Direct reduced iron production using cold bonded carbon bearing pellets Part 1 – Laboratory metallisation

Abstract

A new cold bonding technology for producing coal bearing composite pellets was developed. Alumina cement was used as binder, which gave high mechanical strength to the pellet even at elevated temperatures. Laboratory test results showed that the metallisation rate of the pellets was high owing to the intimate contact of the particulates of coal and the iron ore in the pellet. The developed cold bonding method can also be used to recycle electric arc furnace (EAF) dust, from which valuable zinc and lead can also be recovered.     

铁矿球团用有机黏结剂研究进展

 随着钢铁行业绿色低碳转型,使用有机黏结剂替代膨润土已经是铁矿球团工序提质降耗的必然趋势。然而,有机黏结剂彻底替代膨润土的技术壁垒仍未突破,严重限制了其在工业生产中的广泛应用。有机黏结剂的黏结效用也是控制球团强度的关键因素,研究其在球团生产中的作用机理对提高球团强度以及开发具有国内知识产权的新型有机黏结剂意义重大。通过总结有机黏结剂在铁矿球团中的研究进展,旨在为其在中国钢铁行业的广泛应用以及新型有机黏结剂的研发工作提供理论指导与试验依据。在介绍理想有机黏结剂分子结构模型的基础上,揭示了4种常见有机黏结剂的结构及特性。重点讨论了黏度和吸水性对有机黏结剂黏结效用的作用机理,有机黏结剂的高黏度特性能够调节球团颗粒间液桥黏滞力大小,从而显著提高生球强度;吸水性是有机黏结剂调控生球自由水含量的重要特性,只有在最佳吸水率下,才能获得强度较高、粒径均匀的生球。总结了有机黏结剂的常见优缺点,其主要优点是微量高效、烧失量大、基本不影响球团铁品位,缺点是生产球团矿缺乏渣相固结而强度不足。分析了优化原料粒度组成、添加含硼化合物及分散剂等强化有机黏结剂球团生产的调控手段,并展望了有机黏结剂未来的发展方向。     

The Effect of Calcined Colemanite Addition on the Mechanical Strength of Magnetite Pellets Produced with Organic Binders

Iron ore pellets must have sufficient mechanical strengths against degradation in all stages of pellet production. Low strength is also a problem for product pellets since they abrade during transportation to the reduction furnaces. The use of a binder is necessary to provide sufficient strength to the pellets and for better operation and handling of pellets. Bentonite is the standard binder in the industry; however, it is considered an impurity due to its acid oxide contents. Organic binders have been tested for many years as alternative binder to bentonite. They have been found to give sufficient wet pellet properties. However, they failed to provide sufficient strength to the preheated and fired pellets due to lack of slag bonding. It has been assumed that one possible effective method to improve the preheated and fired pellet strengths is addition of a slag-bonding constituent. In this study, calcined colemanite was added to the pellet feed to overcome the lower strength problem encountered with organic binder use. The strength of pellets produced with organic binders and calcined colemanite alone and in combination was comparatively studied against the strength of pellets made with standard bentonite binder in magnetite concentrate pelletizing. The results showed that addition of calcined colemanite into the pellet mixture improved the preheated and fired pellet strengths of pellets produced with organic binders.     

DRI production using cold bonded carbon bearing pellets Part 2 – Rotary kiln process modelling

Abstract

A new cold bonding technology for producing coal bearing composite pellet was developed. Laboratory tests showed that the cold bonded pellet has enhanced mechanical strength, from which good quality DRI can be produced. Based on the laboratory test results, a rotary kiln process was designed for producing DRI. Because of the high metallisation rate of the pellets and the corresponding novel operation conditions, the proposed rotary kiln process has significantly higher energy efficiency than the SL/RN process, hence emitting less CO₂.     

Replacement of bentonite in hematite ore pelletisation using a combination of sodium lignosulphonate and copper smelting slag

Bentonite is the most common binder used in iron ore pelletisation owing to its good bonding properties in green and dry pellets at both ambient and elevated temperatures. However, due to its high alumina and silica content, it increases the slag volume and energy consumption in downstream processes. Organic binders may be used to replace bentonite; however, they fail to provide strength at a high temperature (700–900°C) due to poor thermal stability during pellet induration. In the present study, an organic binder Na lignosulphonate (NLS) has been used along with copper smelting slag (Cu-SS). FeO in Cu-SS provides diffusion bonding at high temperature and maintains the strength of pellets even after evaporation/burning of NLS. It also enhances recrystallisation bonding at relatively lower temperature to provide good strength. The study has been carried out with hematite ore and varying amounts of NLS and Cu-SS. Copper smelting slag (1.0%) addition with 0.5%NLS has been found to be optimum to provide very good green properties and ～300?kg/pellet cold crushing strength (CCS) at 1250°C induration temperature. However, hematite pellets of similar basicity with 0.5% bentonite requires higher induration temperature (1300°C) to achieve a similar CCS. The developed pellet also shows better reducibility (80%), similar reduction degradation index (18%) and swelling index (10%) to the usual bentonite pellet. Thus, the induration temperature of hematite pellet has been lowered by 50°C using a combination of NLS and Cu-SS eliminating bentonite completely, which can provide a considerable energy and cost saving.     

Development of fluxed micropellets for sintering utilising iron oxide waste fines

Abstract

Ultrafine iron oxide wastes such as slime, blue dust and Linz–Donawitz (LD) converter sludge have very limited use in sintering of iron ore due to their excessive fineness (?50 μm). Pelletisation of these ultrafine materials for use in blast furnace involves high temperature curing, which is a highly energy intensive process. Briquetting of LD sludge requires costly binders and contains high moisture, which creates problem at high temperature of the downstream process. In order to alleviate these problems, the current study has developed a process for preparing micropellets of waste iron oxide fines (2–6 mm size) without using any binder. The strength of the micropellet has been increased by a novel CO₂ treatment process at room temperature. Developed micropellets exhibit very suitable drop strength (125 Nos), tumbler properties and cold compressive strength (～9 kg/pellet) to withstand cold handling. Low lime containing micropellets have the possibility of being used as a mixed material in usual sinter making, and high lime containing micropellets may be exploited for making super fluxed sinter that can be used as synthetic flux in the basic oxygen furnace process towards the formation of low melting oxidising slag at the early stage of blow.     

粉尘冷固结球团高温复合粘接机理研究

先以布袋灰、电炉灰、焦粉、水泥制成冷固结球团,进行高温自还原试验。再以纯水泥试样进行差热试验。最后以纯试剂四氧化三铁和石墨粉,配加纯氧化铝粉末并且不添加粘结剂制成的冷固结球团进行自还原试验。通过检测其抗压强度、扫描电子显微镜-能谱分析等方法分析了粉尘冷固结球团高温复合粘接机理,研究表明:低温下粉尘冷固结球团的强度主要靠水泥粘结相保证,随着温度升高,水泥逐渐失效,在1 000℃后金属铁连晶开始生成,并成为主要粘结相,未熔固态成渣物质对金属铁连晶的形成具有负面的影响,当其含量超过15%时就会对金属体连晶的形成产生显著的影响。     

Pelletization Using Humic Substance-based Binder

Humic substances exist widely in lignite coal as high molecular weight organic molecules. They can be used as binders in iron ore pelletization mostly in the form of salt, such as sodium humate and amine humate via extraction from lignite coal. It is worth determining if lignite can be used as a binder without extraction. As a composite binder of organic and inorganics, due to the combustion of humic substance, the strength of fired pellets made with humic substance-based binder decreases slightly. To compensate for this defect and make stronger pellets, cheap calcium bentonite was added into humic substance binder. In this study, a fluxed hematite concentrate was pelletized with various types of binders: lignite plus sodium hydroxide, calcium bentonite activated with modified humic acid (MHA), and MHA binder. Good quality pellets were obtained at optimal parameters. The results show that without extraction procedure, lignite plus sodium hydroxide can be directly used as a binder in pelletization of fluxed hematite; that calcium bentonite improves pellet strength when added to MHA; and that humic substance can partly replace calcium bentonite, reducing the dose of calcium bentonite.     

Cold Briquetting of DRI Fines for Use in Steel Making Process

DRI fines, generated during its manufacture and handling, generate high content of fines in the size fraction less than 2 mm. It has iron content above 80%. It is difficult to directly use such iron-rich material in the primary steel making process, without agglomeration. At JSW Steel Vijayanagar, around 50 to 70 tons per day of DRI fines with < 2 mm size fraction get generated. The fines are used in base sinter mix or it may be agglomerated suitably to use it as a coolant in the primary steel making process. Since the fines are extremely reactive, they are susceptible to oxidation if it is not agglomerated as soon as it is generated. The present study brings out the development of an agglomeration process for the DRI fines to a dense metallized briquette, for use as a coolant in basic oxygen furnace. Initially, the conditions for briquetting such as use of binder, hardener, lime, dust, moisture, briquetting and curing conditions were established in a 10 kg batch size. This was followed by industrial-scale processing, at 500 kg batch size. The physical and chemical characteristics of the fines and briquettes were assessed at different stages. The cold compressive strength of the cured briquette was found to be a function of moisture content. The handling parameters in the production condition, for long-term pile-up of briquettes against oxidation, were brought out. The successful use of the briquettes in basic oxygen process was demonstrated.     

Use of Iron Ore Fines in Cold-Bonded Self-Reducing Composite Pellets

The feasibility of producing direct reduced iron from cold-bonded, self-reducing composite pellets, constituted from beneficiated iron ore slime, coke, and different binders (dextrin, bentonite, calcium lignosulfonate, and carboxymethyl-cellulose [CMC]) was studied. This was done using a design of experiments approach. It was found that as-received beneficiated iron ore slime is suitable as a raw material for the production of self-reducing composite pellets with carboxymethylcellulose as the most suitable binder. Dry strengths in excess of 300 N/pellet were attained by curing the pellets under ambient conditions. The composite pellets reduced within 20 min to degrees of metallization in excess of 90% at 1100°C, with decrepitation indices significantly below 5%. The degree of metallization of composite pellets increased with an increase in reduction temperature (from 1000 to 1100°C), reduction time (20 min. vs. 40 min), and coke quantity (15% vs. 20%). CMC was identified as the most economical and suitable binder for the Sishen concentrate.     

新型复合粘结剂提高生球质量的作用机理及构效关系

降低膨润土用量是提高球团品位、实现节能减排的有效途径之一。基于新型高效复合粘结剂,通过生球制备、线性拟合分析、生球力学特征分析等手段研究了复合粘结剂对生球质量的影响规律及与重要指标的构效关系,阐明了复合粘结剂提高生球质量的作用机理。结果表明:配比（质量分数）为1.2%膨润土+0.028%有机粘结剂的复合粘结剂球团,落下强度（0.5 m高度落下次数）达到6.2、平均抗压强度达到14.5 N、爆裂温度达到542 ℃,与2.0%膨润土球团相比,生球质量相近,但膨润土消耗减少40%;基于构效关系分析,有机粘结剂对生球落下强度、爆裂温度作用显著,膨润土对干球强度影响更大;有机粘结剂通过增强颗粒的亲水性、毛细力和黏性力强化了生球落下强度,干燥时在表层形成少量孔隙,有利于球团内水分的排出,提高了生球爆裂温度,干燥后以固态连接桥的形式强化干球强度,但是孔隙的位点和尺寸可能会降低干球强度,因此,对干球强度起决定性作用的是膨润土,有机粘结剂对干球强度的影响呈现多面性。      

不锈钢除尘灰冷固结团块抗压强度的影响因素

采用冷固结成型法对不锈钢除尘灰进行造块,在微机控制电子式万能试验机上进行抗压强度测试。通过单因子实验,研究闷料时间、持压时间和球团失水各因素对团块强度的影响规律。并设计正交实验研究了石墨粉、水分、蔗糖和团压压力4个因素对球团强度影响的主次性。结果表明,闷料步骤对不锈钢除尘灰冷固结成型至关重要,球团失水对提高球团强度作用显著,持压时间对球团强度也有一定程度的影响;石墨粉等对团块抗压强度影响大小顺序为:水分蔗糖石墨粉团压压力。并且得到最优配比(质量分数):配加水分为13%、蔗糖为13%、石墨粉为11%,团压压力为30 MPa,此时球团可获得27 MPa以上的抗压强度。     

Study of nonisothermal reduction of iron ore-coal/char composite pellet

Cold-bonded composite pellets, consisting of iron ore fines and fines of noncoking coal or char, were prepared by steam curing at high pressure in an autoclave employing inorganic binders. Dry compressive strength ranged from 200 to 1000 N for different pellets. The pellets were heated from room temperature to 1273 K under flowing argon at two heating rates. Rates of evolution of product gases were determined from gas Chromatographie analysis, and the temperature of the sample was monitored by thermocouple as a function of time during heating. Degree of reduction, volume change, and compressive strength of the pellets upon reduction were measured subsequently. Degree of reduction ranged from 46 to 99 pct. Nonisothermal devolatilization of coal by this procedure also was carried out for comparison. It has been shown that a significant quantity (10 to 20 pct of the pellet weight) of extraneous H₂O and CO₂ was retained by dried pellets. This accounted for the generation of additional quantities of H₂ and CO during heating. Carbon was the major reductant, but reduction by H₂ also was significant. Ore-coal and ore-char composites exhibited a comparable degree of reduction. However, the former showed superior postreduction strength due to a smaller amount of swelling upon reduction. Formerly Graduate Student, Department of Metallurgical Engineering, Indian Institute of Technology, Kanpur, India     

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。     

Influence of raw material particle size on quality of pellets

Abstract

Pellet plant (4·2 MPta capacity) of JSW Steel Ltd imports iron ore fines from different mines to produce pellets for its Corex and Blast Furnace plants. The pelletisation process involves drying the ore fines to reduce the moisture content to less than 1%, grinding in open circuit ball mills to get required fineness. To produce good quality of pellets certain additives are important and limestone is employed for modifying the pellet basicity. Iron ore fines of ?10 mm size and limestone are ground together in a ball mill to get sufficient fineness for the balling process. However, as limestone is harder than iron ore fines the + 100 mesh size limestone particles is higher than required and not all the limestone is fully consumed in the reaction for melt formation. Microstructural studies were conducted under a Leica DMRX polarized microscope at different level fineness (?325# ? 56, 58 and 60%) to investigate its effect on the pellet quality. The cold crushing strength of the pellet improved from 203 to 220 kg p^?1 with increase in fineness. With increase in percentage of ?325# particle size in the ground product RDI of the pellet decreased from 13·8 to 11·9% with increased melt formation from 5 to 9%. With increase in fineness ?325# from 56 to 60% the 150 to 500 μm size pores decreased from 51·8 to 13·6%.     

Improvement of sintering performance of sinter mixtures containing high ratio of specularite fines

Although specularite fines possess high iron grade and low impurities, their granulation performance was poor so that the ratio of specularite fines is kept below 20% in sinter ore blends because of low permeability and productivity and weak strength. In order to increase its ratio in sintering, binders were used to improve the granulation performance of sinter blends containing high ratio of specularite fines in sintering pot test. Results show that cold permeability of the sintering bed increases by 19. 05% by adding 0. 65mass% bentonite or by 27. 98% by 0. 55mass% BF composite binder respectively when 36 mass% specularite fines are proportioned in sinter blends. In addition, the hot permeability is also improved by adding bentonite or BF composite binder, respectively, resulting in an increase in the productivity of 11. 67% and 7. 50% as well as an decrease in solid fuel consumption of 2. 82kg/t and 4. 01kg/t, respectively, while the tumble index, chemical composition and metallurgical performance meet the requirement of blast furnace. So using suitable binders is one of effective ways to improve the granulation and sintering performance of sinter ore blends comprising high ratio of specularite fines.     

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.     

铁矿球团生球的固结机理及强化途径

通过生球强度破坏机理分析,得出通过对造球原料进行润磨可以有效的增大晶粒间的范德华力,增加生球的机械强度,添加能够通过范德华力、静电力、氢键、化学键、配位键等与铁矿颗粒表面发生作用的粘结剂也可以有效地提高生球的机械强度;提高球团的爆裂温度的有效方法是均衡球团表面气化和内部扩散作用,均衡球团表面气化和内部扩散作用的主要措施是降低球团表面气化的速度,使表面扩散速度减小,添加具有亲水基的有机粘结剂和膨润土可以降低自由水或毛细水的扩散速度,提高球团的爆裂温度;通过对造球原料的改性对生球的强度的提高是有限的,添加有机粘结剂或复合粘结剂强化生球强度仍然是今后发展的一个重要方向。     

铁矿球团复合粘结剂技术经济评价

基于国内外球团矿复合粘结剂研究情况,介绍了球团矿粘结剂的理想模型及复合作用机理,详细论述了复合粘结剂种类、化学成分、基本物性,重点阐述了复合粘结剂对生球质量、成品球团质量、显微组织及其经济性的影响。目前,生产中广泛应用的是由膨润土和有机粘结剂制备的复合粘结剂,而添加镁质复合粘结剂、SF碱性粘结剂和含铁复合粘结剂是改善球团矿品质的重要途径,但其在生产中推广应用还有待进一步研究。     

Increasing the sustainability of steel production in the electric arc furnace by substituting fossil coal with biochar agglomerates

Biochar fines from a wood gasification plant and from pyrolysis of agricultural residues were investigated as substitutes for fossil coal used in the steel production in the electric arc furnace (EAF). During previous tests biochar fines with high specific surface showed problematic burn-off behaviour. Therefore the agglomeration behaviour of the biochar fines was investigated. Different binary and ternary mixtures of biochar with water and binders were tested in a hydraulic stamp press and evaluated with regard to green strength and fatigue strength of the briquettes after 3 days. One selected mixture was used to produce pillow briquettes in a double roll press. The abrasion behaviour of the produced briquettes was tested and compared to an anthracite reference coal (RC). Melting tests in a pilot EAF showed that the agglomerated biochar reacts similar to the RC. The briquetting leads to reduced reactivity and slower burn-off compared to the biochar fines.