Selection of desulfurizing agents and optimization of operational variables in hot metal desulfurization

The growing demand for steels with tighter compositional specifications led the Companhia Siderúrgica Nacional (CSN) to develop more efficient processes. To solve this problem this paper aims to identify the operational variables more impacting in the desulfurization process, specifically in torpedo car, as well as its causes and solutions. Then select and test, with laboratorial and industrial tests, desulfurizing agents based of CaC 2, CaO, CaCO3, and Mg to assess the cost per quantity of product desulfurized. The mixture with best results was not that one with highest content of CaC2. It is believed that this mixture showed better efficiency because of the increased agitation of the bath, produced by the releasing of gas from compound CaCO3 present in this mixture. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hot metal desulfurization by marble waste and fluorspar

The objective of this paper is to present an analysis of the use of residual marble mixtures in the pig iron desulfurization process. The study involved the use of: marble waste, fluorspar, lime, and hot metal. Four mixtures were made and added to a liquid hot metal - with known chemical composition - at a temperature of 1450ºC. The mass of each element was calculated from its chemical analysis and compared with an industrial mixture. All of the four mixtures used in the experiments were stirred by a mechanical stirrer. Samples were collected by vacuum sampling for times of 5, 10, 15, 20, and 30 minutes, and analysis was performed to check sulfur variation in the bath with time. The results were analyzed and they verified that it was possible to use marble waste as a desulfurizer.

American standard safety code for forging and hot metal stamping.

Mode of access: Internet.

Estudo da substituição da fluorita por alumina ou sodalita e de cal por resíduo de mármore em escórias sintéticas dessulfurantes.

A siderurgia vem sofrendo transformações que buscam inovação e matérias-primas alternativas. Dentro deste contexto, o uso de resíduos industriais para a formação de escórias sintéticas é tido como alternativa na busca de novos materiais e rotas de reaproveitamento de resíduos. Portanto, este trabalho teve como objetivo estudar o uso de escórias sintéticas na etapa de dessulfuração do ferro-gusa, aço e ferro fundido. Assim como, propor a utilização da sodalita e da alumina em substituição à fluorita e o resíduo de mármore em substituição à cal convencional. Inicialmente, o resíduo foi caracterizado utilizando as seguintes técnicas: análise química, análise granulométrica, área de superfície específica, difração de raios-X, microscopia eletrônica de varredura (MEV) e análise de espectroscopia por energia dispersiva (EDS). Os resultados da caracterização mostraram que aproximadamente 90% das partículas do resíduo de mármore estão abaixo de 100m e sua área superficial foi de 0,24m²/g. Através da difração de raios-X foi observado que o resíduo é composto por CaCO3, MgCO3 e SiO2. Na sequência, foram feitas simulações com o software Thermo-Calc para obter dados termodinâmicos das fases presentes nas misturas e compará-los com os resultados experimentais. Além disso, também foram calculados dados de capacidade de sulfeto (Cs), partição de enxofre (Ls) e basicidade ótica () das misturas iniciais. Posteriormente, foram realizados os ensaios experimentais em escala laboratorial para ferro-gusa, ferro fundido e aço, respectivamente nas temperaturas de 1400°C, 1550°C e 1600°C. Nos ensaios de dessulfuração do aço e do ferro-gusa, utilizou-se um rotor de alumina com o objetivo de favorecer a agitação no metal e aumentar a remoção de enxofre. Na etapa de dessulfuração do ferro-gusa, constatou-se que a fase sólida de CaO é a responsável pela remoção de enxofre e que a presença das fases silicato tricálcio e aluminato tricálcio (3CaO.SiO2 e 3CaO.Al2O3) limitam a reação, sendo maiores suas concentrações nas escórias que utilizaram o resíduo de mármore e sodalita, devido a presença de SiO2 e Al2O3 nestas matérias-primas. Já para o aço e o ferro fundido, que foram estudados com escórias à base de CaO e Al2O3, observou-se que o aumento da fase líquida favoreceu a dessulfuração. Verificou-se que a dessulfuração no ferro fundido foi por escória de topo e no aço por um processo misto, onde a fase líquida e fase sólida participaram da dessulfuração.

Behaviour of biofuel addition on metallurgical properties of sinter

Blast furnace gas yield is essentially controlled by a gas-solid reaction phenomenon, which strongly influences hot metal manufacturing costs. As a result of rising prices for reducing agents on the international market, Companhia Siderurgica Nacional decided to inject natural gas into its blast furnaces. With more gas inside the furnace, the burden permeability became even more critical. To improve blast furnace gas yield, a new technological approach was adopted; raising the metallic burden reaction surface. To that end, a special sinter was developed with permeability being controlled by adding micropore nucleus forming agents, cellulignin coal, without, however, degrading its mechanical properties. This paper shows the main process parameters and the results from physicochemical characterisation of a sinter with controlled permeability, on a pilot scale, compared to those of conventional sinter. Gas flow laboratory simulations have conclusively corroborated the positive effects of micropore nucleus forming agents on enhancing sinter permeability.

Towards sustainable Iron- and steelmaking with economic optimization

The iron and steelmaking industry is among the major contributors to the anthropogenic emissions of carbon dioxide in the world. The rising levels of CO2 in the atmosphere and the global concern about the greenhouse effect and climate change have brought about considerable investigations on how to reduce the energy intensity and CO2 emissions of this industrial sector. In this thesis the problem is tackled by mathematical modeling and optimization using three different approaches. The possibility to use biomass in the integrated steel plant, particularly as an auxiliary reductant in the blast furnace, is investigated. By pre-processing the biomass its heating value and carbon content can be increased at the same time as the oxygen content is decreased. As the compression strength of the preprocessed biomass is lower than that of coke, it is not suitable for replacing a major part of the coke in the blast furnace burden. Therefore the biomass is assumed to be injected at the tuyere level of the blast furnace. Carbon capture and storage is, nowadays, mostly associated with power plants but it can also be used to reduce the CO2 emissions of an integrated steel plant. In the case of a blast furnace, the effect of CCS can be further increased by recycling the carbon dioxide stripped top gas back into the process. However, this affects the economy of the integrated steel plant, as the amount of top gases available, e.g., for power and heat production is decreased. High quality raw materials are a prerequisite for smooth blast furnace operation. High quality coal is especially needed to produce coke with sufficient properties to ensure proper gas permeability and smooth burden descent. Lower quality coals as well as natural gas, which some countries have in great volumes, can be utilized with various direct and smelting reduction processes. The DRI produced with a direct reduction process can be utilized as a feed material for blast furnace, basic oxygen furnace or electric arc furnace. The liquid hot metal from a smelting reduction process can in turn be used in basic oxygen furnace or electric arc furnace. The unit sizes and investment costs of an alternative ironmaking process are also lower than those of a blast furnace. In this study, the economy of an integrated steel plant is investigated by simulation and optimization. The studied system consists of linearly described unit processes from coke plant to steel making units, with a more detailed thermodynamical model of the blast furnace. The results from the blast furnace operation with biomass injection revealed the importance of proper pre-processing of the raw biomass as the composition of the biomass as well as the heating value and the yield are all affected by the pyrolysis temperature. As for recycling of CO2 stripped blast furnace top gas, substantial reductions in the emission rates are achieved if the stripped CO2 can be stored. However, the optimal recycling degree together with other operation conditions is heavily dependent on the cost structure of CO2 emissions and stripping/storage. The economical feasibility related to the use of DRI in the blast furnace depends on the price ratio between the DRI pellets and the BF pellets. The high amount of energy needed in the rotary hearth furnace to reduce the iron ore leads to increased CO2 emissions.

Behaviour of biofuel addition on metallurgical properties of sinter

Blast furnace gas yield is essentially controlled by a gas-solid reaction phenomenon, which strongly influences hot metal manufacturing costs. As a result of rising prices for reducing agents on the international market, Companhia Siderurgica Nacional decided to inject natural gas into its blast furnaces. With more gas inside the furnace, the burden permeability became even more critical. To improve blast furnace gas yield, a new technological approach was adopted; raising the metallic burden reaction surface. To that end, a special sinter was developed with permeability being controlled by adding micropore nucleus forming agents, cellulignin coal, without, however, degrading its mechanical properties. This paper shows the main process parameters and the results from physicochemical characterisation of a sinter with controlled permeability, on a pilot scale, compared to those of conventional sinter. Gas flow laboratory simulations have conclusively corroborated the positive effects of micropore nucleus forming agents on enhancing sinter permeability.

Corrosion behavior in graphite refractories impregnated with ZrO 2 and CeO 2 carrying solutions

This paper investigates corrosion behavior in graphite refractory hot metal impregnated with ZrO 2 and CeO 2 carrying solutions used in Blast Furnace hearth, consisting of 50% graphite and 50% anthracite. Corrosions tests were carried out by means of finger test method in an induction furnace, using bar-shaped 30×30×280 mm test specimens and hot metal from CSN#2 Blast Furnace runner. The temperature chosen for this test was 1520°C and sixty-minute isotherm. Upon test completion, test specimens were characterized by their dimensional variation, X-ray diffractometry and Scanning Electronic Microscopy (SEM).

Estudo da combustão de carvões e misturas com o coque verde de petróleo injetadas em altos fornos

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Modeling of burden distribution in the blast furnace

The blast furnace is the main ironmaking production unit in the world which converts iron ore with coke and hot blast into liquid iron, hot metal, which is used for steelmaking. The furnace acts as a counter-current reactor charged with layers of raw material of very different gas permeability. The arrangement of these layers, or burden distribution, is the most important factor influencing the gas flow conditions inside the furnace, which dictate the efficiency of the heat transfer and reduction processes. For proper control the furnace operators should know the overall conditions in the furnace and be able to predict how control actions affect the state of the furnace. However, due to high temperatures and pressure, hostile atmosphere and mechanical wear it is very difficult to measure internal variables. Instead, the operators have to rely extensively on measurements obtained at the boundaries of the furnace and make their decisions on the basis of heuristic rules and results from mathematical models. It is particularly difficult to understand the distribution of the burden materials because of the complex behavior of the particulate materials during charging. The aim of this doctoral thesis is to clarify some aspects of burden distribution and to develop tools that can aid the decision-making process in the control of the burden and gas distribution in the blast furnace. A relatively simple mathematical model was created for simulation of the distribution of the burden material with a bell-less top charging system. The model developed is fast and it can therefore be used by the operators to gain understanding of the formation of layers for different charging programs. The results were verified by findings from charging experiments using a small-scale charging rig at the laboratory. A basic gas flow model was developed which utilized the results of the burden distribution model to estimate the gas permeability of the upper part of the blast furnace. This combined formulation for gas and burden distribution made it possible to implement a search for the best combination of charging parameters to achieve a target gas temperature distribution. As this mathematical task is discontinuous and non-differentiable, a genetic algorithm was applied to solve the optimization problem. It was demonstrated that the method was able to evolve optimal charging programs that fulfilled the target conditions. Even though the burden distribution model provides information about the layer structure, it neglects some effects which influence the results, such as mixed layer formation and coke collapse. A more accurate numerical method for studying particle mechanics, the Discrete Element Method (DEM), was used to study some aspects of the charging process more closely. Model charging programs were simulated using DEM and compared with the results from small-scale experiments. The mixed layer was defined and the voidage of mixed layers was estimated. The mixed layer was found to have about 12% less voidage than layers of the individual burden components. Finally, a model for predicting the extent of coke collapse when heavier pellets are charged over a layer of lighter coke particles was formulated based on slope stability theory, and was used to update the coke layer distribution after charging in the mathematical model. In designing this revision, results from DEM simulations and charging experiments for some charging programs were used. The findings from the coke collapse analysis can be used to design charging programs with more stable coke layers.

Developments in hot-filament metal oxide deposition (HFMOD)

Hot-filament metal oxide deposition (HFMOD) is a variant of conventional hot-filament chemical vapor deposition (HFCVD) recently developed in our laboratory and successfully used to obtain high-quality, uniform films of MOx WOx and VOx. The method employs the controlled oxidation of a filament of a transition metal heated to 1000 degrees C or more in a rarefied oxygen atmosphere (typically, of about 1 Pa). Metal oxide vapor formed on the surface of the filament is transported a few centimetres to deposit on a suitable substrate. Key system parameters include the choice of filament material and diameter, the applied current and the partial pressures of oxygen in the chamber. Relatively high film deposition rates, such as 31 nm min(-1) for MoOx, are obtained. The film stoichiometry depends on the exact deposition conditions. MoOx films, for example, present a mixture of MoO2 and MoO3 phases, as revealed by XPS. As determined by Li+ intercalation using an electrochemical cell, these films also show a colouration efficiency of 19.5 cm(2) C-1 at a wavelength of 700 nm. MOx and WOx films are promising in applications involving electrochromism and characteristics of their colouring/bleaching cycles are presented. The chemical composition and structure of VOx films examined using IRRAS (infrared reflection-absorption spectroscopy), RBS (Rutherford backscattering spectrometry) and XPS (X-ray photoelectron spectrometry) are also presented. (c) 2007 Elsevier B.V. All rights reserved.