Lietuvoje nėra didelių iškastinio kuro išteklių (akmens anglies, gamtinių dujų ar naftos), galinčių patenkinti šalies energetinius poreikius. Todėl Lietuvai yra ypač svarbus tinkamas vietinių ir atsinaujinančių energijos išteklių galimybių išnaudojimas. Didžiausią potencialą Lietuvoje turi biomasė ir biokuras. Taip pat ne mažiau reikšmingas bioenergijos gamybos ir naudojimo privalumas yra mažesnis neigiamas poveikis aplinkai bei klimatui. Magistrantūros baigiamojo darbo tikslas yra išanalizuoti Lietuvos medienos išteklius bei jų atsinaujinimą. Išanalizuoti biokuro katilinių parametrus esant skirtingam šiluminiam našumui ir sudaryti bandymų lentelę remiantis energetiniame objekte sumontuota pakura. Darbe atliekama kietojo biokuro sudėties ir charakteristikų analizė. Aprašomas technologinio proceso automatinis valdymas, katilinės sandara ir t.t. / Lithuania there are no significant fossil fuel resources (coal, natural gas or oil) that can meet the country's energy needs. Therefore, the country is vital to the local and renewable energy opportunities. Lithuania has the highest potential of biomass and biofuels. It is also no less important bioenergy production and use of the advantage of a lower negative impact on the environment and climate. Master's thesis is to analyze the Lithuanian wood resources and their regeneration. Also consider biofuel combustion process using the latest technology of biofuels through the regime of the test results table. The work carried out in the solid biofuel composition and characteristics of the analysis. Chosen object and the regime carried out research and calculations to determine the biomass boiler parameters at different thermal performance. Describe the process automatic control, boiler structure.

A mathematical model of a steam-methane reformer (SMR) was developed for use in process performance simulations and on-line monitoring of tube-wall temperatures. The model calculates temperature profiles for the outer-tube wall, inner-tube wall, furnace gas and process gas. Reformer performance ratios and composition profiles are also computed. The model inputs are the reformer inlet-stream conditions, the geometry and material properties of the furnace and catalyst-bed. The model divides the furnace and process sides of the reformer into zones of uniform temperature and composition. Radiative-heat transfer on the furnace side is modeled using the Hottel Zone method. Energy and material balances are performed on the zones to produce non-linear algebraic equations, which are solved using the Newton-Raphson method with a numerical Jacobian. Model parameters were ranked from most-estimable to least estimable using a sensitivity-based estimability analysis tool, and model outputs were fitted to limited data from an industrial SMR. The process-gas outlet temperatures were matched within 4 ºC, the upper and lower peep-hole temperatures within 12 ºC and the furnace-gas outlet temperature within 4 ºC. The process-gas outlet pressure, composition and flow rate are also accurately matched by the model. The values of the parameter estimates are physically realistic. The model developed in this thesis has the capacity to be developed into more specialized versions. Some suggestions for more specialized models include modeling of separate classes of tubes that are in different radiative environments, and detailed modeling of burner configurations, furnace-gas flow patterns and combustion heat-release patterns. / Thesis (Master, Chemical Engineering) -- Queen's University, 2009-01-06 21:50:35.04

The purpose of this project was to produce a “greener” cement from granulated ground blast furnace slag (GGBS) using non-Portland cement activation. By eventually developing “greener” cement, the ultimate goal of this research project would be to reduce the amount of Portland cement used in concrete, therefore reducing the amount of carbon dioxide emitted into the atmosphere during cement production. This research studies the behavior of mineral binders that do not contain Portland cement but instead comprise GGBS activated by calcium compounds or fluidized bed combustion (FBC) bottom ash. The information described in this paper was collected from experiments including calorimetry, which is a measure of the release of heat from a particular reaction, the determination of activation energy of cement hydration, mechanical strength determination, and pH measurement and identification of crystalline phases using X-ray diffraction (XRD). The results indicated that it is possible to produce alkali-activated binders with incorporated slag, and bottom ash, which have mechanical properties similar to ordinary Portland cement (OPC). It was determined that the binder systems can incorporate up to 40% bottom ash without any major influence on binder quality. These are positive results in the search for “greener cement”.

The thermodynamic conditions for the behaviour of silicon in the lower part of the blast furnace have been the focus of the thesis. More specifically, the influences of temperature, carbon activity, total gas pressure and Fe reoxidation on silicon have been studied. Calculations show that an increased temperature gives higher equilibrium ratio between silicon in hot metal and slag. Furthermore, laboratory reduction studies shows that the carbon activity in the cohesive zone increase with an increased reduction time. Increased carbon activity will increase the equilibrium silicon content in liquid metal. Equilibrium calculations based on tapped hot metal and slag shows that the equilibrium silicon content of the liquid metal phase is higher than measured at tapping. Around the raceway area the equilibrium silicon content is very high. The high equilibrium silicon content makes it important to differ between the conditions under operation and the conditions of samples taken out of the blast furnace before studied. The equilibrium silicon content is strongly correlated to the CO gas partial pressure. Often this partial pressure is changed during sampling and cooling of samples. At tapping the equilibrium partial pressure of CO has been calculated to higher values than the total gas pressure inside the blast furnace. Metal droplets found in tapped slags are probably formed by reduction of FeO. In the periphery part of the lower part of the blast furnace, it is believed that mainly FeO oxidises silicon in hot metal. It is not expected that the metal droplets in the slag is formed if FeO oxidises dissolved silicon. Instead, the iron droplets may form at reactions with gas, coke carbon or coal powder carbon. Around some droplets increased magnesium content has been found. This may be due to reactions with gaseous magnesium that, according to thermodynamic conditions, is easy to form. It has been reported that much FeO may be formed in the raceway area. The metal droplets may indicate how much FeO that reacts with other components than liquid iron. The iron found in metal droplets in the slag corresponds to between 0.02 and 0.2 wt-% FeO in the slag.

Graphite Furnace Atomic Absorption Spectroscopy (GFAA) and Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES) are two primary means of analyzing metals at the elemental level. Both techniques are widely accepted as tools for basic research. Each technique is performed differently and has its own distinct advantages as well as disadvantages. The choice of which technique to employ is determined by the needs of the analysis and the limitations of the instrumental technique.The idea to merge the two techniques was originallydeveloped by the research group of Dr. Michael W. Blades of the University of British Columbia, Vancouver, in 1989, who successfully demonstrated a "mini" plasma within a graphite furnace. The goal of the research was to design a device that would combine the advantages of both techniques and hopefully eliminate or minimize the unfavorable characteristics of each technique.The sustaining of a "mini" plasma has been demonstrated by this group. Although the end result was similar to that of Blades' group, the method of achieving the plasma was such that the "new" instrument could easily be mounted onto the furnace via a small Interface/Power Coupling device. The advantages of this system are: existing GFAA instruments can be used; modification of the furnace and RF supply is minimal; RF electronics can be remotely located; removal of the interface device is quickly achieved; and sample introduction, through the use of an autosampler, can be facilitated with small modification.Background spectra were acquired using helium, argon, and a mixture of argon/helium. It was found that all the plasmas have highly structured backgrounds and demonstrate the potential for many analysis regions. Two methods of sample introduction were used in acquiring the line emission of magnesium: injection through the sample inlet port to the furnace and end window injection. Inlet port injection suffers from a loss of sensitivity, when compared to end cap injection, but is more easily performed. / Department of Chemistry

Die vorliegende Arbeit beinhaltet die theoretische Betrachtung des Glasschmelzprozesses in Glasschmelzöfen und die Darstellung von fünf Bewertungsprinzipien zur qualitativen Bewertung von Glasschmelztechnologien für die Abschmelz-, Restquarz- und Läuterzone. Es konnte gezeigt werden, dass zum verbesserten Einschmelzen des Gemenges nicht nur der Energieeintrag, sondern auch der Abtransport der neu entstehenden Schmelze intensiviert werden muss. Bei der qualitativen Bewertung und der Auswahl von Schmelztechnologien zur Beschleunigung der Restquarzlösung wurde dargestellt, dass der Einfluss der Schmelztechnologie auf das Verweilzeitverhalten und damit rückwirkend auf die Effizienz der Restquarzlösezone bei der Vorauswahl von Schmelztechnologien berücksichtigt werden muss. Für die Läuterzone wurde nachgewiesen, dass zwei teils in der Literatur diskutierte Bewertungsprinzipien zur Läuterung von Glasschmelzen abzulehnen sind bzw. zu überschätzten Aussagen zur Effizienz von Läutertechnologien führen. Weiterhin konnte gezeigt werden, dass für den theoretischen Fall einer Läuterbank ohne Konvektionsströmungen die Blasenwachstumsgeschwindigkeiten für Konstruktionen mit minimalen Kosten im Bereich von 4-12*10-7 m/s mit möglichen Ausreißern zu 5*10-6 m/s bei Massengläsern liegen sollten.

[pt] A indústria de minério de ferro tem importante papel na melhoria das condições de vida da população mundial por ser o principal insumo à produção de aço que, por sua vez, é o material mais utilizado e com as mais variadas aplicações no mundo. Neste contexto, é de suma importância o desenvolvimento tecnológico das empresas de mineração no âmbito de produzir seus minérios com mais qualidade, em maior escala e com menores custos para o benefício de toda a cadeia. Foi desenvolvido neste trabalho um modelo de medição do Valor em Uso de cargas metálicas no processo de Alto-Forno, que é a rota mais importante e responsável por 94 por cento da produção mundial de ferro primário. Os resultados do modelo desenvolvido foram validados com dados reais de 23 Altos-Fornos de 7 países, os quais possuem práticas operacionais distintas. Este modelo apresentou um desvio médio de 4 por cento entre os resultados obtidos e os dados de operação. O estudo de caso para cálculo de Valor em Uso foi realizado focando um dos 23 Altos-Fornos, operando com uma distribuição de carga metálica composta de sínter, pelota e lump, similar à média mundial. A proporção de pelotas na carga metálica foi variada de 17 a 50 por cento. Em um dos cenários avaliados, a adição de valor no processo siderúrgico, advinda desta variação, foi de 4,6 por cento na margem de contribuição, e de 2,1 por cento na produtividade do Alto-Forno. Caso este ganho em valor fosse transferido ao preço do insumo pelota de minério de ferro, este poderia ser acrescido em 11 por cento. Os resultados obtidos evidenciam o quão importante é o desenvolvimento das ferramentas de análise de Valor em Uso para uma maior explicitação dos ganhos ou perdas proporcionados pelos diferentes tipos de minérios de ferro. Além disso, a análise de Valor em Uso demonstrou estar relacionada com as condições específicas do mercado e dos acordos comerciais estabelecidos e, sem dúvida, se constitui numa poderosa ferramenta para o desenvolvimento das indústrias de minério de ferro e aço. / [en] As steel is the most utilized and applied material in the world the iron ore industry has a very important role to society on improving human beings life conditions. It is of single importance the technological development of iron ore companies on producing higher quality materials, in larger scales and at lower costs creating value to the whole. It was developed an iron ore burden Value In Use assessment model for the Blast Furnace process which is responsible for producing 94 percent of all iron in the World. The outputs from the model were cross checked with real operational data of 23 Blast Furnaces with distinct practices, from 7 countries. The model exhibited an average deviation achieved was of 4 percent between the calculated outputs and the operational data set. For the case study one out of the 23 Blast Furnaces was chosen due its world average equivalent burden distribution in terms of sinter pellets and lump to perform an iron ore Value In Use assessment. Scenarios were built with pellet participation in the metallic burden varying from 17 to 50 percent, achieving 4,6 percent gains in the contribution margin and 2,1 percent incremental BF productivity in one of the scenarios. If all this gain is reverted to the pellet price, it could be increased by 11 percent. The obtained results show how important the development of Value In Use analysis tools are as to revel true gains or losses from each iron ore type to the process. Further Value In Use analysis is an important tool to mining and steel industries and is always made against one reference case, relating it to a specific market and commercial conditions being applied to a single operation.

A injeção de carvão pulverizado (PCI — pulverized coal injection) nos altos-fornos (AFs) é uma tecnologia utilizada pelas usinas siderúrgicas para aumentar a produtividade e diminuir o consumo de coque no AF. Nas últimas décadas as taxas de injeção de carvão pulverizado aumentaram na maior parte dos AFs. O principal problema associado à utilização de altas taxas de PCI é a geração de char (carvão incombusto) na zona de combustão. Este material percorre um caminho ascendente junto ao fluxo gasoso, podendo acumular-se e assim prejudicar a permeabilidade do AF. A presença, nas amostras sólidas recolhidas do gás de saída do AF, de altos teores de char pode ser o resultado da injeção de um carvão pulverizado com uma combustibilidade inadequada e de uma operação instável do AF. Portanto, conhecer a proporção de char que sai do AF contribuirá na seleção do tipo de carvão utilizado e na otimização da prática de PCI. Análises químicas das amostras de pó do AF revelam, sem distinguir, a presença de materiais carbonosos. A microscopia ótica foi utilizada para estudar estas amostras sólidas, mas apresenta certas limitações. A difração de raios-X (DRX) é uma técnica padrão para caracterizar a estrutura cristalina dos materiais. Ela também pode ser utilizada para quantificar as dimensões dos cristalitos (Lc, La, etc.) dos materiais carbonosos. Uma vez que a estrutura do coque é mais ordenada que a do char, seria possível quantificar a proporção destes materiais nas amostras de pó do AF através da DRX combinada a análises químicas. O objetivo principal deste trabalho foi identificar e quantificar os componentes carbonosos (char e finos de coque) presentes no pó de balão (PB) do AF, por DRX e análise elementar de carbono. O efeito da temperatura sobre a grafitização do coque também foi avaliado, a fim de identificar a possível origem dos finos de coque gerados no AF. Três amostras de PB coletadas de um AF, uma em operação a coque e duas a PCI, foram selecionadas. Os pós foram fracionados e analisados quimicamente. Após, as frações destas amostras foram moídas, desmineralizadas e analisadas por DRX e análise elementar de carbono. Amostras de char produzidas em laboratório e respectivos carvões foram utilizados como padrões para a quantificação. Amostras de coque foram tratadas termicamente a diferentes temperaturas, sendo posteriormente analisadas por DRX. Este estudo mostrou que a DRX pode ser usada como técnica padrão para identificar as estruturas do char e do coque podendo ser utilizada para quantificar a proporção destes materiais carbonosos no pó de balão do AF. Além disto, observou-se que quanto maior a temperatura de tratamento térmico mais ordenada fica a estrutura cristalina do coque. / In a Blast Furnace (BF), Pulverized coal injection (PCI) is the most popular injection technology used worldwide to reduce coke consumption and to increase the productivity. In the last decades the PCI injection rates raised in the most of BFs. One of the problems during the PCI operation in BF is the unburnt char formation. Higher char levels in the BF stack could impact burden permeability. The off gas BF solid samples contain char, coke fines, metallic oxides, etc. The quantification of the carbonaceous materials content in these samples could be used to improve the PCI performance in operating BF. Chemical analysis in the BF dust samples reveal without differentiates some carbonaceous material. The optical microscopy was used to study these solid samples but with some restrictions. XRD (X-ray diffraction) is a standard means of characterizing the structure of materials. This technique has been utilized to determine the crystallite sizes (Lc, La, etc.), in carbonaceous materials. Since the coke structure is more ordered than the char structure, it would be possible to quantify the proportion of these materials in the off-gas BF samples by chemical analysis in combination with XRD. The aim of this work is to identify and quantify carbonaceous components (coal, char and coke fines) in the flue dust BF samples through the use of the XRD technique and ultimate analysis. Besides, the effect of temperature on coke graphitization will be studied aiming to identify the possible origin of coke fines in the BF dust. Four dusts collected in the off-gas BF, two at all coke and two at PCI operations, were selected for this investigation. The dusts were fractioned and chemically analyzed. After the fractions were grounded, demineralized and analyzed by ultimate analysis and XRD. Besides, were investigated the atomic structure of raw coals and its laboratory char, and raw coke and its laboratory heattreated samples. This study has shown that the XRD technique could be used as a standard procedure to identify the char and coke structures and could be used to quantify the fines proportions of these carbonaceous materials in the BF flue dust. It was concluded that the bigger the annealing temperature the more ordered becomes the atomic coke structure.

O ferro-esponja ou DRI (Direct Reduced Iron) é obtido pelo processo de redução direta onde o minério de ferro é transformado em ferro metálico através de reações químicas envolvendo o estado sólido (minério) e o gasoso (gases redutores). Neste processo o minério de ferro não passa pelo estado líquido como ocorre com o ferro-gusa. Isto confere ao ferro-esponja algumas desvantagens que prejudicam o seu desempenho nas aciarias. Pode-se citar a redução no rendimento metálico e o maior consumo de energia elétrica como principais impactos de sua utilização intensiva. O ferro-esponja apresenta menor quantidade de ferro total (maior quantidade de impurezas) do que o ferro-gusa e também apresenta óxidos de ferro remanescentes em sua estrutura (menor metalização). Para torná-lo mais competitivo, inúmeras melhorias no processo têm sido promovidas para aumento da metalização. No entanto, o limite superior alcançado na prática tem ficado ao redor de 95%. Visando contribuir para melhorar a qualidade do ferro-esponja este trabalho apresenta uma proposta inovadora a partir da técnica de auto-redução. O objetivo é aumentar o grau de metalização do ferro-esponja através de seu aquecimento. Para isso, foram realizadas análises termogravimetrias e aquecimentos em forno mufla; análises químicas por via úmida, difração de raios-x, espectroscopia mössbauer e análise de microssonda de raios-x. As análises estruturais foram realizadas utilizando microscópio eletrônico de varredura para confirmar a efetividade da técnica apresentada. Nesta dissertação pode-se comprovar que, através da técnica de auto-redução, o ferro-esponja alcança metalizações acima de 98% em detrimento da queda do teor de carbono total. Um aumento de 4% na metalização traz um ganho estimado de 5 a 10% no consumo de energia elétrica nos fornos de fusão e um acréscimo proporcional na produção horária das aciarias. / The direct reduced iron is obtained by direct reduction process, where iron ore is transformed in metallic iron via chemical reactions involving solid (ore) and gaseous (reductant gases) states. In this process the iron ore does not pass by liquid state like pig iron. This become to direct reduced iron some disadvantages, which decrease its performance in the steelmaking process. It can be mentioned the reduction of metallic yield and the higher consumption of electric energy as the main impacts of its intensive use. The direct reduced iron presents lower amount of total iron (higher amount of impurities) than pig iron and presents iron oxides remained in its structure (lower metallization). To become more competitive, several improvements in the reduction process have been carried out to increase its metallization. However, the highest level of metallization, which has been reached, is 95%. To improve the direct reduced iron quality, the present work evaluates, in an innovative way, using the technique of self reduction. The objective is increase of metallization of the direct reduced iron through its heating. Thermal, chemical and structural characterization was carried out to check the effectiveness of the investigated technique. The research confirms that the direct reduced iron can reach a metallization higher than 98% with a decrease of total carbon amount using the technique presented in this work. An improvement of 4% in the metallization brings savings of 5 to 10% in the electric energy consumption of the electric arc furnaces and a proportional increase of the production in the steelmaking plants.

O presente trabalho tem como objetivo a caracterização do carvão da mina de Leão IIcamada inferior, com a finalidade de gerar carvão pulverizado para a injeção nas ventaneiras do alto-forno na indústria siderúrgica. Esta prática visa diminuir o custo do coque, através do aumento da taxa de substituição do coque por carvões brasileiros de baixo rank. Para o estudo foram realizados ensaios de beneficiamento, análise imediata e elementar, poder calorífico, análise petrográfica e índice de inchamento livre. Na 1ª etapa de ensaios de beneficiamento, usaram-se densidades entre: 1,3-2,4g/cm3, com intervalo de diferença de 0,1 e 0,2 para as densidades de 1,3-1,9 e 2,0-2,4 g/cm3, respectivamente.Verificou-se que a fração de densidade 1,3 g/cm3 apresentou uma menor recuperação (2,0%) e um teor de cinzas de 4,3%. As maiores massas foram obtidas nas densidades de 1,4; 1,5 e 2,4 g/cm3, com recuperação de 11,1%;14,3% e 22,2% e teores de cinzas de 14,9%; 24,3% e 83,4%, respectivamente. Foram escolhidas as frações de densidades 1,4 e 1,5 g/cm3 com maior recuperação na 1ª etapa e com teor de cinzas em torno de 12 a 18%, conforme as curvas lavabilidade. Na 2ª etapa foi flutuado o carvão nas densidades de interesse escolhidas para o PCI e obtiveram-se recuperações mássicas de 13,11% e 27,00%, respectivamente. Assim as recuperações das médias ponderadas corresponderam a 22,46% para os carvões de interesse com alto teor de matéria carbonosa enquanto para as frações indesejadas obteve-se 80,45% em massa. A partir da análise imediata foram obtidos os teores das frações densidades flutuadas de 1,4 e 1,5 g/cm3, obteve-se os seguintes teores: U%- 14,45%; Cz(%bs)-15,22%;MV(bs)-36,04%; MV(bsic)- 42,51%; CF(bs) -50,54% e CF(bsic)- 59,6%. As médias da análise elementar obtida das duas frações foram: enxofre total-0,54%, hidrogênio total-5,44% e carbono total-56.74%, respectivamente. O poder refletor da vitrinita médio foi de 0,46 a 0,48% Ro, sendo classificado como sub-betuminosoB de acordo com a ASTM. O valor do poder calorífico médio foi de 5462 kcal/kg. A fração FL 1,4 é levemente aglutinante com 0,5 de perfil de inchamento, pois concentrou mais vitrinita e perfil zero (0) para fração de FL 1,5g/cm3 e NB, não sendo aglutinante. A partir dos resultados o carvão de leão II apresenta altos voláteis, bom poder calorífico superior; baixo S<1% e teores de cinzas e umidade razoáveis após beneficiamento em densidade de 1,4 a 1,5g/cm3. Assim pode ser usado para PCI, mas há necessidade de se fazer a devida mistura com carvão de médio e/ou alto rank para ajustar algumas propriedades de interesse de acordo com as exigências de cada alto-forno. / The present study concerns itself with the characterization of coal from the mine of Leão II (lower layer), for use in the steel industry with the purpose of generating pulverized coal for injection in the blast furnace. This practice is intended to reduce the cost of coke, by increasing the rate of replacement of Coke by Brazilian low-rank coals. For the study, were carried processing trials, proximate(%) and ultimate(%) analysis, calorific value, petrographic analysis and free swelling index. In the first step of processing tests, it was used density in between densities: 1.3-2, 4 g/cm3, with range of difference of 0.1 and 0.2 to 1.3 densities-1.9 and -2.0 2.4 g/cm3, respectively. It was found that the fraction of 1.3 g/cm3 density showed a minor recovery (2.0%) and an ash content of 4.3%. The biggest masses were obtained in 1.4; 1.5 and 2.4 g/cm3 densities, with 11.1%; 14.3% and 22.2% recovery and 14.9%; 24.3% and 83.4% ash content, respectively. There were chosen the fractional density 1.4 and 1.5 g/cm3 with greater recovery on the first step and with ash content around 12 to 18%, as the washability curves. The second stage was floated coal in densities of interest chosen for PCI and led to mass recalls of 13.11% and 27.00%, respectively. So recoveries of weighted averages corresponded to 22.46% to the coals with high carbon content while the unwanted fraction was 80.45% by mass. From the immediate analysis were obtained the contents of the fractions of floated densities of 1.4 and 1.5 g/cm3, the following levels: U%- 14.45%; as (% bd)- 15.22%; VM (bd)- 36.04%; VM (daf)- 42.51%; FC(bd)- 50.54% and FC (daf)- 59.6%. The averages of the elemental analysis obtained from two fractions were: total sulphur- 0.54%, total hydrogen- 5.44% and total carbon- 56.74%, respectively. The vitrinite reflector medium power was of 0.46 to 0.48% Ro, being classified as Sub-bituminous B in accordance with the ASTM standard. The value of the calorific average was of 5462 kcal/kg. The fraction FL 1.4 is slightly binder with 0.5 swelling profile because it obtained more vitrinite and focused profile of zero (0) for FL1.5 g/cm3 fraction and NB not agglutinative. From the results the Leão II coal has it was obvious presenting high volatile, good upper calorific value; low levels of S<1% and ashes and humidity reasonable after processing in density of 1.4 to 1.5 g/cm3. So it can be used for PCI, but there is need to do proper mixture with medium carbon and/or high rank to set some properties of interest according to the requirements of each blast furnace.