<p>The reduction of iron oxide from slag is involved in many processes, such as, bath smelting, EAF steelmaking and copper slag cleaning processes, and it is known to occur via gaseous intermediates. Four possible rate determining steps are involved during the reduction. Among them, these two interfacial chemical reactions, gas slag and gas carbon could ultimately limit the enhancement of these processes.</p><p>In this work, the gas slag reaction kinetics in slag cleaning of copper slags has been studied. The dissociation rate of CO2 on the surface of liquid copper slags is measured using an isotope exchange method, where the mass transfer in the gas phase was eliminated by using a sufficiently high gas flowrate.</p><p>It is found that, for slag of the FexO-SiO2-Al2O3-Cu2O system, the apparent rate constant remains fixed with Cu2O content from 1-10 wt pct at higher oxygen potentials. The rate constant becomes approximately 2 times higher after metallic copper is reduced from the slag, this is due to the suspension of small metal drops on the slag surface.</p><p>The effect of temperature in the range from 1200-1450°C on the rate constants was also studied. The activation energy was 190 kJ/mole for slag of composition 60FexO30SiO2-1 0Al2O3. In the presence of Cu metal~10%, the activation energy was reduced to 122 kJ/mole.</p> / Thesis / Master of Engineering (MEngr)

The inorganic chemistries of coal and petroleum differ because of their disparate geologic environments of formation, the physical state of the fuels, and the type and quantity of minerals and organic compounds in the fuels. Commercial coals typically contain 2 to 25% ash (average ~ 10%) while petroleums contain 0.003 to 0.07% ash (average ~ 0.01 %). Globally averaged, coal ash is dominated by Si, Fe, Ca, AI, and S, whereas petroleum ash contains significant quantities of V, Ni, S, Fe, Ca, Na, K, Mg, Si and AI. This larger number of important elements causes petroleum combustion slags to have more complex phase assemblages. The high vanadium contents of petroleum-based combustion feedstocks yield numerous crystalline V -oxides with stoichiometric amounts of Ca, Fe, Mg, AI, Ni andlor Na in the resulting slags. Slightly lower nickel contents yield abundant NiFe and Ni sulfides. The dominance of metals over silicon results in the formation of crystalline silicates following metal saturation of immiscible Si-rich glasses. High gasification temperatures (1200 - 1500°C) promote the development of equilibrial assemblages. Chemical variations between individual feedstock cokes coupled with nonuniform operational conditions result in three principal categories of petroleum coke slag; 1) sulfide dominant, 2) silica dominant, and 3) oxide dominant. Sulfide dominant slags are not necessarily derived from feedstocks with high sulfur contents, instead they appear to derive from feedstocks rich in chalcophile elements, predominantly Fe and Ni, by attracting sulfur otherwise lost by volatilization. Slagging additives can change the chemical categorization of resulting slags through phase modifications and the formation of new phases; this in tum can strongly alter the physical behavior of the slags. Compositionally diverse spinel oxides are the most common crystalline slag phase because of their wide thermal and compositional stability ranges, refractory nature, and rapid growth kinetics. Spinel compositions are strongly influenced by the inorganic chemistry of the feedstock, the composition of host phases, and the composition of additives. Coke slag spinels are generally enriched in AI, Fe, V, Mg, and Ni, and often contain Cr that is derived from reaction with refractory material. / Ph. D.

京都大学 / 新制・課程博士 / 博士(エネルギー科学) / 甲第25403号 / エネ博第482号 / 新制||エネ||90(附属図書館) / 京都大学大学院エネルギー科学研究科エネルギー応用科学専攻 / (主査)准教授 長谷川 将克, 教授 土井 俊哉, 教授 藤本 仁 / 学位規則第4条第1項該当 / Doctor of Energy Science / Kyoto University / DFAM

Alkaline industrial wastes are considered potential resources for the mitigation of CO2 emissions by simultaneously capturing and sequestering CO2 through mineralization. Mineralization safely and permanently stores CO2 through its reaction with alkaline earth metals. Apart from natural formations, these elements can also be found in a variety of abundantly available industrial wastes that have high reactivity with CO2, and that are generated close to the emission point-sources. Apparently, it is the applicability and marketability of the carbonated products that define to a great extent the efficiency and viability of the particular process as a point source CO2 mitigation measure. This project investigates the valorization of iron- and steel-making slags through methods incorporating the carbonation of the material, in order to achieve the sequestration of sufficient amounts of CO2 in parallel with the formation of valuable and marketable products. Iron- and steel-manufacturing slags were selected as the most suitable industrial byproducts for the purposes of this research, due to their high production amounts and notable carbonation capacities. The same criteria (production amount and carbonation capacity) were also used for the selection of the iron- and steel-making slag types that are more suitable to the scope of this work. Specifically for the determination of the slag types with the most promising carbonation capacities, the maximum carbonation conversions resulting from recent publications related to the influence of process parameters on the conversion extent of iron- and steel-manufacturing slags, were directly compared to each other using a new index, the Carbonation Weathering Rate, which normalizes the results based on particle size and reaction duration. Among the several iron- and steel-manufacturing slags, basic oxygen furnace (BOF) and blast furnace (BF) slags were found to combine both high production volumes and significant affinity to carbonation. In the context of this research, two different procedures aiming to the formation of value added materials with satisfactory CO2 uptakes were investigated as potential BF and BOF slags valorization methods. In them, carbonation was combined either with granulation and alkali activation (BOF slag), or with hydrothermal conversion (BF slag). Both treatments seemed to be effective and returned encouraging results by managing to store sufficient amounts of CO2 and generating materials with promising qualities. In particular, the performance of the granulation-carbonation of BOF slag as a method leading to the production of secondary aggregates and the sequestration of notable amounts of CO2 in a solid and stable form, was evaluated in this work. For comparison purposes, the material was also subjected to single granulation tests under ambient conditions. In an effort to improve the mechanical properties of the finally synthesized products, apart from water, a mixture of sodium hydroxide and sodium silicate was also tested as a binding agent in both of the employed processes. According to the results, the granules produced after the alkali activation of the material were characterized by remarkably greater particle sizes (from 1 to 5 mm) compared to that of the as received material (0.2 mm), and by enhanced mechanical properties, which in some cases appeared to be adequate for their use as aggregates in construction applications. The maximum CO2 uptake was 40 g CO2/kg of slag and it was achieved after 60 minutes of the combined treatment of alkali activated BOF slag. Regarding the environmental behavior of the synthesized granules, increased levels of Cr and V leaching were noticed from the granules generated by the combination of granulation-carbonation with alkali activation. Nevertheless, the combination of granulation with alkali activation or that of granulation with carbonation were found not to worsen, if not to improve, the leaching behaviour of the granules with regards to the untreated BOF slag. The formation of a zeolitic material with notable heavy metal adsorption capacity, through the hydrothermal conversion of the solid residues resulting from the calcium- extraction stage of the indirect carbonation of BF slag, was also investigated in this project. To this end, calcium was selectively extracted from the slag by leaching, using acetic acid of specific concentration (2 M) as the extraction agent. The residual solids resulting from the filtration of the generated slurry were subsequently subjected to hydrothermal conversion in caustic solution of two different compositions (NaOH of 0.5 M and 2 M). Due to the presence of calcium acetate in the composition of the solid residues, as a result of their inadequate washing, only the hydrothermal conversion attempted using the sodium hydroxide solution of higher concentration (2 M) managed to turn the amorphous slag into a crystalline material, mainly composed by a zeolitic mineral phase (detected by XRD), namely, analcime (NaAlSi2O6·H2O), and tobermorite (Ca5(OH)2Si6O16·4H2O). Finally, the heavy metal adsorption capacity of the particular material was assessed using Ni2+ as the metal for investigation. Three different adsorption models were used for the characterization of the adsorption process, namely Langmuir, Freundlich and Temkin models. Langmuir and Temkin isotherms were found to better describe the process, compared to Freundlich model. Based on the ability of the particular material to adsorb Ni2+ as reported from batch adsorption experiments and ICP-OES analysis, and the maximum monolayer adsorption capacity (Q0 = 11.51 mg/g) as determined by the Langmuir model, the finally synthesized product can potentially be used in wastewater treatment or environmental remediation applications.

Today, there is a high demand on clean steel for high performance materialproperties. Thus, steel producers try to deliver a steel product with the highestquality and cleanliness to the market. The number of parameters that affect thesteel cleanliness may vary depending on the required material properties of thefinal product. However, the non-metallic inclusion characteristics represent one ofthe most important parameters. More specifically, the composition, size, numberand morphology affect steel cleanliness. In this work, selected parameters affectingthe inclusion characteristics were studied using the following methods: i)thermodynamic calculations (including computational thermodynamiccalculations), ii) inclusion determinations using a cross sectional (CS) method (2Dinvestigations) and iii) inclusion determinations using an electrolytic extraction(EE) method (3D investigations). The computational thermodynamic calculations of the slag-steel and inclusion-steelequilibriums were carried out using the Thermo-Calc software. With the help ofthese calculations, the influence of the slag carryover on the top slag, aluminumcontent in steel and sulfur distribution ratio as well as predictions of stable phasesof inclusions were studied. In addition, inclusion determinations of tool steel gradesamples collected during various stages of the ladle treatment in a scrap-based steelplant were carried out using both 2D and 3D methods. Furthermore, inclusiondeterminations of bearing steel grade samples from a runner system after ingotcasting were performed using a 2D metallographic method (CS-method). Also, theINCAFeature software was used, when using cross sectional method, in order tocollect more statistics of the inclusion characteristics. It was found that slag carryover has a large influence on the composition of theactual top slag as well as the aluminum content in the steel as well as the sulfurdistribution ratio. In addition, steel and slag were found to be in “near”-equilibriumconditions, after the completion of the vacuum degassing operation. Furthermore,the composition of small-size inclusions in samples taken from tool steel was foundto be very scattered. Moreover, the composition of the large-size inclusions wasfound to be less scattered. Furthermore, closer to the top slag composition insamples collected after vacuum degassing. Finally, the accuracy of the inclusioncomposition determinations of tool steel samples using the electrolytic extractionmethod was found to be better than for the cross sectional method. The worseaccuracy of the CS-method is due to a considerable effect of matrix elements oninclusion composition. / QC 20100709

In recent years, there has been a growing trend for the use of industrial by-products in the production of blended cements because of economical, environmental, ecological and diversified product quality reasons. Granulated blast furnace slag, a by-product of the transformation of iron ore into pig-iron in a blast furnace, is one of these materials which is used as a cementitious ingredient. The aim of this study is to investigate the properties of Portland slag cement (CEMII/B-S) by using separate grinding and intergrinding of granulated blast furnace slag and Portland cement clinker. For this purpose, granulated blast furnace slag was used as mineral admixture replacing 30% of the clinker. Clinker and granulated blast furnace slag were ground to four different Blaine fineness values of 3000 cm2/g, 3500 cm2/g, 4000 cm2/g and 4500 cm2/g by intergrinding and separate grinding in a laboratory ball mill. Then, eight Portland slag cement mixes and four Portland cement control mixes were prepared, in order to determine and compare 2-, 7-, 28-, and 90-day compressive and flexural strengths, normal consistencies and setting times. It was found that for the Blaine fineness values of 3000 cm2/g, 3500 cm2/g and 4000cm2/g, the 2-, 7-, 28-, and 90-day compressive strength of the interground Portland slag cements had higher values than the separately ground Portland slag cements. However, for the Blaine fineness values of 4500 cm2/g, separately ground Portland slag cement specimens had slightly higher 2-, 7-, 28-, and 90-day compressive strength values than the interground ones.

<p>This thesis work aimed to provide a better knowledge of inclusion behavior at the steel-slag interface. All results are based on mathematical modeling of liquid and solid inclusion separation to the slag. The model descriptions of the inclusion transfer are based on the equation of motion at the system. It is assumed that the inclusion transfer is governed by four forces acting on the inclusion as it has reached the steel-slag interface. These are the buoyancy force, the added mass force, the drag force and the rebound force. The models assume two cases of inclusion separation depending on the inclusion Reynolds number. In the case where Reynolds number is larger or equal to unity, Re≥1, a steel film is formed between the inclusion and the slag. This steel film must first be drained before the inclusion can separate to the slag. If Reynolds number, Re<1, then no steel film is formed and the inclusion will be in direct contact with the slag. The mathematical models also propose three types of inclusion behavior as the inclusion crosses the steel-slag interface. The inclusion can either, pass and separate to the slag, oscillate at the interface with the possibility of reentering the steel bath with the steel flow or it can remain at the interface not completely separated to the slag. A parameter study for 20 μm inclusions showed that the most important parameters controlling the inclusion behavior at the steel-slag interface are the slag viscosity and the interfacial tensions between the phases. For 100μm inclusions also the inclusion density affects the inclusion behavior. The models were applied to ladle and tundish conditions. Since the slags in the chosen industrial conditions have not been studied experimentally before, estimations of the important physical property parameters were made. Future measurements will therefore be needed in order to make predictions of inclusion transfer behavior at the steel-slag interface which are more relevant for the industry. The main conclusion is that useful plots can be made in order to illustrate the tendency for the inclusion transfer and how to manipulate the physical property parameters in order to increase the inclusion separation in ladles and tundishes.</p>

Utilizando um modelo físico de uma panela siderúrgica agitada com gás, de base elíptica e escala reduzida, foram realizados estudos para verificar a influência de diversas variáveis operacionais na otimização dos processos de mistura, fenômenos de emulsificação, e comportamento da abertura do olho da coluna de bolhas durante a agitação do aço líquido. Para esses estudos foram utilizados água e querosene como simuladores do aço e escória industrial, respectivamente. Os tempos de mistura foram determinados por medidas de condutividade. O escoamento do líquido foi caracterizado por meio da técnica PIV (velocimetria por imagem de partícula) e dispersão de traçador. Ambos experimentos, assim como os fenômenos de emulsificação e abertura do olho da coluna de bolhas, foram registrados por uma câmera de vídeo. Os resultados experimentais mostram que os tempos de mistura diminuem com o aumento da vazão de gás, porém aumentam na presença de uma camada de escória. Das configurações testadas, os menores tempos de mistura foram obtidos para uma adição do traçador (ou liga) no olho da coluna de bolhas e uma posição de injeção de gás a meio raio. Os fenômenos de emulsificação aumentam com o aumento da vazão de gás, com o deslocamento da posição de injeção de gás desde a parede para o centro da panela e com o aumento da camada de escória. A abertura do olho da coluna de bolhas cresce linearmente com o aumento da vazão de gás e diminui com o aumento da camada de escória. As correlações empíricas encontradas na literatura prevêm satisfatoriamente os resultados experimentais do modelo físico. / Utilized gas stirring ladle cold model, elliptic shape and reduced scale, were carried out study for verify effects of operational variables in optimization process mixing, emulsification phenomena, behavior exposed eye of the bubble column or plume and removal inclusions during stirring steel liquid. For these study were utilized water and kerosene how simulators steel and slag industrial. The mixing time was measured by an electrical conductivity method. Fluid flow characterization were realized through PIV (particle image velocimetry) technique and tracer dispersion experiments. This is experiments as well as behavior emulsification and aperture eye of the bubble column or plume were registered by the video recordings. Experimental results show decreases mixing time with increment gas flow rate however, increment in presence of slag layer covered the bath. From the tests configurations, is low mixing time were obtained for location addition tracer (or alloy) in eye of the bubble column or plume and half radius gas position injection. This emulsification phenomena increment considerably with gas flow rate, as gas position injection is moved from the wall ladle to center and increment slag layer thickness. The aperture eye of the bubble column or plume increases linearly with increment gas flow rate and decrease with increment slag layer thickness. Empirical correlations in literature agreement satisfactory the experimental result of physical model.

Utilizando um modelo físico de uma panela siderúrgica agitada com gás, de base elíptica e escala reduzida, foram realizados estudos para verificar a influência de diversas variáveis operacionais na otimização dos processos de mistura, fenômenos de emulsificação, e comportamento da abertura do olho da coluna de bolhas durante a agitação do aço líquido. Para esses estudos foram utilizados água e querosene como simuladores do aço e escória industrial, respectivamente. Os tempos de mistura foram determinados por medidas de condutividade. O escoamento do líquido foi caracterizado por meio da técnica PIV (velocimetria por imagem de partícula) e dispersão de traçador. Ambos experimentos, assim como os fenômenos de emulsificação e abertura do olho da coluna de bolhas, foram registrados por uma câmera de vídeo. Os resultados experimentais mostram que os tempos de mistura diminuem com o aumento da vazão de gás, porém aumentam na presença de uma camada de escória. Das configurações testadas, os menores tempos de mistura foram obtidos para uma adição do traçador (ou liga) no olho da coluna de bolhas e uma posição de injeção de gás a meio raio. Os fenômenos de emulsificação aumentam com o aumento da vazão de gás, com o deslocamento da posição de injeção de gás desde a parede para o centro da panela e com o aumento da camada de escória. A abertura do olho da coluna de bolhas cresce linearmente com o aumento da vazão de gás e diminui com o aumento da camada de escória. As correlações empíricas encontradas na literatura prevêm satisfatoriamente os resultados experimentais do modelo físico. / Utilized gas stirring ladle cold model, elliptic shape and reduced scale, were carried out study for verify effects of operational variables in optimization process mixing, emulsification phenomena, behavior exposed eye of the bubble column or plume and removal inclusions during stirring steel liquid. For these study were utilized water and kerosene how simulators steel and slag industrial. The mixing time was measured by an electrical conductivity method. Fluid flow characterization were realized through PIV (particle image velocimetry) technique and tracer dispersion experiments. This is experiments as well as behavior emulsification and aperture eye of the bubble column or plume were registered by the video recordings. Experimental results show decreases mixing time with increment gas flow rate however, increment in presence of slag layer covered the bath. From the tests configurations, is low mixing time were obtained for location addition tracer (or alloy) in eye of the bubble column or plume and half radius gas position injection. This emulsification phenomena increment considerably with gas flow rate, as gas position injection is moved from the wall ladle to center and increment slag layer thickness. The aperture eye of the bubble column or plume increases linearly with increment gas flow rate and decrease with increment slag layer thickness. Empirical correlations in literature agreement satisfactory the experimental result of physical model.

Utilizando um modelo físico de uma panela siderúrgica agitada com gás, de base elíptica e escala reduzida, foram realizados estudos para verificar a influência de diversas variáveis operacionais na otimização dos processos de mistura, fenômenos de emulsificação, e comportamento da abertura do olho da coluna de bolhas durante a agitação do aço líquido. Para esses estudos foram utilizados água e querosene como simuladores do aço e escória industrial, respectivamente. Os tempos de mistura foram determinados por medidas de condutividade. O escoamento do líquido foi caracterizado por meio da técnica PIV (velocimetria por imagem de partícula) e dispersão de traçador. Ambos experimentos, assim como os fenômenos de emulsificação e abertura do olho da coluna de bolhas, foram registrados por uma câmera de vídeo. Os resultados experimentais mostram que os tempos de mistura diminuem com o aumento da vazão de gás, porém aumentam na presença de uma camada de escória. Das configurações testadas, os menores tempos de mistura foram obtidos para uma adição do traçador (ou liga) no olho da coluna de bolhas e uma posição de injeção de gás a meio raio. Os fenômenos de emulsificação aumentam com o aumento da vazão de gás, com o deslocamento da posição de injeção de gás desde a parede para o centro da panela e com o aumento da camada de escória. A abertura do olho da coluna de bolhas cresce linearmente com o aumento da vazão de gás e diminui com o aumento da camada de escória. As correlações empíricas encontradas na literatura prevêm satisfatoriamente os resultados experimentais do modelo físico. / Utilized gas stirring ladle cold model, elliptic shape and reduced scale, were carried out study for verify effects of operational variables in optimization process mixing, emulsification phenomena, behavior exposed eye of the bubble column or plume and removal inclusions during stirring steel liquid. For these study were utilized water and kerosene how simulators steel and slag industrial. The mixing time was measured by an electrical conductivity method. Fluid flow characterization were realized through PIV (particle image velocimetry) technique and tracer dispersion experiments. This is experiments as well as behavior emulsification and aperture eye of the bubble column or plume were registered by the video recordings. Experimental results show decreases mixing time with increment gas flow rate however, increment in presence of slag layer covered the bath. From the tests configurations, is low mixing time were obtained for location addition tracer (or alloy) in eye of the bubble column or plume and half radius gas position injection. This emulsification phenomena increment considerably with gas flow rate, as gas position injection is moved from the wall ladle to center and increment slag layer thickness. The aperture eye of the bubble column or plume increases linearly with increment gas flow rate and decrease with increment slag layer thickness. Empirical correlations in literature agreement satisfactory the experimental result of physical model.