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.     

贵州鲕状赤铁矿的氢气还原行为

在800～1100℃范围内、H2体积分数为99.99％的气氛条件下,采用气基直接还原工艺对贵州鲕状赤铁矿进行了恒温还原研究,使用X射线衍射仪和光学显微镜对还原产物进行了表征,通过阿伦尼乌斯公式计算了还原反应的表观活化能,并采用未反应核模型判断了还原反应的限制性环节.结果表明:当还原温度为1100℃,还原时间为150 min,二元碱度为1.0时,可以获得金属化率为91.15％的直接还原产物,原矿中加入CaO促进了FeAl2O4和Fe2SiO4的还原,是还原产物金属化率提高的主要原因.动力学结果表明:原矿在900～1 100℃的还原过程中受气体内扩散控制,其表观活化能为18.95 kJ/mol,并且在典型气体内扩散范围内.     

高炉粉尘造泡沫渣过程中FeO还原动力学的研究

为了循环利用高炉粉尘,研究了用宝山钢铁股份有限公司高炉粉尘与沥青焦粉混合后加入电弧炉造泡沫渣过程中FeO的还原动力学。结果表明,随粉尘加入量的增加和温度的升高,FeO的还原速率加快;用固体碳还原渣中FeO的反应为表观二级反应,其表观活化能为276kJ／mol;用固体碳还原渣中FeO的反应总速率由CO还原FeO的界面化学反应和炉渣的流动传质共同控制。     

含MnO钛渣中氧化钒还原能力的研究

对配加０－５％ＭｎＯ钛渣中氧化钒的还原能力进行了研究。结果表明：Ｓｉ－Ｖ耦合反应的显平衡常数随渣中ＭｎＯ实始含量增加而增加，随ＴｉＯ２初始含量的增加而减少，随炉渣碱度的升高而升高，但高碱度炉渣会降低显平衡常数值，高人氧化钒带反应没有达到平衡。氧化钒还原受动力学条件控制，还原反应为二级，表观活化能为１７２ｋＪ／ｍｏｌ。还原初期还原速度受渣中Ｖ＾２＋扩散控制，当Ｓｉ－Ｖ耦合反应达到平衡后还原速率受Ｓｉ     

Reduction Characteristics and Kinetics of Bayanobo Complex Iron Ore Carbon Bearing Pellets

 The kinetics of isothermal reduction of the carbon bearing pellets, which were mainly composed of Bayanobo complex iron ore and pulverized coal, was investigated by thermogravimetry at the temperature of 1273-1673 K. The effects of xC/xO and the atmospheres on the extent of reduction also were investigated. The results indicate that the fractional reaction increased proportionally with temperature increasing and heating temperature is the significant influence factor to the reaction of carbon bearing pellets. The optimum xC/xO is 1. 2 and the effect of atmosphere on the reduction of iron oxides is almost negligible. The results can be interpreted that the reaction was initially controlled by a mixed controlled mechanism of carbon gasification and interface chemical reaction, and in the later stage, interface chemical reaction became the rate-controlling step. Apparent activation energy values of reduction at different levels of fractional reaction were calculated. Before F (fraction of reaction)=0. 5, the apparent activation energy ranges from 66. 39 to 75. 64 kJ/mol, while after F=0. 5, the apparent activation energy is 80. 98 to 85. 37 kJ/mol.     

生物质焦与煤共气化特性研究

本文利用非等温热重分析法研究了生物质焦与煤的共气化特性,探讨了生物质焦与煤共气化反应特征温度的变化情况,并分别运用Doyle和Coats-Redfern近似函数计算了反应动力学参数.采用Doyle法计算时,相关系数R2值比Coats-Redfern法更大,因此Doyle法计算结果更合理.采用Doyle法计算出：生物质焦的气化反应活化能为134.97 kJ/mol,烟煤和无烟煤分别是197.85 kJ/mol和171.36 kJ/mol.随着无烟煤、烟煤中生物质焦掺混的比例增加,反应活化能不断下降.研究结果表明：生物质焦可以促进两种煤的气化反应,降低煤的最终反应温度和气化反应活化能.     

Kinetics of iridium reduction by hydrogen in hydrochloric acid solution

The effects of stirring speed, initial iridium ion concentration, hydrogen pressure, hydrochloric acid, chloride concentrations, seeding, and temperature on the reduction rate of iridium ion by hydrogen have been investigated. The whole process of reduction occurs in a complicated heterogeneous stage. The reduced metallic Ir serves itself as a catalyst for the reduction. The rate in the earlier stage of the reduction (including the nucleation period) is controlled by chemical reaction; the apparent activation energy obtained in the temperature range of 363 to 423 K was 76.1 kJ/mol. The order of the reaction with respect to the iridium ion concentration and the hydrogen partial pressure was found to be one, and the reaction rate increased with the increase of HC1 and Cl concentrations. The rate in the later stage was controlled by diffusion, and the apparent activation energy was reduced to 25.5 kJ/mol. The reaction mechanism has been given by the analysis of experimental results. Formerly Graduate Student, Department of Extractive Metallurgy, Institute of Precious Metals     

氧化锌球团还原的机理研究

采用等温法研究了纯氧化锌配加石墨碳粉制成含碳氧化锌球团的还原动力学 ;考察了坩埚尺寸对氧化锌还原的影响 ;并研究了铝浴条件下对含碳或不含碳氧化锌球团还原的影响。结果表明 :根据Arrhenius方程计算出 ,当碳气化反应和界面还原反应为限制环节时 ,在 12 73～ 14 2 3K下其活化能分别为 3 7 615kJ/moL和 43 192kJ/moL ,碳还原氧化锌的还原速度由气相扩散所控制 ,12 73～ 14 2 3K下其活化能为 46 5 48～ 5 3 2 80kJ/moL ,含碳球团在大坩埚中的还原速度快 ,有铝浴存在的还原速度快 ;在 12 73～ 15 2 3K下铝浴与氧化锌球团 (不含碳 )基本不发生还原反应     

Reduction Kinetics of Cold-Bonded Briquette Prepared from Return Fines of Sinter with Carbon Monoxide and Coke

The reduction kinetics of cold-bonded briquette prepared from return fines of sinter is studied. The results reveal that cold-bonded briquettes with coke (CBBC) have a higher reduction velocity index (RVI) value than cold-bonded briquettes without coke (CBB). Interfacial chemical reaction controls the early stages of the CBB reduction process at 900 and 950 °C, followed by both interfacial chemical reaction and internal diffusion. At 1000, 1050, and 1100 °C, the early and final stages of the CBB reduction process are controlled by interfacial chemical reaction and internal diffusion, respectively, while both interfacial chemical reaction and internal diffusion control middle stage. The apparent activation energies of the different stages are 46.20, 56.74, 38.24, and 40.74 kJ mol⁻¹, respectively. The gasification of carbon reaction controls the reduction process of CBBC, and the apparent activation energy is 32.42 kJ mol⁻¹. According to the Friedman method, the apparent activation energy of CBB and CBBC is reasonable. Coke promotes the phase transformation in CBBC. Scanning electron microscopy results show that the CBBC sample is more fully reduced than the CBB sample and that it has smoother corners and edges of the iron-bearing phase or the metallic iron phase than the CBB sample.     

Reduction kinetics of molybdenum oxide in slag

The reduction rate of Mo oxide in slag by iron-carbon melt under different stirring conditions, reaction temperatures and slag composition has been investigated. Results indicate that the reduction of Mo oxide is a fast reaction; both stirring and temperature have evident influence upon the reaction; while the initial concentration of Mo oxide and content of fluoride in slag have also some influence upon the reaction. The reduction of Mo oxide is an apparent first order reaction. At 1440–1500°C, the reduction rate of Mo oxide is mainly controlled by Mo transfer in slag, with its diffusion activation energy of 223 kJ/mol. At 1500–1590°C, the transfer of Mo in metal turns to be the main limiting step, with its diffusion activation energy of 81.5 kJ/mol.     

低温下氢气还原氧化铁的动力学研究

 用热重分析法研究了低温下不同粒度氧化铁的氢还原动力学,得出在同一温度下,铁矿粉粒度从107.5 μm降到2.0 μm后,由于粉体的表面积大幅度增加,提高了粉气接触面积,从而使得化学反应的速度提高了8倍左右,还原反应的表观活化能从78.3 kJ/mol降低到36.9 kJ/mol;当反应速度相同时, 粒度6.5 μm的粉体的反应温度比107.5 μm的降低了80 ℃左右。同时,通过理论推导和实验结果表明,当反应扩散层厚度相同时,铁矿粉粒度越小,反应扩散层厚度越薄,其还原率越高。     

Reaction mechanism of FeO reduction by solid and dissolved carbon

The reduction reactions of FeO by carbon have been studied in order to be able to understand the fundamental phenomena occurring in smelting reduction process. The reduction of pure FeO by solid carbon proceeds mostly according to the same reaction mechanism as that by dissolved carbon in iron, the rate of which was experimentally determined to be controlled by the interfacial chemical reaction between Fe-C melt and intermediate CO₂ gas. Hence, the reduction rate of pure FeO by solid carbon is also chemically controlled by the Boudouard reaction between the dissolved carbon and CO₂ at the interface of by-product Fe droplet/gas phase, the activation energy of which was found to be about 193.2 kJ/mol. In addition, the reduction reaction of FeO in CaO-SiO₂-Al₂O₃-FeO slags by the dissolved carbon in Fe melt was also investigated over the FeO mass content less than 20 %. The reduction rate shows first order dependence with respect to FeO concentration. The surface active sulphur content in iron does not affect the reduction rate, and the temperature dependence of reduction rate gives the activation energy of 24.78 kJ/mol. Therefore, the reduction rate of FeO in slags by the dissolved carbon can be safely mentioned to be controlled by the liquid phase mass transfer of FeO through the slag phase diffusion-resistant boundary layer over the limited FeO concentration range. The empirical expression for the mass transfer controlled reactioe, deren Aktivierungsenergie ca. 193.2 kJ/mol beträgt. Außerdem wurde die Reduktion von FeO in CaO-SiO₂-Al₂O₃-FeO-Schlacken mit dem in der Eisenschmelze gelöstem Kohlenstoff fär FeO-Massengehalte von weniger als 20% untersucht. Die Reduktionsgeschwindigkeit weist hinsichtlich der FeO-Konzentration eine Abhängigkeit 1. Ordnung auf. Der Anteil an oberflächenaktivemn rate was determined as r = 5.94(±0.07).10^?6.exp(-24780/RT).(%FeOP)^0.96 over the reaction conditions employed.     

硫铁矿还原烧渣酸浸液试验研究

研究了硫铁矿精矿还原硫酸烧渣酸浸液及其反应机理。试验结果表明:当浸出液中Fe3+浓度为1.1 mol/L时,在液固比为3∶2、90℃、搅拌速度500 r/min的条件下,反应3 h,酸浸液中的Fe3+的还原率达到96.5%,其反应级数为1.66,表观活化能为60.26 kJ/mol。     

氢气还原氧化铁动力学的非等温热重方法研究

 用非等温热重分析法对氢气还原不同粒度细微氧化铁的动力学进行了研究。研究表明：铁矿粉粒度越小,起始反应温度越低,反应速度越快,反应达到平台期时所对应的还原率越高;平均粒度为3.5 mm的铁矿粉在400 ℃还原反应开始,700 ℃左右开始反应加快,达到平台期时的还原率为77%,而平均粒度为2 μm的铁矿粉在100 ℃已经开始反应,350 ℃反应加快,达到平台期时的还原率为98%,而且在600 ℃时还原率就达到了100%;铁矿粉粒度从3.5 mm降到2 μm后,还原反应的表观活化能从73.3 kJ/mol降低到30.46 kJ/mol;同时通过分析氢气还原氧化铁的反应机理得出,内扩散和界面化学反应均对整个反应过程起限制作用。     

外包法直接还原钛铁矿过程的动力学研究

采用外包还原剂的方法对钛铁矿进行直接还原试验,研究了直接还原钛铁矿的动力学。结果表明,半焦粉直接还原钛铁矿分为两个阶段,第一阶段是升温阶段和恒温的初始阶段,受界面化学反应控制,表观活化能为113.14kJ/mol;第二阶段为恒温阶段,受固相中气体的内扩散控制,表观活化能为180.13kJ/mol。温度对还原度和还原速率的影响显著。随着温度的升高,还原度随之升高,反应速率加快;延长恒温时间也可以提高还原度,但恒温阶段反应速率增加缓慢     

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.     

Application of a nonisothermal thermogravimetric method to the kinetic study of the reduction of metallic oxides: Part I. A general treatment and its application to the reduction of the oxides of molybdenum by hydrogen

A theoretical treatment to evaluate activation energies of reactions by means of nonisothermal experiments was developed. The treatment considers the case where either the surface reaction or the intraparticle diffusion could be rate-controlling. Complementary to the theoretical treat-ment, thermogravimetric experiments have been carried out under both isothermal and noniso-thermal conditions. The reduction of MoO₃ to Mo was found to pass through an intermediate MoO₂ phase. The rate of reduction to MoO₂ seems to be controlled by surface reaction, and the activation energy obtained from isothermal studies is 205.7 kJ/mol. This is comparable to the value of 211.6 kJ/mol obtained from nonisothermal reduction studies using the present theoretical treatment. The rate of reduction to Mo appears to be influenced by gas diffusion through voids. The activation energy from isothermal studies is 85.2 kJ/mol.     

Reduction of Solid Iron Oxide by Carbon

The reduction of pre‐reduced iron oxide by carbon was investigated from a kinetic viewpoint. The experimental procedure included thermogravimetric analysis to measure the weight change of the iron oxide pellet. The activation energy of the overall reaction was calculated to be 210 kJ/mol in the temperature range from 1273 to 1573 K. The overall reduction rate of FeO by carbon is believed to be mixed‐controlled by the Boudouard reaction and by the FeO reduction by CO gas in the temperature range investigated. The critical carbon concentration for the FeO reduction was estimated under the assumption that the activities of FeO and Fe are unity.     

乙二胺四乙酸对铝酸钠溶液种分附聚的影响

添加0.01 mol/L的乙二胺四乙酸(EDTA)在实验条件下能够提高单位时间的分解率,宏观动力学研究结果表明,添加EDTA使实验条件下种分过程的表观反应活化能从42.97 kJ/mol降低到32.97kJ/mol,EDTA能够促使铝酸钠溶液晶种分解的附聚与成核。     

钼酸钙直接还原动力学的研究

研究了碳与碳化硅两种还原剂对CaMoO4还原动力学的影响规律。结果表明：碳还原CaMoO4的反应级数为一级，反应表观活化能为197kJ／mol，碳的还原性能由于碳化硅，更适宜还原钼酸钙。