红格含铬钒钛磁铁矿球团矿物学和等温氧化动力学

研究了红格钒钛磁铁矿(HCVTM)球团等温氧化动力学及其矿物学特征. 在不同的温度(1073~1373 K)和不同的时间(10~60 min)范围内,对HCVTM球团矿进行了等温氧化动力学实验. 首先分析了球团在不同温度和时间下的微观结构和矿物组成规律. 然后根据定义的氧化率,计算和分析了氧化率及其变化规律,以及矿相结构对氧化率的影响. 最后结合缩核模型、修正的氧化率函数和阿伦尼乌斯公式,计算了反应速度常数、修正系数和反应活化能,并判断了反应限制性环节. 研究表明:随温度的提高,低熔点液相增加,赤铁矿晶粒的生成、长大和再结晶,形成连续的黏结相,空隙数量减少. 随时间的增加,生成的液相促进了赤铁矿晶粒间的黏结和长大,但是晶粒间硅酸盐相和钙钛矿类物相恶化了球团结构. 同时,钙钛矿和铁板钛矿相生成. HCVTM球团矿空隙数量的减少和黏结相的生成,表现在氧化速率随时间增加而减慢. HCVTM球团氧化反应主要受扩散控制,球团氧化前期的反应活化能为13.74 kJ·mol-1,氧化后期的活化能为3.58 kJ·mol-1,氧化率函数的修正参数u₂=0.03.      

Kinetics of Oxidation Reaction for Magnetite Pellets

An experiment for the oxidation process of single magnetite pellet and theoretical analysis based on modified unreacted core shrinking (MUCS) model were carried out, and the controlling mechanisms of the initial and developing reactions were examined, respectively. From the study of the initial reaction, it was found that the chemical reaction of surface is the controlling step of the overall reaction when the temperature is up to about 750 K, while the mass transfer through the gaseous boundary layer dominates the reaction rate when the temperature is above 750 K. As the reaction developing within the pellet, the mass transfer through the produced layer becomes the controlling step. In addition, the effects of reaction conditions (such as oxygen concentration, temperature) on the fractional oxidation of magnetite pellet were determined.     

Non-Isothermal Kinetics of Reduction Reaction of Oxidized Pellet Under Microwave Irradiation

 The microwave heating characteristics of the mixture with oxidized pellet and coal was studied, and the non-isothermal reduction dynamics is discussed. The results show that, the slow-heating stage of the temperature rising process can be segmented into two heating temperature curves approximately that have good linear relationship. They can be seen as temperature programming. In the first stage, between 827 and 1073 K, the reaction mechanism obeys diffusion controlled model. In the second stage, between 1093 and 1323 K, the reaction mechanism also obeys diffusion controlled model. The apparent activation energies are found to be 7513 kJ/mol for the first stage and 5317 kJ/mol for the second stage. That is lower than the apparent activation energy under conventional heating. The microstructure of the reduced pellets shows that microwave can improve the kinetics of the reduction. Microwave has anxo-action to the reaction obviously.     

磁铁矿球团氧化机理的研究

磁铁矿球团高温恒温氧化时，氧气向球团的扩散为限制性环节，低温恒温氧化或升温氧化，球团内磁铁矿颗粒氧化为限制性环节。磁铁矿颗粒氧化按温度划分为两段。在较低温度下主要是铁离子扩散，较高温度下氧离子扩散的扩散能力增强。     

Reduction behavior and mechanism of Hongge vanadium titanomagnetite pellets by gas mixture of H2 and CO

Hongge vanadium titanomagnetite(HVTM)pellets were reduced by H_2-CO gas mixture for simulating the reduction processes of Midrex and HYL-III shaft furnaces.The influences of reduction temperature,ratio ofφ(H_2)toφ(CO),and pellet size on the reduction of HVTM pellets were evaluated in detail and the reduction reaction kinetics was investigated.The results show that both the reduction degree and reduction rate can be improved with increasing the reduction temperature and the H_2 content as well as decreasing the pellet size.The rational reduction parameters are reduction temperature of 1050°C,ratio ofφ(H_2)toφ(CO)of 2.5,and pellet diameter in the range of 8-11 mm.Under these conditions(pellet diameter of 11mm),final reduction degree of 95.51% is achieved.The X-ray diffraction(XRD)pattern shows that the main phases of final reduced pellets under these conditions(pellet diameter of 11 mm)are reduced iron and rutile.The peak intensity of reduced iron increases obviously with the increase in the reduction temperature.Besides,relatively high reduction temperature promotes the migration and coarsening of metallic iron particles and improves the distribution of vanadium and chromium in the reduced iron,which is conducive to subsequent melting separation.At the early stage,the reduction process is controlled by interfacial chemical reaction and the apparent activation energy is 60.78kJ/mol.The reduction process is controlled by both interfacial chemical reaction and internal diffusion at the final stage,and the apparent activation energy is 30.54kJ/mol.     

Oxidation of iron ore at moderate and high temperatures

The oxidation of magnetite and titanomagnetites in iron-ore sinter at moderate (400–1000°C) and high (1000–1350°C) temperatures is subjected to physicochemical analysis. The oxidation kinetics is studied on briquets of Olkhovsk magnetite concentrate and Kachkanar titanomagnetite concentrate, as well as samples of unfluxed Kachkanar pellets and pellets fluxed to a basicity of 1.3. At moderate temperatures, the limiting stage in oxidation is the diffusion of the reagent to sections of the surface smaller than the total spherical surface. At high temperatures, in both isothermal and nonisothermal conditions, the limiting stage in oxidation is the diffusion of oxygen in pellet pores. From the kinetic equations for isothermal oxidation, the apparent activation energy with the specified degree of conversion is calculated; its variation is associated with change in the type of reagent diffusion through the layer of reduction products. The apparent diffusion coefficients of oxygen in Kachkanar pellets are determined at 500–1000°C. A method has been developed for determining the degree of pellet oxidation as a function of the time and the temperature in nonisothermal conditions. This method may be used to calculate the oxidation of the pellets in roasting on conveyer machines. The results may be used to determine the degree of oxidation in the roasted pellet bed and to optimize the heat-treatment parameters in roasting systems.     

Reduction Kinetics of Vanadium Titano-Magnetite Carbon Composite Pellets Adding Catalysts Under High Temperature

Experiments were carried out by adding CaF2 and NaF as catalysts in an Ar atmosphere to study the isothermal reduction kinetics of vanadium titano-magnetite carbon composite pellets under high temperature in the range from 1 473 to 1 673 K. The scanning electron microscope (SEM) was used to characterize the microstructure of product. By analyzing reduction mechanism, it was found that the rate controlling step was gas diffusion, and the activation energy was 178.39 kJ/mol without adding any catalysts. Adding CaF2 or NaF of 3% to vanadium titano-magnetite carbon composite pellets can decrease the apparent activation energy of reduction, and the decrease extent was 14.95 and 15.79 kJ/mol, respectively. In addition, temperature was an important factor influencing on reaction rate.     

石煤脱硅渣中钒浸出动力学

以石煤熔融水淬后碱浸脱硅渣为原料,采用液固多相反应的缩芯模型研究了石煤脱硅渣中钒的浸出动力学,考察了浸出温度、初始硫酸浓度对钒浸出率的影响。结果表明,脱硅渣的浸出分为两个阶段:反应刚开始时的快速浸出阶段和2min之后的缓慢浸出阶段,这两个阶段均受固膜扩散控制,反应活化能为13.88kJ/mol。     

Kinetic studies of the oxidation of γ-aluminum oxynitride

The present article deals with the investigations of the oxidation kinetics of γ-aluminum oxynitride (AlON) in the temperature range of 1173 to 1773K by thermogravimetry. Oxidation experiments with AlON powder and plates have been carried out in air, both in isothermal as well as nonisothermal modes. Oxidation of AlON resulted in the formation of Al₂O₃. The results showed that the rate of oxidation was negligible below 1273 K and, at higher temperatures, showed an increase with increasing temperature. Both isothermal studies as well as experiments with ramped temperature clearly indicated that the mechanism of the reaction changes around 1600 K. In the nonisothermal mode, the oxidation curve showed a plateau region in this temperature range. The difference between the two reaction steps was explained on the basis of the formation of a metastable alumina phase in the lower temperature region and stable corundum phase at higher temperatures. The buildup of the product layer would lead to a diffusion-controlled reaction kinetics. In the nonisothermal experiments, the phase transformations in alumina product layer at higher temperatures would lead to crack formation, thereby leading to even direct chemical reaction. From the experiments for the isothermal oxidation of AlON powder, the overall activation energy for the reaction rate with chemical control was determined to be 218 kJ/mole in the temperature range of 1273 to 1573 K and 78 kJ/mole in the range of 1573 to 1773 K. The overall activation energy for the diffusion step was found from the isothermal oxidation of AlON plates to be 227 kJ/mole.     

Sintering characteristics and kinetics of acidic haematite ore pellets with and without mill scale addition

Haematite ore pellets require very high induration temperature (>1573?K) while, magnetite ore pellets require much lower temperature due to the oxidation of magnetite during induration. Mixing of some magnetite in haematite ore can improve the sintering property of pellets during induration. Mill scale is a waste material of steel plant which contains mainly FeO and Fe₃O₄. It can also be blended in haematite ore pellet mix which can enhance diffusion bonding and recrystallisation bonding and facilitate sintering at the lower temperature like magnetite ore. The extent of improvement in sintering property, sintering mechanism and its kinetics in the presence of mill scale is very imperative to study. In current study, the sintering characteristics of acidic iron ore pellet with 15% mill scale and without mill scale has been studied separately through microstructure observation, apparent porosity measurement and volume change. The volume changes due to heating at varying temperature and time has been measured by mercury displacement method and the data has been exploited for sintering kinetics study, wherein, extent of sintering α has a power relation with time. Several kinetics parameters such as time exponent (n), rate constant (k) and activation energies have been estimated for above two pellets and compared. While acidic pellet without mill scale requires 385?k?cal?mol^?1, acidic pellet with 15% mill scale requires only 310?k?cal?mol^?1 activation energy.     

Kinetics of vanadium dissolution from black shale in pressure acid leaching

The leaching kinetics of vanadium from black shale in the sulphuric acid-oxygen system is presented. The effects of agitation speed, leaching temperature in the range of 110-150 °C, sulphuric acid concentration, oxygen partial pressure and particle size on the rate of vanadium leaching were determined. The results indicate that the rate is nearly independent of agitation above 200 rpm and increases with increasing temperature, sulphuric acid concentration and oxygen partial pressure. As leaching occurs, there is a progressive dissolution of a vanadium-bearing alumino-silicate phase, while the inert quartz phase assembles onto the mineral surface and remains as an “ash” layer. The leaching kinetics was analyzed by using a new variant of the shrinking core model (SCM) in which both the interfacial transfer and diffusion across the product layer affect the leaching rate. The determined activation energy was found to be 40.14 kJ/mol and the reaction orders with respect to sulphuric acid concentration and oxygen partial pressure were 0.61 and 1.67, respectively. A semi-empirical rate equation was derived to describe the process.     

The reduction of stannic oxide with carbon

The rate of reduction of stannic oxide (cassiterite) with carbonaceous materials was investigated in the temperature range 1073 to 1273 K, using thermogravimetic analysis. The effects of the type, the particle size, and the relative amount of carbon were studied. The results indicate that cassiterite is reduced directly to Sn proceeding through the gaseous intermediates of CO and CO₂. The overall rate of reduction is controlled by the oxidation of carbon by CO₂ · An energy of activation of 220.9 kj/mole (52.8 kcal/mole) was calculated for the reduction of SnO₂ with coconut charcoal within the temperature range 1073 to 1173 K and 323.8 kjJ.mole (77.4 kcalJ.mole) with graphite within the temperature range 1198 to 1273 K. A direct comparison was made between the rate of oxidation of coconut charcoal in CO₂- CO mixtures and the rate of reduction of SnO₂ with coconut charcoal, which are not in agreement. The reason for this disagreement was found to be the catalytic action of the tin formed during the reduction. Formerly Graduate Student in the Department of Metallurgy and Metallurgical Engineering, University of Utah.     

The nitriding of Fe-V alloys

Fe-V alloys containing 1.06 wt pct V, 5.23 wt pct V and 15.55 wt pct V, have been nitrided in purified NH₃ gas in temperatures ranging between 773 K and 1173 K. The nitriding kinetics of all these alloys in this temperature range obey a parabolic rate law. The comparison of the nitriding rate constants evaluated from experimental results and from the calculations based on Wagner's internal oxidation model show a deviation which is explained in terms of the effect of the lattice strains on the solubility and diffusivity of nitrogen in the Fe matrix. The hardness of the nitrided zone increases with the vanadium content in solution and reaches a saturation value of about 1300 VHN (12.75 GNm⁻²) which corresponds to about 4 wt pct V. The hardening in the nitrided region is cuased by the precipitation of VN which cannot be observed on specimens nitrided at the lower limits of the temperature range. Precipitates grown in size can be seen on specimens nitrided at 1073 K and 1173 K.     

Early Gaseous Oxygen Enrichment to Enhance Magnetite Pellet Oxidation

It is suggested that oxygen enrichment in the gas atmosphere, during continuous heating of magnetite pellets, can cause pellets to be oxidized throughout their volumes, eliminating unoxidized cores. The peculiarities of the oxidation kinetics of magnetite concentrate imply that such oxygen enrichment might be particularly effective at lower temperatures. This suggestion was tested by developing and testing a mixed-control model for pellet oxidation (to allow the sizes of unreacted cores to be predicted), and by experimentally testing the effects of oxygen enrichment at relatively low temperatures (“early oxygen enrichment”). The results confirmed that the extents (depth) of oxidation and pellet strength were both improved significantly by applying oxygen enrichment up to 873 K (600 °C), as part of a heating cycle up to 1073 K (800 °C).     

Kinetic studies of reduction of CoO and CoWO4 by hydrogen

The present work deals with the studies of the kinetics of reduction of CoO and CoWO₄ in flowing hydrogen gas by thermogravimetric method. The reduction studies for CoO were carried out in the temperature range of 637 to 837 K, while for CoWO₄ reduction, the temperature range was 837 to 1173 K. In the case of the reduction of CoWO₄, the reaction products after reduction were analyzed by X-ray diffraction as well as scanning electron microscopy. The activation energy for the reduction of CoO was found to be of 54.3 kJ/mol. Cobalt tungstate was reduced to a mixture of Co₇W₆ and W, and the activation energy for the reaction is 90.0 kJ/mol. The results are discussed in the light of the reduction kinetics of other transition metal oxides and tungstates under similar conditions.     

Preparation of a Nickel–Holmium Alloy Coating in an Equimolar HoCl<Subscript>3</Subscript>-Containing NaCl–KCl Melt

Cyclic voltammetry is used to study the electrolytic reduction of holmium ions on a nickel electrode in a holmium chloride-containing equimolar molten mixture of sodium and potassium chlorides in a temperature range of 1073–1173 K. The potentials of formation of nickel–holmium intermetallic compounds (IMCs) are determined. Nickel–holmium intermetallic compounds are synthesized by controlled potential electrolysis. Under the selected electrolysis conditions, the prepared coating is shown to be single-phase and its composition corresponds to the HoNi₂ stoichiometry. The coefficients of reaction diffusion of holmium in nickel are calculated and the activation energy of alloy-formation process is determined.     

原料高压辊磨对球团氧化活化能的影响

利用阿伦尼乌斯公式分析了磁铁矿原料辊磨前后球团氧化反应的活化能。研究表明，原料不辊磨时球团氧化反应的活化能为33．96kJ／mol，经辊磨后则为31．28kJ／mol，这说明辊磨可降低球团氧化反应的活化能。