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.

Afin de permettre la mise en place d’une filière de valorisation du CO2 issu de l’industrie sidérurgique, cette étude a pour but de proposer un nouveau procédé de dépoussiérage des fumées de hauts fourneaux qui serait placé à la suite des filières actuelles de traitement pour améliorer leur épuration. L’originalité de la technologie retenue, un lit granulaire arrosé, permet de maintenir la perte de charge constante en facilitant le réentraînement en continu des particules collectées à l’aide d’un écoulement de liquide (formant un film à la surface des collecteurs) pour ainsi pallier le problème de colmatage. Une étude hydrodynamique et des mesures d’efficacité vis-à-vis de particules de diamètre compris entre 0,5 et 10 µm ont montré que la perte de charge et l’efficacité initiale augmentaient avec la diminution du diamètre des collecteurs, ce qui est en accord avec les résultats de la littérature pour des lits granulaires secs. La présence d’un filet d’eau augmente l’efficacité initiale de collecte au détriment toutefois d’une perte de charge plus élevée. Ces observations sont liées à la diminution de la porosité du lit lorsque ce dernier est arrosé par un débit d’eau. Un bon compromis entre perte de charge et efficacité a été trouvé avec un lit composé de 50 cm de billes de 5 mm de diamètre et un débit d’eau de 12 L.min-1 pour un débit de gaz à traiter de 20 m3.h-1. Des essais de colmatage longue durée ont mis en évidence que l’efficacité du lit reste globalement constante au cours du temps, à une valeur proche de la valeur initiale. La perte de charge, bien que supérieure en début d’expérience à celle d’un lit granulaire sec, se stabilise rapidement à une valeur bien plus faible que celle mesurée pour un lit sec pour une même masse de particules collectées. Les expériences ayant été menées sur 30 h dans des conditions défavorables, nous pouvons nous attendre à ce que dans des conditions réelles de fonctionnement la perte de charge soit stable sur des temps beaucoup plus longs. Ainsi la présence de l’eau remplit bien le rôle prévu en limitant l’évolution du colmatage du lit granulaire par le réentrainement des particules collectées par le lit. Cette étude s’est achevée par le développement d’un modèle permettant de déterminer la perte de charge et l’efficacité initiale d’un lit granulaire arrosé, ce qui a abouti sur un exemple de pré-dimensionnement à échelle industrielle / In order to enable the establishment of a CO2 recovery chain sector from the steel industry, this study aims to propose a new filtration device for the dust removal of blast furnace fumes that would be placed after the current treatment chain to improve their purification. The originality of the chosen technology, a trickle bed, permits to maintain a constant pressure drop by re-entraining continuously the particles trapped on collectors thanks to a water film flow to overcome the clogging problem. A hydrodynamic study and efficiency measurements lead with particles (in a range of diameters between 0.5 and 10 μm) showed that the pressure drop and the initial efficiency increase with the decrease of the collector diameter, which is in agreement with the results of the literature for dry granular beds. The presence of water increases the initial collection efficiency at the expense of a higher pressure drop. These observations are related to the decrease of the bed porosity in presence of a water flow. A good compromise between pressure drop and efficiency was found for an air flow rate of 20 m3.h-1, a liquid flow rate of 12 L.min-1 and using a 50 cm bed composed of glass beads of 5 mm diameter. Long-term clogging tests showed that the efficiency of the bed remains globally constant over time at a value close to the initial one. The pressure drop, although higher at the beginning of the experiment than that of a dry granular bed, stabilizes rapidly at a much lower value than that measured for a dry granular bed for the same mass of particles collected. The experiments have been carried out over 30 h under disadvantageous conditions, and we can expect that under real operating conditions the pressure drop will be stable over much longer times. Thus, the presence of water plays its part by limiting the clogging evolution of the granular bed by the re-entrainment of particles collected by the bed. This study was completed by the development of a model to determine the pressure drop and initial efficiency of a trickle bed, which resulted in an example of pre-sizing of a process on an industrial scale

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.

La lignine est une macromolécule, constituant de la biomasse lignocellulosique, qui est composée d’unités propylphénoliques. Cette matière est produite par l’industrie papetière en tant que coproduit de la cellulose. Actuellement, sa valorisation se limite en grande partie à des applications énergétiques. Or, la lignine peut être une source alternative de phénols si elle est dépolymérisée efficacement. Ce travail porte sur la transformation de la lignine en synthons aromatiques dans l’eau et en mélange eau-alcools en conditions sous-critique (225°C et 40-80 bar). Dans un premier temps, des études de conversion sont réalisées en réacteur fermé en utilisant l’eau comme solvant sur une lignine Kraft en présence de catalyseurs (Pt, Pd, Ru sur Al2O3,TiO2, ZrO2), le catalyseur Pd/ZrO2 nous a permis d’obtenir un rendement en phénols identifiés de 2%en 3 heures. Afin d’améliorer la conversion de la lignine en minimisant les réactions de condensations entre unités phénoliques, l’eau est remplacée par un mélange eau/alcool (éthanol, méthanol, isopropanol). La combinaison eau/isopropanol sans catalyseur nous permet d’augmenter le rendement en phénols identifiés de 5%. Nous avons ensuite essayé d’appliquer notre approche en réacteur continu. Même si le mélange eau/isopropanol était le meilleur solvant en réacteur fermé, le passage en réacteur continu s’est avéré complexe par la formation de produits solides. L’utilisation d’un mélange eau/éthanol a permis d’éviter ce problème et un rendement en gaiacol jusqu’à 1% est obtenu. L’éthanol permet de stabiliser des synthons instables dans le milieu par alkylation et estérification / Lignin is a macromolecule comprising lignocellulosic biomass, and is composed of propylphenyl units. Lignin is produced in large amounts by the paper industry when cellulose is isolated from biomass. Currently, its value is largely limited to source of energy and heat in recovery boilers. Nonetheless lignin can be an alternative source of aromatics if depolymerized effectively. The present work focuses on the transformation of lignin into aromatic building blocks using sub-critical water and mixtures of water/alcohols (225°C and 40-80 bar). Preliminary studies were carried out in a batch reactor; water was used as a solvent for the conversion of a Kraft lignin in the presence of catalysts (Pt, Pd, Ru on Al2O3, TiO2, ZrO2). The Pd/ZrO2 catalyst gave the highest yield of identified phenols with 2% in 3 hours. To improve the conversion of the lignin by minimizing condensation reactions between phenolic units, the water was replaced with a mixture water/alcohol (ethanol, methanol, isopropanol). The combination water/isopropanol without catalyst allowed us to increase the yield of identified phenols to 5%. The results obtained in batch reactor were extrapolated to a trickle-bed reactor. Even though the water/isopropanol mixture gave the best results in batch reactor, the implementation on a continuous reactor proved to be complex (formation of solids clogging the reactor). The use of a water/ethanol mixture prevented this problem and a yield in guaiacol of up to 1 % was obtained. Ethanol helps stabilize unstable building blocks by alkylation and esterification. This is evidenced by the NMR and chromatographic analysis

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/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.

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.

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.

No description available.