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Catalytic hydrotreating (HDT) is a mature process technology practiced in the petroleum refining industries to treat oil fractions for the removal of impurities (such as sulfur, nitrogen, metals, asphaltene). Hydrotreating of whole crude oil is a new technology and is regarded as one of the more difficult tasks that have not been reported widely in the literature. In order to obtain useful models for the HDT process that can be confidently applied to reactor design, operation and control, the accurate estimation of kinetic parameters of the relevant reaction scheme are required. This thesis aims to develop a crude oil hydrotreating process (based on hydrotreating of whole crude oil followed by distillation) with high efficiency, selectivity and minimum energy consumption via pilot plant experiments, mathematical modelling and optimization. To estimate the kinetic parameters and to validate the kinetic models under different operating conditions, a set of experiments were carried out in a continuous flow isothermal trickle bed reactor using crude oil as a feedstock and commercial cobaltmolybdenum on alumina (Co-Mo/γ-Al2O3) as a catalyst. The reactor temperature was varied from 335°C to 400°C, the hydrogen pressure from 4 to10 MPa and the liquid hourly space velocity (LHSV) from 0.5 to 1.5 hr-1, keeping constant hydrogen to oil ratio (H2/Oil) at 250 L/L. The main hydrotreating reactions were hydrodesulfurization (HDS), hydrodenitrogenation (HDN), hydrodeasphaltenization (HDAs) and hydrodemetallization (HDM) that includes hydrodevanadization (HDV) and hydrodenickelation (HDNi). An optimization technique is used to evaluate the best kinetic models of a trickle-bed reactor (TBR) process utilized for HDS, HDAs, HDN, HDV and HDNi of crude oil based on pilot plant experiments. The minimization of the sum of the squared errors (SSE) between the experimental and estimated concentrations of sulfur (S), nitrogen (N), asphaltene (Asph), vanadium (V) and nickel (Ni) compounds in the products, is used as an objective function in the optimization problem using two approaches (linear (LN) and non-linear (NLN) regression). The growing demand for high-quality middle distillates is increasing worldwide whereas the demand for low-value oil products, such as heavy oils and residues, is decreasing. Thus, maximizing the production of more liquid distillates of very high quality is of immediate interest to refiners. At the same time, environmental legislation has led to more strict specifications of petroleum derivatives. Crude oil hydrotreatment enhances the productivity of distillate fractions due to chemical reactions. The hydrotreated crude oil was distilled into the following fractions (using distillation pilot plant unit): light naphtha (L.N), heavy naphtha (H.N), heavy kerosene (H.K), light gas oil (L.G.O) and reduced crude residue (R.C.R) in order to compare the yield of these fractions produced by distillation after the HDT process with those produced by conventional methods (i.e. HDT of each fraction separately after the distillation). The yield of middle distillate showed greater yield compared to the middle distillate produced by conventional methods in addition to improve the properties of R.C.R. Kinetic models that enhance oil distillates productivity are also proposed based on the experimental data obtained in a pilot plant at different operation conditions using the discrete kinetic lumping approach. The kinetic models of crude oil hydrotreating are assumed to include five lumps: gases (G), naphtha (N), heavy kerosene (H.K), light gas oil (L.G.O) and reduced crude residue (R.C.R). For all experiments, the sum of the squared errors (SSE) between the experimental product compositions and predicted values of compositions is minimized using optimization technique. The kinetic models developed are then used to describe and analyse the behaviour of an industrial trickle bed reactor (TBR) used for crude oil hydrotreating with the optimal quench system based on experiments in order to evaluate the viability of large-scale processing of crude oil hydrotreating. The optimal distribution of the catalyst bed (in terms of optimal reactor length to diameter) with the best quench position and quench rate are investigated, based upon the total annual cost. The energy consumption is very important for reducing environmental impact and maximizing the profitability of operation. Since high temperatures are employed in hydrotreating (HDT) processes, hot effluents can be used to heat other cold process streams. It is noticed that the energy consumption and recovery issues may be ignored for pilot plant experiments while these energies could not be ignored for large scale operations. Here, the heat integration of the HDT process during hydrotreating of crude oil in trickle bed reactor is addressed in order to recover most of the external energy. Experimental information obtained from a pilot scale, kinetics and reactor modelling tools, and commercial process data, are employed for the heat integration process model. The optimization problem is formulated to optimize some of the design and operating parameters of integrated process, and minimizing the overall annual cost is used as an objective function. The economic analysis of the continuous whole industrial refining process that involves the developed hydrotreating (integrated hydrotreating process) unit with the other complementary units (until the units that used to produce middle distillate fractions) is also presented. In all cases considered in this study, the gPROMS (general PROcess Modelling System) package has been used for modelling, simulation and parameter estimation via optimization process.

A utilização de microtubos vem crescendo especialmente em países pobres da Ásia e África, onde organizações internacionais lutam pelo desenvolvimento dos pequenos agricultores por meio da implantação de tecnologias de baixo custo. Dentro desse contexto e com o intuito de oferecer embasamento técnico-científico para o desenvolvimento de uma irrigação de baixo custo e alto nível tecnológico, este trabalho teve como objetivos: desenvolver um modelo matemático para dimensionamento de microtubos em que a perda de carga localizada, a perda de carga no microtubo e a energia de velocidade estivessem explícitos na equação; desenvolver um software para dimensionamento de microtubos, com base no modelo proposto; apresentar os custos e verificar a viabilidade técnica da utilização de microtubos em duas condições de campo: irrigação localizada por gravidade para hortas e irrigação pressurizada para pomares; e realizar simulações hidráulicas para verificar a influência da temperatura no desempenho hidráulico do sistema com microtubos. O modelo matemático que considerou constante o coeficiente K da equação de perda carga localizada pode ser utilizado para representar o fenômeno de perda de energia no microtubo, o mesmo representou melhor este fenômeno do que o modelo que não considera a perda de carga localizada, portanto a perda de carga localizada é um fator que deve ser considerado. O software para o dimensionamento de linhas laterais com microtubos proporcionou precisão e rapidez nos cálculos. Em condição de campo o sistema de irrigação com microtubos apresentou bom desempenho técnico. A proposta de utilização do sistema de irrigação localizada com microtubos por gravidade demonstrou possuir também vantagens econômicas, devido ao baixo custo de investimento, mão-de-obra e operação do sistema. A proposta de utilização do sistema de irrigação localizada com microtubos em pomares apresentou uma redução de 45,7% no custo com linhas laterais e emissores em comparação com tubos-gotejadores. Dentro das condições estudadas, a vazão média foi o parâmetro que sofreu a maior influência com a variação de temperatura. A cada 5ºC de aumento na temperatura da água, a vazão média aumentou em 5%, já a Uniformidade de Distribuição de água sofreu um efeito reduzido, visto que um aumento de 5ºC reduziu em apenas 1,2% o seu valor. / The use of microtubes has been increasing especially in poor countries of Asia and Africa, where international organizations struggle for the development of small farmers through the insertion of low cost technologies. Within this context and with the intention of offering technical and scientific background for the development of a low cost and high technological level irrigation, this work presented the following goals: to develop a mathematical model for microtubes design in which the localized head loss, the head loss in the microtube and the velocity head are clear in the math equation; to develop a software for microtubes design based on the proposed model; to present the costs and to verify the technical viability of the use of microtubes in two field conditions: gravity drip irrigation for vegetable gardens and pressured irrigation for orchards; and to perform hydraulic simulations to verify the temperature influence in the hydraulic performance of the systems with microtubes. The mathematical model, that considered constant the K coefficient of the localized head loss equation, can be used to represent the phenomenon of the power loss in the microtube; it represented this phenomenon better than the model that does not consider the localized head loss, therefore the localized head loss needs to be consider in the phenomenon. The software for the laterals design with microtubes provided precision and swiftness. In the field condition the irrigation system with microtubes showed good technical performance. The proposition for the use of the gravity drip irrigation system with microtubes also showed economical advantages due to the low investment cost, labor and system operation. The proposition for the use of drip irrigation with microtubes in orchards showed a cost reduction of 45.7% with laterals and emitters compared to in line emitters. In the analyzed conditions, temperature variation influenced the average discharge rate of the system. With 5ºC of increase in the water temperature, the average discharge increased in 5%, but temperature variation had little influence in water distribution uniformity, because an increase of 5ºC reduced only 1,2% in your value.

Orientador: Raimundo Leite Cruz / Banca: Antonio Evaldo Klar / Banca: Tarlei Arriel Botrel / Resumo: O uso de águas residuárias de esgoto doméstico tratado permite uma otimização dos recursos hídricos disponíveis, melhorando assim a sua oferta. O uso para fins agrícolas a cada dia se mostra uma possibilidade vantajosa de reúso, pois aceita o uso de águas com qualidade inferior ao exigido pelo abastecimento urbano e necessita de grandes quantidades. Segundo Almeida et al.(2006), a uniformidade possui maior importância quando o sistema de irrigação é utilizado para fazer a fertirrigação, pois, para o bom desempenho, é necessário o conhecimento das características hidráulicas do emissor e uniformidade de aplicação de água do sistema de irrigação utilizado. Diante desta realidade de reúso de efluentes para irrigação por gotejamento, o presente trabalho teve como objetivo determinar a vazão dos gotejadores, a curva relação vazão-pressão, a sua equação característica, o coeficiente de variação de vazão (CVQ), e também avaliar a uniformidade de aplicação de água, calculando os seguintes coeficientes: coeficiente de uniformidade de distribuição (CUD), o coeficiente de uniformidade de Christiansen (CUC) e o coeficiente de uniformidade estatístico (CUE), do tubo gotejador da marca Netafim, modelo Tiran 17, utilizado para a irrigação com água residuária de esgoto doméstico tratado.O experimento foi realizado em uma bancada de ensaios no Laboratório de Irrigação da UNESP-FCA, Campus de Botucatu-SP. Foi utilizado um segmento do tubo gotejador contendo 25 emissores, onde se mediu a vazão com as seguintes pressões: 40, 50, 80, 100, 120, 150, 200, 250, 300 kPa, com quatro repetições para cada gotejador. Após os ensaios, o tubo gotejador foi submetido a 1000 horas de trabalho com água residuária de esgoto doméstico tratado. Foram realizados os mesmos ensaios iniciais após 500 horas e 1000 horas de trabalho com água tratada... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The use of wastewater of treated household drain allows an optimization of available hydro resources, increasing the offer of a scarce product. The use in agriculture becomes, each day, more advantageous for its reuse due to its acceptance of water with a lower quality in view of the water demanded by the urban supply and the demanding of a great quantity. According to Almeida et al.(2006), the uniformity is more important when the system of irrigation is used to make the fertirrigation. For a good performance it's important to know the hydraulic characteristics of the emitter and uniformity of water application of the irrigation system. In order of the reuse of effluents for drip irrigation, this paper aims to determine the flow of drippers, the curve relation flow-pressure, its equation, the flow coefficient of variation (CVQ) as well as to evaluate the uniformity of water application by calculating the follow coefficients: distribution uniformity coefficient (CUD), Christiansen uniformity coefficient (CUC) and the statistical uniformity coefficient (CUE) of the drip pipeof the Netafim brand, model Tiran 17, used for irrigation with wastewater of treated household drain. The experiment was accomplished in a test bank in the Irrigation Laboratory of UNESP-FCA, Campus of Botucatu in São Paulo state. It was used 25 drippers where the flow was measured with increasing pressures of 40, 50, 80, 100, 120, 150, 200, 250, 300 kPa, with four repetitions for each dripper. After the tests the drip pipe was submitted to 1000 hours of work with wastewater of treated household drain. The same tests were carried out after 500 hours and 1000 hours of working but with treated water. The results of the new pipe after the 500 working hours with treated household effluents for CVQ, were classified as good, according to the ABNT (1987) chart. The CUD, CUC and CUE not only before but also... (Complete abstract click electronic access below) / Mestre

Made available in DSpace on 2016-06-02T19:55:30Z (GMT). No. of bitstreams: 1 DoutSMP.pdf: 1317200 bytes, checksum: 79dde377784158c00b81b651c941bf26 (MD5) Previous issue date: 2003-06-23 / Universidade Federal de Minas Gerais / A laboratory-scale investigation of SO2 scrubbing was carried out in a 77.92mm (diameter) × 80.00mm trickle bed with 2.00-2.36mm activated carbon particles using continuous and periodically interrupted liquid flows. The effects of cycle period (10 and 20 minutes), cycle split (0.1, 0.2 and 0.3), superficial gas velocity (20, 40 and 60mm/s), and superficial liquid velocity (2mm/s) on SO2 removal and sulfuric acid production were investigated using a simulated flue gas containing SO2 at 500, 1,000 and 1,500ppm. The average removal efficiency of the periodic operation varied from 40 to almost 100%. The major variables controlling periodic operation performance were found to be the superficial gas velocity and the SO2 concentration. The extent of SO2 removal increased with decreasing cycle period and increasing split. Continuous operation runs achieved practically 100% scrubbing efficiency in all tests performed. Sulfuric acid production rates ranged from 0.649×10-8 to 0.256×10-7mol/g catalyst.s. The concentration of sulfuric acid produced was proportional to both the initial SO2 concentration and the gas superficial velocity. Some sulfuric acid production rates data for periodic operation overlapped those obtained in continuous liquid flow experiments. The advantage for the periodic operation was the higher acid concentrations produced and the lower pressure drops across the trickle bed without carbon losses. However, sulfuric acid production should not be regarded as an end in itself for the periodic operation, as the main goal of this gas treatment route is the removal of sulfur dioxide. / O desempenho dos modos periódico e contínuo de operação para o tratamento de uma mistura gasosa de SO2 em ar foi analisado utilizando-se um reator de aço inox, em escala de bancada de 77,92mm de diâmetro interno, contendo leito fixo de carvão ativado de 80,00mm de altura, com partículas de 2,00 a 2,36mm. Foram obtidas as eficiências médias de remoção do gás e as concentrações de ácido sulfúrico produzido nas soluções líquidas de saída, em função da concentração inicial de SO2 (500, 1.000 e 1.500ppm), da velocidade superficial do gás (20, 40 e 60mm/s), da velocidade superficial do líquido (2mm/s) e, no caso da operação periódica, da duração dos ciclos (períodos de 10 e 20 minutos) e da fração de descarga (0,1, 0,2 e 0,3). A eficiência média de remoção da operação periódica variou de 40 a aproximadamente 100%. O desempenho do processo sofreu maior influência da variação da velocidade superficial do gás e de sua concentração inicial. A remoção do dióxido de enxofre foi mais efetiva ao se diminuir o período e se aumentar a fração de descarga. Com a operação contínua foram obtidas eficiências médias de remoção de aproximadamente 100% em todos os casos. As taxas de produção de ácido sulfúrico variaram entre 0,649×10-8 e 0,256×10-7mol/g catalisador.s. Em alguns casos, a operação periódica foi responsável por taxas de produção de ácido sulfúrico maiores que as da operação em estado estacionário. A concentração de ácido produzido foi proporcional à concentração inicial e à velocidade superficial do gás. Os resultados indicam que a vantagem da interrupção periódica do escoamento de líquido é o potencial para produção de ácido sulfúrico mais concentrado com menor perda de carga no leito sem perdas expressivas de carvão. Porém, a produção de ácido sulfúrico não deve ser encarada como um fim em si para a operação periódica, uma vez que o principal objetivo dessa via de tratamento do gás é o abatimento do dióxido de enxofre.

A utilização de microtubos vem crescendo especialmente em países pobres da Ásia e África, onde organizações internacionais lutam pelo desenvolvimento dos pequenos agricultores por meio da implantação de tecnologias de baixo custo. Dentro desse contexto e com o intuito de oferecer embasamento técnico-científico para o desenvolvimento de uma irrigação de baixo custo e alto nível tecnológico, este trabalho teve como objetivos: desenvolver um modelo matemático para dimensionamento de microtubos em que a perda de carga localizada, a perda de carga no microtubo e a energia de velocidade estivessem explícitos na equação; desenvolver um software para dimensionamento de microtubos, com base no modelo proposto; apresentar os custos e verificar a viabilidade técnica da utilização de microtubos em duas condições de campo: irrigação localizada por gravidade para hortas e irrigação pressurizada para pomares; e realizar simulações hidráulicas para verificar a influência da temperatura no desempenho hidráulico do sistema com microtubos. O modelo matemático que considerou constante o coeficiente K da equação de perda carga localizada pode ser utilizado para representar o fenômeno de perda de energia no microtubo, o mesmo representou melhor este fenômeno do que o modelo que não considera a perda de carga localizada, portanto a perda de carga localizada é um fator que deve ser considerado. O software para o dimensionamento de linhas laterais com microtubos proporcionou precisão e rapidez nos cálculos. Em condição de campo o sistema de irrigação com microtubos apresentou bom desempenho técnico. A proposta de utilização do sistema de irrigação localizada com microtubos por gravidade demonstrou possuir também vantagens econômicas, devido ao baixo custo de investimento, mão-de-obra e operação do sistema. A proposta de utilização do sistema de irrigação localizada com microtubos em pomares apresentou uma redução de 45,7% no custo com linhas laterais e emissores em comparação com tubos-gotejadores. Dentro das condições estudadas, a vazão média foi o parâmetro que sofreu a maior influência com a variação de temperatura. A cada 5ºC de aumento na temperatura da água, a vazão média aumentou em 5%, já a Uniformidade de Distribuição de água sofreu um efeito reduzido, visto que um aumento de 5ºC reduziu em apenas 1,2% o seu valor. / The use of microtubes has been increasing especially in poor countries of Asia and Africa, where international organizations struggle for the development of small farmers through the insertion of low cost technologies. Within this context and with the intention of offering technical and scientific background for the development of a low cost and high technological level irrigation, this work presented the following goals: to develop a mathematical model for microtubes design in which the localized head loss, the head loss in the microtube and the velocity head are clear in the math equation; to develop a software for microtubes design based on the proposed model; to present the costs and to verify the technical viability of the use of microtubes in two field conditions: gravity drip irrigation for vegetable gardens and pressured irrigation for orchards; and to perform hydraulic simulations to verify the temperature influence in the hydraulic performance of the systems with microtubes. The mathematical model, that considered constant the K coefficient of the localized head loss equation, can be used to represent the phenomenon of the power loss in the microtube; it represented this phenomenon better than the model that does not consider the localized head loss, therefore the localized head loss needs to be consider in the phenomenon. The software for the laterals design with microtubes provided precision and swiftness. In the field condition the irrigation system with microtubes showed good technical performance. The proposition for the use of the gravity drip irrigation system with microtubes also showed economical advantages due to the low investment cost, labor and system operation. The proposition for the use of drip irrigation with microtubes in orchards showed a cost reduction of 45.7% with laterals and emitters compared to in line emitters. In the analyzed conditions, temperature variation influenced the average discharge rate of the system. With 5ºC of increase in the water temperature, the average discharge increased in 5%, but temperature variation had little influence in water distribution uniformity, because an increase of 5ºC reduced only 1,2% in your value.

This essay aims to establish a marxist perspective upon a phenomena that could be seen as typical neoliberal–femvertising. I have noticed an expanding trend in fashion; the use of feminism as branding. Fashion brands such as Dior and H&M have lately profiled themselves with feminism, framing it as radical as well as feminist. Meanwhile, the theory of reification by Georg Lukács claims that capitalism fools us to believe that we may acccomplish human aims and characteristics through commodities. I will investigate if it is possible to look upon this phenomena as an example of reification? The attempt brings the capitalistic dimension of femvertising into daylight and questions it´s feminist pretense.

Residence time distributions have become an important analytical tool in the analysis of many types of flow systems. Residence time distributions have proven to be effective for analysing trickle bed reactors, as it allows determination of parameters under operating conditions allowing no interference of these conditions. By studying the residence time distribution a great amount of information can be obtained and therefore used to determine a number of hydrodynamic parameters. Due to recent findings that prewetting has a tremendous effect on a number of hydrodynamic parameters such as holdup, wetting efficiency and pressure drop, it is therefore the aim of this study to investigate the effect of trickle flow morphology or prewetting on a trickle bed reactor. The residence time distribution is obtained whereby hydrodynamic parameters are determined and therefore the effect the flow morphology has on various hydrodynamic parameters is highlighted. A number of methods were used to determine these parameters, namely that of the best-fit method, whereby the PDE model was used, and the method of moments. Operating conditions included varying gas and liquid flow rates for porous and non-porous catalyst particles at atmospheric pressure. The different prewetting procedures used during this work included the following: <ul><li>Non-wetted </li> <li>Levec-wetted </li> <li>Super-wetted</li></ul> From this investigation the following conclusions were made: <li>Prewetting has a great effect on the hydrodynamic parameters of trickle bed reactors</li> <li>The differences in prewetting can be attributed to differing flow morphologies for the different prewetted beds i.e. the dominant flow morphology for a non-wetted bed is that of rivulets and for prewetted beds that of film flow</li> <li>It was also found that at low liquid flow rates the flow morphology in prewetted beds changes from film flow to a combination of rivulet and film flow</li> <li>The different flow morphologies for prewetted and non prewetted beds was confirmed by the residence time distributions and various parameters obtained there from</li> <li>At low liquid flow rates the flow morphology becomes a more predominant factor in creating the tailing effect present in residence time distribution for prewetted beds</li> <li>The tailing effect in residence time distributions is a result of both internal diffusion and liquid flow morphology, where the liquid flow morphology is the more dominant factor</li> <li>The use of residence time distributions to determine a number of hydrodynamic parameters proved to be very useful and accurate by means of different methods, i.e. method of moments and best-fit method</li> <li>Differences in the liquid holdup determined from the method of moments and the weighing method confirmed that different flow morphologies exist for different prewetted beds</li> <li>An increase in the dispersion coefficient with prewetting was observed indicating that the amount of micro mixing is different for the different prewetted beds</li> <li>Differences in residence times and high values for the dynamic holdup, for the porous packing, confirmed that the PDE model does not model well the porous packing response curves due to the lack of internal diffusion and internal holdup in this model</li> <li>The dynamic-static mass transfer showed that film flow, as in prewetted beds, results in slower mass transfer as opposed to rivulet flow and therefore it is concluded that prewetting results in different flow morphologies.</li></ul> Following this study it is recommended that a residence time distribution model be used or developed that incorporates the effects of internal diffusion and internal holdup as present in porous catalyst particles. In addition, it was found that very few correlations could accurately predict hydrodynamic parameters due to the absence of the effect of prewetting and therefore it is recommended that correlations be developed that incorporate the effect of prewetting. / Dissertation (MEng)--University of Pretoria, 2008. / Chemical Engineering / unrestricted

News reports in relation to criminality are often considered a trustworthy and factual source of information. However, media consumers often disregard the discourses within the content they consume as well as the power structures it reproduces. News criminality discourses, in particular, are expressions of power that contextualize and shape identity configurations as well as social relations. It is these discourses that reproduce patterns of inequality in a trickle-down manner. Following a period of mass immigration, the Swedish crime and criminality discourse has blended with the immigration discourse in news articles with ethnonationalist undertones. With the purpose to identify the descriptions of different entities and agents depicted in the crime and criminality discourse and the relationships the press establishes between these groups, this thesis applies elements from Critical Discourse Analysis to analyze 72 newspaper articles (36 from Aftonbladet and 36 from Expressen). This analysis highlights the presence of a spectrum of righteousness by which the press places European identities on the right end of the spectrum opposite to nonwestern immigrant identities. Such discourses elevate European identities and legitimize intolerant attitudes which limit newcomers’ access to resources and opportunities for upward social mobility. Additionally, this analysis relates previous findings to the Swedish context and presents possible implications that the blending of these discourses has had on the integration process and social cohesion overall.