This work explored the viability of two solid adsorbents, limestone and cement powder, for use in a flow-through packed-bed column for HCl and HF gas neutralization following refrigerant destruction. Neutralization tests performed at 408 K using 5% HCl in N2 and 5% HF in N2, showed that limestone had a significantly higher adsorption capacity for both HF & HCl, future tests therefore utilized limestone only. The results showed that ~49% of the fed HCl and between 7.8% - 16.2% of the fed HF gases were adsorbed by 0.007 kg of limestone for a 6.67×10-6 m3/s (STP) flow rate over 30 – 180 minutes. Applying the shrinking core model, effective diffusivities (De) of HCl & HF into the limestone particles were 1.5×10-9 & 2.2×10-9 m2/s respectively. Under these conditions, complete particle conversion times were 227 hours for HCl–limestone and 154 hours for HF–limestone. Estimating De values at plasma-reactor temperatures gave 5.61x10-9 m2/s & 8.24x10-9 m2/s for HCl–limestone and HF–limestone respectively. Correspondingly, particle consumption times were reduced to 61 and 41 hours for HCl–limestone and HF–limestone. Considering the conversion times for the 1 mm particle sizes, shorter conversion times would require micron-scale particle sizes, suitable for entrained flow but not for a packed-bed arrangement.

No description available.

Calcination is important for modern society as we know it since products from the reaction is used inseveral industries. Calcination is a chemical reaction where a solid particle, e.g., limestone, is exposedto high temperature which causes volatile impurities to be released from the particle.One of the main challenges with lime production is the mere scale of commercial production. Ensuringgood calcination and high-quality lime in laboratory scale is relatively easy, whereas commercial limekilns produce 100 – 800 tons lime each day, causing the conditions to be much more challenging. Theenvironment inside a lime kiln is extreme, with temperatures exceeding 1200°C, and a moving stonebed makes measurements difficult to perform. To obtain information about the calcination processand the extreme environment that arises in commercial lime kilns, companies and researchers havedeveloped simulation programmes to evaluate how changes in ambient condition affect the calcinationprocess.In this project, a shrinking core model has been used to simulate calcination of limestone with variedgeometry and size in different ambient condition. A transient model was used to simulate the heatingphases before and after the calcination phase. The results obtain from the simulation are compared tomeasured data obtain by others.There are many similarities between the measured data and the simulation, a reoccurringphenomenon is that the transit model, during the pre-heating, heats the limestone faster compared tothe measured data. However, in one case, the transient model is slower. A reason for this may be thatthe transient model does not account for morphological effects, as they are included in the heattransfer coefficient instead, such as the thermal conductivity coefficient and specific heat transfercoefficient. The post heating phase, after the reaction phase, required further work.The simulation with the Shrinking core model shows that a cylindrical geometry requires longercalcination duration, or a higher ambient temperature compared to a spherical geometry, even if bothgeometries have same material properties and radius. The factor with the most influence uponcalcination time is the ambient temperature in combination with reaction temperature. A highercarbon dioxide pressure, above atmospheric CO2 partial pressure, has relatively small effect comparedto a low ambient temperature, less than 1000°C.

No description available.

[pt] A drenagem ácida de minas (DAM) é um problema ambiental capaz de comprometer a qualidade dos recursos hídricos, que decorre da oxidação de sulfetos. A adoção de medidas corretivas e/ou preventivas dependerá do programa de predição escolhido, este geralmente inclui testes do potencial de geração de acidez (método estático), e da velocidade com que ocorre o processo (método cinético). No presente trabalho avaliou-se o potencial de geração de DAM usando o teste de Balanço Ácido Base Modificada (BABM), e monitorou-se a qualidade da água da drenagem dos rejeitos, durante 23 semanas, usando o método das colunas de lixiviação segundo a Acid Drainage Technology Initiative, para amostras de rejeitos provenientes da Carbonífera Criciúma e da Carbonífera Metropolitana. As duas amostras da Carbonífera Criciúma (SRA e SRB) apresentaram potencial de geração de acidez e as amostras da Metropolitana apresentam um pequeno risco de gerar acidez, segundo os resultados do BABM. Porém os resultados do método cinético, para todos os casos, mostram valores de pH menores que 4 e valores crescentes para a concentração do SO4 -2, acidez e o Eh, que mostra que são geradoras de DAM. Deve se ter em conta que o teste de BABM não leva em consideração a cinética das reações para a produção de acidez e sua neutralização. Os valores de concentração para o Zn, Mn e Al excedem os padrões de qualidade de água (segundo a Resolução No 357, CONAMA). No caso do Pb, os resultados não foram conclusivos devido ao alto limite de detecção do equipamento. Utilizando o modelo do núcleo não reagido, a etapa controladora da taxa de oxidação para a pirita (de FeS2 a SO4 -2) para as amostras SRA e SRB foi transferência de massa através da camada limite, com tempos teóricos para conversão completa (t) de 2,7 e 1,6 anos respectivamente, para as condições ensaiadas. A outra amostra da Carbonífera Criciúma (VR) apresentou como etapa controladora nas semanas iniciais a transferência de massa através da camada cinza e nas semanas finais a reação química propriamente dita, sendo t estimado em 3,4 anos para as condições ensaiadas. / [en] The acid rock mine drainage (ARD) arising from sulfides oxidation in mining areas is a serious environmental problem that markedly affects the quality of the surrounding water. Choosing the measure for remediation and/or preventing pollution effect depends on a suitable evaluation through a prediction program, it has principally tests of the acid generation potential (static method), and rate of the corresponding chemical reactions (kinetic methods). The present study aimed to evaluate the potential of ARD of wastes from two coal mines Criciúma and Metropolitana, using a Modified Acid Base Accounting (MABA) and evaluated the drainage water quality during 23 weeks using leaching columns test according Acid Drainage Technology Initiative protocol. According MABA results two coal mine Criciúma Samples (SRA e SRB) indicated an acid generation potential, and Metropolitana samples present a small risk to generate acidity. However the kinetic method results, for all the samples present pH < 4 and increasing concentrations values for SO4 -2, acidity and Eh that indicate acid generation potential. The MABA test does not consider the reaction rate of acid production and its neutralizations reactions. The concentrations values of Zn, Mn and Al exceeds water quality standard (Resolução No 357, CONAMA). In the case of Pb the results were inconclusives due to the equipment high detection limit for this element. Shrinking Core Model was used to determinate rate control to pyrite oxidation kinetic (de FeS2 a SO4 -2). SRA and SRB samples the layer diffusion control was the control rate, with complete conversion theoretical time (t) of 2.7 and 1.6 years, respectively, for the test conditions. The Criciúma Coal Mine sample (VR) presents product layer diffusion as control rate at the beginning weeks and then the chemical reaction was the control rate at the final weeks of the test and for this control the calculated t was 3.4 years for the test conditions.

[pt] Processos de ustulação cloretante podem ser realizados de forma direta, utilizando o Cl2 como agente cloretante, ou através de agentes cloretantes alternativos. Neste contexto, compostos organoclorados são promissores, pois além de serem facilmente volatizados, já apresentam na mesma molécula o agente cloretante e redutor. O presente estudo teve como principal objetivo a avaliação quantitativa da cinética de cloração do pentóxido de tântalo com tetracloroetileno através dos modelos do núcleo não reagido (SC) e auto catalítico (AC). Tanto o material inicial, quanto o mesmo após o processo, bem como o produto sólido depositado na saída do reator foram caracterizados via DRX e MEV/EDS. Através de simulações termodinâmicas foi possível verificar a viabilidade de cloração de amostras puras de Ta2O5 com C2Cl4 diluído em atmosfera de N2 na faixa de temperatura entre 800 a 950 graus Celsius, sendo os principais cloretos gasosos formados, TaOCl3 e TaCl5. Verificou-se ainda a possível decomposição térmica do agente cloretante no caminho entre a entrada do reator e a amostra. Os resultados provenientes das caracterizações comprovaram as tendências apontadas pelas simulações termodinâmicas, comprovando a formação exclusiva de cloretos voláteis. No que diz respeito à modelagem cinética ambos os modelos permitiram o ajuste dos dados em nível quantitativo, sendo os valores de energia de ativação global iguais a 93,8 kJ/mol (SC) e 32 kJ/mol (AC). A comparação dos valores obtidos com dados da literatura sugere que o controle é de natureza química, sendo a decomposição do C2Cl4 na superfície das nanopartículas de Ta2O5, possivelmente, a etapa controladora. / [en] Chlorination roasting can be carried out directly, using Cl2 as a chlorinating agent, or through alternative reagents. In this context, organochlorine compounds are promising, since besides being easily volatilized, they already present in the same molecule the chlorinating and reducing agents. The present study had as main objective the quantitative evaluation of the chlorination kinetics of tantalum pentoxide with tetrachlorethylene through the shrinking core (SC) and auto catalytic (AC) models. The initial material, as well as post-processed materials, and also the solid product deposited at the reactor s exit were characterized through DRX and MEV/EDS. By means of thermodynamic simulations, it was possible to verify the viability of pure Ta2O5 samples chlorination with C2Cl4 diluted in N2 in the temperature range of interest (800 - 950 Celsius Degree), thereby producing only gaseous chlorides, TaOCl3 and TaCl5. The possible C2Cl4 thermal decomposition in the path between the reactor inlet and sample was also identified. The characterization results were in accordance with the tendencies indicated by the thermodynamic simulations, proving the exclusive formation of volatile chlorides. With regard to the kinetic study, both tested models allowed quantitative adjustment of the conversion data, with overall activation energies equal to 93.8 kJ/mol (SC) and 32 kJ/mol (AC). The comparison of the values obtained with literature data suggests that the control is of chemical nature, the decomposition of C2Cl4 on the surface of the Ta2O5 nanoparticles being, possibly, the main control reaction step.

Le procédé adopté par COMURHEX pour le traitement des effluents très chargés en fluor est basé sur l’addition d’un composé alcalin Ca(OH)2 (portlandite) pour faire précipiter de la fluorine (CaF2). Mis en œuvre par le passé dans un décanteur le développement d’un nouveau procédé en lit fluidisé a été envisagé pour augmenter l’efficacité du traitement des effluents. Des essais concluants ont été réalisés sur une installation pilote qui ont démontré l’efficacité de la précipitation en lit fluidisé à assurer une réduction satisfaisante de la concentration du fluor. Cependant, les phénomènes mis en jeu dans le réacteur sont mal connus.Notre objectif principal est la maîtrise de la précipitation de la fluorine dans le réacteur à lit fluidisé ainsi qu’une meilleure compréhension des mécanismes mis en jeu. Pour ce faire, il a été nécessaire de reprendre l’étude thermodynamique du système KOH-portlandite-calcite-fluorine, de manière à étendre les données existantes aux fortes concentrations de KOH en solution. Un modèle thermodynamique capable de prédire la solubilité des solides en présence de variations de la concentration de la potasse et de la température du système a été établi.La deuxième partie du travail a été focalisée sur la compréhension des mécanismes mis en jeu pendant la formation de la fluorine. Les expériences réalisées au laboratoire ont conduit à l’obtention d’une fluorine issue d’une conversion de la portlandite. Ce mécanisme a été modélisé en considérant que le remplacement de la portlandite par la fluorine s’explique par un modèle à cœur rétrécissant contrôlé par la limitation diffusionnelle du fluorure dans la couche de fluorine formée. La dernière partie expérimentale de ce travail a été réalisée sur le pilote à lit fluidisé. Les expériences effectuées n’ont pas donné de résultats satisfaisants. Il n’a pas été possible de faire faire fonctionner le pilote de façon cohérente avec les objectifs de son dimensionnement. En particulier, compte-tenu de la très petite taille des particules, les débits de fonctionnement conduisent à l’envolement de celles-ci, mais pas à l’établissement de l’état fluidisé. / The method used by COMURHEX for the treatment of fluorine-rich effluents relies on the addition of solid Ca(OH)2 (portlandite) to precipitate fluorite (CaF2) in strongly alkaline solutions. This method is effective in a settler, and the development of a new fluidized bed process has been proposed to increase its efficiency. Successful assays were conducted on a pilot scale and they demonstrated that precipitation in a fluidized bed reactor actually ensures a satisfactory defluorination. However, the phenomena involved remained poorly known, and the main goal of the present work was to elucidate the mechanisms, their kinetics, and to control the crystallization.Our first contribution is a thermodynamic reappraisal of the KOH–portlandite–calcite system that extends existing solubility data to higher KOH concentrations in solution and incorporates new solubility data for fluorite. The outcome is an aqueous speciation model (Pitzer type) accounting for the solids solubility as a function of the KOH concentration and the temperature, and allowing portlandite undersaturation and fluorine supersaturation to be evaluated in process solutions.Our second contribution focuses on the kinetics and the mechanisms involved during the formation of fluorite, using various mixing designs in batch reactors. Reaction rates are fast, except in experiments involving dilute reactants. Microprobe and granulometric data both indicate that much of the fluorine results from the conversion of the portlandite grains. A shrinking core model controlled by diffusive transfer of fluoride in the porous fluorite corona successfully fits the kinetics of fluorine uptake and the particle grain size.The last part of the experimental work was carried out on a small fluidized bed pilot. These experiments were poorly conclusive. The very small particle size and the large flow rates lead to particle blow off, but not to fluidization. As a consequence, the capacity of the fluidized bed to promote an increase of the particle grain size remains largely unknown.

Ces travaux de thèse s’intègrent au sein du projet Biocarb lancé par le Commissariat à l’Énergie Atomique dont l’objectif est de développer des procédés de production de carburants liquides ou gazeux à partir de gaz de synthèse riche en H2 et CO obtenu par gazéification de la biomasse lignocellulosique. L’objectif de cette étude est d’étudier le comportement de particules de biomasse millimétriques lors de la pyrolyse dans des conditions types de gazéifieurs industriels tels que les réacteurs à lit fluidisé ou à flux entraîné, qui fonctionnent pour des flux de chaleur élevés (105 – 106 W⋅m-2) et pour de hautes températures (>800°C). Tout d’abord, des expériences de pyrolyse sont menées à 800 et 950°C dans un four à chute de laboratoire sur des particules de bois entre 350 et 800 μm. Les résultats montrent que dans les conditions de l’étude, l’augmentation de la taille de la particule augmente seulement la durée de la pyrolyse mais ne modifie pas les rendements ou la composition du solide et du gaz au cours de la pyrolyse. Par ailleurs, des mesures basées sur la technique de PTV (Particle Tracking Velocimetry) sont réalisées à température ambiante pour caractériser la taille et la densité des particules de bois brut et de résidu, et valider une corrélation donnant le coefficient de traînée qui sert à calculer le temps de séjour des particules dans le réacteur. On constate à la fin de la pyrolyse une diminution de la densité comprise entre 70 et 80% ainsi qu’une diminution de la taille des particules entre 25 et 40%. Les résultats montrent également que la vitesse de glissement de la particule et l’évolution de ses propriétés doivent être prises en compte lors du calcul de sa vitesse. Enfin, à partir des résultats expérimentaux, un modèle unidimensionnel à coeur rétrécissant est développé pour décrire le comportement d’une particule de bois lors de sa pyrolyse. Le modèle est capable de prévoir l’évolution du rendement en solide, en gaz total et en goudrons au cours de la pyrolyse ainsi que la vitesse de glissement de la particule et son temps de séjour dans le réacteur.L’analyse de sensibilité du modèle montre que même pour des particules millimétriques, une connaissance précise de la chaleur de réaction associée à la pyrolyse, de la densité du bois et de la conductivité thermique du résidu solide est essentielle / The present work is part of a project of the French energy research centre Commissariat à l’Energie Atomique. The goal of the project is to develop processes of production of gaseous or liquid fuel from synthesis gas obtained by gasification of lignocellulosic biomass. The objective of the present work is to study the pyrolysis behaviour of millimetric biomass particles under the operating conditions encountered in fluidized bed or entrained flow gasifiers, namely high external heat flux (105 – 106 W⋅m-2) and high temperature (> 800°C). First, pyrolysis experiments are conducted at 800 and 950°C in a lab-scale drop tube reactor on wood particles between 350 and 800 μm. The results show that under the explored conditions, the increase of the particle size only increases the time required for pyrolysis but does not affect the product distribution during pyrolysis. Since in the pyrolysis experiments, the particle residence time cannot be directly measured, PTV (Particle Tracking Velocimetry) measurements are performed at room temperature to characterize the evolution of the particle size and density along pyrolysis and to validate a drag coefficient correlation for the particle residence time calculation. The optical measurements show that at the end of pyrolysis there is a decrease of particle density of 70 – 80% and of particle size of 25 – 40%. It is also proven that the particle slip velocity cannot be neglected and that the change of these particle properties must be taken into account for the calculation of the particle slip velocity and residence time. Finally, based on these experimental results, a 1D shrinking-core model is developed that is able to predict the solid/gas/tar yields and the residence time of a single particle along pyrolysis in the drop tube reactor. It is validated on both the pyrolysis and optical experiments. The model sensitivity analysis shows that even for millimetric particles, the accurate knowledge of the heat of pyrolysis, of the wood density and of the char thermal conductivity is essential

M. Tech. (Department of Chemical Engineering, Faculty of Engineering and Technology): Vaal University of Technology / Strict environmental regulation on flue gas emission has led to the implementation of FGD technologies in power stations. Wet FGD technology is commonly used because it has high SO2 removal efficiency, high sorbent utilization and due to availability of the sorbent (limestone) used. SO2 is removed by passing flue gas through the absorber where it reacts with the slurry containing calcium ions which is obtained by dissolution. This study presents the findings of the dissolution of a calcium-based material (limestone) for wet FGD process. This was done using a pH stat apparatus and adipic acid as acid titrant. Adipic acid was used because of its buffering effect in wet FGD process. The conditions used for this study are similar to what is encountered in a wet FGD process. The extent of dissolution was determined by analyzing the amount of calcium ions in solution at different dissolution periods. The dissolution kinetics were correlated to the shrinking core model and it was found out that chemical reaction at the surface of the particle is the rate controlling step. This study also investigated the dissolution of coal fly ash and bottom ash. Their dissolution kinetics showed that the diffusion through the product layer was the rate controlling step due to an ash layer formed around the particle. The formation of ash layer was attributed to pozzolanic reaction products which is calcium-alumino-silicate (anorthite) compounds were formed after dissolution. The effect of fly ash on the dissolution of rate of limestone was also studied using response surface methodology. Limestone reactivity was found to increase with increase in the amount of fly ash added and the pH was found to be strong function of the rate constant compared to other dissolution variables. The presence of silica and alumina in fly ash led to a significant increase in the specific surface area due to hydration products formed after dissolution. / Eskom

Dans cette thèse, des simulations numériques tridimensionnelles instationnaires d'une installation expérimentale de combustion en boucle chimique sont réalisées. Le pilote expérimental, d'une puissance de 120 kWth, utilise un matériau perovskite, à base de Ca-Mn, comme transporteur d'oxygène. Les simulations numériques sont réalisées par le code NEPTUNE_CFD, selon une approche Euler-Euler pour les deux phases (solide et gazeuse), avec des modèles de fermeture spécifiques pour modéliser les transferts de masse, de mouvement et d'énergie. Les réactions hétérogènes (i.e. réactions gaz-solide) de réduction et d'oxydation sont décrites au moyen d'un modèle à cœur rétrécissant dans le grain, qui prend en compte les mécanismes compétitifs dans le processus global de réaction gaz-solide: réaction chimique à la surface interne des particules,diffusion à travers la couche de produits et transfert externe autour des particules. Les résultats des simulations numériques sont validées avec des mesures expérimentales et analysées afin de mieux comprendre le comportement local/instationnaire de l'écoulement gaz-particules réactif dans ce système de combustion en boucle chimique. L'outil théorique/numérique développé dans ce travail sera utilisé pour le dimensionnement d'une unité pilote à l’échelle des installations industrielles. / In this work, reactive unsteady three-dimensional numerical simulations of a Chemical Looping Combustion (CLC) plant are performed. The plant is a 120 kWth pilot working with Ca-Mn-based material as selected oxygen carrier. Numerical simulations are performed by NEPTUNE_CFD code using an Euler-Euler approach which computes both the gas and the solid phases in an Eulerian fashion accounting for specific closures in order to model interphase mass, momentum and energy transfers. Reduction and oxidation heterogeneous (i.e. gas-solid) reactions are modeled by means of a grain model (shrinking core model in the grain) accounting for both the competing mechanisms of chemical reaction at the particle internal surface and gaseous diffusion through the product layer. Results from numerical simulations are validated against experimental measurements and analyzed in order to gain insight in the local behaviour of the reactive gas-particle flow in the CLC system. The theoretical/numerical tool developed in this work will be used for design upgrade recommendation in the stage of scaling-up from pilot to industrial facilities.