Analysis of Gas Thermodynamic Utilization and Reaction Kinetic Mechanism in Shaft Furnace

The technology of coal gasification in shaft furnace is an effective way to develop direct reduction iron in China.In order to clarify the process of the reduction of oxidized pellets in shaft furnace by carbon monoxide or hydrogen in two ways,i.e.thermodynamics and kinetics,the gas utilization and reaction mechanism were studied by theoretical computations and isothermal thermogravimetric experiment.The results showed that the gas utilization increased with the rise of temperature when xH 2 /xCO ≥1and with the increase of xCO /(xH 2 +xCO)when temperature is less than 1 073K.The water-gas shift reaction restrains efficient utilization of gas,particularly in high temperature and hydrogen-rich gas.The gas utilization dropped with increase of carburization quantity of direct reduction iron(DRI)and oxygen potential of atmosphere.With the increase of both temperature and content of H2 in inlet gas, the reaction rate increased.At 100% H2 atmosphere,the interfacial chemical reaction is the dominant reaction restricted step.For the H2-CO mixture atmosphere,the reduction process is controlled by both interfacial chemical reaction and internal diffusion.     

Effects of Temperature and Atmosphere on Pellets Reduction Swelling Index

 After taking into account the conditions of the domestic iron resources and the non-coking coal resources, the process of coal gasification-shaft furnace is an effective way to develop direct reduction iron in China. The following tasks are very critical to choose suitable process of shaft furnace and gasification, including the production of oxidized pellets with excellent comprehensive properties as well as the study of the reaction behavior and mechanism of swelling. The results showed that the oxidized pellets of using domestic magnetic iron concentrate as raw materials have favorable comprehensive properties, including higher mechanical strength both before and after reduction, faster reduction rate and lower reduction swelling index (RSI). All of these properties can meet the shaft furnace yielding requirement. When the temperature was below 1223 K, the pellets′ RSI was lower than 20%. With increasing of the content of H2 in atmosphere, the pellets reaction rate accelerated, crushing strength enhanced and RSI decreased. The RSI dropped to 10.26% at 1323 K in 100% H2 atmosphere, and it is up to 39.88% in 100% CO atmosphere. The iron grains mainly presented in platelike when pellets were reduced by H2, however, in CO atmosphere the iron grains were precipitated in flocculent. The whisker shape of iron grains and heating effects of reduction reaction are the major factors leading to the poor pellets strength and increase of RSI. Appropriately controlling the temperature and increasing the ratio of H2 to CO in atmosphere are good for dropping the RSI.     

MgO质量分数对氧化球团性能的影响

 为了改善澳洲某磁铁矿氧化球团的冶金性能,研究了MgO质量分数对其质量的影响。研究结果表明,随着MgO质量分数的提高,生球落下强度和爆裂温度提高,MgO质量分数对生球抗压强度影响较小。随着MgO质量分数提高,预热球团和焙烧球团抗压强度降低,还原度有所改善;提高MgO质量分数可以有效抑制球团的低温还原粉化和球团的还原膨胀,软化开始温度、软化结束温度和滴落温度均有所提高,软熔性能得以改善。这主要是由于提高MgO质量分数,渣相中铁酸镁和钙镁橄榄石质量分数升高,在还原过程中Mg2+与Fe2+发生晶格取代,生成FeO与MgO的固溶体,具有稳定晶格的作用,从而抑制还原膨胀和低温还原粉化。     

Effects of MgO Containing Additive on Low-Temperature Metallurgical Properties of Oxidized Pellet

 As a main charging form of BF (blast furnace), pellets play an important role in blast furnace process. However, comparing with sinters, pellets have many disadvantages, such as reduction swelling, low softening and melting temperature and so on. Therefore, the flux pellets have been applied in blast furnace widely, especially MgO containing pellets. The light burned magnesite is applied as MgO containing additive in pellet production. The characters of light burned magnesite are explored. Meanwhile, the effects of it on low-temperature metallurgical properties are investigated such as low-temperature reduction degradation index (RDI), compressive strength (CS) and the reduction swelling index (RSI). The light burned magnesite calcined at 850 ℃ manifests better grindability, larger specific surface area, and higher hydration activity. It is found that the addition of light burned magnesite can improve low-temperature metallurgical properties (RDI, RSI) of the pellets. With the increase of light burned magnesite in pellets, the RSI and RDI decrease gradually; when the proportion of light burned magnesite does not exceed 2. 0% in pellets, the CS decreases slightly, but it still surpasses 2689 N, which can still meet the demand of BF.     

温度对氢气还原铁氧化物过程膨胀性能的影响

摘要：为探究球团矿还原过程中产生恶性膨胀的问题，研究了温度对H2还原Fe2O3样条过程中膨胀性能的影响，并采用PCY G膨胀仪进行在线检测，通过对比不同温度条件下还原产物的外观形貌与显微结构，解释还原反应产生膨胀差异的原因。实验结果表明，H2还原气氛下，随着还原温度的升高，800℃下样条膨胀最大，样条的最大膨胀量出现先增加后减小的趋势；还原反应达到最大膨胀量所用时间逐渐缩短。随着还原温度的升高，铁相连接更加紧密，样条内外产生更大应力差，致使900℃条件下的还原反应提前进入铁相收缩的状态。     

Characteristics of Calcined Magnesite and Its Application in Oxidized Pellet Production

Calcined magnesite is a binding additive and an MgO-bearing flux for pellets production.The effects of calcination temperature and time on the characteristics of calcined magnesite were investigated.Experimental results indicated that the best calcination condition was 850℃and 1h.Under this condition,the hydration activity of the calcined magnesite was 80.56%,and the average diameter of crystal grain D,specific surface area Sand the medium particle size D50 were 25.4nm,45.40m2/g and 3.41μm,respectively.This kind of calcined magnesite was a good binding additive for pellets production.At the same proportion of calcined magnesite,the effects of activities of calcined magnesite on metallurgical properties of green pellet and indurated pellet showed that calcined magnesite with high activity could improve the dropping strength and compressive strength of green pellet and enhance the burst temperature of green pellet;however,the effects of activity on compressive strength,low-temperature reduction degradation index,reduction swelling index and reduction index of indurated pellet were not obvious.     

Swelling Behavior of Iron Ore Pellets during Reduction in H2 and N2/H2 Atmospheres at Different Temperatures

The need to develop green steelmaking techniques has led to the replacement of reducing agents such as CO with H₂. H₂ and N₂/H₂ mixtures can be used for the carbothermal reduction of iron ore. Herein, the reduction swelling index (RSI) of iron ore pellets in a forming gas (N₂/H₂) atmosphere at temperatures of 700–1000 °C is investigated and it is compared with that in pure H₂. It is showed in the experimental results that the RSI increases with increasing temperature for both the H₂ and N₂/H₂ atmospheres. The maximum swelling is reached approximately 5 min into the H₂ reduction process, while in the N₂/H₂ atmosphere, it is reached after 25–45 min of reduction, depending on the temperature. When the reduction temperature exceeds 900 °C, the RSI is greater than 20%. Scanning electron microscopy/energy-dispersive X-ray spectroscopy is performed to detect the changes in the microstructure and chemical composition of the samples. The nonreduced areas in the reduced pellets during the N₂/H₂ reduction process are analyzed using light optical microscopy.     

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.     

冶金尘泥含碳球团直接还原机制的试验研究

摘要：以气固反应相继发生动力学模型为基础开展冶金尘泥含碳球团直接还原试验,考察还原速率、还原率以及还原气氛等表征还原特性的特征参数在整个还原过程的变化,研究冶金尘泥含碳球团的还原行为及过程的作用机制。结果表明：冶金尘泥含碳球团的还原过程由孕育启动期、快速反应期和反应结束期组成,反应进程快,3~5min就能达到碳气化和铁氧化物还原剧烈进行的温度。在1270℃以下,升高温度对含碳球团还原有明显加速作用,但进一步提高温度,球团n(C)/n(O)( (C、O摩尔比))及球团中碳的消耗对还原过程的影响更为显著,表现在最大还原速率维持时间延长,还原率大幅提高。碳气化反应是含碳球团还原过程最重要的环节,其反应生成的CO决定了铁氧化物还原反应物的供给速度。反应过程处于明显的还原性气氛中,气氛中CO2来自于部分CO的进一步氧化,其含量多少取决于气氛中CO的数量和反应的进程。     

含钒钛铁精矿氧化球团气基竖炉直接还原模拟试验

我国钒钛磁铁矿资源丰富,但综合利用难度大,现有工艺仍存在一些问题,工艺流程还有待完善和革新。气基竖炉直接还原-电炉熔分新工艺为钒钛磁铁矿资源清洁高效综合利用提供了新途径。以含钒钛的铁精矿为原料制备氧化球团,模拟气基竖炉直接还原条件,研究了还原气组分和温度对球团的还原进程、还原膨胀以及还原强度的影响。结果表明:以钒钛铁精矿为原料,配加1%膨润土,在1 250℃下焙烧20 min后,所制备氧化球团性能良好,具有较高的抗压强度。在恒定还原气组分(纯H2、H2/CO=2.5、H2/CO=1、H2/CO=0.4和纯CO)和温度(850、900、950和1 000℃)下,钒钛铁精矿球团还原速率快、还原膨胀率小(<20%),可满足气基竖炉直接还原工艺要求。煤制气-气基竖炉直接还原凭借其能耗小、环境友好、单机产能大、产品质量好等优点,将在钒钛磁铁矿资源高效清洁综合利用领域得到发展。     

球团矿抗压强度对其冶金性能的影响

对一种细粒度磁铁精矿粉制备的生球团,通过调整其预热及焙烧工艺参数,生产出不同抗压强度的球团矿,并对其孔隙率以及还原度和还原膨胀率进行了测定。试验结果表明,随着球团矿抗压强度的提高,其孔隙率呈下降趋势,其900℃还原度也呈下降趋势,而还原膨胀率变化不大。对不同抗压强度球团矿的矿相进行了测定,结果表明,预热时间的延长,使球团初期的预热氧化过程更加完全,Fe2O3微晶键更好地发育和长大,而焙烧温度的升高,则可以促进后期Fe2O3的再结晶和长大,提高晶键互连程度,晶粒紧密连接成片,孔隙率下降,使焙烧球团具有较高的抗压强度,但结构致密,变得难以还原。     

Studies on the Reduction–Swelling Behaviors of Hematite Iron Ore Pellets with Noncoking Coal

Studies on the reduction and swelling behaviors of fired pellets, made by mixing hematite iron ore fines of ?100, ?18 + 25, and ?10 + 16 mesh sizes in different proportions, were carried out with low-grade coal in the temperature range of 850–1000°C with an aim to promote the massive utilization of fines in ironmaking. The rate of reduction in all the fired iron ore pellets increased markedly with an increase in temperature up to 1000°C and it was more intense in the first 15-min soak time. Relatively higher reduction rates and swellings/shrinkage were observed in the pellets made by the addition of larger size (+100 mesh) particles in the matrix of ?100 mesh size fines. In general, highest swelling was observed in the fired pellets at a reduction temperature of 850°C, followed by a decrease at 900°C. At both these temperatures, the percentage of swelling increased with reduction time up to the range studied (120 min). The fired pellets reduced at temperatures of 950°C and 1000°C, showed shrinkage, and the extent of this shrinkage increased with increase in exposure time at 950°C. The percentage swelling/shrinkage in the fired pellets was found to be related to their crushing strengths and porosities.     

Hydrogen-Based Direct Reduction of Iron Oxides Pellets Modeling

The present study deals with the analyses of the direct reduction kinetics during the hydrogen reduction of industrial iron oxide pellets. Various types of pellets with different percentage of total iron content and metal oxides are examined. They are reduced at different temperatures and pressure (700–1100 °C and 1–6 bar) in hydrogen atmosphere. The reduction behavior is described in terms of time to reduction, rate of reduction, and kinetics constant. All the obtained results are analyzed through the employment of a commercial multiobjective optimization tool to precisely define the weight that each single parameter has on the reduction behavior. It is shown that from the point of view of the processing conditions, temperature is the main factor influencing the time to total reduction. From the point of view of the pellets properties, it is mainly influenced by the total iron percentage and then by porosity and basicity index. Also, the kinetics behavior is largely influenced by the reduction temperature even if it is mainly governed by the porosity and pores size from the point of view of the reduced pellets. The reduction rate is also mainly influenced by temperature and then by iron percentage, gas pressure, basicity index, and porosity.     

Reduction swelling behaviour of haematite/magnetite agglomerates with addition of MgO and CaO

Abstract

The influence of three kinds of CaO and MgO additives (dolomite, burnt lime and serpentine) on the reduction swelling behaviour of haematite–magnetite (H–M) concentrates pellets was studied. Burnt lime and dolomite increased the reduction swelling index of H–M oxidised pellets, while the reduction swelling index was able to be reduced when serpentine was added. CaO accelerated the formation and growth of metallic iron whiskers and led to abnormal swelling of the magnetite briquettes, while MgO was able to be dissolved in wüstite and reduced the migration rate of Fe²⁺; therefore, there was no catastrophic swelling in either the haematite or magnetite briquettes. As far as H–M concentrate pellets were concerned, because the solubility of CaO in magnetite was greater than that in the primary haematite and the secondary haematite generated from magnetite during the oxidation was easy to be reduced to wüstite, there was abnormal swelling in the reduced H–M pellets with CaO addition.     

PMC矿粒度及球团预热、焙烧工艺参数的选择

 为了促进PMC矿粉的高效利用,研究了PMC矿粉粒度和预热、焙烧温度对球团矿抗压强度、还原度、低温还原粉化、膨胀率、转鼓强度、孔隙率和熔滴性能的影响。结果表明,随着预热、焙烧温度的升高,改善了球团矿的抗压强度、还原度、转鼓强度和软熔滴落性能,低温还原粉化率变化幅度较小。随着焙烧温度的升高,膨胀率先升高后降低,孔隙率降低。随着预热温度的升高,1号球团矿 (PMC 0.074 mm)的膨胀率下降,2号球团矿(PMC 0.045 mm)的膨胀率小幅度升高;随预热温度的升高,两种PMC球团矿孔隙率先降低然后升高,在预热温度为950 ℃时,孔隙率最低。根据上述研究结果,通过加权灰色关联度法确定了PMC矿球团生产最佳工艺参数,粒度为0.074 mm,预热温度为925 ℃,焙烧温度为1 300 ℃。     

The Effect of Reduction Parameters on Iron Nugget Production From Composite Pellets

Composite pellets which contain a reducing agent and are produced only by cold bonding process are improved instead of traditionally hardened pellets by sintering. The new ironmaking technologies that are able to utilize these pellets have been developed from pilot plant to commercial scale. Iron nuggets which have a similar composition to pig iron can be produced by using composite pellets at high temperatures (1350–1400°C) and in a short reduction time (15–20 min) by smelting reduction process. In this study, the effect of reduction parameters and basicity of composite pellets on the reduction properties and product quality are investigated. Composite pellets containing magnetite concentrate with a reducing agent (coke) and a flux are processed at different temperature and at times by smelting reduction process. The increasing temperature and time has a positive effect on reduction and melting of the pellets. Excessive carbon prevents the metal droplets from coalescing. The iron nugget that is produced from the sample with the basicity (CaO/SiO₂) of 0.68 has the optimal physical and chemical properties. It is also determined that a decrease or increase of basicity has a negative effect on the properties of the iron nuggets.     

球团矿恒温和升温直接还原膨胀行为试验

 将球团矿分别在900 ℃恒温和升温试验条件下还原,研究了球团矿的还原膨胀行为;分析了2种温度条件下球团膨胀机理;对比了2种条件下的试验结果,观察分析了还原后球团的外观和微观组织形貌,得到了导致2种温度条件下球团膨胀差异的原因。研究结果表明：恒温还原球团的最大膨胀值为18.3%,升温还原时为8.3%,恒温还原球团的膨胀行为更加明显;裂纹和气孔的形成以及金属铁的析出形态差异是造成膨胀差异的主要原因。由此得出,为了得到与实际生产相近的还原膨胀行为,球团矿应该在升温条件或模拟的生产条件下进行还原试验。     

氧化球团微波加热煤基直接还原过程微观机制

为了解决常规加热煤基直接还原的反应时间长、还原温度高、产品质量差等问题,基于微波加热特性结合直接还原理论提出了采用微波加热进行氧化球团煤基直接还原的新工艺。通过采用扫描电镜、能谱分析仪和显微硬度计等检测手段对常规加热和微波加热煤基直接还原过程进行了深入研究,探究氧化球团微波加热煤基直接还原过程微观机制。研究结果表明,微波加热不仅改变了球团矿的微观结构和能量分配,而且在某种程度上表现出微波加热的“非热效应”,常规加热时,在还原温度1050℃下还原150 min,球团金属化率仅为89.38％;氧化球团煤基直接还原过程采用微波加热,从室温上升到1050℃后再等温14 min,球团金属化率达到92.67％。     

Reduction and Swelling of Fired Hematite Iron Ore Pellets by Non-coking Coal Fines for Application in Sponge Ironmaking

In the present investigation, the reduction and swelling behaviors (in low grade coal) of fired iron ore pellets, prepared by blending hematite iron ore fines of ?100, ?18 + 25, and ?10 + 16 mesh sizes in different proportions, have been studied in the temperature range of 850–1000°C with an objective to promote massive utilization of fines in sponge ironmaking. An increase in temperature up to the range studied (850–1000°C) substantially enhanced the reduction rate and the rate was found to be highest in the first 15–30 min at all these temperatures. All the fired pellets, made by mixing iron ore particles of ± 100 mesh size, have shown approximately the same reduction rates and slightly higher swelling indices than those made from fines of ?100 mesh size only. In all the fired pellets reduced at temperatures of 850°C and 900°C, the results indicated an increase in the extent of swelling with reduction time. Reduction of fired pellets at temperatures of 950°C and 1000°C exhibited shrinkage in their reduced products, and the extent of this shrinkage increased with increase in exposure time.     

球团矿高温还原过程中抗压强度变化及机理

 运用自行设计制造的固态物料高温抗压强度与蠕变在线测试仪,分别测试球团矿在不同温度及还原度状态下的抗压强度及蠕变量,用以表征球团矿在高炉内不同位置的抗压能力。研究发现：未发生还原反应球团矿在中性气氛中,当温度达到1 000 ℃时,球团矿的抗压强度为2 750 N以上,继续升温,球团矿抗压强度下降迅速;球团矿在还原气氛下,还原初期球团矿抗压强度比同温度下中性气氛球团矿抗压强度有较大下降,当温度高于900 ℃时,球团矿抗压强度只有1 250 N,且在抗压试验中形变明显。微观结构分析表明：还原过程中高价铁氧化物到低价铁氧化物变化过程中晶格增大、新生铁相基体孔隙增加、裂纹产生以及颗粒间固相固结减弱是导致强度下降的主要原因。