Since the late 1980s there has been a greater awareness of the need to manage organisational knowledge resources, which are seen as vital to the value proposition of any organisation. This has resulted in the development of a multiplicity of Organisational Knowledge Management (OKM) approaches, systems and processes. OKM as a concept is however experiencing a prolonged period of practitioner and academic dissatisfaction, which is impacting its credibility. Commentators claim that this emanates from the fact that a general model, as a diagnostic mechanism for the field, has not yet emerged, an indicator of immaturity in the field and a destabilising influence on practitioner confidence. This research sets out to explore OKM, with the aim of understanding and attempting to help address this dissatisfaction. The literature review focuses on environmental drivers of OKM as a concept from both practitioner and academic perspectives. This highlights a need for (1) an agreed definition of purpose for OKM systems and (2) a general diagnostic model or framework for those systems that identifies common constructs across sectors or geographic locations. In turn, these require appropriate research evidence. The research reported on in this thesis utilises Soft Systems Methodology as a framework for enquiry. By means of a meta-analysis of literature, the enquiry progresses to a descriptive survey, with findings being illustrated and analysed through fractal analysis. The data is then compared against a sample of models from the field before being translated into a new OKM diagnostic model and supporting toolkit, using logic modelling and a Participatory Integrated Assessment Tool. The application of these to a case study, carried out within in a large multinational organisation, is reported on and evaluated. Findings are that 'self-similarity' exists across existing views of OKM; that the need for knowledge to be used as an organisational resource is a persistent one; that a methodology can be developed that reacts to the needs of academics and practitioners in responding to the challenges from the field; that a proposition for a general organisation diagnostic model is possible; that a robust evidence-based definition for the concept, as well as a general diagnostic model for the coordination of organisational knowledge resources is needed and are provided; and that such a general diagnostic tool, such as has been developed in the research on which this thesis is based, can be applied within an organisation to identify gaps in systems designed to coordinate organisational knowledge resources.

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.

The behaviour of a large nuclear reactor can be described with sufficient accuracy using a nodal model, like the spatial model of a 540 MWe large Pressurized Heavy Water Reactor (PHWR). This model divides the reactor into divisions or nodes to create a spatial model in order to control the xenon induced oscillations that occur in PHWRs. However, being such a large scale system, a 72nd-order model, it makes controller design challenging. Therefore, a reduced order model is much more manageable. A convenient method of model reduction while maintaining the important dynamics characteristics of the process can be done by decoupling. Also, due to the nature of the system, decentralized controllers could serve as a better option because it allows each controller to be localized. This way, any control input to a zone only affects the desired zone and the zones most coupled with, thus not causing a respective change in neutron flux in the other zones. In this thesis, three decentralized controllers were designed using the spatial model of a 540 MWe large PHWR. A decoupling algorithm was designed to divide the system into three partitions containing 20, 27, and 25 states each. Reduced order sub-systems were thus created to produce optimal decentralized controllers. An optimal centralized controller was created to compare both approaches. The decentralized versus centralized controllers’ system responses were analyzed after a reactivity disturbance. A fail-safe study was done to highlight one of the advantages of decentralized controllers. / UOIT

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.

In dieser Arbeit werden lambda-Strukturen und s-Strukturen eingeführt, und Funktionen S und Lambda entwickelt, die lambda-Strukturen auf s-Strukturen abbilden und umgekehrt. lambda-Strukturen sind eng verwandt mit den in von Jensen untersuchten Prämäusen (iterierbare Prämäuse dieser Art sind lambda-Strukturen), und s-Strukturen wurden in Anlehnung an die von Mitchell und Steel betrachteten Prämäuse definiert. Wieder sind iterierbare Prämäuse dieser Art auch s-Strukturen. Für die Definition dieser Strukturen wurde eine neue, schwache Form der initial segment condition entwickelt (die s'-ISC), die stark genug für die Anwendungen ist. Um zu zeigen, dass die hier entwickelten Funktionen die gewünschte Korrespondenz realisieren, wurden Methoden zur Übersetzung von Formeln entwickelt, die teilweise sehr allgemein gehalten sind. So ist die Übersetzung von Sigma-1-Formeln, die in einer Nachfolgerstufe der Jensen-Hierarchie gelten, in entsprechende Sigma-omega-Formeln in der Vorgängerstufe, anwendbar auf beliebige J-Strukturen. Es werden normale s-Iterationen eingeführt, die den normalen Iterationen von Prämäusen im Sinne von Mitchell-Steel nachgebildet sind, aber auf lambda-Strukturen angewandt werden, und es wird gezeigt, dass die entwickelten Funktionen komponentenweise auf Iterationen angewandt werden können, um normale s-Iterationen von lambda-Strukturen in normale Iterationen von s-Strukturen zu übersetzen, und umgekehrt. Mit diesen Methoden lassen sich auch Iterationsstrategien übersetzen, und man erhält, dass die entwickelten Funktionen normal s-iterierbare lambda-Strukturen auf normal iterierbare s-Strukturen abbilden, und umgekehrt. Auch bleiben die wesentlichen feinstrukturellen Größen, wie bspw. Projekta, und unter gewissen Voraussetzungen (soundness und 1-solidity) auch die Standard-Parameter, erhalten. / In this work we introduce lambda-structures and s-structures, and develop functions S and Lambda, which map lambda-structures to s-structures and vice versa. lambda-structures are closely related to the premice studied in recent work of Jensen (iterable premice of this kind are lambda-structures), and s-structures were defined with the premice developed by Mitchell and Steel in mind. Again, iterable premice of this kind are s-structures. For the definition of these structures, a new form of the initial segment condition condition, called s'-ISC, was developed, which is a common weakening of the versions used in by Steel and Jensen. It still suffices for the applications. In order to show that the functions introduced establish the desired correspondence, we developed methods for translating formulae, which in part are very generally applicable. For instance, the translation of Sigma-1-formulae which hold in a successor level of the Jensen-hierarchy into corresponding Sigma-omega-formulae in the predecessor level, can be applied to arbitrary J-structures. We introduce normal s-iterations, which have been designed so as to rebuild the iterations of premice in the sense of Mitchell-Steel but are applied to lambda-structures. It is shown that the translation functions can be applied component-wise to normal iterations, in order to translate normal s-iterations of lambda-structures into normal iterations of s-structures, and vice versa. Using these methods, we can also translate iteration strategies and the result is that the functions introduced in this work map normally s-iterable lambda-structures to normally iterable s-structures, and vice versa. Also,the fundamental fine structural notions, such as projecta, and under additional hypotheses (soundness and 1-solidity) standard-parameters, are preserved.

[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.