Yes / Phenol and phenolic derivatives found in different industrial effluents are highly toxic and extremely harmful to human and the aquatic ecosystem. In the past, trickle bed reactor (TBR), reverse osmosis (RO) and other processes have been used to remove phenol from wastewater. However, each of these technologies has limitations in terms of the phenol concentration in the feed water and the efficiency of phenol rejection rate. In this work, an integrated hybrid TBR-RO process for removing high concentration phenol from wastewater is suggested and model-based simulation of the process is presented to evaluate the performance of the process. The models for both TBR and RO processes were independently validated against experimental data from the literature before coupling together to make the hybrid process. The results clearly show that the combined process significantly improves the rejection rate of phenol compared to that obtained via the individual processes.

Wastewater treatment and re-use of industrial process water is a critical issue for the suitable development of human activities. The need for effective water recycling has reinforced the research on tailored low cost pollution abatement since the existing solutions are not longer universal. In particular, the emerging Catalytic Wet Air Oxidation (CWAO) process is one of the most promising technologies for the remediation of moderately concentrated and/or biotoxic water pollutants, when a stable and active catalyst can be provided. To this purpose, the catalytic activity and stability of active carbon was tested in the CWAO of the target compound, phenol, at mild conditions of temperature and pressure. The active carbon, which is a relatively inexpensive catalytic material is shown to be stable and to yield higher phenol destruction and less toxic partial mineralisation products, compared to a widely used copper oxide catalyst. During the CWAO of phenol, numerous partial oxidation products appeared and the knowledge of the kinetics that control their oxidation process is fundamental for the design, modelling and scale up of CWAO pilot plant or industrial units. Complex kinetic modelling was undertaken using both the classical gradient based method and a stochastic algorithm termed Simulated Annealing (SA). SA was shown to perform better in the identification of multiparameter kinetic reaction schemes, allowing to improve the kinetic modelling of CWAO beyond the actual state of art in this field. Detailed kinetic analysis of CWAO is scarce in the literature and the same situation holds for engineering studies. There is a clear need for the simultaneous development of process chemistry and engineering aspects. Consequently, we parallely focused on the state of art modelling of a Trickle Bed Reactor (TBR), being the priority candidate of best performing CWAO reactor. First, the ability of TBR in CWAO was affirmed by appropriate experimental comparison of batch slurry reactor and continuous fixed bed reactors operating either in the cocurrent downflow mode (TBR), or upflow mode (FBR) of the gas and liquid flow. A phenomenological transport-reaction model of the TBR was then developed and programmed. The TBR model implements the previously obtained oxidation kinetics and emphasis on important aspects of TBR, namely catalyst wetting, and mass transfer between the phases. Non-isothermal operation is also accounted for to face the need for autothermal operation, lowering the global process costs. The validation of the model was successfully done with the available experimental data from the laboratory TBR and thus provided a reliable tool for the scale up study of the CWAO process. The outcomings of this model aided scale up, allow to give recommendation on the design and operation of industrial units, thereby making more reliable the implementation of CWAO units on an industrial level. / El tratamiento y el reciclaje de afluentes acuosos son de máximo interés para conseguir un desarrollo sostenible de las actividades humanas. La necesidad de aprovechar en un futuro cercano las aguas residuales de procesos industriales de un modo eficaz ha reforzado la investigación sobre métodos de bajo coste para su recuperación, dado que las tecnologías existentes ya no son universalmente aplicables. La oxidación catalítica por vía húmeda (CWAO) es uno de los procesos emergentes más prometedores particularmente para el tratamiento de aguas contaminadas con materia orgánica, en concentraciones medio altas, y/o biotóxica. Sin embargo, la implementación del método es adecuada siempre que se use un catalizador activo y estable. Con este propósito, la actividad catalítica y la estabilidad del carbón activo se ha comprobado en la CWAO usando como compuesto modelo el fenol. En condiciones de temperatura y presión moderadas el carbón activo ha demostrado ser un material catalítico barato, que a la vez, es estable, mas activo en la conversión de fenol, además produciendo menor cantidad de productos de oxidación parcial tóxicos que los catalizadores soportados convencionales. Durante la CWAO del fenol, numerosos productos intermedios se forman, por lo que el conocimiento de la cinética de su oxidación es fundamental para el diseño, modelización y escalado fiable del proceso a escala de planta piloto o incluso industrial. Debido a la insuficiencia de los clásicos métodos de optimización para llevar acabo la estimación de parámetros en modelos de alta complejidad, el uso de algoritmos estocásticos se ha probado con éxito, permitiendo el desarrollo de modelos cinéticos más avanzados que los que se implementan actualmente en el campo de la CWAO. El desarrollo de modelos cinéticos complejos es escaso en la literatura actual, así como los estudios que tratan los aspectos químicos y de ingeniería del proceso de la CWAO. Sin embargo, hay una necesidad clara para el desarrollo simultaneo de los aspectos químicos y de ingeniería de la tecnología. Consecuentemente, en paralelo se ha enfocado en la modelización de un reactor de goteo (TBR), según el estado de arte actual en el campo de estos reactores. Es demostrado que estos reactores son más adecuados que los reactores agitados con catalizador en suspención para la CWAO de compuestos orgánicos que tienden a reacciones de polimerización en fase liquida. Además se han probado dos distintos modos de operación, con flujo de gas y liquido cocorriente descendiente o ascendiente, y se ha demostrado que la primera forma de operación es la mas adecuada para este sistema. A continuación un modelo fenomenológico para el TBR ha sido desarrollado y programado. El modelo implementa la cinética previamente obtenida, y además se ha puesto énfasis en la incorporación de los efectos de mojado, y de transferencia de materia. La operación no isotérmica se ha estudiado también para investigar la posibilidad de operar de modo autotérmico, disminuyendo así los costes de operación del proceso. La validación del modelo fenomenológico con los datos experimentales obtenidos en el TBR del laboratorio ha sido favorable. Posteriormente, este modelo ha sido utilizado como una herramienta fiable para el escalado del proceso. Los resultados obtenidos de la modelización del escalado permiten la extracción de recomendaciones sobre el diseño y la operación de unidades industriales, haciendo más fiable la aplicación del método a escala industrial.

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.

Several types of reactors are encountered in industry where reagents in a gas and a liquid phase need to be catalysed by a solid catalyst. Common reactors that are used to this end, are trickle-bed reactors, where gas and liquid flow cocurrently down a packed bed of catalyst. Apart from the catalytic process itself, several mass transfer steps can influence the rate and/or selectivity of a solid catalysed gas-liquid reaction. In trickle-bed reactors, flow morphology can have a major effect on these mass transfer steps. This study investigates the interaction between liquid flow morphology and mass transfer in trickle-bed reactors from three different angles. The primary focus is on liquid-solid mass transfer and internal diffusion as affected by the contacting between the liquid and the catalyst. First, the contacting between the liquid and the solid in trickleflow, or wetting efficiency, is characterised using colorimetry. Though this investigation is limited to the flow of nitrogen and water over a packed bed at ambient conditions, it provides useful information regarding liquid flow multiplicity behaviour and its influence on the distribution of fractional wetting on a particle scale. The colorimetric study also provides descriptions of the geometry of the liquid-solid contacting on partially wetted particles. These are used in a second investigation, for the numerical simulation of reaction and diffusion in partially wetted catalysts. This second investigation uses numerical simulations to evaluate and develop simple theoretical descriptions of liquid-solid contacting effects on catalyst particle efficiency. Special attention is given to the case where external and intraparticle mass transfer rates of both a volatile and non-volatile reagent affect the overall rate of reaction. Also, since these are not often considered in theoretical studies, some suggestions are made for the evaluation of the particle efficiency of eggshell catalyst. Finally, liquid-solid contacting is investigated in a high-pressure pilot reactor. Wetting efficiency is measured with a useful technique that does not rely on descriptions of particle kinetics or liquid-solid mass transfer rates. Liquid-solid mass transfer coefficients are also measured and results agree well with the colorimetric investigation, suggesting the existence of different types of flow within in the hydrodynamic multiplicity envelope of trickle-flow. Since it consists of different investigations of liquid-solid contacting from different angles, the study highlights several aspects of liquid-solid contacting and how it can be expected to influence trickle-bed reactor performance. / Thesis (PhD)--University of Pretoria, 2009. / Chemical Engineering / unrestricted

No description available.

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

科学研究費補助金 研究種目:一般研究(C) 課題番号:62550695 研究代表者:中村 正秋 研究期間:1987-1988年度

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.