resource are stranded, flared or re-injected due to constraints pertaining to its utilisation. The major constraint in the utilisation of this resource is linked to its properties, which makes it difficult to transport or store. Although the resource presents an excellent opportunity for the Gas-to-Liquid (GTL) technology (process for converting natural gas into high energy liquid fuels with qualities that surpass the most stringent current and future clean-fuel requirements), the further processing of this resource is still impeded by high cost of transportation. However, it is believed that the emerging Floating GTL concept could offer superb opportunities to bring such offshore stranded natural gas reserves to markets by converting the gas into high quality liquid fuels, at the production sites, before it is transported using conventional oil tankers or vessels. But the question is: can this venture be profitable or economically viable? In response, an Economic Model (the EV Model) to review the economic viability of the Floating GTL option was developed. Analyses on technical and economical aspects of the floating GTL application offshore are presented with case studies on Syntroleum's and Statoil's floating GTL designs. Profitability analyses were conducted using the EV model to evaluate economic parameters such as Net Present Value (NPV), Internal Rate of Return (IRR), Discounted PayBack Period (DPBP), Profitability index (PI), Break-Even Analysis (BEA) and Scale Economies for some assumed case scenarios involving both designs. In addition, sensitivity analyses were also carried out to find the most sensitive parameters which affect the viability of the floating GTL option. The economic analyses revealed that, a modest feedstock cost (~0 - $3/MSCF), high crude oil price (that stays above $30 per barrel) and reduction trend in capital expenditure (for stand alone Floating GTL plant) up to $20,00O/BPD or lower in the next few years, will open windows for the floating GTL concept. Finally, the energy policy needed to achieve the capitalisation of the plenteous offshore stranded gas resource via floating GTL is also discussed. / Thesis (M.Ing. (Development and Management))--North-West University, Potchefstroom Campus, 2007.

Devido à sua natureza, o gás natural (GN) tem na distância aos pontos de consumo um obstáculo para sua utilização, a qual vai além simples queima para geração de energia ou obtenção de calor. Portanto, é importante que sejam discutidos novos métodos para distribuí-lo e transformá-lo em fontes de energia de maior valor agregado ou em matéria-prima para fabricação de produtos a serem utilizados na indústria química. Uma opção é a conversão do GN em combustíveis líquidos de pronto uso como óleo diesel, gasolina e querosene de aviação através da rota Gas-To-Liquids (GTL). O presente trabalho avalia o potencial da tecnologia GTL no contexto do crescimento da oferta de gás natural no Brasil pelos gasodutos Rota 2 e Rota 3, contextualizando o cenário brasileiro desse energético, as perspectivas futuras e o estado da tecnologia GTL com o processo Fisher-Tropsch. Para tanto, é simulado e analisado o desempenho econômico de uma planta de diesel GTL operante por 30 anos em cenários de preços de insumo e produto obtidos por projeções de reconhecimento internacional. / The usage of natural gás (NG) is related to the distance to the final customers, that is a real obstacle to its full utilization which is beyond the usage as fuel for electricity or heat generation. It is important to prospect, analyze and propose new methods for distribution and transformation of this important energy suppy to more value added products or special raw material for the chemical industry. The transformation in ready for use liquid fuels like diesel, gasoline and kerosene through the gas-to-liquid route (GTL) is one of the options. This dissertation evaluates the GTL technology in a context of the NG additional volume available through 2 new pipelines coming from offshore, Rota 2 and Rota 3 in the Brazilian context of NG current usage and its future perspectives taking advantage of this additional availability via the traditional and long term tested GTL Fischer-Tropsch (FT) technology. A GTL FT Diesel plant operating for 30 years was taken as an example considering different scenarios for NG and Oil prices retrieved from the IEA data base that is internationally considered as a consistent source of information.