Kinetics and mechanism of smelting reduction of fluxed chromite Part 1 Carbon–chromite–flux composite pellets in Fe–Cr–C–Si melts

Abstract

Experimental studies on the smelting reduction of fluxed carbon–chromite composite pellets in Fe–Cr–C–Si alloys were carried out at 1520–1600°C. The reduction reaction was found to be favoured by high temperatures, a high lime addition in the pellets, a long pellet dissolution time, and a moderate melt Cr content. For a given CaO addition, however, the reduction rate initially slowed before increasing with an increasing silica addition to the pellets. A three stage reduction mechanism is proposed. The first stage is very likely to be controlled by solid state and/or gas diffusion with an apparent activation energy of 472 kJ mol^-1 for pellets fluxed with 15%CaO and 25%SiO₂ . The third stage proceeds via smelting mechanisms, with mass transfer in the slag phase possibly rate controlling.     

Fundamental research on phosphorus behaviour in the smelting reduction process

The behaviour of phosphorus in the smelting reduction process was investigated in this paper. Experiments were carried out under the conditions of smelting reduction: the phosphate reduction in molten slag by solid carbon, liquid iron saturated with carbon and CO gas, respectively. Furthermore, experiments on the phosphate reduction in pre-reduced iron ore by liquid iron saturated with carbon were carried out respectively when liquid iron was in permanent contact with molten pre-reduced iron ore, and when powders of the pre-reduced iron ore were injected into the iron bath from the bottom. The results showed that there was considerable unreduced P₂O₅ in the slag. Part of the reduction product of phosphorus escaped from the bath, while the other part was absorbed by liquid iron. The pig iron with low content of phosphorus can be obtained by smelting reduction in comparison with blast furnace. In the process of liquid iron bath with coal-oxygen-ore injection, the phosphorus content in liquid iron could be kept constant in 100 kg scale tests.     

Morphology and reduction kinetics of fluxed iron ore pellets

Abstract

The present paper describes studies of the reduction and sintering behaviour, followed by examination of the structural changes taking place, during direct reduction of fluxed composite (ore plus coal) pellets. The kinetics and morphological aspects of the direct reduction of fluxed composite pellets are compared with those for the gaseous reduction of fluxed ore pellets without carbon addition. It is shown that the chemical reaction is the rate limiting factor for fluxed composite pellets, and the mass transport of reactant gas through the reaction product iron layer governs the overall reduction process in the case of fluxed ore pellets. Microscopic analysis of the fluxed composite pellets has indicated no tendency to form a reduction inhibition iron shell towards the end of the reduction, as found in the case of gaseous reduction of fluxed ore pellets under identical reduction process conditions. The effects of basicity, Fe/C, temperature, and other variables on morphological and microstructural changes in the directly reduced fluxed composite pellets have been experimentally investigated in the present work.     

Effect of fluxing agents on reduction degradation behaviour of hematite pellets

During induration at a high temperature, a considerable amount of slag/melt phase forms inside the iron ore pellets, comprising SiO₂, Al₂O₃, CaO, MgO and FeO. After cooling, the slag phase solidifies and acts as an important bonding phase in the finished pellets and influences their room temperature as well as high temperature properties, especially reduction degradation. Fluxing agents play an important role in forming these bonding phases depending on the type and amount of flux. In the present study, the effect of different fluxing agents, namely, limestone, dolomite, magnesite and pyroxenite, on melt formation and microstructure during induration and on reduction degradation behaviour during reduction was examined. From the results, it was understood that to reduce the disintegration during reduction it is essential to increase the amount and distribution of bonding phases like silicates, which are more stable as compared to oxide phases like hematite. Acid pellets exhibited highest reduction degradation due to the presence of more hematite bonds and less silicate bonds. In limestone fluxed pellets, reduction degradation index dropped considerably with increasing CaO content due to the formation of more amount of bonding phase. Dolomite–pyroxenite pellets, on the other hand, showed lower reduction degradation index up to 0.4 basicity, and beyond that, higher degradation was observed due to the increased pore size, which resulted in poor strength of the reduced pellet matrix and hence more degradation. Low reduction degradation observed in pyroxenite and magnesite fluxed pellets could be due to the formation of magnesioferrite and silicate melt, which are more stable phases compared to hematite.     

渣系碱度对含碳球团渣相组成和渣铁分离的影响

采用煤基直接还原熔分技术和FactSage热力学分析软件以及XRD分析手段,研究了渣系碱度wCaO/wSiO2对高铁铝土矿含碳球团渣相组成和渣铁分离效果的影响。实验结果表明,渣系碱度对含碳球团的渣系组成和渣铁分离效果有重要影响。当碱度为1.0和1.5时,粒铁尺寸最大,渣铁的分离效果最好,粒铁收得率分别为91.55%和91.86%;当碱度为0.5时,粒铁尺寸较小,渣铁分离效果较差,粒铁收得率为65.43%。当碱度为2.0时;粒铁尺寸最小,渣铁分离效果最差,粒铁收得率只有44.53%。XRD分析结果表明,当渣系碱度分别为0.5、1.0、1.5和2.0时,熔分渣的主要组成分别为α-Al2O3-CaAl2Si2O8、α-Al2O3-CaO·6Al2O3-Ca2Al2SiO7、CaO·6Al2O3-Ca2SiO4-Ca2Al2SiO7、Ca2Al2SiO7-Fe2SiO4。FeAl4O7、CaAl4O7以及金属铁在熔分渣中的含量较少。     

超大型高炉高球比低碳冶炼技术应用

为实现低碳炼铁生产,首钢基于秘鲁矿粉资源高品位低硅含量的特点,确定了高炉高球团比例冶炼的技术路线。依据炉渣碱度平衡、球团性能和炉料结构软熔性能试验研究,开发出35%碱性球团矿 + 20%酸性球团矿+ 40%烧结矿 + 5%块矿的高炉基础炉料结构。根据高比例球团矿同时抑制边缘和中心的特性,通过料序控制减少球团在边缘与中心的分布,实现酸碱性炉料的均匀混合,并采用中心加焦布料方式开放中心、适当疏导边缘,以稳定煤气分布。在活跃炉缸基础上,通过高富氧高顶压控制炉腹煤气指数来降低压差提高冶炼强度。低渣比下通过提高镁铝比至0.60~0.65来改善脱硫排碱能力。55%球团比例下高炉实现了高效稳定顺行,平均利用系数达到2.3 t/(m3·d),渣比低于220 kg/t,燃料比降至480 kg/t,炼铁系统碳排放降低8.6%。     

红土镍矿选择性还原-熔分制备镍铁合金

以硅镁型红土镍矿为原料,采用金属化焙烧-熔分工艺,通过正交试验制备金属化球团,将所得金属化球团在1500℃条件下熔融分离30 min提取镍铁合金,考察影响因素对实验结果的影响.结果表明:在选择性还原制备金属化球团过程中,对金属化率的影响程度从大到小的因素依次是C/O摩尔比、焙烧温度、焙烧时间和碱度;实验可获得镍品位19%的镍铁合金;在碱度为0.8-1.2范围内,S和P分配比随着碱度的升高而增大.利用X射线衍射和扫描电镜对金属化球团及熔融分离出的渣进行微观分析,发现加入的石灰石与复杂矿相反应可释放出简单镍氧化物和铁氧化物,促进还原反应的进行,当石灰石不足时,少量铁以Fe3+的形式存在于铁金属化率70%的金属化球团中.      

碱度对镁质熔剂性球团性能的影响

 为改善镁质熔剂性球团矿质量,以唐钢铁精粉为原料,进行了造球焙烧试验,研究了碱度对镁质熔剂性球团质量的影响,并结合矿相结构进行了分析。结果表明,随着碱度的升高,生球强度呈略微降低趋势,爆裂温度整体呈降低趋势,碱度高于1.2时,爆裂温度急剧下降;球团抗压强度呈升高趋势,但当碱度高于1.2时,抗压强度急剧下降;低温还原粉化性能变化不大,基本为90%以上;球团软化开始温度整体呈升高趋势。随着碱度增加,铁酸钙质量分数增加,晶粒长大,气孔率呈先降低后增加的趋势;球团黏结率呈增加趋势,碱度每提高0.1,黏结率增加1.4%。     

酸性含钛炉渣泡沫化问题的研究

为解决攀钢熔分深还原电炉冶炼钒钛磁铁矿金属化球团过程中出现的泡沫化严重的问题,采取提高炉渣二元碱度、控制金属化球团w(FeO)和残碳量、减少低温电炉加料量等措施,使炉内泡沫化严重的现象得到控制,保证了冶炼过程的连续进行。同时钒还原率提高了13%,冶炼时间缩短了45min。     

链箅机-回转窑工艺生产碱性球团矿工业试验

在实验室研究的基础上,开展了链箅机-回转窑工艺生产碱性球团矿工业试验.结果表明,生产二元碱度(CaO/SiO2)为1.0左右的球团矿时,与酸性球团矿生产工艺相比,将预热段温度提高30℃左右,回转窑窑头温度降低10℃左右,链箅机的机速降低0.3m/min左右,成品球团矿的抗压强度可达到或稍高于酸性球团矿.碱性球团的还原膨...     

Simple Method for Estimating the Electrical Conductivity of Oxide Melts with Optical Basicity

The electrical conductivity of oxide melts is an important physicochemical property for designing the electric smelting furnaces. Although the data of many slag systems have been measured, the quantitative relationships of electrical conductivity to slag composition and temperature are still limited. In this article, a model is proposed based on the optical basicity corrected for the cations required for the charge balance of \textAlO ₄ ^5- {\text{AlO}}_{ 4}^{ 5- } , in which Arrhenius Law is used to describe the relationship between electrical conductivity and temperature. In this model, the activation energy is expressed as a linear function of the corrected optical basicity. Successful applications to CaO-MgO-Al₂O₃-SiO₂ and CaO-Al₂O₃-SiO₂ systems indicate that this model can work well in the electrical conductivity estimation.     

Formation and effects of slag foaming in smelting reduction

Research was carried out on the foaming phenomenon in the bath of the smelting reduction process with a hydrodynamic model and with high-temperature experiments. There are two mechanisms of slag foaming: when foam is generated by injected gas, the height of the slag foaming can be regulated. Contrarily, the production of gas during the reduction of iron oxides causes slag foaming which can hardly be controlled. High temperature as well as low slag basicity reduce the foam stability. In smelting reduction a large slag volume is expected. A rinse-spot in the slag layer, which can prevent slag foaming, disappears under these conditions. Wall-effects play an important role for the foam stability.     

Study on Foaming Behaviour of Molten Slag during Smelting Reduction with Iron Bath

ＳｔｕｄｙｏｎＦｏａｍｉｎｇＢｅｈａｖｉｏｕｒｏｆＭｏｌｔｅｎＳｌａｇｄｕｒｉｎｇＳｍｅｌｔｉｎｇＲｅｄｕｃｔｉｏｎｗｉｔｈＩｒｏｎＢａｔｈＬｉｕＱｉｎｇｃａｉＡｂｓｔｒａｃｔ：Ｔｈｅｍｏｌｔｅｎｓｌａｇｉｎｓｍｅｌｔｉｎｇｒｅｄｕｃｔｉｏｎｗｉｔｈ...     

High Temperature Properties of BOF Slag and its Behaviour in the Blast Furnace

Slag formation in the bosh and raceway is an important issue in the blast furnace process. SSAB works in Luleå operate with 100 % olivine pellets. A small amount of basic fluxes is added from the top, slag and limestone are used. To improve the control of slag formation, a concept with injection of BOF slag was evaluated and tested in the LKAB experimental blast furnace (EBF). In this paper, the behaviour of BOF slag as a slag former, when it is top‐charged or tuyere‐injected, is evaluated based on the results from a laboratory study including reduction tests, softening and melting tests, XRD analyses and SEM analyses. Samples taken from the EBF during excavation, and with a burden probe during operation, are examined. The evaluations show that the melting point of BOF slag is quite low and will not be increased, because of the partial reduction that occurs in the BF shaft. When carbon is present at high temperatures, reduction proceeds and a high basicity slag with a high melting point, consisting of di‐ and tricalcium silicates, is formed. When pellets with a basicity of B2 ~ 1 are used, a slag with similar properties can be formed as a result of interaction with the BOF slag. BOF slag in combination with olivine pellets with a low basicity generates a slag with intermediate basicity and the reduction of iron oxides in the slag has a small effect on the melting temperature. The BOF slag decreases the melting point of coal and coke ashes.     

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.     

高炉冶炼钒钛磁铁矿合理炉料结构的研究

合理的炉料结构是高炉冶炼钒钛磁铁矿最重要的内容之一.本文基于现场生产条件,在保证炉渣二元碱度、焦比、煤比等不变的条件下,进行不同碱度钒钛烧结矿和不同球团比例的综合炉料软熔滴落的试验,研究了高炉冶炼钒钛磁铁矿的合理炉料结构.结果表明,随着综合炉料中烧结矿碱度的提高和球团比例的增加,综合炉料的软化开始温度T4基本不变,软化终了温度T40升高,软化区间（T40-T4）变宽;综合炉料的熔化开始温度TS逐渐升高,熔化终了温度TD逐渐上升,熔化区间TD-Ts明显收窄,综合炉料的透气性能明显改善;同时初铁中V、Cr含量增加,V、Cr收得率明显提高.因此,在一定的范围内,提高综合炉料中钒钛烧结矿的碱度和球团比例,有利于高炉冶炼钒钛矿合理炉料结构的形成.     

基于铝土矿配碳球团还原熔分过程的渣相组成

 试验采用煤基直接还原熔分技术和热力学分析手段,对高铁铝土矿含碳球团在还原熔分过程中的渣相组成机理进行了研究。试验结果表明,渣系碱度对粒铁的收得率和粒铁尺寸以及渣系组成有重要影响。当碱度为1.00、2.00、3.85时,粒铁收得率分别为91.55%、44.53%和88.48%,粒铁尺寸分别为15.50、7.00 和8.54 mm;熔分渣的相组成（质量分数）分别为55%A-34%CA6-6%C2AS-4%Fe、64%A-35%C2AS-2%Fe、24%C2S-62%C12A7-7%C2AS-4%C3AS3-3%Fe;当渣系碱度为3.85时,还原熔分渣系的组成主要为C2S和C12A7,两者质量分数约为85%;只有当混合物处在C2S到C12A7的渣线上或者渣线附近时（即[R]=3.85时）,冷却析晶的平衡相中才会出现C2S和C12A7。     

碱度对白云鄂博铁精矿压团矿抗压强度的影响

发展熔剂球团矿是当前炼铁原料工艺技术发展的方向和热点之一,球团矿的碱度不同,其理化性质及冶金性能也不同。通过分析不同碱度的白云鄂博铁精矿压团矿矿相结构的变化规律,探究碱度对白云鄂博铁精矿压团矿抗压强度的影响规律。结果表明,随着碱度的升高,压团矿的抗压强度先增加后降低,液相量的增加使得孔隙率降低,压团强度升高,但过多的液相会破坏赤铁矿的整体性结构,渣相强度低于赤铁矿强度,压团的强度逐渐降低。     

碱度和MgO质量分数对球团抗压强度的影响

为研究含镁熔剂性球团的抗压强度,在实验室条件下,研究了焙烧时间、球团矿碱度和MgO质量分数对球团矿抗压强度的影响。试验研究结果表明,膨润土质量分数保持2.0%不变时,含镁熔剂性球团矿碱度(R)为0.80~1.00、MgO质量分数为1.60%~1.80%,焙烧时间为25 min,球团矿的黏结相以Fe₃O₄氧化为Fe₂O₃、然后Fe₂O₃再结晶为主。另外,还有少量的铁酸镁、铁酸钙相,这种球团矿的抗压强度大于2 500 N/个。当含镁熔剂性球团的矿碱度大于1.00,同时,MgO质量分数小于1.60%时,球团矿的黏结相含有大量的玻璃体硅酸盐,使球团矿的抗压强度大大降低。     

基于熔剂性生球的复合造块工艺处理钒钛磁铁矿

摘要：复合造块工艺是处理低品位复杂共生矿的重要途径之一,传统复合造块工艺一般为高碱度基体料配加酸性生球。实验研究了配加熔剂性生球的复合造块工艺处理钒钛磁铁矿,将烧结用生石灰细磨后加入钒钛磁铁矿精粉制备熔剂性生球,生球碱度控制在0.6～1.2,烧结料综合碱度为1.76。研究结果表明,随熔剂性生球碱度增加,生球强度增加,混合料料层透气性改善,烧结矿成品率增加。将烧结用焦粉细磨后加入钒钛磁铁矿制备含碳生球,焦粉加入量应控制在04%(质量分数)左右。当生球碱度为09时,烧结矿转鼓强度最高。分析结果表明,随着烧结料中熔剂性生球碱度增加,成品烧结矿中球团在基体中的嵌入程度更高,球团与基体边界逐渐变窄,边界处复合铁酸钙和硅酸盐含量增加,并有少量钙钛矿生成。