强化巴西赤铁矿链篦机—回转窑球团焙烧技术及其在中国的工业应用
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摘要
随着中国钢铁工业的快速发展,作为强化高炉冶炼的优质炉料,球团矿产量进一步扩大。然而,虽然中国铁矿石储量很大,但原矿铁品位低,需经过选矿,生产的磁铁精矿铁品位低,含杂高,其产量也远不能满足球团生产需要,中国钢铁工业面临着严重的球团原料短缺。因此,中国每年需要进口大量铁品位高、杂质含量低的赤铁矿用于球团生产。巴西淡水河谷公司是世界最大的铁矿公司,拥有丰富的赤铁矿资源,但其与磁铁矿相比,球团焙烧性能差,属于难处理铁矿,特别是其中的镜铁矿的利用尤为困难。因此,本文对强化巴西淡水河谷赤铁矿球团焙烧技术进行研究,对保障中国球团工业拥有充足的球团原料供应及改善球团质量具有重要意义。
本论文采用链篦机-回转窑球团工艺,对强化巴西淡水河谷赤铁矿球团焙烧技术进行研究,并且通过小型、扩大试验、工业试验及工业应用三个阶段,开发了三个技术方案：通过湿式球磨、高压辊磨(HPRG)或两者的联合技术对造球原料进行预处理；添加细磨石灰石提高球团矿碱度；赤铁矿外加磁铁精矿的配矿方案优化,以期提高成球性、强化球团焙烧及改善成品球团矿冶金性能。对巴西淡水河谷赤铁矿性能进行了系统研究,包括其粒度组成、比表面积、颗粒形貌、可磨度、成球性及单矿焙烧性能,揭示了巴西镜铁矿类型的赤铁矿难焙烧的内在机制。研究中对湿式球磨、高压辊磨(HPRG)以及两者结合的工艺方案强化赤铁矿球团焙烧的改善效果进行了比较；对小型试验、扩大试验和工业试验的工艺参数,包括造球原料预处理工艺参数、造球原料结构、膨润土配比和种类、造球工艺参数、预热和焙烧工艺参数进行了优化。采用SEM检测赤铁矿预处理前后的微观结构和表面性质,并通过检测生球和焙烧球团的物理化学性质,研究焙烧球团的冶金性能和工艺矿物学等手段,揭示相关技术方案强化赤铁矿球团焙烧及改善球团矿冶金性能的机理,并将这些强化球团焙烧技术方案运用于工业生产进行了研究。
研究结果表明,从化学成分和粒度组成上来看,巴西淡水河谷赤铁矿是优质的球团原料,铁品位高达66.79%,含2.47%SiO2,0.82%Al2O3,杂质含量较少,S、P含量分别为0.017%、0.024%,而且粒度非常细,-0.074mm为91.14%、-0.043mm达61.59%。但是,其成球性较差,静态成球性指数仅为0.15,而且其比表面积低,仅有520cm2/g,难以直接应用于球团生产。不能采用常规的铁精矿粒度作为评价其成球性指标。在球团生产中必须将其进一步细磨预处理,提高其成球性,改善球团焙烧性能。但是其可磨性差,球磨机功指数高达24.4Kwh/t。即使通过球磨将这种赤铁矿细磨到-0.043mm90%,比表面积达到1320cm2/g,制备的球团在预热温度1150℃、预热时间15min和焙烧温度1330℃、焙烧时间15min的小型试验最佳条件下,预热球团和焙烧球团抗压强度也分别只有369N/个和1365N/个,预热球团和焙烧球团矿抗压强度远低于500N/个和2500N/个的要求。因此,对巴西镜铁矿型赤铁矿必须开发高效预处理技术,提高其成球性,强化球团焙烧。
论文开发了三个技术方案来强化淡水河谷赤铁矿球团工艺,分别为：在赤铁矿中配入30%的磁铁精矿作为球团原料；通过球磨预处理将赤铁矿比表面积由520cm2/g提高到1140-1320cm2/g,然后通过高压辊磨处理将其比表面积增加到1500-1700cm2/g；三是提高球团碱度,用100%的赤铁矿(自然碱度为0.04)为铁原料,添加细磨石灰石,制备碱度为0.2-0.3的球团矿。这三种手段均可以使预热球团和焙烧球团矿抗压强度分别提高到500N/个和2500N/个的目标值以上。与不对原料进行预处理的方案相比,这三种技术方案显著提高了巴西淡水河谷镜铁矿型赤铁矿的成球性及球团的预热焙烧性能,并能以70-100%的巴西赤铁矿为原料,采用链篦机—回转窑工艺生产出优质球团矿。
造球试验从不同角度比较了三种膨润土的性能优劣。从提高生球落下强度和抗压强度的角度考虑,印度膨润土比Fanchang膨润土性能好,而后者又优于Husi膨润土。但如果从生球爆裂温度方面考虑,使用Hlusi膨润土比使用Fanchang膨润土效果好,而后者比印度膨润土好。国内膨润土的添加量需要1.5%-2.0%,而印度膨润土的适宜用量为1.0%-1.3%。
试验先使用80%粒度为-0.045mm90%的赤铁精矿配加20%的2#磁铁精矿,2.0%Fanchang膨润土的配料条件进行参数优化试验。然后在最佳试验参数下比较配加不同磁铁精矿比例的混合料制备球团的效果。试验得出的适宜造球参数如下：
●赤铁精矿比表面积达到1500cm2/g以上,相应的细度为85%-90%小于0.043mm;
●配加30%的2#磁铁矿；
●国内膨润土的适宜添加量为1.5%-2.0%；
●生球适宜水分为10.0士0.2%；
●生球粒度范围为8-16mm；
●生球落下强度达到3次/(0.5m)以上；
●生球抗压强度达到15N/个以上；
●生球热爆裂温度达到350℃以上。(4)预热-焙烧扩大试验得出适宜的球团焙烧系统参数如下：
●料层高度：150mm；
●鼓风干燥温度：210±10℃；
●鼓风干燥时间和风速分别为：2min,1.0m/s；
●抽风干燥温度：340±10℃；
●鼓风干燥时间和风速分别为：8min,1.2m/s；
●适宜的预热制度为：1130±10℃预热15min,预热风速2.2m/s；
●适宜的焙烧制度为：1300±10℃焙烧15-20min。
在适宜的造球、预热和焙烧制度下具体研究三个技术方案的效果。首先,对于赤铁精矿配加30%磁铁精矿的配矿方案,在最佳的预热和焙烧条件下,焙烧球团矿物理性能良好,其抗压强度可达到2500N/个以上,转鼓指数(+6.3mm)为97.52%,抗磨指数(-0.5mmm)为2.78%,97%的焙烧球团粒径处于8-16mm的范围内。焙烧球团铁品位高,全铁含量达到65.82%。
●焙烧球团的还原膨胀指数(RSI)较高：配加20%与30%的2#磁铁矿的还原膨胀指数分别为35.86%、20.36%。这意味着还需要采取其他措施来降低RSI。焙烧球团的还原性指数处于正常水平,其软化/熔滴温度较高且温度区间较窄。焙烧球团主要依靠再结晶和聚结来获得较好的还原性和机械强度。
●试验结果表明,直接采用100%的赤铁精矿制备合格氧化球团矿较为困难；赤铁精矿配加磁铁精矿是制备合格酸性球团的一个适宜方法。然而,即使配加了磁铁精矿,焙烧球团的还原膨胀指数仍然较高,还需要采取一些措施来改善。
其次,通过调节碱度可以改善赤铁精矿球团制备过程。在膨润土用量1.8%并添加1.09-1.76%的石灰石进行造球的条件下,生球落下强度达到3次/0.5m以上。然而,随着石灰石添加量的增加,生球强度和爆裂温度均会稍微下降。
●对于采用具有适宜比表面积的100%赤铁矿粉矿做铁原料的球团工艺,提高球团碱度可以显著改善球团焙烧行为。在自然碱度0.04(不添加任何熔剂)时,在预热温度1130±10℃、预热时间15min、预热风速1.9m/s及焙烧温度1300±10℃和焙烧时间15min的扩大试验最优条件下,预热球团和焙烧球团矿的抗压强度分别为382N/个和885N/个,预热球团和焙烧球团矿的转鼓强度分别为96.38%和73.73%,远低于要求的指标。当添加细磨石灰石造球,将球团矿碱度提高到0.3时,在相同的预热和焙烧条件下,预热球团和焙烧球团矿的抗压强度分别为1214.9N/个和2623.5N/个,预热球团和焙烧球团矿的转鼓强度分别为95.9%和95.73%,达到了要求的指标。由此可看出,与自然碱度焙烧球团相比,调节碱度至0.2或者0.3之后的焙烧球团的抗压强度明显提高,达2500N/个以上。这说明了焙烧球团的抗压强度可以通过添加石灰石调节球团的碱度来改善。
●与配加2#磁铁精矿的焙烧球团相比,碱度增加到0.2或者0.3的焙烧球团的还原性变好,还原膨胀指数RSI稳定在21%-26%的范围内,与配加30%的2#磁铁精矿的结果相近。碱度为0.3的焙烧球团矿物组成和微观结构良好。良好的结构强度使球团抗压强度达到2500N/个以上,满足了高炉生产的要求。
●球团焙烧行为的改善得益于低温下铁酸钙的形成,它强化了固相扩散反应和球团的固相固结。总体上看,添加石灰石增加球团碱度至0.2-0.3可以达到改善球团物理性能的效果,但其冶金性能还有待提高。
从经济和技术方面来讲,高压辊磨处理是强化赤铁矿球团工艺最有效的方法。研究提出了两种高压辊磨预处理流程：第一种是开路流程,球团原料依次通过两台高压辊磨机进行预处理,这种方式需要串联安装两台高压辊磨机；第二种是闭路流程,只采用一台高压辊磨机,在一定的循环负荷下对原料进行预处理,从高压辊磨机出来的部分边料返回辊磨机的给料中,与新给料一道经过高压辊磨机进行细磨。由70%赤铁矿配加30%磁铁精矿组成的造球混合料经高压辊磨预处理,进行造球和球团焙烧,取得的良好指标如下：
●通过高压辊磨处理获得的赤铁精矿成球性能良好。分别采用210%循环负荷的高压辊磨闭路流程和两次高压辊磨预处理开路流程预处理,可以将巴西赤铁矿比表面积从1100cm2/g分别提高到1495cm2/g和1294cm2/g,静态成球性指数由0.15分别增加到0.628和0.798。虽然铁精矿粒度组成变化不大,但其比表面积增加,成球性显著得到改善。首次提出“铁精矿比表面积是评价其成球性的最有效的指标”。
●高压辊磨预处理不仅强化了造球过程,还可以降低膨润土用量。研究中对比了几种国产膨润土和优质印度膨润土对生球性能的影响。结果表明,不经预处理,膨润土配比通常为2-3%,生球强度才能达到要求的指标。经过高压辊磨预处理,膨润土用量可降低到0.7-1.0%,在生球水分9.0%士0.5%和造球时间6-10min的条件下,生球落下强度和抗压强度分别大于5次/(0.5m)和15N/个,生球爆裂温度高于450℃。
●两次高压辊磨开路流程预处理赤铁矿制备的球团具有良好的焙烧性能,在较低的焙烧温度下就可以获得较好的指标。扩大试验结果表明,在预热温度1100-1130±10℃、预热时间10-13min、预热风速2.2m/s及焙烧温度1280±±10℃、焙烧时间13min的条件下,预热球团和焙烧球团抗压强度分别达到771和2759N/个,转鼓强度分别为95.76%(+3mm)和93.73%。相对而言,采用210%循环负荷的高压辊磨闭路流程预处理赤铁矿制备的优质球团需要较高的温度,在预热温度1130±±100C、预热时间12min、预热风速2.2m/s及焙烧温度1300±10℃、焙烧时间15min的扩大试验条件下,预热球团和焙烧球团抗压强度分别达到707和2745N/个,转鼓强度分别为97.98%(+3mm)和93.47%。此外,高压辊磨改善了焙烧球团的还原膨胀指数,将其控制在15%以下。
●高压辊磨的作用机理可能是,高压辊磨将机械能转变为颗粒表面的化学能,使赤铁矿颗粒得到机械活化,颗粒形成较多的裂纹、更高程度的晶格畸变和缺陷。这些机械活化作用使赤铁矿颗粒表面亲水性增加、成球性提高,生球的预热、焙烧行为也得到改善,焙烧球团具有良好的冶金性能。
高压辊磨预处理原料、赤铁矿中配加磁铁精矿、提高赤铁矿球团碱度,或者这些措施的组合可以显著改善赤铁矿球团的冶金性能,效果如下：
●成品球团矿的粒度组成为8-16mm占90%左右,铁品位为65-66%、FeO含量为0.5%,而杂质含量很低：3.05-4.15%SiO2,0.87-1.92%Al2O3,0.011-0.020%S,0.021-0.046%P。这说明配加铁品位高、杂质含量低的巴西淡水河谷赤铁矿,可显著改善焙烧球团的质量。
●增加磁铁矿在赤铁矿球团原料中的比例可以控制焙烧球团的还原膨胀行为。当配入30%磁铁矿时,焙烧球团还原膨胀指数(RSI)降低至20.36%。由100%赤铁矿制备的球团低温还原粉化很严重,低温还原粉化指数分别如下：RDI+3.15=51.45%,RDI.0.5=44.81%。当在赤铁矿球团原料中配入30%磁铁矿时,RDI+3.15提高到97%以上,RDI-o.5降低至2.5%以下。低温还原粉化被显著地抑制。
●将焙烧球团碱度从自然碱度提高到0.2-0.3的效果与在赤铁矿中配加30%磁铁矿得到的结果相似,焙烧球团还原膨胀指数为20-26%,RDI+3.15提高到97%以上,低温还原粉化率很低。
●以80%赤铁矿配加20%磁铁矿为原料,采用210%循环负荷的高压辊磨闭路流程和两次高压辊磨开路流程分别预处理后,制备的两种焙烧球团矿冶金性能都很好,其指标依次如下：还原度指数(RI)分别为67.18%和77.54%,还原膨胀指数(RSI)分别为13.08%和6.64%,低温还原粉化指数(RDI+3.15)分别为81.74%和75.21%。
焙烧球团矿的矿相分析结果表明,不管是何种配矿方案,球团中的矿物绝大部分是赤铁矿,因为在预热、焙烧过程中磁铁矿得到充分氧化,FeO含量低于1%。由100%淡水河谷赤铁矿制备的焙烧球团微观结构较差,Fe203晶粒细小,Fe203再结晶不能较好连接起来。因此,成品球团矿抗压强度远低于2500N/个。这可能是以下原因造成的：淡水河谷赤铁矿为镜铁矿类型,其高温反应性低,赤铁矿晶粒非常细小,在焙烧过程中难以生长。不过,焙烧球团矿的矿物组成、微观结构可以通过以下措施得到改善：
●配加磁铁矿的赤铁矿焙烧球团的微观结构得到明显改善,赤铁矿晶粒充分长大和再结晶,形成粗粒的赤铁矿,而且赤铁矿晶粒互连良好。因此,焙烧球团抗压强度可以达到2500N/个。
●提高焙烧球团碱度也可以改善其微观结构。将石灰石添加到赤铁矿球团原料,钙离子会扩散进入到赤铁矿晶格中,形成了铁酸钙,加速了赤铁矿晶粒的生长和再结晶。这些过程增加了球团结构强度。碱度为0.3的焙烧球团矿物组成合理,微观结构良好。因此,预热球团和焙烧球团矿拥有较高的抗压强度和转鼓强度,抗压强度达到2500N/个以上,转鼓强度达到93-95%,满足了生产要求。
采用链篦机—回转窑工艺,以巴西镜铁矿型赤铁矿为主要原料,以本研究成果为基础,对设计和建设年产量为120万吨球团矿的珠海粤裕丰球团厂项目进行了可行性研究,投产调试、工业试验和生产应用研究。生产实践结果表明,球团原料为70-100%的淡水河谷赤铁矿,配加20-30%的磁铁矿,球团碱度控制在0.2左右,生产出优质球团矿,经过生产调试,目前已经达到和超过设计产量,焙烧球团矿抗压强度为2700-3100N/个,转鼓强度为91.5-93.2%,冶金性能达到了大型高炉要求。这些研究成果已经推广到了巴西淡水河谷与安阳钢铁公司的合资球团厂、武钢矿业公司球团厂等单位。这些单位的焙烧球团抗压强度达到2500N/个以上,冶金性能指标满足了高炉生产要求。这是在国内率先成功采用大型链篦机-回转窑工艺,利用100%的赤铁矿作为原料生产酸性氧化球团的工业实践。这些研究成果是“大型链篦机-回转窑赤铁球团矿生产关键技术开发和应用”项目的一部分,该项目获得了“2010年度中国国家科技进步二等奖”。
With the fast development of the steel industry in China, the production of pellets has been further expanded. Pellets are used as a high quality charge for blast furnaces. However, the steel industry in China has been confronted with a serious shortage of domestic pellet feed due to the low iron grade of Run-of-Mine ore in spite of massive iron ore reserves. Therefore, more pellet feed, mainly hematite, has been im5ported for pellet production due to its high iron grade and low impurities. However, VALE hematite fines, especially the specularite type, is refractory for pelletising. It is of significance to improve the pelletising of VALE hematite fines for supplying of hematite type pellet feed with Chinese pellet industry.
In this thesis a study of the improvement of the pelletization of VALE hematite fines using grate-kiln process was carried out, and pretreating of VALE hematite fines by high pressure roller grinding, elevating pellet basicity and designing of blends comprising VALE hematite fines and magnetite concentrates as pellet feed were developed in small scale and pilot scale tests. Pretreating process and full flowsheet parameters were optimized. The corresponding mechanisms were demonstrated by measuring the microstructure and surface properties of iron ores, properties of green balls and fired pellets, metallurgical performance and mineralogy of fired pellets. And industry application of the improvement measures was carried out successfully.
It is shown that VALE hematite fines, assaying grade of66.79%Fe, low silica and alumina, and minor impurities, are good pellet feed in chemistry. However they possess poor ballability and are refractory for pelletising due to low specific surface areas of520cm2/g and poor ballability index of0.15in spite of a fine size of91.14%passing0.074mm and61.59%passing 0.043mm. Even the hematite fines are finely ground by ball milling up to1320cm2/g, the compressive strength of preheated and fired pellets are only369and1365Newton per pellet when preheating at1150℃for15min and firing at1330℃for15min, far below the target of2500Newton per pellet.
Three technological solutions have been developed to improve the pelletization of VALE hematite fines, such as blending30%magnetite concentrate with hematite fines as pellet feed, pretreating of VALE hematite fines by ball milling of hematite to1140-1320cm2/g from520cm2/g, followed by pressing through HPRG up to1500-1700cm2/g, and elevating the basicity of fired pellets to0.2-0.3basicity made of100%hematite fines with natural0.04basicity. In all cases, the compressive strength of preheated and fired pellets are higher than the target of500and2500Newton per pellet, respectively.
HPRG is the most effective way to improve the pelletising of hematite fines technically and economically. Two types of roller press circuits are recommended, one is the open circuit with the pellet feed passing through two separate rollers continuously, the other is the closed circuit with only one roller pressing machine operating at certain recirculating load. The improvement for pelletising of blends consisting of30%magnetite and70%hematite is achieved as follows:
●Specific surface areas of hematite pretreated by HPRG at210%recirculation load and in open circuit with two-pass reached1495cm2/g and1294cm2/g from1100cm2/g, resulting in statistic ballability index of0.798and0.628from0.15, respectively. The specific surface areas are used to assess the ballability of iron ores.
●HPRG not only elevates improve balling, but also decrease the dosage of bentonite. The optimum conditions for balling are as follows:0.7%-1.0%bentonite,9.0%●0.5%moisture, balling for6to10min. The drop numbers and compressive strength of green balls are over5time from 0.5m and15Newton per pellet, respectively.
●Fired pellets made of feed pretreated by HPRG with two-pass have good firing performance at a relative low induration temperature. The compression strength of preheated and fired pellets can reach over771and2759N/pellet when preheating at1100-1130±10℃for10to13min and with air flow rate of2.2m/s, firing at1280±10℃for13min. In contrast, for firing of pellets made of hematite pretreated by HPRG at210%recirculation load, the compression strength of preheated and fired pellets can reach over707and2745N/pellet when preheating at1130±10℃for12min and with air flow rate of2.2m/s, roasting at1300±10℃for15min, respectively.
●The functions of HPRG are probably explained that the hematite particles are mechanically activated by transferring the mechanical energy into chemical energy on the surface, leading in more cracks formed in the particles and higher lattice deformation and defects. All of which result in the improvement of higher surface hydrophilicity, better ballability of hematite fines, excellent firing behaviours of green balls and metallurgical performance of fired pellets.
The firing behaviours of green balls made of100%hematite fines with suitable specific surface areas are dramatically enhanced by elevating the basicity of fired pellets. Especially the compressive strength of fired pellets is elevated from1100Newton per pellet to over2500Newton per pellet from natural basicity of0.04to0.15-0.3basicity. Which is ascribed to the formation of calcium ferrite at low temperature, enhancing the solid diffusion reactions and consolidation of pellets.
The metallurgical performance of fired hematite pellets are significantly improved by HPRG, blending magnetite concentrates and elevating basicity, respectively or in combinative patterns, as follows:
●The size distributions of product pellets are over90%between8and16mm, assaying65-66%iron,0.5%FeO and very impurities. Which means that VALE hematite fines can help to elevate the iron grade of fired pellet.
●Blending more magnetite into hematite pellet feed can control the reduction swelling. Pellet reduction swelling index drops to20.36%when30%magnetite2is blended. The fired pellets made of100%hematite possess strong temperature reduction degradation, with high values of RDI+3.15of51.45%and RDI.0.5of44.81%. When30%magnetite are blended into hematite feed, resulting in RDI+3.15elevated up to over97%and RDI.0.5dropped to less than2.5%.
●Elevating the basicity of fired pellets from natural to0.2-0.3basicity is similar to that by blending30%magnetite with hematite fines. The reduction swelling index ranges between21%to26%and RDI+3.15is beyond97%.
●Pellets, made of blends comprising80%hematite and20%magnetite concentrate2pretreated by HPRG in closed circuit at210%recirculation load and open circuit with two-pass, possess the best metallurgical performance, such as RI of67.18%and77.54%, RSI of13.08%and6.64%, RDI+3.15of81.74%and75.21%being achieved.
All of the above achievements are proven by the industry practice in Zhuhai YPM pellet plant with an annual capacity of1.20million tons of fired pellets, where pellet feed comprises70-100%VALE hematite and some0.2basicity. Also they have been spreading to Joint Venture Plant of Anyang Steel, WISCO Minerals, etc., the compressive strength is over2500Newton per pellet, and all the metallurgical performance index meet the requirement for blast furnace. The achievements are included in the project "Key Techniques Development and Their Application of Large Scale Grate-kiln Pelletising of Hematite", which was granted the Second Class Prize of China Science and Technology Progress Prize in2010.
本论文采用链篦机-回转窑球团工艺,对强化巴西淡水河谷赤铁矿球团焙烧技术进行研究,并且通过小型、扩大试验、工业试验及工业应用三个阶段,开发了三个技术方案：通过湿式球磨、高压辊磨(HPRG)或两者的联合技术对造球原料进行预处理；添加细磨石灰石提高球团矿碱度；赤铁矿外加磁铁精矿的配矿方案优化,以期提高成球性、强化球团焙烧及改善成品球团矿冶金性能。对巴西淡水河谷赤铁矿性能进行了系统研究,包括其粒度组成、比表面积、颗粒形貌、可磨度、成球性及单矿焙烧性能,揭示了巴西镜铁矿类型的赤铁矿难焙烧的内在机制。研究中对湿式球磨、高压辊磨(HPRG)以及两者结合的工艺方案强化赤铁矿球团焙烧的改善效果进行了比较；对小型试验、扩大试验和工业试验的工艺参数,包括造球原料预处理工艺参数、造球原料结构、膨润土配比和种类、造球工艺参数、预热和焙烧工艺参数进行了优化。采用SEM检测赤铁矿预处理前后的微观结构和表面性质,并通过检测生球和焙烧球团的物理化学性质,研究焙烧球团的冶金性能和工艺矿物学等手段,揭示相关技术方案强化赤铁矿球团焙烧及改善球团矿冶金性能的机理,并将这些强化球团焙烧技术方案运用于工业生产进行了研究。
研究结果表明,从化学成分和粒度组成上来看,巴西淡水河谷赤铁矿是优质的球团原料,铁品位高达66.79%,含2.47%SiO2,0.82%Al2O3,杂质含量较少,S、P含量分别为0.017%、0.024%,而且粒度非常细,-0.074mm为91.14%、-0.043mm达61.59%。但是,其成球性较差,静态成球性指数仅为0.15,而且其比表面积低,仅有520cm2/g,难以直接应用于球团生产。不能采用常规的铁精矿粒度作为评价其成球性指标。在球团生产中必须将其进一步细磨预处理,提高其成球性,改善球团焙烧性能。但是其可磨性差,球磨机功指数高达24.4Kwh/t。即使通过球磨将这种赤铁矿细磨到-0.043mm90%,比表面积达到1320cm2/g,制备的球团在预热温度1150℃、预热时间15min和焙烧温度1330℃、焙烧时间15min的小型试验最佳条件下,预热球团和焙烧球团抗压强度也分别只有369N/个和1365N/个,预热球团和焙烧球团矿抗压强度远低于500N/个和2500N/个的要求。因此,对巴西镜铁矿型赤铁矿必须开发高效预处理技术,提高其成球性,强化球团焙烧。
论文开发了三个技术方案来强化淡水河谷赤铁矿球团工艺,分别为：在赤铁矿中配入30%的磁铁精矿作为球团原料；通过球磨预处理将赤铁矿比表面积由520cm2/g提高到1140-1320cm2/g,然后通过高压辊磨处理将其比表面积增加到1500-1700cm2/g；三是提高球团碱度,用100%的赤铁矿(自然碱度为0.04)为铁原料,添加细磨石灰石,制备碱度为0.2-0.3的球团矿。这三种手段均可以使预热球团和焙烧球团矿抗压强度分别提高到500N/个和2500N/个的目标值以上。与不对原料进行预处理的方案相比,这三种技术方案显著提高了巴西淡水河谷镜铁矿型赤铁矿的成球性及球团的预热焙烧性能,并能以70-100%的巴西赤铁矿为原料,采用链篦机—回转窑工艺生产出优质球团矿。
造球试验从不同角度比较了三种膨润土的性能优劣。从提高生球落下强度和抗压强度的角度考虑,印度膨润土比Fanchang膨润土性能好,而后者又优于Husi膨润土。但如果从生球爆裂温度方面考虑,使用Hlusi膨润土比使用Fanchang膨润土效果好,而后者比印度膨润土好。国内膨润土的添加量需要1.5%-2.0%,而印度膨润土的适宜用量为1.0%-1.3%。
试验先使用80%粒度为-0.045mm90%的赤铁精矿配加20%的2#磁铁精矿,2.0%Fanchang膨润土的配料条件进行参数优化试验。然后在最佳试验参数下比较配加不同磁铁精矿比例的混合料制备球团的效果。试验得出的适宜造球参数如下：
●赤铁精矿比表面积达到1500cm2/g以上,相应的细度为85%-90%小于0.043mm;
●配加30%的2#磁铁矿；
●国内膨润土的适宜添加量为1.5%-2.0%；
●生球适宜水分为10.0士0.2%；
●生球粒度范围为8-16mm；
●生球落下强度达到3次/(0.5m)以上；
●生球抗压强度达到15N/个以上；
●生球热爆裂温度达到350℃以上。(4)预热-焙烧扩大试验得出适宜的球团焙烧系统参数如下：
●料层高度：150mm；
●鼓风干燥温度：210±10℃；
●鼓风干燥时间和风速分别为：2min,1.0m/s；
●抽风干燥温度：340±10℃；
●鼓风干燥时间和风速分别为：8min,1.2m/s；
●适宜的预热制度为：1130±10℃预热15min,预热风速2.2m/s；
●适宜的焙烧制度为：1300±10℃焙烧15-20min。
在适宜的造球、预热和焙烧制度下具体研究三个技术方案的效果。首先,对于赤铁精矿配加30%磁铁精矿的配矿方案,在最佳的预热和焙烧条件下,焙烧球团矿物理性能良好,其抗压强度可达到2500N/个以上,转鼓指数(+6.3mm)为97.52%,抗磨指数(-0.5mmm)为2.78%,97%的焙烧球团粒径处于8-16mm的范围内。焙烧球团铁品位高,全铁含量达到65.82%。
●焙烧球团的还原膨胀指数(RSI)较高：配加20%与30%的2#磁铁矿的还原膨胀指数分别为35.86%、20.36%。这意味着还需要采取其他措施来降低RSI。焙烧球团的还原性指数处于正常水平,其软化/熔滴温度较高且温度区间较窄。焙烧球团主要依靠再结晶和聚结来获得较好的还原性和机械强度。
●试验结果表明,直接采用100%的赤铁精矿制备合格氧化球团矿较为困难；赤铁精矿配加磁铁精矿是制备合格酸性球团的一个适宜方法。然而,即使配加了磁铁精矿,焙烧球团的还原膨胀指数仍然较高,还需要采取一些措施来改善。
其次,通过调节碱度可以改善赤铁精矿球团制备过程。在膨润土用量1.8%并添加1.09-1.76%的石灰石进行造球的条件下,生球落下强度达到3次/0.5m以上。然而,随着石灰石添加量的增加,生球强度和爆裂温度均会稍微下降。
●对于采用具有适宜比表面积的100%赤铁矿粉矿做铁原料的球团工艺,提高球团碱度可以显著改善球团焙烧行为。在自然碱度0.04(不添加任何熔剂)时,在预热温度1130±10℃、预热时间15min、预热风速1.9m/s及焙烧温度1300±10℃和焙烧时间15min的扩大试验最优条件下,预热球团和焙烧球团矿的抗压强度分别为382N/个和885N/个,预热球团和焙烧球团矿的转鼓强度分别为96.38%和73.73%,远低于要求的指标。当添加细磨石灰石造球,将球团矿碱度提高到0.3时,在相同的预热和焙烧条件下,预热球团和焙烧球团矿的抗压强度分别为1214.9N/个和2623.5N/个,预热球团和焙烧球团矿的转鼓强度分别为95.9%和95.73%,达到了要求的指标。由此可看出,与自然碱度焙烧球团相比,调节碱度至0.2或者0.3之后的焙烧球团的抗压强度明显提高,达2500N/个以上。这说明了焙烧球团的抗压强度可以通过添加石灰石调节球团的碱度来改善。
●与配加2#磁铁精矿的焙烧球团相比,碱度增加到0.2或者0.3的焙烧球团的还原性变好,还原膨胀指数RSI稳定在21%-26%的范围内,与配加30%的2#磁铁精矿的结果相近。碱度为0.3的焙烧球团矿物组成和微观结构良好。良好的结构强度使球团抗压强度达到2500N/个以上,满足了高炉生产的要求。
●球团焙烧行为的改善得益于低温下铁酸钙的形成,它强化了固相扩散反应和球团的固相固结。总体上看,添加石灰石增加球团碱度至0.2-0.3可以达到改善球团物理性能的效果,但其冶金性能还有待提高。
从经济和技术方面来讲,高压辊磨处理是强化赤铁矿球团工艺最有效的方法。研究提出了两种高压辊磨预处理流程：第一种是开路流程,球团原料依次通过两台高压辊磨机进行预处理,这种方式需要串联安装两台高压辊磨机；第二种是闭路流程,只采用一台高压辊磨机,在一定的循环负荷下对原料进行预处理,从高压辊磨机出来的部分边料返回辊磨机的给料中,与新给料一道经过高压辊磨机进行细磨。由70%赤铁矿配加30%磁铁精矿组成的造球混合料经高压辊磨预处理,进行造球和球团焙烧,取得的良好指标如下：
●通过高压辊磨处理获得的赤铁精矿成球性能良好。分别采用210%循环负荷的高压辊磨闭路流程和两次高压辊磨预处理开路流程预处理,可以将巴西赤铁矿比表面积从1100cm2/g分别提高到1495cm2/g和1294cm2/g,静态成球性指数由0.15分别增加到0.628和0.798。虽然铁精矿粒度组成变化不大,但其比表面积增加,成球性显著得到改善。首次提出“铁精矿比表面积是评价其成球性的最有效的指标”。
●高压辊磨预处理不仅强化了造球过程,还可以降低膨润土用量。研究中对比了几种国产膨润土和优质印度膨润土对生球性能的影响。结果表明,不经预处理,膨润土配比通常为2-3%,生球强度才能达到要求的指标。经过高压辊磨预处理,膨润土用量可降低到0.7-1.0%,在生球水分9.0%士0.5%和造球时间6-10min的条件下,生球落下强度和抗压强度分别大于5次/(0.5m)和15N/个,生球爆裂温度高于450℃。
●两次高压辊磨开路流程预处理赤铁矿制备的球团具有良好的焙烧性能,在较低的焙烧温度下就可以获得较好的指标。扩大试验结果表明,在预热温度1100-1130±10℃、预热时间10-13min、预热风速2.2m/s及焙烧温度1280±±10℃、焙烧时间13min的条件下,预热球团和焙烧球团抗压强度分别达到771和2759N/个,转鼓强度分别为95.76%(+3mm)和93.73%。相对而言,采用210%循环负荷的高压辊磨闭路流程预处理赤铁矿制备的优质球团需要较高的温度,在预热温度1130±±100C、预热时间12min、预热风速2.2m/s及焙烧温度1300±10℃、焙烧时间15min的扩大试验条件下,预热球团和焙烧球团抗压强度分别达到707和2745N/个,转鼓强度分别为97.98%(+3mm)和93.47%。此外,高压辊磨改善了焙烧球团的还原膨胀指数,将其控制在15%以下。
●高压辊磨的作用机理可能是,高压辊磨将机械能转变为颗粒表面的化学能,使赤铁矿颗粒得到机械活化,颗粒形成较多的裂纹、更高程度的晶格畸变和缺陷。这些机械活化作用使赤铁矿颗粒表面亲水性增加、成球性提高,生球的预热、焙烧行为也得到改善,焙烧球团具有良好的冶金性能。
高压辊磨预处理原料、赤铁矿中配加磁铁精矿、提高赤铁矿球团碱度,或者这些措施的组合可以显著改善赤铁矿球团的冶金性能,效果如下：
●成品球团矿的粒度组成为8-16mm占90%左右,铁品位为65-66%、FeO含量为0.5%,而杂质含量很低：3.05-4.15%SiO2,0.87-1.92%Al2O3,0.011-0.020%S,0.021-0.046%P。这说明配加铁品位高、杂质含量低的巴西淡水河谷赤铁矿,可显著改善焙烧球团的质量。
●增加磁铁矿在赤铁矿球团原料中的比例可以控制焙烧球团的还原膨胀行为。当配入30%磁铁矿时,焙烧球团还原膨胀指数(RSI)降低至20.36%。由100%赤铁矿制备的球团低温还原粉化很严重,低温还原粉化指数分别如下：RDI+3.15=51.45%,RDI.0.5=44.81%。当在赤铁矿球团原料中配入30%磁铁矿时,RDI+3.15提高到97%以上,RDI-o.5降低至2.5%以下。低温还原粉化被显著地抑制。
●将焙烧球团碱度从自然碱度提高到0.2-0.3的效果与在赤铁矿中配加30%磁铁矿得到的结果相似,焙烧球团还原膨胀指数为20-26%,RDI+3.15提高到97%以上,低温还原粉化率很低。
●以80%赤铁矿配加20%磁铁矿为原料,采用210%循环负荷的高压辊磨闭路流程和两次高压辊磨开路流程分别预处理后,制备的两种焙烧球团矿冶金性能都很好,其指标依次如下：还原度指数(RI)分别为67.18%和77.54%,还原膨胀指数(RSI)分别为13.08%和6.64%,低温还原粉化指数(RDI+3.15)分别为81.74%和75.21%。
焙烧球团矿的矿相分析结果表明,不管是何种配矿方案,球团中的矿物绝大部分是赤铁矿,因为在预热、焙烧过程中磁铁矿得到充分氧化,FeO含量低于1%。由100%淡水河谷赤铁矿制备的焙烧球团微观结构较差,Fe203晶粒细小,Fe203再结晶不能较好连接起来。因此,成品球团矿抗压强度远低于2500N/个。这可能是以下原因造成的：淡水河谷赤铁矿为镜铁矿类型,其高温反应性低,赤铁矿晶粒非常细小,在焙烧过程中难以生长。不过,焙烧球团矿的矿物组成、微观结构可以通过以下措施得到改善：
●配加磁铁矿的赤铁矿焙烧球团的微观结构得到明显改善,赤铁矿晶粒充分长大和再结晶,形成粗粒的赤铁矿,而且赤铁矿晶粒互连良好。因此,焙烧球团抗压强度可以达到2500N/个。
●提高焙烧球团碱度也可以改善其微观结构。将石灰石添加到赤铁矿球团原料,钙离子会扩散进入到赤铁矿晶格中,形成了铁酸钙,加速了赤铁矿晶粒的生长和再结晶。这些过程增加了球团结构强度。碱度为0.3的焙烧球团矿物组成合理,微观结构良好。因此,预热球团和焙烧球团矿拥有较高的抗压强度和转鼓强度,抗压强度达到2500N/个以上,转鼓强度达到93-95%,满足了生产要求。
采用链篦机—回转窑工艺,以巴西镜铁矿型赤铁矿为主要原料,以本研究成果为基础,对设计和建设年产量为120万吨球团矿的珠海粤裕丰球团厂项目进行了可行性研究,投产调试、工业试验和生产应用研究。生产实践结果表明,球团原料为70-100%的淡水河谷赤铁矿,配加20-30%的磁铁矿,球团碱度控制在0.2左右,生产出优质球团矿,经过生产调试,目前已经达到和超过设计产量,焙烧球团矿抗压强度为2700-3100N/个,转鼓强度为91.5-93.2%,冶金性能达到了大型高炉要求。这些研究成果已经推广到了巴西淡水河谷与安阳钢铁公司的合资球团厂、武钢矿业公司球团厂等单位。这些单位的焙烧球团抗压强度达到2500N/个以上,冶金性能指标满足了高炉生产要求。这是在国内率先成功采用大型链篦机-回转窑工艺,利用100%的赤铁矿作为原料生产酸性氧化球团的工业实践。这些研究成果是“大型链篦机-回转窑赤铁球团矿生产关键技术开发和应用”项目的一部分,该项目获得了“2010年度中国国家科技进步二等奖”。
With the fast development of the steel industry in China, the production of pellets has been further expanded. Pellets are used as a high quality charge for blast furnaces. However, the steel industry in China has been confronted with a serious shortage of domestic pellet feed due to the low iron grade of Run-of-Mine ore in spite of massive iron ore reserves. Therefore, more pellet feed, mainly hematite, has been im5ported for pellet production due to its high iron grade and low impurities. However, VALE hematite fines, especially the specularite type, is refractory for pelletising. It is of significance to improve the pelletising of VALE hematite fines for supplying of hematite type pellet feed with Chinese pellet industry.
In this thesis a study of the improvement of the pelletization of VALE hematite fines using grate-kiln process was carried out, and pretreating of VALE hematite fines by high pressure roller grinding, elevating pellet basicity and designing of blends comprising VALE hematite fines and magnetite concentrates as pellet feed were developed in small scale and pilot scale tests. Pretreating process and full flowsheet parameters were optimized. The corresponding mechanisms were demonstrated by measuring the microstructure and surface properties of iron ores, properties of green balls and fired pellets, metallurgical performance and mineralogy of fired pellets. And industry application of the improvement measures was carried out successfully.
It is shown that VALE hematite fines, assaying grade of66.79%Fe, low silica and alumina, and minor impurities, are good pellet feed in chemistry. However they possess poor ballability and are refractory for pelletising due to low specific surface areas of520cm2/g and poor ballability index of0.15in spite of a fine size of91.14%passing0.074mm and61.59%passing 0.043mm. Even the hematite fines are finely ground by ball milling up to1320cm2/g, the compressive strength of preheated and fired pellets are only369and1365Newton per pellet when preheating at1150℃for15min and firing at1330℃for15min, far below the target of2500Newton per pellet.
Three technological solutions have been developed to improve the pelletization of VALE hematite fines, such as blending30%magnetite concentrate with hematite fines as pellet feed, pretreating of VALE hematite fines by ball milling of hematite to1140-1320cm2/g from520cm2/g, followed by pressing through HPRG up to1500-1700cm2/g, and elevating the basicity of fired pellets to0.2-0.3basicity made of100%hematite fines with natural0.04basicity. In all cases, the compressive strength of preheated and fired pellets are higher than the target of500and2500Newton per pellet, respectively.
HPRG is the most effective way to improve the pelletising of hematite fines technically and economically. Two types of roller press circuits are recommended, one is the open circuit with the pellet feed passing through two separate rollers continuously, the other is the closed circuit with only one roller pressing machine operating at certain recirculating load. The improvement for pelletising of blends consisting of30%magnetite and70%hematite is achieved as follows:
●Specific surface areas of hematite pretreated by HPRG at210%recirculation load and in open circuit with two-pass reached1495cm2/g and1294cm2/g from1100cm2/g, resulting in statistic ballability index of0.798and0.628from0.15, respectively. The specific surface areas are used to assess the ballability of iron ores.
●HPRG not only elevates improve balling, but also decrease the dosage of bentonite. The optimum conditions for balling are as follows:0.7%-1.0%bentonite,9.0%●0.5%moisture, balling for6to10min. The drop numbers and compressive strength of green balls are over5time from 0.5m and15Newton per pellet, respectively.
●Fired pellets made of feed pretreated by HPRG with two-pass have good firing performance at a relative low induration temperature. The compression strength of preheated and fired pellets can reach over771and2759N/pellet when preheating at1100-1130±10℃for10to13min and with air flow rate of2.2m/s, firing at1280±10℃for13min. In contrast, for firing of pellets made of hematite pretreated by HPRG at210%recirculation load, the compression strength of preheated and fired pellets can reach over707and2745N/pellet when preheating at1130±10℃for12min and with air flow rate of2.2m/s, roasting at1300±10℃for15min, respectively.
●The functions of HPRG are probably explained that the hematite particles are mechanically activated by transferring the mechanical energy into chemical energy on the surface, leading in more cracks formed in the particles and higher lattice deformation and defects. All of which result in the improvement of higher surface hydrophilicity, better ballability of hematite fines, excellent firing behaviours of green balls and metallurgical performance of fired pellets.
The firing behaviours of green balls made of100%hematite fines with suitable specific surface areas are dramatically enhanced by elevating the basicity of fired pellets. Especially the compressive strength of fired pellets is elevated from1100Newton per pellet to over2500Newton per pellet from natural basicity of0.04to0.15-0.3basicity. Which is ascribed to the formation of calcium ferrite at low temperature, enhancing the solid diffusion reactions and consolidation of pellets.
The metallurgical performance of fired hematite pellets are significantly improved by HPRG, blending magnetite concentrates and elevating basicity, respectively or in combinative patterns, as follows:
●The size distributions of product pellets are over90%between8and16mm, assaying65-66%iron,0.5%FeO and very impurities. Which means that VALE hematite fines can help to elevate the iron grade of fired pellet.
●Blending more magnetite into hematite pellet feed can control the reduction swelling. Pellet reduction swelling index drops to20.36%when30%magnetite2is blended. The fired pellets made of100%hematite possess strong temperature reduction degradation, with high values of RDI+3.15of51.45%and RDI.0.5of44.81%. When30%magnetite are blended into hematite feed, resulting in RDI+3.15elevated up to over97%and RDI.0.5dropped to less than2.5%.
●Elevating the basicity of fired pellets from natural to0.2-0.3basicity is similar to that by blending30%magnetite with hematite fines. The reduction swelling index ranges between21%to26%and RDI+3.15is beyond97%.
●Pellets, made of blends comprising80%hematite and20%magnetite concentrate2pretreated by HPRG in closed circuit at210%recirculation load and open circuit with two-pass, possess the best metallurgical performance, such as RI of67.18%and77.54%, RSI of13.08%and6.64%, RDI+3.15of81.74%and75.21%being achieved.
All of the above achievements are proven by the industry practice in Zhuhai YPM pellet plant with an annual capacity of1.20million tons of fired pellets, where pellet feed comprises70-100%VALE hematite and some0.2basicity. Also they have been spreading to Joint Venture Plant of Anyang Steel, WISCO Minerals, etc., the compressive strength is over2500Newton per pellet, and all the metallurgical performance index meet the requirement for blast furnace. The achievements are included in the project "Key Techniques Development and Their Application of Large Scale Grate-kiln Pelletising of Hematite", which was granted the Second Class Prize of China Science and Technology Progress Prize in2010.
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