Kinetic model for reduction of iron oxide in molten slags by iron-carbon melt

Rate of reduction of iron oxide in iron and steelmaking slags by mass contents of dissolved carbon (>3%) in molten iron depends upon activity of FeO, temperature, mixing of bulk slag and other experimental conditions. A general kinetic model is developed by considering mass transfer of FeO in slag, chemical reaction at gas-metal interface and chemical reaction at gas-slag interface, respectively, as the three rate controlling steps. A critical analysis of the experimental data reported in literature has been done. It is shown that in the case of slags containing mass contents of less than 5% FeO, the reduction of FeO is controlled by mass transfer of FeO in slag plus chemical reaction at gas-metal interface; when slags contain more than 40% FeO, the reduction of FeO is controlled by chemical reaction at gas-metal interface plus chemical reaction at gas-slag interface; at intermediate FeO mass contents (between ～ 5 and 40% FeO), the reduction of FeO is controlled by all three steps, namely, mass transfer of FeO in slag, chemical reaction at gas-metal interface and chemical reaction at gas-slag interface. The temperature dependence of rate constant for the gas-slag reaction is obtained as: In k₂ = –32345.4(&6128)/ T + 19.0(&3.42); σ_lnk2,1/T = &0.3. where k₂ is expressed in mol m^-2 s^-1 bar^-1. The mass transfer coefficient of iron oxide in bulk slag is found to vary in the range 1.5 × 10^-5 to 5.0 × 10^-5 m/s, depending upon the slag composition as well as experimental conditions.     

Determination of the melting time of an Fe-Al ferroalloy in an iron-carbon melt

The melting times of ferroaluminum alloys of various compositions have been calculated. A model for the melting of these ferroalloys in an iron-carbon melt is presented. The melting time is found to depend on the aluminum content in the alloy, the ferroaluminum lump size, and the iron-carbon melt temperature.     

Rates and mechanisms of FeO reduction from slags

The rate of FeO reduction from CaO?SiO₂ slags has been determined in a stationary magnesia crucible with a graphite rod as the reductant. At 1650°±35°C, with a slag basicity CaO/SiO₂=1.2±0.3, and in the total iron concentration,C, range of 10 pct<C<40 pct, the specific rate,Q _E , of reduction in g-moles per min per sq cm was found to beQ _E =8.25×10^?6 C ^1.77 According to this and previous literature results, the reduction rates span three possible stages. The order of reaction in regard to concentration varies from first order in the low concentrations (0.1 pct<C<1.5 pct) to second order in the intermediate concentrations (1.5 pct<C<15 pct) and finally to 1.77th order in the high concentrations (15 pct<C<40 pct). The reduction reaction can best be interpreted by convective mechanisms because the observed rates fall between the rates of the chemically limited graphite gasification and the rates predicted from molecular diffusion.     

Kinetics of simultaneous reactions between liquid iron-carbon alloys and slags containing MnO

The oxidation rates of carbon, phosphorus, and silicon; the desulfurization rate of liquid iron; and the simultaneous reduction rate of MnO from slag were examined at 1450 °C to 1550 °C by using high carbon iron alloys and CaO-SiO₂-CaF₂ slags containing MnO and FeO. The reaction rates were well reproduced by a kinetic model describing the reaction between the slag and multicomponent iron alloys. The controlling steps applied for the reactions considered in the present kinetic simulation were as follows. The rate of decarburization is controlled by the chemical reaction at the slag-metal interface, and those of the other reactions are controlled by the transport in slag and metal phases. Both observation and simulation results showed that MnO was not a strong oxidizer compared with FeO in the slag, but was an effective component for desulfurization. The simulation results also showed that the interfacial oxygen activity using MnO-based slag was much lower than that using FeO-based slag. The apparent equilibrium constants of phosphorus and sulfur, which were obtained by the kinetic modeling of experimental results, were found to increase with increasing the (MnO + CaO)/SiO₂ ratio of the slag. The controlling step(s) of each element transport across the slag-metal interface was discussed with the aid of the kinetic model.     

Kinetics of manganese oxide reduction from basic slags by carbon dissolved in liquid iron

The reduction of manganese oxide from a basic slag by carbon dissolved in liquid iron is a slow reaction, failing to approach equilibrium closely in 20 hr. Furthermore, the rate of stirring has no apparent effect on the reaction rate. This identifies the rate-controlling step as a chemical reaction at the interface. Only the model for the reactionO ²⁻ =O + 2e ⁻ gave a consistent interpretation as the melt geometry, and concentration of manganese oxide and carbon were varied. The rate constant for this reaction was found to be 1.28 × 10⁻⁵ mole per sq cm per min at 155O°C. The effect of temperature is substantial with a calculated energy of activation for the system of 25 kcal per mole. Formerly Graduate Student, The University of Michigan This paper is based on a portion of a thesis submitted by W. L. DAINES in partial fulfillment of the requirements for the degree Doctor of Philosophy at The University of Michigan.     

On the problem of zinc extraction from the slags of lead heat

The possibilities of zinc extraction from the slags of lead heat are studied as applied to the ZAO Karat-TsM lead plant to be built for processing ore lead concentrates. The process of zinc extraction into commercial fumes using the technology of slag fuming by natural gas developed in Gintsvetmet is recommended for this purpose. Technological rules are developed for designing a commercial fuming plant, as applied to the conditions of the ZAO Karat-TsM plant.     

Kinetics of iron oxide reduction from CaO-MgO-FeOn-SiO2 slags by silicon dissolved in liquid iron

At steelmaking temperatures, the kinetics of slag-metal reactions is usually determined by mass transfer. This occurs in two ways: normal mass transfer which is induced by stirring, and mass transfer by interfacial convection induced by interfacially active elements like oxygen and sulphur. In the present work, mass transfer during the reduction of iron oxide from a basic slag by silicon dissolved in liquid iron was studied under defined conditions of gas stirring by argon in MgO crucibles with 1500 g iron and 250 g slag. The variations of the FeO content in the slag and the silicon content in the iron during the reaction were measured by sampling. Trials were carried out with stirring gas flow rates between 1 and 20.4 l/h(STP). The experimental data were evaluated with the multi-component transport model in order to determine the mass transfer coefficients of the reaction components. Simultaneously, the coefficients of normal mass transfer were calculated with the boundary layer theory of liquid-liquid mass transfer for non-turbulent flow conditions. The measured mass transfer coefficients were by a factor 2.5 larger than the theoretically calculated. The difference indicates the presence of mass transfer by interfacial convection. Mass transfer by interfacial convection is superimposed to normal mass transfer.     

Titanium-vanadium slags produced upon the direct reduction of iron from titanomagnetite concentrates

The phase compositions of complex titanium-vanadium slags that form upon the processing (using the direct reduction of iron) of titanium-magnetite concentrates of ten CIS deposits are studied by X-ray diffraction and optical and scanning electron microscopies. Depending on the phase composition, these slags can be divided into the following three groups: spinellide, anosovite-spinellide, and anosovite slags. The general laws of element distribution between slag phases are determined. In the titanium-vanadium slags, vanadium is shown not to form individual phases and to enter into the compositions of solid solutions, namely, ansovite and spinellides. In ansovite, vanadium is present in the trivalent state in the form of V₂TiO₅. In the absence of the ansovite phase, vanadium concentrates in spinellide solid solutions, which are partly represented by MTiO₄ solutions. The solubility of vanadium in the spinellide MgAl₂O₄ is controlled by the MgO: Al₂O₃ molar ratio in a slag, and part of the aluminum is substituted by vanadium with the formation of an Mg(Al,V)₂O₄ solid solution only if aluminum is deficient.     

Tin and zinc separation from tin,zinc bearing complex iron ores by selective reduction process

Abstract

Tin, zinc bearing complex iron ores are typically intractable and have not been efficiently utilised in China. In this investigation, the process mineralogy of the tin, zinc bearing iron ores and reduction behaviours of iron, tin and zinc oxides by CO were investigated. A selective reduction roasting process was initially developed to separate tin and zinc from the complex iron ores. Under optimum conditions, most of the tin and zinc were effectively removed from the iron ore pellets, and the roasted pellets could be used as high quality ironmaking burdens for large scale blast furnaces.     

Influence of slag and foam characteristics on reduction of FeO-containing slags by solid carbon

The present study reports experimental results on the reduction of FeO in molten CaO-SiO₂-Al₂O₃-MgO-FeO slags by solid carbon in an extended-arc plasma reactor. The reduction reaction was found to be controlled by mass transport of FeO in liquid slag. The CO gas generated stirs the bath to establish a convective mass transport system. CO also causes foaming. An analysis using dimensionless numbers provides correlations between the rate constant, k, as well as the foaming index, Σ, with some properties of the slag such as viscosity, surface tension, and density. A correlation between k and Σ is also developed using these parameters for slag characteristics.     

锌焙砂的选择性还原焙烧硫酸浸出工艺研究

研究了选择性还原焙烧-硫酸浸出两段工艺处理高铁锌焙砂的方法.首先在CO还原气氛下将锌焙砂中的铁酸锌选择性转化为氧化锌和磁铁矿,然后采用硫酸浸出使可溶锌溶出而铁存留于渣中,实现铁锌有效分离.主要考察了还原焙烧以及硫酸浸出的工艺条件对铁锌分离效果的影响,并采用化学分析法及XRD、SEM-EDS的检测手段对焙烧样品进行分析.以可溶性锌和亚铁的含量作为焙烧评价指标,得出最佳焙烧条件为:焙烧温度750℃,焙烧时间60 min,CO浓度8%,CO/(CO+CO2)气氛比例20%,此条件下可溶锌率由原焙砂中的79.64%提高到91.75%;以铁锌浸出率为考察指标,得出最佳浸出条件为∶常温浸出,浸出时间30 min,浸出酸度90 g/L,液固比10∶1,此条件下锌铁浸出率分别为91.8%和7.17%.     

Evaluation of the reduction of iron oxide from liquid slags using a graphite rotating disk

The rotating disk methodology has been used for examination of the reduction of FeO from CaO-FeO-SiO₂ liquid slags (20 and 60 pct FeO) with a CaO/SiO₂ ratio equal to 0.66 and 1.27, in the temperature range 1350 °C to 1420 °C. It has been found that the reduction proceeds under diffusion control. The calculated diffusion coefficients fall in the range 0.76·10⁻⁷ to 1.6·10⁻⁶ cm²/s. Comparison of these values with those given in the literature suggests that the calculated coefficients are related to the diffusion of oxygen ions in the slag. The calculated thickness of the limiting diffusion layer, δ, ranges from 0.65·10⁻³ to 5.25·10⁻³ cm, depending on the reduction conditions. The largest decrease in the limiting diffusion layer thickness takes place at low rotational speeds, i.e., 100 and 400 rev/min. The maximum value of the mass transfer coefficient is 1.71·10⁻³ cm/s for reduction from slag with a CaO/SiO₂ ratio of 1.27, 60 pct FeO, at 1420 °C and 2000 rev/min, and the minimum value is 0.27·10⁻⁴ cm/s for reduction from slag with a CaO/SiO₂ ratio of 0.66, 20 pct FeO, at 1350 °C and 100 rev/min. Good agreement has been found between experimental and calculated reduction rates at low disk rotations (100 and 400 rev/min).     

The density of liquid iron-carbon alloys

The density of liquid Fe-C alloys at temperatures ranging from 1250 °C to 1550 °C was measured by the sessile drop profile method. An accurate method of digital image processing was de-veloped to capture, enhance, and determine the coordinates of the X-ray shadow image of the droplet. Laplace's equation was then solved to obtain the volume and density of the droplet. The density of iron-carbon alloys was then determined as a function of carbon content (from 0 to 4 wt pct) and temperature (1250 °C to 1550 °C). A least-squares analysis of our data points gives an equation for the density of liquid iron-carbon alloys as a function of temperatureT [K] and carbon content [pct C] [wt pct]: ρ[g/cm³] = (7.10 - 0.0732[pct C]) - (8.28 - 0.874[pct C]) × 10^-4(T - 1823) These results will give a value to within ±1.5 pct of the data of Lucas, [3] Widawski and Sauerwald, [2] and the present work.     

转底炉直接还原铜渣回收铁、锌技术

采用转底炉直接还原工艺,将铜渣含碳球团在高温条件下直接还原得到金属化球团和高品位氧化锌粉尘,再通过熔分或磨矿磁选方式将铁回收,得到的铁产品可作为冶炼含铜钢的原料.转底炉中试结果表明:采用"转底炉直接还原—燃气熔分"流程处理铜渣,可获得TFe品位94%以上、铁回收率93%以上的熔分铁水;采用"转底炉直接还原—磨矿磁选"流程处理铜渣,可获得TFe品位90%以上、铁回收率85%以上的金属铁粉;采用两种流程处理铜渣,均可获得锌品位60.02%的ZnO粉尘.结果表明,经过转底炉直接还原,铜渣中的铁橄榄石Fe_2SiO_4和磁铁矿Fe_3O_4相转变为含有金属铁Fe、二氧化硅SiO_2和少量辉石相Ca(Fe,Mg)Si_2O_6的金属化球团,具备通过磨选或熔分进行进一步富集的条件.     

铜渣熔融还原过程中硫的行为特征

对铜渣熔融还原过程中硫的行为特征进行了研究.结果表明,熔渣碱度从0.8增至1.4,渣硫容量增大脱硫作用增强,铁水硫含量由0.6%降至0.13%;铁水脱硫为吸热反应,熔渣温度由1 773 K升至1 823 K渣脱硫能力提升,铁水含硫由0.13%降至0.089%.熔渣-铁水硫理论分配比远大于实验时间条件下硫分配比,保温时间延长铁水脱硫率提高.熔渣碱度1.4、保温温度1 823 K和保温时间40 min时,处理后铁水含硫为0.11%,含量仍较高,需进一步对铁水进行脱硫预处理才可用于炼钢.     

高磷铁矿气基还原冶炼低磷铁

针对鄂西鲕状高磷铁矿难选、难冶的特点,从该矿矿相结构分析出发,在使用HSC计算化学软件的热力学模拟和具体实验的基础上,提出了气基还原+电炉熔分冶炼高磷铁矿的新型工艺.实验结果与HSC软件模拟结果吻合.实验室含P 1.28%的高磷铁矿通过CO还原后熔分,得到含P 0.27%的低磷铁;通过H₂还原后熔分,得到含P 0.33%的低磷铁.由熔分铁的SEM和EDS结果证实,P仍以夹杂物的形态存在,可以在熔分时通过去除铁水中夹杂物的方法进一步脱磷,以满足炼钢的要求.     

Carbothermal reduction of zinc ferrite

The carbothermal reduction of zinc ferrite was studied using X-ray diffractometer (XRD), wet chemical analysis, scanning electron microscope (SEM), surface area meter, and thermogravimetrical analysis (TGA) systems. Zinc ferrite was found to be decomposed to ZnO and Fe₂O₃ initially and carbothermal reduction of ZnO and Fe₂O₃ took place simultaneously. The results of the surface area measurement indicated that the surface area of the solid sample increased with reaction time. Pore volume and average pore diameter were found to increase, reach a maximum, and then decrease with reaction time. These results were explained by considering the escape of zinc vapor, the expansion of the iron oxide grain, and the sintering of the iron. A mechanism and a model were proposed to explain the reaction. The experimental results of the thermogravimetrical analysis indicated that the reaction rate can be increased by increasing either the argon flow rate or the reaction temperature. Furthermore, the reaction rate was found to increase with a decrease in either the sample height, the molar ratio of ZnFe₂O₄/C, the size of the carbon agglomerate, or the initial bulk density.     

Intergranular embrittlement of iron-carbon alloys by impurities

It is shown that plain Fe-C alloys can be embrittled by certain heat treatments if they are doped with Sb, Sn, As or P. Embrittlement occurs when these elements are rejected from precipitating carbides during cooling, and it results from a piling-up of the elements ahead of the carbide and the concomitant lowering of cohesion along the carbide-ferrite interface. It is a transient (non-equilibrium) condition and disappears upon continued holding at elevated temperatures. Embrittlement by equilibrium segregation of these impurities in unalloyed ferrite apparently does not occur. A model for this transient embrittlement is proposed and tested. This model is relevant to the phenomenon of “500°F” embrittlement in alloy steels, and it is also consistent with most aspects of temper embrittlement. J.R. RELLICK, formerly Research Fellow, Department of Metallurgy and Materials Science, University of Pennsylvania