新型黏结剂强化冷固结球团的作用机理

 黏结剂在冷固结球团中必不可少,目前广泛使用的冷固结球团有机、无机黏结剂如CMC、膨润土和水泥等均会在高温下失效,导致球团高温强度严重下降,因此,寻找一种高温强度良好的黏结剂是目前需要解决的问题。采用新型黏结剂制备冷固结球团,通过XRD和SEM-EDS等对新型黏结剂球团制备原料及球团性能特征进行分析,同时探讨黏结剂对球团冷态抗压强度及高温强度的影响及其作用机理。试验结果表明,黏结剂以流动状态存在于冷固结球团中,可有效吸附或包裹铁矿粉颗粒,增加黏结剂配比可同时提高球团的冷态抗压强度及高温抗压强度;在高温还原性气氛下焙烧冷固结球团,由于发生还原反应,球团金属化率提高,铁矿粉颗粒间空隙增大,导致球团强度下降,焙烧时间为30～90 min时,球团金属化率及抗压强度变化趋势最明显;焙烧初期,球团抗压强度不会发生快速下降,且焙烧结束后球团强度仍可保持为100 N/个左右。     

球团配加赤铁精矿的试验研究

利用球团模拟试验炉对配加10%～50%的赤铁精矿进行了试验,试验条件：干燥温度600℃,时间10 min;预热温度900℃,时间20 min;强氧化性气氛,焙烧30 min。结果表明,生产强度〉200 kg/个的球团矿,赤铁精矿配比30%以下时,需要的最低焙烧温度为1 180℃;35%时,最低为1 200℃;40%～50%时,则最低为1 220℃以上。赤铁精矿配比从10%增加到50%,可使球团矿的铁品位增加约0.7%、SiO2含量降低1%;还原度及低温还原120粉化率相差不大。同时,进行了配加煤粉、焦粉、有机黏结剂和PT粉的探索试验,试验表明,添加物对降低焙烧温度和提高球团矿强度有较好的作用,配加3%的PT粉,赤铁精矿配比30%球团矿的焙烧温度可降低50℃以上。     

高铝铁矿和高锰铁矿共还原行为的研究

高铝铁矿和高锰铁矿是两种储量丰富但又极难分选的铁矿资源,实现铁、锰、铝的高效综合利用具有重要意义.本文研究了这两种铁矿石工艺矿物学,考查了单矿种及两者的混合矿种的直接还原行为及还原过程中的矿物组成演变,揭示了相应的还原机理.结果表明:高铝铁矿难还原,其机理为经还原后仅部分铁氧化物转化为金属铁,其余的铁与铝、硅矿物形成难还原的铁橄榄石和铁尖晶石;高锰铁矿易还原,其中的铁氧化物大部分被还原成金属铁,锰氧化物与铝、硅矿物结合形成锰尖晶石和锰橄榄石,促进了铁氧化物的还原.而且在相同还原条件下,高锰铁矿球团金属化率比高铝铁矿高30个百分点,前者还原性明显优于后者.两种矿进行共还原,当高锰铁矿配比达到60%时,球团金属化率就可大于90%.锰氧化物的存在对高铝铁矿石中铁氧化物的还原具有显著的促进作用.     

双层结构对提高含碳球团强度的影响

为了提高含碳球团强度,提出了内层为含碳球团,外层为精矿粉的双层结构复合含碳球团新工艺.研究了不同外层厚度球团的强度和金属化率,分析了球团强度形成的机理.研究结果表明:外层厚度适中的复合含碳球团强度能得到有效提高.该复合球团生球落下强度为普通含碳球团的2倍,400℃预热球抗压强度可达147.6N/个.900℃后,随着温度的增加,球团抗压强度提高,1150℃恒温还原30 min后抗压强度为2 080 N/个.且研究发现复合含碳球团能有效提高碳素利用率,C/O物质的量之比nC/nO为2∶3的复合球团还原后金属化率可达93.90％,其中外层金属化率为92.46％.通过显微结构分析,发现球团还原后外层生成了致密的金属铁外壳,这种外壳的独特力学性能是球团强度提高的主要原因.     

钒钛铁精矿内配碳球团的高温快速还原

 钒钛铁精矿是一种铁、钒、钛等多元素共生的复合矿,具有很高的综合利用价值。通过采用实验室转底炉对钒钛铁精矿内配碳球团进行了高温快速还原的可行性研究,分别考察了配碳比、还原温度、添加剂、还原时间等参数对球团金属化率的影响。结果表明,配碳比（1.5：1）、还原温度（1350℃）、添加剂（2%）、还原时间（20min）时金属化率可以达到88%以上。对原料、还原样品进行x射线衍射分析表明,钒钛铁精矿粉中的磁铁矿、钛磁铁矿和钛铁矿通过还原转变为单质铁、含铁黑钛石。     

台车连续炉直接还原法

开发了一种在台车连续炉中实现铁矿直接还原的方法。台车连续炉的炉膛是直条形,炉底由若干个台车组成。含碳球团料层铺在台车上,通过炉膛时进行还原焙烧。为了得到高金属化率,在料层表面覆盖薄焦炭层保护。此方法已经成功地用于唐钢石人沟铁矿。生产线所用的炉子长70 m,宽2 8 m。炉底由26 个台车组成。用这种方法生产的海绵铁产品成分如下:金属化率大于92%,全铁约90%,硫小于0 08%。一座炉子的产量为5 t/h,总煤耗低于700 kg/t。和转底炉比较,台车连续炉的优点是:结构简单,供热点少,台车维修方便,主要缺点是台车运转速度不能太快,焙烧时间较长。     

Reduction Behaviour of Olivine Iron Ore Pellets in the Experimental Blast Furnace

An experimental study was conducted to determine the reduction behaviour of olivine iron ore pellets and associated reduction mechanisms in the experimental blast furnace (EBF) located at Luleå. Two sets of EBF samples, namely slowly annealed excavated samples and rapidly quenched probe samples of olivine bearing iron ore pellets were examined in detail. Pellet samples were analysed using SEM, XRD and SIROQUANT analysis to quantitatively determine iron ore phase transformations during descent in the EBF. In the tested EBF campaign, up to 75% of reduction occurred at less than 1100°C, i.e. before the pellet reached the cohesive zone while rest of 25% reduction was completed when pellets reached a temperature of 1300°C and hence within the cohesive zone. The reduction degree of pellets was found to have a linear correlation with distance from the stock line of the EBF. This study showed that the presence of olivine did not have a significant effect on reduction degree for temperatures less than 1100°C in the upper zone of the EBF. However, olivine increased the reduction rate in the final stage of reduction for temperatures in excess of 1100°C in the cohesive zone, which was attributed to the formation of an increased amount of molten FeO containing slag within the pellet. This study is expected to make important contributions towards further improvements in the pellet design as well as the optimization of blast furnace operation and efficiency.     

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.     

硼铁矿直接还原过程中金属铁颗粒的生长特性

 硼铁矿是中国含硼原料的主要来源,其加工利用的关键在于硼和铁的分离。研究了不同条件下硼铁矿在直接还原过程中金属铁颗粒的生长特性,可为硼铁矿中硼和铁的有效分离提供理论支撑,从而达到硼铁矿资源化利用的目的。采用Leica DMI5000M光学显微镜获得还原球团中金属铁颗粒的显微图像后,通过Image-Pro Plus 6.0图像软件对显微图像进行金属铁颗粒粒径的分析统计,并采用化学分析的方法对还原产品中铁的金属化率进行检测,同时利用扫描电镜研究了Na₂CO₃促进铁氧化物还原的作用机理和金属铁颗粒的生长行为。结果表明,Na₂CO₃作用下硼铁矿球团中的铁氧化物能有效被还原,随着还原时间的延长,还原球团中铁的金属化率和金属铁颗粒的平均粒径均有效增大,在还原温度为1 100 ℃、还原时间为60 min的条件下,不添加Na₂CO₃的焙烧产物中铁的金属化率和金属铁颗粒的平均粒径分别为84.36%和8.55 μm,而在添加15%Na₂CO₃后于同样条件下焙烧,产物中铁的金属化率和金属铁颗粒的平均粒径分别为91.72%和14.07 μm;SEM-EDS分析结果说明,Na₂CO₃不仅有促进金属铁和其他物质分离的作用,而且还会影响金属铁颗粒在还原焙烧过程中的迁移行为;在直接还原过程中,金属铁颗粒先由“点”接触变为“颈”接触,然后重新相交形成新的晶界成为多边形颗粒,最后多边形颗粒间互相连接形成致密化集合体。     

铁矿直接还原用台车连续炉

介绍一种用于铁矿直接还原的台车连续炉，含碳球团料层铺在台车上并通过炉膛进行焙烧和还原。此炉子已经成功地用于铁精矿粉还原焙烧，所得到的海绵铁产品的金属化率大于92％，全铁约90％。和转底炉比较，台车连续炉的优点是结构简单，供热点少，台车维修方便；主要缺点是台车运转速度不能太快，焙烧时间较长。     

Reduction of Pellets‐Nut Coke Mixture under Simulating Blast Furnace Conditions

In recent years an intensive work has been carried out to decrease the coke losses of the blast furnace through mixing small‐sized coke called “nut coke” in the iron ore burden layers. In order to clarify the influence of nut coke on the pellets reducibility, industrial iron ore pellets were reduced with and without nut coke participation under different temperatures and atmospheres. Isothermal and non‐isothermal reduction tests under simulating blast furnace conditions were performed using an experimental laboratory rig. Furthermore, reflected light microscopy, scanning electron microscopy and X‐ray technique were applied to characterize the microstructure and different phases developed in the origin and reduced pellets. Pellets reduced isothermally without nut coke participation exhibited reduction retardation (RR) at elevated temperature (≥1373 K) whereas the presence of nut coke had a positive effect of preventing such phenomena. The non‐isothermal reduction of pellets showed that, as the amount of nut coke in pellets bed increased, the reducibility of pellets increased, too. The rate controlling mechanism of pellets and pellets‐nut coke mixtures was predicted from the correlation between apparent activation energy calculations and microstructure examination.     

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.      

CHARACTERIZATION OF PROPERTIES AND REDUCTION BEHAVIOR OF IRON ORES FOR APPLICATION IN SPONGE IRONMAKING

Studies on the chemical and physical properties, and the reduction behavior (in coal) of hematite iron ores procured from 10 different mines of Orissa, were undertaken to provide information for the iron and steel industries (sponge iron plants in particular). The majority of the iron ores were found to have high iron and low alumina and silica contents. All these iron ores were free from the deleterious elements (S, P, As, Pb, alkalies, etc.). The results indicated lower values of shatter and abrasion indices, and higher values of tumbler index in all the iron ore lumps except Serazuddin (previous) and Khanda Bandha OMC Ltd. For all the fired iron ore pellets, the degree of reduction in coal was more intense in the first 30 min, after which it became small. Slow heating led to higher degree of reduction in fired pellets than rapid heating. All the iron ores exhibited more than a 90% reduction in their fired pellets in 2-h time interval at a temperature of 900°C. Iron ore lumps showed a lower degree of reduction than the corresponding fired pellets.     

高炉使用含碳复合炉料的原理

 高炉炼铁正朝着高产、低污染、低能耗的方向发展,为了实现这一目标,包括高炉使用含碳复合炉料等一些革新的炼铁技术已经被提出或实际应用。铁焦、热压含碳球团是将铁矿粉和煤粉按一定比例混合后制成的新型含碳复合炉料。研究结果指出,含碳复合炉料相比于传统的高炉炉料（烧结矿和球团矿）具有高温强度高、还原性能好以及原料适应性强等优势。阐明了高炉使用含碳复合炉料的基本原理,介绍了铁焦制备的工艺流程及应用情况,重点进行了热压含碳球团制备工艺流程、冷态冶金性能、高温冶金性能、高炉使用热压含碳球团等试验研究,最后利用多流体高炉数学模型对高炉使用热压含碳球团操作进行了模拟研究。研究表明,高炉使用一定量的含碳复合炉料可以降低热空区温度,增加产量,降低焦比,高炉热利用效率明显提高,操作性能得到有效改善。     

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.     

Effect of CaO on the reduction behaviour of iron ore–coal composite pellets in multi-layer bed rotary hearth furnace

The effect of CaO on the reduction behaviour of iron ore–coal composite pellets has been studied in a laboratory scale multi-layer bed rotary hearth furnace at 1250°C for 20?min. Reduced pellets have been characterised through weight loss, porosity measurement, phase analysis by XRD, and morphology study by SEM. The addition of CaO to the composite pellets showed different effects at different carbon levels. For higher carbon-containing pellets (C/Fe₂O₃ molar ratio at the upper stoichiometric level of 3), the addition of CaO increased the extent of reduction for all three layers significantly up to a certain limit (4?wt-%); and thereafter the degree of reduction is decreased with a further increase in CaO percentage in the pellets. For low carbon-containing pellets (C/Fe₂O₃ molar ratio of 1.66), the addition of CaO to the pellets did not show any beneficial effect.     

Can Modified Starch be Used As A Binder For Iron Ore Pellets?

Organic binders are often desired when making low-silica iron ore pellets. Corn and wheat are grown in large quantities near certain iron ore pelletizing facilities and their starches are easily modified to form cold-water-soluble powders that can be used as binders. We investigated how starch cold-water solubility, starch dose, starch hydration time, green ball moisture content, and firing temperature affected pellet quality. With a fluxed, hematite concentrate, the high-soluble starch led to good wet and dry balls, but weak and friable indurated pellets compared to the standard binder, bentonite clay. As expected, the low-soluble starch did not make as good green balls as the high-soluble starch. Thermogravimetric analyses of unfired pellets and their abrasion products showed that modified starch was inhomogeneously distributed in pellets, with a high concentration near the ball surfaces. The surface concentration increased, and the core concentration decreased, as pellets grew during the pelletizing process. This suggests that starch enrichment near surfaces is a consequence of the agglomeration–compaction process, and may occur with other pelletizing binders. Abrasion mass losses were 81% greater with modified starch than with bentonite at 1100°C, and 31% greater at 1250°C. However, starch contents near the surfaces did not qualitatively correlate to roughness, as the highest starch dose tested gave the smoothest and least dusty pellets.     

Effects of Binder on the Properties of Iron Ore-Coal Composite Pellets

Large amounts of fines and superfines are generated in Indian iron ore and coal mines due to mechanized mining and mineral dressing operations. Utilization of these fines for extracting metal is of vital concern for resource utilization and pollution control. For agglomeration of these fines, a suitable binder is required. Iron ore-coal composite pellets were prepared by cold bonding. Various binders such as lime, Ca(OH)₂, slaked lime, dextrose, molasses, and sodium polyacrylate (SPA), alone or in combination, were employed for making composite briquettes. The slaked lime–dextrose combination produced the highest strength among the various binders employed for producing composite briquettes and was therefore selected for producing composite pellets for the smelting reduction. In cold bonding, the composite pellets attain the requisite properties due to physico-chemical changes of the binder in ambient conditions. It was possible to obtain a dry strength of more than 300 N per pellet in some cases and more than 200 N per pellet in many trials. Drop strength and shatter index values of composite pellets were also measured. In the present paper an attempt has been made to evaluate the mechanical properties of cold-bonded composite pellets so as to throw some light on the capacity of these pellets to withstand stresses during handling and transportation.     

Humic Substance-based Binder In Iron Ore Pelletization: A Review

Due to the reducing ability and bonding effect, a humic substance-based binder has been added into iron ore pellets, both as a reductant and a binder. However, humic substance-based binders were not commonly used in pelletization since some pelletizing results indicated they were not as good asbentonite or other binders. Thus, there were few detailed investigations using humic substance-based binders in pelletization before the 1980s. Funa, which is a type of humic substance-based binder extracted from lignite, was successfully invented and applied in cold-bonded pellets in China. Since the organic fraction in the humic substance-based binder is burnt away during heating, leaving no contaminant in pellets and improving the iron content of the pellets, humic substance-based binders were also gradually utilized in oxidized pellets. On the basis of Funa binder research, the extracting procedure of a humic substance-based binder was modified, and a composite binder named Modified Humic Acid (MHA)was prepared for oxidized pellets, especially for making Vanadium-Titanium (V-Ti) magnetite pellets, and achieved qualified V-Ti magnetite oxidized pellets in industrial testing. The behaviors of humic substance-based binders in wet balls, dry balls and fired balls were well investigated. Moreover, MHA binder was gradually tested in a lab for pelletization of several other types of iron ore concentrates, such as magnetite from different districts, specularite and fluxed hematite, and good quality pellets were obtained. A review of the development of a humic substance-based binder and its characteristics, preparing method, and behaviors in pelletizing were considered in this paper.     

Effect of alumina on slag–metal separation during iron nugget formation from high alumina Indian iron ore fines

Abstract

Iron nuggets can be obtained from ore–coal composite pellets by high temperature reduction. Alumina in the ore plays a vital role in slag–metal separation during nugget formation, as it increases the liquidus temperature of the slag. In this study, the effect of carbon content, reduction temperature and lime addition on slag–metal separation and nugget formation of varying alumina iron ore fines were studied by means of thermodynamic modelling. The results were validated by conducting experiments using iron ore fines with alumina levels ranging from 1·85 to 6·15%. Results showed that increase in reduction temperature enhances slag metal separation, whereas increasing alumina and carbon content beyond the optimum level adversely affects separation. Carbon below the required amount decreases the metal recovery, and carbon above the required amount reduces the silica and alters the slag chemistry. Optimum conditions were established to produce iron nuggets with complete slag–metal separation using iron ore–coal composite pellets made from high alumina iron ore fines. These were reduction temperature of 1400°C, reduction time minimum of 15 min, carbon input of 80% of theoretical requirement and CaO input of 2·3, 3·0 and 4·2 wt-% for 1·85, 4·0 and 6·15 wt-% alumina ores respectively.