This is a thesis includes both experimental and modeling studies for high temperature slag/metal reaction system. / Bloating of metal droplets in emulsion is an important phenomenon in BOF steelmaking in controlling the kinetics of refining. This bloating controls the kinetics by mainly increasing the residence time (from ~¼th of a second to ~10-15 seconds) of the droplets in emulsion and the slag/metal surface (~5-6 times) area. The bloating behavior is determined by the decarburization kinetics. This work aims to develop fundamental understanding of the bloating phenomena through series of experiments and mathematical modeling to explore various factors affecting the kinetics of decarburization. An experimental study on varying the droplet carbon concentration, slag FeO concentration and basicity evidenced mixed controlled kinetics including transport of oxygen in the slag, interfacial (slag/metal) chemical reaction, nucleation and growth of CO bubbles. A mathematical model including these kinetic steps was developed. The model was able to demonstrate the partitioning of oxygen at the slag/metal interface into external (at the slag/metal interface) and internal (within droplet) decarburization in presence of the surface-active element sulfur. The model was developed using a single data set and validated for a wide range of experimental conditions. The model showed excellent agreement with experimental data for most of the reaction period but failed to predict a premature shutdown for droplets reacting with low conductivity slag. In order to understand this discrepancy, the slag ionic and electronic conductivity were varied which showed a premature shutdown of decarburization reaction with low conductivity slag and continuation of the reaction to the thermodynamic limit with high conductivity slag. A mechanism of generation of local electric field by accumulation of charge at the slag/metal interface was proposed to explain the premature shutdown of the reaction for low basicity slags. In all experiments with low conductivity slag sulfur was observed to delay the onset of internal decarburization. However, this effect was diminished or disappeared completely with high conductivity slag. This observation motivated additional experiments to study the competitive adsorption of oxygen and sulfur at the slag/metal interface both through experiments and modelling. It was shown that for low conductivity slag, sulfur poisoning inhibited reaction at the surface whereas for the high conductivity slags the faster transport of oxygen allowed oxygen to compete with sulfur for adsorption sites creating pathways for oxygen into the droplet. By including the possibility of competitive adsorption in the model it was possible to predict the behavior of high sulfur droplets in conductivity slags where the only modification to the model was to change the mass transfer coefficient as appropriate to the higher conductivity. Extension of this study to include silicon in the droplet showed significant effect on decarburization both in delaying bloating as well as increasing peak rate of decarburization. / Thesis / Candidate in Philosophy

Orientador: Everson Alves Miranda / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química / Made available in DSpace on 2018-08-17T00:24:12Z (GMT). No. of bitstreams: 1 Silva_AlanHenriqueda_M.pdf: 1835038 bytes, checksum: 8f53d7e3503d526bab0e9fb0f812bd6c (MD5) Previous issue date: 2010 / Resumo: Fermentações para a produção de ácidos orgânicos se mostram cada vez mais importantes em química e petroquímica verde, seja devido a uma futura escassez de petróleo (base de produção destas moléculas) ou pelo apelo ambiental. Há alguns anos, estes processos biotecnológicos não eram economicamente viáveis, devido principalmente às etapas de recuperação e purificação das biomoléculas (RPB), sendo estas um forte componente no custo de produção. Seu estudo se torna então de suma importância para reduzir custo e aumentar a viabilidade técnico-econômica destes bioprocessos. A adsorção se mostra uma operação unitária muito estudada, robusta, de fácil escalonamento e operação, o que a torna uma opção atrativa para a RPB de tais ácidos. No entanto, estudos existentes até o momento não são completos necessitando uma maior abrangência para se desenvolver um processo eficiente. Com base neste quadro, este trabalho visou o estudo experimental de adsorção, em carvão ativado e resinas poliméricas de aplicação industrial, de ácidos orgânicos passíveis de produção por via fermentativa e de relevância em petroquímica verde. Isotermas de adsorção dos ácidos acético, propiônico e butírico foram avaliadas para verificar o efeito de temperatura, água, etanol e n-propanol utilizando sistemas monocomponentes e binários. Modelos de isotermas de adsorção foram avaliados quanto ao ajuste aos dados experimentais para ambos os sistemas. Os estudos de adsorção monocomponente mostraram que as resinas têm capacidade de adsorção maior que os carvões (cerca de 35%). A temperatura apresentou efeito pouco significativo na adsorção. Os estudos de adsorção de sistemas binários dos ácidos estudados identificaram que houve competição entre estes na adsorção, onde moléculas de maior cadeia carbônica têm uma maior afinidade pela superfície do adsorvente. Nos estudos de isotermas de adsorção utilizando etanol e propanol como possíveis solventes para dessorção, a resina apresentou altos valores de adsorção, ao contrário dos carvões. Uma simulação dos processos de adsorção e dessorção mostrou que a resina PLA133 apresentou melhores resultados como adsorvente e o propanol como melhor eluente, em um processo de dessorção de três estágios em contra-corrente. No entanto, a recuperação final do ácido, sendo o melhor resultado 70%, pode não ser satisfatória, dependendo da aplicação deste, de forma que ainda pode ser necessário uma melhoria no processo. / Abstract: Fermentations for the production of organic acids are becoming very important in green chemistry due to a future scarcity of oil (base of production of these acids) and environmental protection. A few years ago, these biotechnological processes were not economically viable mainly due to the downstream process (DSP) stages which are a strong component of production costs. The study of these bioprocesses becomes very important to increase their technical and economic feasibility. Adsorption - a widely studied unit operation - is robust and easy to operate, so it is an attractive option for the DSP of organic acids. However, current studies reported in the literature about this subject are not complete and therefore more through integrated studies need to be associated to develop an efficient process. The present work is an experimental study about adsorption of organic acids of relevance in green chemistry. Industrial activated carbons and polymeric resins (weak base resins were used as adsorbents. Equilibrium adsorption studies in single and binary systems of acetic, propionic and butyric acids were carried out to evaluated the effect of temperature and solvents (water, ethanol and n-propanol) on the adsorption. Equilibrium isotherm models were tested to represent the data in single and binary systems. The adsorption studies showed that resins had a higher adsorption capacity than activated carbons (about 35%). Adsorption in single systems was not significantly affected by temperature in the studied range. Data from adsorption of binary systems suggested that there was competition between the acids and the affinity of the acids for the surface is dependent on acids carbon chain size. In studies using ethanol and propanol as desorbents, the resin showed a high adsorption capacity, unlike the activated carbons. A simulation of the adsorption unit operation showed that the resins yielded better results than activated carbons; propanol was the best eluent in a three-stage counter-current desorption process. However, the best acid recovery of 70% may not be satisfactory depending on the application of the acid, so it can be necessary to improve the process for better results. / Mestrado / Mestre em Engenharia Química

Gegenstand dieser Arbeit ist die Entwicklung funktionalisierter Cellulose-Tiefenfilterschichten. Dazu werden kommerzielle Kationenaustauscher in einer Kugelmühle nass zerkleinert und bei der Herstellung in die Tiefenfilterschichten eingebettet. Die mechanischen Eigenschaften und das Filtrationsverhalten dieser Schichten sind vergleichbar mit kommerziellen Produkten. Der maximale, technisch einsetzbare Masseanteil an Ionenaustauscher beträgt dabei ca. 40 %. In Durchströmungsversuchen wird die Funktion der eigesetzten Partikel innerhalb der Cellulose-Matrix untersucht. Die Adsorptionskinetik kann mit Hilfe eines in der Arbeit weiterentwickelten Modells nach Langmuir beschrieben werden. Für die Austauschkinetik wird auf der Basis dieses Modells eine abweichende Gesetzmäßigkeit ermittelt. Zudem wird eine Anlagen-Auslegung zur maximalen Kapazitätsausnutzung für einen Adsorptionsprozess vorgestellt.

L’assainissement d’effluents résiduaires urbains par filtres plantés de roseaux (FPR) rencontre, depuis plus de trois décennies, un engouement croissant en raison de ses remarquables performances de traitement ainsi que de considérations technico-économiques et écologiques. Néanmoins, des objectifs de traitement de plus en plus contraignants, ainsi qu’un marché de plus en plus concurrentiel, amènent la nécessité d’une meilleure connaissance des processus afin d’en optimiser la conception en fonction du contexte. Une attention toute particulière a été portée au traitement de l’azote, au cours de cette étude, en raison de l’aspect particulièrement contraignant de son élimination. Ces travaux se sont articulés autour de trois axes principaux permettant l’évaluation des principaux mécanismes d’élimination de l’azote (nitrification, dénitrification et adsorption, respectivement). Un premier volet, conduit sur unités pilotes alimentées en effluents domestiques réels, s’est attaché à identifier l’impact respectif de divers critères de dimensionnement et opérationnels (profondeur de filtration, surface de filtration, charges hydrauliques et organiques) afin de proposer des consignes de conception adaptées aux objectifs de traitement sur l’azote ammoniacal ainsi que la matière organique et la pollution particulaire. Une seconde partie de l’étude, mené à échelle pilote à partir d’effluents semi-synthétiques, s’est quant à elle focalisée sur le processus de dénitrification afin de mettre en exergue les critères majeurs (composition des effluents, paramètres de conception et fonctionnement) pour l’atteinte de performances poussées sur le traitement des nitrates. Enfin, un dernier axe de recherche, effectué en laboratoire en colonne, a visé à évaluer l’effet de l’adsorption d’ammonium sur matériaux filtrants réactifs (zéolithe) en vue d’optimiser par la suite le temps de rétention de cette espèce au regard des cinétiques de dégradation biologique. Une synthèse des connaissances acquises au cours de cette étude a donné lieu à des conseils de conception ainsi qu’à des recommandations pour d’éventuelles études complémentaires. / The treatment of domestic wastewater by constructed wetlands (CWs) meets, from more than three decades, an increasing interest because of its high treatment efficiency as well as technological, economic and ecological issues. However, with treatment objectives that are growing ever stricter and an increasingly competitive market, fine knowledge of removal processes is required in order to optimize design in regards with context. A particular attention was paid to nitrogen removal, through this study, because of its particularly coercive dimension in treatment process. This work is partitioned in three axes which enable the assessment of the main mechanisms ensuring nitrogen removal (nitrification, denitrification and sorption, respectively). A first part, conducted in pilot-scaled units fed in real domestic wastewater, aimed at identifying the respective effects of various design and operational parameters (filtration height, filtration area, hydraulic and organic loads) in order to provide design recommendations for an efficient removal of ammonium as well as organic matter and suspended solids. A second part of this work, carried out in pilot-scaled units fed with semi-synthetic wastewater, focused on denitrification process in order to highlight driving parameters (influent composition, design and operational parameters) of full nitrate removal. Last but not least, a third research axis, conducted in column-scaled units, assessed the ammonium adsorption onto reactive material (i.e. zeolite) in order to optimize the retention time of ammonium within the system in regards with nitrification kinetic. These results were then summarized in order to provide design guidelines as well as recommend further complementary experiments.

Gegenstand dieser Arbeit ist die Entwicklung funktionalisierter Cellulose-Tiefenfilterschichten. Dazu werden kommerzielle Kationenaustauscher in einer Kugelmühle nass zerkleinert und bei der Herstellung in die Tiefenfilterschichten eingebettet. Die mechanischen Eigenschaften und das Filtrationsverhalten dieser Schichten sind vergleichbar mit kommerziellen Produkten. Der maximale, technisch einsetzbare Masseanteil an Ionenaustauscher beträgt dabei ca. 40 %. In Durchströmungsversuchen wird die Funktion der eigesetzten Partikel innerhalb der Cellulose-Matrix untersucht. Die Adsorptionskinetik kann mit Hilfe eines in der Arbeit weiterentwickelten Modells nach Langmuir beschrieben werden. Für die Austauschkinetik wird auf der Basis dieses Modells eine abweichende Gesetzmäßigkeit ermittelt. Zudem wird eine Anlagen-Auslegung zur maximalen Kapazitätsausnutzung für einen Adsorptionsprozess vorgestellt.

Humic acids and humates are principal components of humic substances major organic constituents of soil, peat, coal and water around the world. I was involved in research into molecular dynamics simulations of interactions of quartz surfaces with aqueous solutions of ions and small organic molecules representing basic building blocks of larger biomolecules and functional groups of organic matter. We studied interactions of molecules with surfaces for a set of surface charge densities corresponding to the experimentally or environmentally relevant ranges of pH values employing molecular mechanics, molecular dynamics and ab initio techniques. Simulated quartz surfaces covered the range of surface charge densities 0.00, -0.03, -0.06 and -0.12 C-m-2, approximately corresponding to pH values 4.5, 7.5, 9.5 and 11. As model molecules, benzoic acid, phenol, o-salicylic acid and their conjugated bases were chosen. My task was to prepare topologies and parametric models of selected organic matter basic building blocks organic molecules. I focused on studying interactions of these molecules in an aqueous environment with mineral surface quartz. The aim was to process simulation results and analyse conformations of the adsorption complexes and their thermodynamic properties such as interaction energies, free energies and adsorption geometries.