The publication and interchange of RDF datasets online has experienced significant growth in recent years, promoted by different but complementary efforts, such as Linked Open Data, the Web of Things and RDF stream processing systems. However, the current Linked Data infrastructure does not cater for the storage and exchange of sensitive or private data. On the one hand, data publishers need means to limit access to confidential data (e.g. health, financial, personal, or other sensitive data). On the other hand, the infrastructure needs to compress RDF graphs in a manner that minimises the amount of data that is both stored and transferred over the wire. In this paper, we demonstrate how HDT - a compressed serialization format for RDF - can be extended to cater for supporting encryption. We propose a number of different graph partitioning strategies and discuss the benefits and tradeoffs of each approach.

Submitted by Fabio Sobreira Campos da Costa (fabio.sobreira@ufpe.br) on 2016-07-28T15:36:12Z No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) Dissertação de mestrado - Douglas Fernandes de Albuquerque - Eng. Química UFPE.pdf: 3870346 bytes, checksum: 5761fe7b587741384858becbacc00121 (MD5) / Made available in DSpace on 2016-07-28T15:36:12Z (GMT). No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) Dissertação de mestrado - Douglas Fernandes de Albuquerque - Eng. Química UFPE.pdf: 3870346 bytes, checksum: 5761fe7b587741384858becbacc00121 (MD5) Previous issue date: 2016-02-25 / CAPEs / Devido à formulação de leis mais rigorosas com relação à preservação do meio ambiente, sobretudo no que diz respeito ao teor de enxofre presente nos combustíveis fósseis, as refinarias de todo o mundo estão sendo desafiadas a adequarem seus processos de refino a condições operacionais mais severas, que permita a produção dos derivados do petróleo de ultrabaixo teor de enxofre. Maior atenção é dada aos destilados intermediários, tais como a gasolina e o óleo diesel, por apresentaram vasta empregabilidade no setor de transporte, que é por sua vez o setor da economia que mais consome combustíveis fósseis. Sendo o derivado de petróleo mais consumido no setor de transportes e responsável por grande parcela da emissão de compostos tóxicos durante a queima em motores de combustão, o óleo diesel é hoje submetido a normas legais que limitam o teor de enxofre para 10 mg/kg, o que torna mais difícil o processamento do destilado, uma vez que o petróleo utilizado está cada vez mais pesado. Diante disso, no presente trabalho uma unidade de hidrotratamento de diesel oriundo de um petróleo pesado foi modelada e simulada em estado estacionário, utilizando o software Aspen HYSYS® como ferramenta computacional, sendo avaliados os principais parâmetros de processos e o desempenho da unidade frente a suas variações, com o objetivo de determinar condições de trabalho que garantissem uma produção de óleo diesel com no máximo 10 mg/kg de enxofre, obtendo simultaneamente um alto rendimento de produção. Inicialmente foram propostas algumas hipóteses e as condições operacionais da unidade com base em dados relatados na literatura. De acordo com as condições de trabalho empregadas, foi possível atingir um óleo diesel tratado com 3,55 mg/kg de enxofre, 3,21 mg/kg de nitrogênio e 0,03 mg/kg de água, alcançando uma recuperação de 81,00 m/m% dos compostos constituintes da faixa de destilação do óleo diesel presentes na carga da unidade. Em conjunto também foi analisado o gasto energético da unidade a fim de se obter uma estimativa da viabilidade econômica do processo, sendo constatado que as utilidades e as colunas conferem os maiores consumos de energia. Com base nas análises de sensibilidade realizadas, ainda foi possível estabelecer a relação entre os resultados analisados em cada seção da unidade e os parâmetros envolvidos no controle dos mesmos. E a partir das respostas obtidas, foi elaborada a otimização do processo a partir da Metodologia de Superfície de Resposta através do emprego do software Statistica, conferindo condições mais eficientes de trabalho, garantindo assim a produção de um óleo mais purificado, contendo cerca de 0,10 mg/kg de enxofre, com maior recuperação dos compostos do diesel (aproximadamente 85,11 m/m%), além de gerar menores gastos energéticos, alcançando uma redução de 16,54 % referente à simulação mantida nas condições padrão de trabalho. Em adição, no caso otimizado ainda foi possível atingir maiores valores de recuperação dos demais cortes de petróleo constituintes da alimentação da unidade. / Due to the development of stricter laws regarding the preservation of the environment, especially in relation to the sulfur content in fossil fuels, refineries around the world are being challenged to adapt their refining processes to more severe operating conditions, that they are able to product ultra-low sulfur petroleum distillates. Greater attention is given to intermediate distillates, such as gasoline and diesel oil, due to their extensive employment in the transport sector, which is the sector of the economy that consumes more fossil fuels. Diesel oil is the petroleum product most consumed in the transportation sector and accounts for a large portion of the emission of toxic compounds during combustion in engines, this way diesel is now subject to legal rules that limit the sulfur content to 10 mg/kg, which complicates the processing of the distillate, since the petroleum used is heavier. Therefore, in this paper a unit of diesel hydrotreating come from a heavy oil was modeled and simulated in steady state, using the Aspen HYSYS® software as computational tool, and the main process parameters and performance unit against their variations are evaluated, by purpose of determining working conditions that would ensure diesel production with a maximum of 10 mg/kg of sulfur, at the same time achieving a high production yield. Initially some hypotheses and unit operating conditions were proposed based on data reported in the literature. According to the working conditions employed, it was possible to achieve a diesel fuel treated with 3.55 mg/kg sulfur, 3.21 mg/kg nitrogen and 0.03 mg/kg water, obtaining 81.00 wt% recovery of constituent compounds of distillation range of diesel oil present in the unit load. Together it was also analyzed the energy expenditure of the unit in order to obtain an estimate of the economic viability of the process, and it was found out that the utilities and columns required the highest energy consumption. Based on the sensitivity analysis performed, it was still possible to establish the relationship between the results analyzed in each section of the unit and the parameters involved in their control. Since the answers were obtained, the optimization of the process through the Response Surface Methodology by using the Statistica software was developed, providing more efficient working conditions, thus ensuring the production of more purified oil, containing about 0.10 mg/kg of sulfur, with greater recovery of the compounds of diesel (about 85.11 wt%), besides generating lower energy costs, achieving a reduction of 16.54% referring to the simulation maintained in standard working conditions. In addition, the optimized case was still possible to achieve higher recovery value of other of petroleum distillates, which were constituents of the unit feed.

Submitted by Irene Nascimento (irene.kessia@ufpe.br) on 2016-10-13T19:12:36Z No. of bitstreams: 1 Dissertação de Mestrado PPEQ - Alexsandro Fausto de Araújo.pdf: 3235090 bytes, checksum: e4c74119c72ea3471a47fb36a515e632 (MD5) / Made available in DSpace on 2016-10-13T19:12:36Z (GMT). No. of bitstreams: 1 Dissertação de Mestrado PPEQ - Alexsandro Fausto de Araújo.pdf: 3235090 bytes, checksum: e4c74119c72ea3471a47fb36a515e632 (MD5) Previous issue date: 1998-11-13 / Com a crescente exigência dos mercados e da sociedade por produtos derivados do petróleo cada vez mais livres de contaminantes que prejudicam o meio ambiente e a qualidade dos mesmos, os parques de refino de petróleo vêm investindo cada vez mais em tecnologias que permitam uma produção mais limpa, rentável e econômica. Desse modo, O hidrotratamento tem assumido um papel cada vez mais importante dentro das refinarias, sendo aplicado em diversos cortes do petróleo, desde os mais leves até os mais pesados. O hidrotratamento consiste na adição de hidrogênio na carga a ser hidrotratada com o propósito de, através de reações de hidrogenação, reduzir ou eliminar os componentes contaminantes presentes na carga, como o enxofre, nitrogênio, oxigênio, olefinas, diolefinas e metais. A adição de hidrogênio é feita em cocorrente descendente, onde a carga e o hidrogênio entram misturados e pré aquecidos no topo do reator a uma razão pré-definida (Razão H2/Carga), sendo esta forma a mais utilizada em escala industrial devido aos seus inúmeros benefícios. O foco da unidade de HDT é o reator, pois é nele que os contaminantes são removidos da carga. O tipo de reator mais utilizado é o de leito fixo (Trickle Bed Reactor - TBR). A nafta é a principal matéria prima do setor petroquímico nacional, de modo que todas as unidades instaladas são baseadas nela. A partir dela são produzidos os componentes da primeira geração do setor petroquímico. O HDT de nafta ainda é um tema pouco explorado mas que vem recebendo maior importância nos últimos anos. Por isso, este trabalho foi desenvolvido sobre esse tema, construindo e simulando modelos dinâmicos de reatores de leito fixo, com alimentação em cocorrente de uma unidade reacional de HDT de nafta, composta por um reator trifásico de conversão de diolefinas, utilizado para o pré-tratamento da nafta de coqueamento retardado e dois reatores bifásicos (G-S) de HDT de nafta, dispostos em série com resfriamento por quenchs independentes entre os leitos dos reatores e entre os reatores, para a redução de teores de enxofre, nitrogênio e olefinas presentes na nafta através das reações de hidrodessulfurização, hidrodesnitrogenação e saturação de olefinas. Foram construídos dois programas em ambiente MATLAB®, um para simular o reator trifásico de conversão diolefinas e outro para os reatores bifásicos de HDT de nafta, ambos simularam correntes de alimentação de nafta com diferentes níveis de contaminação, para que fossem avaliados os efeitos. Os programas simularam os perfis dinâmicos das temperaturas das fases envolvidas e das concentrações dos contaminantes e hidrogênio. Os resultados obtidos para o reator de conversão de diolefinas e os reatores de HDT de nafta se mostraram bem coerentes com relação aos fenômenos envolvidos. O reator de conversão de diolefinas atingiu o estado estacionário aos 80 minutos e os reatores de HDT de nafta aos 2 minutos, com os teores de contaminantes próximos de zero na saída do reator. Os resultados das simulações realizadas para os dois tipos de nafta apresentaram perfis dinâmicos semelhantes diferindo apenas quanto à temperatura mais elevada atingida no início do primeiro reator de HDT de nafta no caso da nafta com maior teor de contaminação. / With the growing demand of markets and society by oil products increasingly free of contaminants that harm the environment and their quality, oil refining plants have been increasingly investing in technologies to cleaner production, profitable and economical. Thus, the hydrotreating has assumed an increasingly important role in the refinery and is used in many petroleum cuts, from the lightest to the heaviest. The hydrotreating is the addition of hydrogen in the load to be hydrotreated in order to, via hydrogenation reactions, reduce or eliminate the contaminating components present in the load, such as sulfur, nitrogen, oxygen, olefins, diolefins and metals. The addition of hydrogen is done in descending current, where load and hydrogen enter mixed and pre heated at the top of the reactor to a pre-defined (ratio H2/Oil), and this way the most used at industrial scale due to its numerous benefits. The focus of the HDT unit is the reactor, because that is where the contaminants are removed from the load. The most used type of reactor is the fixed bed (Trickle Bed Reactor - TBR). Naphtha is the main raw material of the national petrochemical industry, so that all installed units are based on it. From there, the components of the first generation of the petrochemical industry are produced. The naphtha HDT is still a subject little explored but it's getting more important in recent years. Therefore, this study was conducted on this issue, building and simulating dynamic models of fixed bed reactors with feed in cocurrente of a reactional unit of HDT naphtha, consisting of a three-phase reactor diolefins conversion, used for pretreatment naphtha delayed coking and two dual-phase reactors (G-S) naphtha HDT arranged in series with cooling by independent quenchs between beds of the reactor and between the reactors to reduce contents of sulfur, nitrogen and olefins present in the naphtha through reactions of hydrodesulfurization, hidrodesnitrogenação and saturation of olefins. Were built two programs in MATLAB®, one to simulate the three-phase reactor diolefins conversion and one for the dual-phase reactors naphtha HDT, both simulated currents naphtha feed with different levels of contamination, so that the effects are assessed. The simulated programs dynamic profiles of the temperatures of the phases involved and the concentrations of contaminants and hydrogen. The results obtained for diolefins conversion reactor and the reactors of naphtha HDT were well consistent with relation to the phenomena involved. The diolefins conversion reactor reached steady state at 80 minutes and the HDT reactors naphtha after 2 minutes, with near zero contaminant levels in the reactor output. The results of simulation performed for the two types of naphtha showed similar dynamic profiles differing only as to the highest temperature reached at the beginning of the first naphtha HDT reactor in the case of naphtha higher contamination level.

Com o aumento do processamento de petróleos mais pesados, torna-se interessante realizar um estudo dos possíveis mecanismos de deterioração que poderão ocorrer em função do aumento do Índice de Acidez Total (IAT). Dessa forma, o presente trabalho teve como objetivo principal avaliar as linhas e equipamentos que compõe a bateria de pré-aquecimento da carga de uma unidade de Hidrotratamento (HDT) de diesel. Esse trecho teoricamente está susceptível a ocorrência de corrosão por ácidos naftênicos devido a dois principais fatores: a presença desses ácidos com teores de neutralização superiores a 0,5 mg KOH/g na composição química da carga e a temperatura de processamento, que se encontra em um intervalo de 200 a 400ºC, adequado para existência de tal mecanismo de deterioração. Os dados obtidos em campo referentes à taxa de corrosão das linhas e dos equipamentos foram parametrizados em suas variáveis operacionais e através de uma análise comparativa com dados encontrados na literatura foram obtidas informações importantes para avaliar a ocorrência de corrosão naftênica. / With the increased processing of heavier oils, it is interesting a study of possible mechanisms of deterioration that may occur due to the increase of the Total Acid Number (TAN). Thus, this study aims to evaluate the main lines and equipment that comprise the battery of preheating of the load of a unit of Hydrotreating (HDT) of diesel. This excerpt is theoretically likely to occur from corrosion by naphthenic acids due to two main factors: the presence of these acids with levels of neutralizing more than 0.5 mg KOH/g in the chemical composition of the load and the temperature of processing, which is in a range from 200 º C to 400 º C, suitable for the existence of such a deterioration mechanism. Data from field concerning to the rate of corrosion of the lines and equipment were parameterized in their operational variables and through a comparative analysis with data found in literature were obtained important information to evaluate the occurrence of naphthenic corrosion.

Com o aumento do processamento de petróleos mais pesados, torna-se interessante realizar um estudo dos possíveis mecanismos de deterioração que poderão ocorrer em função do aumento do Índice de Acidez Total (IAT). Dessa forma, o presente trabalho teve como objetivo principal avaliar as linhas e equipamentos que compõe a bateria de pré-aquecimento da carga de uma unidade de Hidrotratamento (HDT) de diesel. Esse trecho teoricamente está susceptível a ocorrência de corrosão por ácidos naftênicos devido a dois principais fatores: a presença desses ácidos com teores de neutralização superiores a 0,5 mg KOH/g na composição química da carga e a temperatura de processamento, que se encontra em um intervalo de 200 a 400ºC, adequado para existência de tal mecanismo de deterioração. Os dados obtidos em campo referentes à taxa de corrosão das linhas e dos equipamentos foram parametrizados em suas variáveis operacionais e através de uma análise comparativa com dados encontrados na literatura foram obtidas informações importantes para avaliar a ocorrência de corrosão naftênica. / With the increased processing of heavier oils, it is interesting a study of possible mechanisms of deterioration that may occur due to the increase of the Total Acid Number (TAN). Thus, this study aims to evaluate the main lines and equipment that comprise the battery of preheating of the load of a unit of Hydrotreating (HDT) of diesel. This excerpt is theoretically likely to occur from corrosion by naphthenic acids due to two main factors: the presence of these acids with levels of neutralizing more than 0.5 mg KOH/g in the chemical composition of the load and the temperature of processing, which is in a range from 200 º C to 400 º C, suitable for the existence of such a deterioration mechanism. Data from field concerning to the rate of corrosion of the lines and equipment were parameterized in their operational variables and through a comparative analysis with data found in literature were obtained important information to evaluate the occurrence of naphthenic corrosion.

Com o aumento do processamento de petróleos mais pesados, torna-se interessante realizar um estudo dos possíveis mecanismos de deterioração que poderão ocorrer em função do aumento do Índice de Acidez Total (IAT). Dessa forma, o presente trabalho teve como objetivo principal avaliar as linhas e equipamentos que compõe a bateria de pré-aquecimento da carga de uma unidade de Hidrotratamento (HDT) de diesel. Esse trecho teoricamente está susceptível a ocorrência de corrosão por ácidos naftênicos devido a dois principais fatores: a presença desses ácidos com teores de neutralização superiores a 0,5 mg KOH/g na composição química da carga e a temperatura de processamento, que se encontra em um intervalo de 200 a 400ºC, adequado para existência de tal mecanismo de deterioração. Os dados obtidos em campo referentes à taxa de corrosão das linhas e dos equipamentos foram parametrizados em suas variáveis operacionais e através de uma análise comparativa com dados encontrados na literatura foram obtidas informações importantes para avaliar a ocorrência de corrosão naftênica. / With the increased processing of heavier oils, it is interesting a study of possible mechanisms of deterioration that may occur due to the increase of the Total Acid Number (TAN). Thus, this study aims to evaluate the main lines and equipment that comprise the battery of preheating of the load of a unit of Hydrotreating (HDT) of diesel. This excerpt is theoretically likely to occur from corrosion by naphthenic acids due to two main factors: the presence of these acids with levels of neutralizing more than 0.5 mg KOH/g in the chemical composition of the load and the temperature of processing, which is in a range from 200 º C to 400 º C, suitable for the existence of such a deterioration mechanism. Data from field concerning to the rate of corrosion of the lines and equipment were parameterized in their operational variables and through a comparative analysis with data found in literature were obtained important information to evaluate the occurrence of naphthenic corrosion.

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.

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/¿-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. / Tikrit University, Iraq

Se realizó el estudio de las propiedades térmicas y mecánicas de mezclas de Poli(Etilén Tereftalato) (PET) con resinas poliméricas basadas enl Bisfenol-A: Poli(Carbonato de Bisfenol-A) (PC) y Poli(Hidroxi-Éter de Bisfenil-A) (PHEB), en contenidos no superiores a un 30% en peso de estos polímeros y preparadas por extrusión doble-husillo.Una evaluación físico-química (ft-IR, densidad y MVR) de ambos sistemas indicó que pueden ocurrir reacciones de transesterificación, principalmente entre el PET y el PC y verificado vía DSC y DMTA, mientras que dichas reacciones tienen una baja extensión en el caso del PHEB, principalmente evidenciado en la pérdida de la capacidad de cristalización del PET (sin mayores cambios en su transición vítrea) en presencia de PC y casi invariabilidad al adicionar PHEB. Con el apoyo de SEM se verificó la presencia de fases ricas de ambos componentes en las mezclas en todo el rango de composiciones, verificándose el carácter inmiscible de ambos sistemas.A través de un fraccionamiento térmico por Autonucleaciones y Recocidos Sucesivos (SSA) y medidas del MVR, ensayos que favorecieron la transesterificación, se estableció que ésta promueve un aumento de la masa molecular en ambos sistemas, donde en las mezclas PET/PC esto se da por reacciones de extensión de cadena y que en las mezclas PET/PHEB conducen a la formación de ramificaciones largas y entrecruzamientos.Las propiedades mecánicas a tracción y flexión indicaron un aumento de la resistencia mecánica y deformabilidad a mayor contenido de fase bisfenólica, al observarse un aumento de los parámetros característicos de estos ensayos, donde módulos elásticos y tensiones siguieron generalmente una desviación positiva de la "Ley Aditiva de Mezcla" (LAM). Tales tendencias indicaron un efecto rigidizante de la fase bisfenólica combinado con interacciones fuertes entre los componentes que favoreció la transmisión de tensiones y la deformabilidad de la mezcla, existiendo una compatibilidad mecánica aceptable al menos a bajas velocidades de deformación, principalmente en las mezclas PET/PC en donde hay evidencias de un aumento en la tenacidad. Se verificó que hay mejoras en la Resistencia al Impacto tanto caída de dardo como pendular al menos hasta un 20% de PC, superando a las mezclas PET/PHEB las cuales manifestaron una fuerte sensibilidad a la entalla.En el análisis de la fractura a través de la Mecánica de la Fractura Elástico Lineal (LEFM) a altas velocidades y el Trabajo Esencial de Fractura (EWF) a bajas velocidades de solicitación, para contenido no superiores a 10% de fase PC y PHEB donde la morfología de fases fue comparable (partículas), se tiene que los parámetros de fractura fueron siempre superiores para las mezclas PET/PC, con una tendencia general de que el PC aporta mejoras a estos parámetros respecto al PET, mientras que el PHEB no los afecta o tiende a disminuirlos. Esto sugiere que que la adhesión interfacial es un factor determinante que favorece la transmisión de tensiones, particularmente favorable en las mezclas PET/PC por su mayor reactividad.A mayores contenidos de fase bisfenólica, el comportamiento es más complejo como consecuencia del particular balance entre tamaño, geometría y orientación de la fase dispersa que tiende a dominar sobre la adhesión interfacial, detectándose procesos de cavitación en la mayoría de las condiciones de ensayos que promovieron pocas mejoras o decaimiento en los parámetros de fractura respecto al PET. Cabe destacar que los parámetros de fractura LEFM indicaron que todos los materiales presentaron una fractura en condiciones mixtas con una componente importante de tensión plana, con excepción de las mezclas PET/PHEB que corresponderían a condiciones de deformación plana, todo lo cual fue corroborado a través del análisis fractográfico.