<p><strong>Apstrakt je obrađen tehnologijama za optičko prepoznavanje teksta (OCR).</strong></p><p>Sumporni oksidi najče&scaron;će prisutni polutanti u atmosferi direktno utiču na zdravlje Ijudi i stvaranje kiselih ki&scaron;a ugrožavajući ekosistem. Razvijen je veliki proj postupaka odsumporavanja otpadnih gasova, dok je u naj&scaron;iroj upotrebi mokri neregenerativni postupak apsorpcije koji koristi jeftine hemikalije, kreč ili krečnjak. Zbog toga se posebna pažnja posvečuje i ispitivanju regenerativnih postupaka kod kojih se apsorpciono sredstvo delimično ili u potpunosti regeneri&scaron;e, a pri čemu su gubici apsorpcionog fluida zanemarljivi. Postupak sa limunskom kiselinom upravo ispunjava poslednji zahtev. Ostale prednosti ovog postupka su fleksibilnost, bez prisustva koplikovanih procesnih postupaka, mali oksidacioni gubici sumpor dioksida i netoksičnost reagensa.<br />Pri projektovanju kolone za odsumporavanje otpadnih gasova neophodno je poznavanje ravnotežnih podatka para-tečnost, hidrodinamičkih parametara (pad pritiska i količina zadržane tečnosti) i prenosa mase kao jednog od direktnih pokazatelja brzine apsorpcije ili ukupne brzine reakcije.<br />Izveden je matematički model ravnoteže za predvidjanje ravnotežnog parcijalnog pritiska sumpor dioksida iznad vodenog rastvora natrijum citrata za ceo opseg pH vrednosti pufera i temperature na osnovu eksperimentalnih vrednosti. Zaustavnom metodom je odredjena količina zadržane tečnosti u koloni. Analizirane su jednačine date u literaturi za predvidjanje pada pritiska i zapreminskih koeficijenata prenosa mase i odabrane one koje se mogu primeniti na odabrani sistem sumpor dioksid/citratni pufer.<br />Na osnovu eksperimentalnih podataka para-tečnost, hidrodinamičkih parametara i odabranih jednačina za prenos mase, izvr&scaron;en je proračun visine apsorpcione kolone sa Raschigovim prstenovima za izdvajanje sumpor dioksida iz otpadnog gasa i pokazano je da pad pritiska za eksperimentalno primenjene protoke gasa i tečnosti odgovara literaturno predloženom opsegu.</p> / <p><strong>Abstract was processed by technology for Optical character recognition (OCR).</strong></p><p>Control of sulfur dioxide emission has a relatively long history, especially in major industrial countries due to its common occurence and harmful effects. A number of dry and wet process comprising regenerable and throw-away process were investigated, but the wet throw-away process become the most widely accepted. The use of the flue gas desulphurization process with sodium citrate solution is recommended, as it is found that sodium citrate meets the specific needs of reversible sulphur dioxide absorption to buffer range as well as its capacity, chemical and physical stability.<br />Packed columns are widely used in the chemical industry for gas/liquid mass and heat transfer operations and they have found special use in small fractionating towers. Their use has also been found to be advantageous where corrosion control is essential. Fundamental steps necessary for design of absorption column for sulfur dioxide removal are:<br />- determination of vapor-liguid eguiiibrium data for the citrate buffer,<br />- determination of hydrodynamic parameters, i.e. holdup and pressure drop,<br />- determination gas-liquid mass transfer coefficients.<br />On the basis of the experimentally determined vapour pressures data, a model of the gas- equilibria was formulated. Holdups were measured for air/sodium citrate solution using the draining method. Also, literature-proposed eguations for determination of pressure drop, volumetric liquid-phase and gas-phase mass transfer coefficient in packed column were presented and chosen those that could be applied to flue gas/citrate puffer system. Therefore, on the base of obtained results the preposition for the design of packed column is presented.</p>

Les procédés XTL de production de carburants de synthèse basés sur la réactionFischer-Tropsch ainsi que les centrales IGCC représentent des alternatives attractives à la productiond'énergie future. Ces deux technologies mettent en oeuvre des gaz de synthèse contenant des impuretésdont H2S. Afin de protéger les unités de la corrosion et les catalyseurs Fischer-Tropsch del'empoisonnement, il est nécessaire de désulfurer ce gaz à l'aide d'oxydes métalliques, tel que ZnO, qui sesulfurent de façon quasi irréversible. Cette étape peut engendrer de larges quantités de déchets solides.La régénération in-situ par voie oxydante des matériaux sulfurés a pour but de permettre le retour à laphase oxyde puis à sa réutilisation. C’est une voie prometteuse vers un procédé plus efficient. Cependantla formation de sulfates réfractaires durant la régénération impose une importante élévation de latempérature afin de pouvoir les décomposer. La recherche de solution conduisant à un abaissement de latempérature de régénération est donc nécessaire. Dans ce travail, nous nous sommes proposés d'étudierles phénomènes physico-chimiques mis en jeu lors de la sulfuration et de la régénération d'oxydessimples et composés. Les oxydes simples étudiés ont été sélectionnés à la suite d’une étudethermodynamique puis expérimentale. L’identification des réactivités singulières de ZnO et MoO3 aconduit à la formulation d’oxydes composés. En particulier, l’oxyde mixte ZnMoO4 est régénérable dès500°C. Des caractérisations in-situ ont mis en évidence les rôles de la texture du solide sulfuré et desphases contenant du molybdène dans le processus de régénération. Enfin, une étude réalisée avec unsolide mis et forme et sur banc de perçage a permis d’aboutir à l’élaboration de règles de design dusolide. / Metal oxide based materials are commonly used for the final desulphurization of syngas in IGCC andFisher-Tropsch based XTL processes. The formation of large amount of solid waste is a major issue forthis process. The in-situ oxidative regeneration is a promising way to avoid the waste formation and toenhance process efficiency. However, the formation of refractory metal sulphates during the regenerationprocess requires an increase of the regeneration temperature, in order to decompose the species and toallow the sorbent regeneration. In this work, we have studied the use of composed metal oxides todecrease the regeneration temperature, and the related physic-chemical phenomena involved.Thermochemical and experimental studies on various single oxides outlined the specific reactivity ofZnO and MoO3 phases. Consequently a more thorough study on ZnO and MoO3 composed metal oxideswas performed. In particular, it was shown that ZnMoO4, zinc molybdate phase can be regenerated attemperature as low as 500°C. This low regeneration temperature was explained by the sulphided solidtexture and the oxidation of the molybdenum species. Finally a shaped ZnMoO4 was synthesized andtexted on a lab-scale breakthrough experimental device to validate the concept and give guideline for thedesign of industrial regenerable sorbent.

Energy technologies interact with the economic, social and environmental systems, and do so not only directly but indirectly as well, through upstream and downstream processes. In addition, the interactions may produce positive and negative repercussions. To make informed decisions on the selection of energy technologies that assist a nation in reaping the socio-economic benefits of power generation technologies with minimal effects on the natural environment, energy technologies need to be understood in the light of the multifaceted system in which they function. But frequently, as disclosed by the literature review conducted in this research, the evaluation of energy technologies lacks clear benchmarks of appropriate assessments, which has resulted in difficulty to compare and to gauge the quality of various assessment practices. The assessment methods and tools tend to be discipline specific with little to no integrations. Parallel with the tools, the technology assessment studies offer piecemeal information that limits deeper understanding of energy technologies and their consequent socio-economic-environmental repercussions. Improved energy technology assessment requires the use of a holistic and integrative approach that traverses the disciplinary nature of energy technology assessment tools, examines the long-term implications of technologies while at the same time embracing energy technologies’ positive-and-negative interactions with the economic, social and environmental systems and in this manner offering economic, social and environmental indicators to assist decision makers in the decision-making process. Accordingly, this study focuses on improving the assessment of energy technologies through the application of a holistic and integrative approach, specifically system dynamics approach along a life-cycle viewpoint. Precisely, focus is on coal-based electricity generation and in particular, the Kusile coal-fired power station near eMalahleni as a case study. A COAL-based Power and Social Cost Assessment (COALPSCA) Model was developed for: (i) understanding coal-based power generation and its interactions with resource inputs, private costs, externalities, externality costs and hence its consequent socio-economic, and environmental impacts over its lifetime and fuel cycle; (ii) aiding coal-based power developers with a useful tool with a clear interface and graphical outputs for detecting the main drivers of private and externality costs and sources of socio-environmental burdens in the system; (iii) aiding energy decision makers with a visual tool for making informed energy-supply decisions that takes into account the financial viability and the socio-environmental consequences of power generation technologies; and for (iv) understanding the impacts of various policy scenarios on the viability of coal-based power generation. The validation of the COALPSCA Model was also conducted. Five structural validity tests were performed, namely structure verification, boundary adequacy, parameter verification, dimensional consistency and extreme condition tests. Behavioural validity was also conducted which included an analysis of the sensitivity of the model outcomes to key parameters such as the load factor, discount rate, private cost growth rates and damage cost growth rates using univariate and multivariate sensitivity analysis. Finally, while attempts were made to incorporate most of the important aspects of power generation in a coal-fired power plant, not all intrinsic aspects were incorporated due to lack of data, gaps in knowledge and anticipated model complication. The shortcomings of the model were highlighted and recommendations for future research were made. / Thesis (PhD)--University of Pretoria, 2015. / tm2015 / Economics / PhD / Unrestricted

Made available in DSpace on 2014-12-17T15:01:56Z (GMT). No. of bitstreams: 1 LuizFSF_TESE.pdf: 2382677 bytes, checksum: 16f0fd92d4efa3b045a66f19b62ab2ea (MD5) Previous issue date: 2013-09-09 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / Natural gas, although basically composed by light hydrocarbons, also presents contaminant gases in its composition, such as CO2 (carbon dioxide) and H2S (hydrogen sulfide). The H2S, which commonly occurs in oil and gas exploration and production activities, causes damages in oil and natural gas pipelines. Consequently, the removal of hydrogen sulfide gas will result in an important reduction in operating costs. Also, it is essential to consider the better quality of the oil to be processed in the refinery, thus resulting in benefits in economic, environmental and social areas. All this facts demonstrate the need for the development and improvement in hydrogen sulfide scavengers. Currently, the oil industry uses several processes for hydrogen sulfide removal from natural gas. However, these processes produce amine derivatives which can cause damage in distillation towers, can cause clogging of pipelines by formation of insoluble precipitates, and also produce residues with great environmental impact. Therefore, it is of great importance the obtaining of a stable system, in inorganic or organic reaction media, able to remove hydrogen sulfide without formation of by-products that can affect the quality and cost of natural gas processing, transport, and distribution steps. Seeking the study, evaluation and modeling of mass transfer and kinetics of hydrogen removal, in this study it was used an absorption column packed with Raschig rings, where the natural gas, with H2S as contaminant, passed through an aqueous solution of inorganic compounds as stagnant liquid, being this contaminant gas absorbed by the liquid phase. This absorption column was coupled with a H2S detection system, with interface with a computer. The data and the model equations were solved by the least squares method, modified by Levemberg-Marquardt. In this study, in addition to the water, it were used the following solutions: sodium hydroxide, potassium permanganate, ferric chloride, copper sulfate, zinc chloride, potassium chromate, and manganese sulfate, all at low concentrations (?10 ppm). These solutions were used looking for the evaluation of the interference between absorption physical and chemical parameters, or even to get a better mass transfer coefficient, as in mixing reactors and absorption columns operating in counterflow. In this context, the evaluation of H2S removal arises as a valuable procedure for the treatment of natural gas and destination of process by-products. The study of the obtained absorption curves makes possible to determine the mass transfer predominant stage in the involved processes, the mass transfer volumetric coefficients, and the equilibrium concentrations. It was also performed a kinetic study. The obtained results showed that the H2S removal kinetics is greater for NaOH. Considering that the study was performed at low concentrations of chemical reagents, it was possible to check the effect of secondary reactions in the other chemicals, especially in the case of KMnO4, which shows that your by-product, MnO2, acts in H2S absorption process. In addition, CuSO4 and FeCl3 also demonstrated to have good efficiency in H2S removal / O g?s natural, embora seja composto basicamente de hidrocarbonetos leves, apresenta tamb?m em sua composi??o gases contaminantes como o CO2 (Di?xido de carbono) e o H2S (Sulfeto de hidrog?nio). O H2S, que comumente ocorre nas atividades de explora??o e produ??o de ?leo e g?s, danifica as tubula??es de transporte do petr?leo e do pr?prio g?s natural. Por isso, a elimina??o do sulfeto de hidrog?nio levar? a significativa redu??o dos custos de opera??o e a uma melhor qualidade do ?leo destinado as refinarias, resultando assim num beneficio econ?mico, ambiental e social. Tudo isso demonstra a necessidade de desenvolvimento e aprimoramento de sequestrantes que removam o sulfeto de hidrog?nio da ind?stria de petr?leo. Atualmente existem v?rios processos para o tratamento do g?s natural, utilizados pela ind?stria petrol?fera para remo??o do H2S, no entanto, eles produzem derivados de aminas que danificam as torres de destila??o, formando precipitados insol?veis que provocam entupimento dos dutos e originam res?duos de grande impacto ambiental. Por isso, a obten??o de um sistema est?vel em meio reacional inorg?nico ou org?nico capaz de remover o sulfeto de hidrog?nio sem formar subprodutos que afetem a qualidade e o custo do processamento, transporte e distribui??o do g?s natural ? de grande import?ncia. Para estudar, avaliar e modelar a transfer?ncia de massa e a cin?tica da remo??o do sulfeto de hidrog?nio (H2S) montou-se uma coluna de absor??o contendo an?is de raschig, por onde o g?s natural contaminado com H2S atravessava uma solu??o aquosa de compostos inorg?nicos estagnada, sendo por esta absorvida. A essa coluna foi acoplado a um sistema de detec??o de H2S com interface com o computador. Os dados e Equa??es do modelo foram resolvidos pelo m?todo de m?nimos quadrados modificado de Levemberg-Marquardt. Neste estudo al?m da ?gua foram utilizadas as solu??es de hidr?xido de s?dio, permanganato de pot?ssio, sulfato de cobre, cloreto f?rrico, cloreto de zinco, cromato de pot?ssio, sulfato de mangan?s, a baixas concentra??es, na ordem de 10 ppm, com o objetivo ? avaliar a interfer?ncia entre par?metros f?sicos e qu?micos da absor??o, ou mesmo buscar um melhor coeficiente de transfer?ncia de massa como ? o caso dos reatores de mistura e colunas de absor??o operando em contra corrente. Nesse contexto a avalia??o da remo??o do H2S surge como um procedimento valioso para o tratamento do g?s natural e destino dos subprodutos do processo. Os estudos das curvas de absor??o obtidos permitiram determinar a etapa controladora da transfer?ncia de massa dos processos envolvidos, os coeficientes volum?tricos de transfer?ncia de massa e as concentra??es de equil?brio, assim como, efetuar um estudo cin?tico. Os resultados mostraram que a cin?tica de remo??o do H2S ? maior para o NaOH, mas como o estudo foi realizado em baixas concentra??es de reagente pode-se verificar o efeito das rea??es secund?rias nos outros reagentes, principalmente no caso do KMnO4, que mostra seu sub produto, MnO2, tamb?m atua na absor??o do H2S. O CuSO4 e o FeCl3 tamb?m apresentaram boa efici?ncia de remo??o

This master thesis deals with the feasibility studies desulphurization of powder granulation K3 boiler at Olomouc heating station. K3 boiler burns black energetic coal and after January 1st, 2016 will not meet new more strict emission limits. The theoretical part of the thesis charts usable desulphurization methods from which the semi-dry NID appears as the most appropriate one. In the practical part there is performed a stoichiometric calculation of the flue gas and the balance of raw materials and output products. The possibility of NID method usage is confirmed here. Next the annual operating cost of the desulfurization process is calculated and some NID systems already installed references are presented.

Ein im Kupolofen erschmolzenes Eisen hat einen höheren Schwefelgehalt, als ein im Induktionsofen hergestelltes Eisen. Ist eine weitere Verwendung für die Herstellung von Gusseisen mit Vermikulargraphit vorgesehen, muss entschwefelt werden. Das Entschwefeln von Gusseisenschmelzen in Zielkorridore ist anspruchsvoll, da die Prozessgrenzen insbesondere bei der Herstellung des Werkstoffs Gusseisen mit Vermikulargraphit äußerst eng sind. Hier können eine zu starke Entschwefelung, und damit ein zu hoher Anstieg des Magnesiumgehaltes in der Schmelze vor der GJV-Behandlung, die Herstellung eines Gussteils aus GJV unmöglich machen. Allein die Kenntnis der absoluten Schwefel- und Magnesiumgehalte ist nicht ausreichend. Die zusätzliche Kenntnis der Sauerstoffaktivität bringt weitere Erkenntnisse. Ziel der Arbeit war es, die metallurgischen Wirkungsweisen der Elemente Schwefel, Magnesium und Sauerstoff während einer Entschwefelung so weit wie möglich zu quantifizieren und folglich Zusammenhänge herauszustellen und nachzuweisen. Zur Anwendung kamen hierbei insbesondere die Sauerstoffaktivitätsmessung und die thermische Analyse.