WO2019056952A1 - 一种kr脱硫搅拌桨浇注料及其制备方法 - Google Patents

一种kr脱硫搅拌桨浇注料及其制备方法 Download PDF

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WO2019056952A1
WO2019056952A1 PCT/CN2018/104508 CN2018104508W WO2019056952A1 WO 2019056952 A1 WO2019056952 A1 WO 2019056952A1 CN 2018104508 W CN2018104508 W CN 2018104508W WO 2019056952 A1 WO2019056952 A1 WO 2019056952A1
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Prior art keywords
castable
desulfurization
paddle
casting material
stirring paddle
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PCT/CN2018/104508
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English (en)
French (fr)
Inventor
姚金甫
甘菲芳
牟济宁
王涛
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宝山钢铁股份有限公司
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Application filed by 宝山钢铁股份有限公司 filed Critical 宝山钢铁股份有限公司
Priority to US16/649,395 priority Critical patent/US11267764B2/en
Priority to JP2020516629A priority patent/JP7019801B2/ja
Priority to KR1020207010712A priority patent/KR102420556B1/ko
Priority to EP18858583.0A priority patent/EP3686175B1/en
Publication of WO2019056952A1 publication Critical patent/WO2019056952A1/zh

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Definitions

  • the invention relates to the field of hot metal desulfurization, in particular to a desulfurization stirring paddle casting material and a preparation method thereof.
  • the KR agitation desulfurization method was started in 1963 by the Nippon Steel Hiroshima Steel Works in Japan. In 1965, it was applied to industrial production of a hot metal furnace desulfurization technology.
  • the desulfurization method is a method of immersing a refractory-mixed stirring blade into a molten iron tank to rotate and stir the molten iron to cause a vortex of the molten iron, and the weighed desulfurizing agent is added to the surface of the molten iron by the feeder, and is vortexed into the molten iron. , mixed with high-temperature molten iron, reaction, to achieve the purpose of desulfurization.
  • the KR desulfurization method has the characteristics of high desulfurization efficiency, low desulfurizer consumption, short working time, low metal consumption and low consumption of refractory materials. Many steel mills are increasingly using KR desulfurization processes.
  • the stirring paddle is an important part of the KR desulfurization device and is composed of a rotating shaft and a cross blade. Therefore, the stirring paddle is also called a stirrer or a stirring head.
  • the stirring core is cast from a metal material, and the working lining is integrally casted into the refractory castable.
  • the general agitating paddle is 4 blades, the steel structure is also 4 leaves, and the steel structure surface is provided with anchors.
  • CN101857446A discloses the invention of "desulfurization paddle castable", sintered zirconium mullite 26-33%, ordinary fused mullite 26-35%, coke gemstone 5-9%, kyanite 4- 7%, special grade high alumina bauxite clinker 5-10%, silicon micropowder 3-5%, ⁇ -Al 2 O 3 micropowder 3-5%, ⁇ -Al 2 O 3 5-8%, pure calcium aluminate cement 1.5-3.5%, dense corundum fine powder 1.5-3.5%.
  • the invention adopts sintered zirconium mullite and dense corundum fine powder, and has high cost, and kyanite is added, and the castable expands greatly, which is disadvantageous against thermal shock resistance.
  • CN200510019721.8 discloses the invention of "refractory castable for hot metal desulfurization stirrer".
  • kyanite, extra-grade high-aluminum and dense corundum fine powder are added, and the disadvantages of the latter three components are added.
  • CN101337821A discloses an invention of "low density refractory castable for KR agitating paddle”. The granules are made of special grade gemstone, silica and silicon carbide.
  • the castable also contains alumina powder, silicon carbide, silica fine powder and alumina cement of less than 0.074 mm.
  • alumina powder, silicon carbide, silica fine powder and alumina cement of less than 0.074 mm.
  • the coke sapphire and the silica in the main raw material of the invention have low density, the corrosion resistance is not good, and silicon carbide is mainly used as a raw material, which is not only costly but also disadvantageous against thermal shock resistance.
  • CN104311071A discloses the invention of "refractory castable for molten iron desulfurization stirrer", 30-35 parts of silica, 20-25 parts of silicon carbide, 30-40 parts of fine sand powder, 40-45 parts of alumina fine powder, magnesium aluminum spinel 20-25 servings.
  • CN201310059252.7 discloses an invention of "a casting production method of a converter hot water desulfurization stirring paddle", which uses capacitor mullite, white corundum, silicon carbide and andalusite.
  • the disadvantages of silicon carbide have been explained above, adding white corundum to confront The thermal shock resistance is unfavorable, and the cost of white corundum is high.
  • the research shows that the mixing paddle is used in the gap type, and the castable material is required to have good thermal shock resistance; the stirring paddle rotates at high speed in high temperature molten iron, and is washed away by molten iron, requiring the castable material to have good anti-scourability; the desulfurizing agent is contained Certain fluorite lime has an erosive effect on the castable, and the castable is required to have good corrosion resistance.
  • the bottom line of the mixing paddle is mainly in two cases. First, the blade is cracked and peeled off. If it is used continuously, it may burn through the steel structure. Second, the blade wears more erosion, and the castable material is thinner and thinner. Stirring desulfurization effect.
  • the castable must have both thermal shock resistance, erosion resistance and erosion resistance.
  • the present invention provides a KR desulfurization paddle castable and a preparation method thereof, and improves and improves the comprehensive performance of the paddle castable, which has excellent thermal shock resistance and good resistance to molten steel flushing. And the corrosion resistance of the anti-desulfurizer, thereby increasing the service life of the stirring paddle.
  • a KR desulfurization paddle castable consisting of a castable base and an additive
  • the castable base material is composed of the following raw materials by weight: M70 sintered mullite 60-80%, coke gemstone 5-20%, fine powder 5-20%, pure calcium aluminate cement 1-5%;
  • the percentage of each component of the additive to the weight of the castable base is 0.05 to 0.2% of the water reducing agent and 1 to 5% of the heat resistant stainless steel fiber.
  • the percentage of Al 2 O 3 in the castable base of the present invention is from 60 to 70%.
  • the main raw material is M70 sintered mullite (the content of Al 2 O 3 in M70 sintered mullite is 70% or more), and the weight percentage accounts for more than 60% of the castable base material, ensuring good thermal shock resistance and medium temperature. Both strength and high temperature strength are controlled at 100-180 MPa, ensuring good resistance to hot metal scouring.
  • the Al 2 O 3 content of the castable is 60-70%, ensuring good corrosion resistance.
  • the ratio of high temperature strength to medium temperature strength is controlled to 1-1.2 to further improve the thermal shock resistance of the castable.
  • the coke gemstone is preferably a gemstone having an Al 2 O 3 content of 43% or more.
  • the fine powder is made of silicon fine powder (SiO 2 content percentage: 92% or more, particle size ⁇ 1 ⁇ m) and/or alumina fine powder (Al 2 O 3 content percentage is 99% or more, particle size ⁇ 3 ⁇ m).
  • the pure calcium aluminate cement is preferably a pure calcium aluminate cement having an Al 2 O 3 content of 70% or more.
  • the heat resistant stainless steel fiber may be 446# heat resistant stainless steel fiber or the like.
  • the high alumina bauxite is added, and although the Al 2 O 3 content of the stirring paddle is high, the castable containing the high bauxite has poor thermal shock resistance.
  • the castable exhibits an expansion characteristic at a high temperature, and if kyanite and andalusite are further added, the castable is expanded to be larger, which is disadvantageous against thermal shock resistance.
  • the M70 sintered mullite content is less than 60%, it is disadvantageous against thermal shock resistance. If the strength is less than 100 MPa, the anti-scouring property of the castable is not enough, higher than 180 MPa, and the strength is too high to resist thermal shock.
  • the Al 2 O 3 content of the castable is less than 60%, the corrosion resistance is insufficient, higher than 70%, and the sintered mullite content is insufficient, which is disadvantageous against thermal shock resistance.
  • the ratio of high temperature strength to medium temperature strength is less than 1, it indicates that the high temperature sintering strength of the castable is insufficient, and the erosion resistance is unfavorable. Above 1.2, the high temperature strength and the medium temperature strength differ greatly, and it is disadvantageous against thermal shock resistance and peeling resistance.
  • the invention also provides a preparation method of the KR desulfurization paddle castable, that is, the castable base material and the additive are weighed according to the ratio, and the mixture is uniformly mixed.
  • the invention improves the comprehensive performance of the casting material of the stirring paddle, has excellent thermal shock resistance, good corrosion resistance against molten steel and anti-desulfurizing agent, thereby improving the service life of the stirring paddle.
  • the castables of Examples 1-3 and Comparative Examples 1-5 were obtained by weighing each of the raw materials according to the ratios in Table 1. Further, the castable bases were added to Examples 1-3 and Comparative Examples 1-5, respectively. A water reducing agent (sodium tripolyphosphate) having a weight of 0.12% and a heat-resistant stainless steel fiber of 3% of 446# were uniformly mixed, and KR desulfurization paddle castables of Examples 1-3 and Comparative Examples 1-5 were respectively obtained.
  • a water reducing agent sodium tripolyphosphate having a weight of 0.12% and a heat-resistant stainless steel fiber of 3% of 446# were uniformly mixed, and KR desulfurization paddle castables of Examples 1-3 and Comparative Examples 1-5 were respectively obtained.
  • the Al 2 O 3 content of the M70 sintered mullite is about 70%.
  • the Al 2 O 3 content in the coke gemstone is about 43%.
  • the fine powder was a mixture of silicon micropowder (SiO 2 content of about 92%, particle size ⁇ 1 ⁇ m) and alumina fine powder (Al 2 O 3 content of about 99%, particle size ⁇ 3 ⁇ m) in a mass ratio of 1:1.
  • the Al 2 O 3 content in the pure calcium aluminate cement is about 70%.
  • the heat resistant stainless steel fiber may be 446# heat resistant stainless steel fiber or the like.
  • the Al 2 O 3 content in the present invention means the weight percentage of Al 2 O 3 .
  • the medium temperature strength and high temperature strength are the compressive strength after burning at 1000 ° C for 3 h (test standard GB/T 5072.1-1998) and the compressive strength after firing at 1400 ° C for 3 h.
  • the strength ratio is the ratio of the compressive strength after burning at 1400 ° C for 3 h and the compressive strength after burning at 1000 ° C for 3 h.
  • the thermal shock resistance (test standard YB/T 2206.2-1998) was observed after 1100 ° C ⁇ water cooling for 35 times.
  • the corrosion resistance index is based on Example 2, and the larger the value, the worse the corrosion resistance.
  • Comparative Example 1 the medium-temperature strength and high-temperature strength of Comparative Example 1 were relatively low, and Comparative Example 2 was more added due to the addition of coke gemstones, and the corrosion resistance was poor.
  • Comparative Example 3 contained more super-grade bauxite and was less resistant to thermal shock.
  • Comparative Example 4 contains more SiC and has poor thermal shock resistance.
  • Comparative Example 5 is too strong in strength ratio and has poor thermal shock resistance.
  • the embodiment 1-3 of the invention improves the comprehensive performance of the caster casting material, has excellent thermal shock resistance, good corrosion resistance against molten steel and anti-desulfurization agent, thereby facilitating the use of the stirring paddle. life.
  • Example 2 The effect of the use of Example 2 and Comparative Example 2 was compared, and the results are shown in Table 3.
  • Example 2 The castable cost of Example 2 was reduced by 8% compared to Comparative Example 2, and the life of the blender was increased by 12%.

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Abstract

提供一种KR脱硫搅拌桨浇注料及其制备方法。浇注料由基料和添加剂组成；基料由如下重量百分比的原料组成：M70烧结莫来石60～80％、焦宝石5～20％、微粉5～20％、纯铝酸钙水泥1～5％；添加剂的各组分占基料重量的百分比为：减水剂0.05～0.2％、耐热不锈钢纤维1～5％。主原料采用M70烧结莫来石和少量焦宝石，确保良好的抗热震性；中温和高温强度控制在100-180MPa，确保良好的抗冲刷性；浇注料的Al 2O 3含量60-70％，确保良好的抗侵蚀性；高温强度和中温强度之比控制在1-1.2，进一步提高浇注料的抗热震性和抗剥落性，从而有利于提高搅拌桨的使用寿命。该浇注料成本降低，实炉使用效果好，并且桨叶开裂、剥落较少，搅拌桨底部侵蚀较轻，桨叶修补次数较少，使用寿命明显提高。

Description

一种KR脱硫搅拌桨浇注料及其制备方法 技术领域
本发明涉及铁水脱硫领域，尤其涉及一种脱硫搅拌桨浇注料及其制备方法。
背景技术
KR搅拌脱硫法是日本新日铁广畑制铁所于1963年开始研究，1965年应用于工业生产的一种铁水炉外脱硫技术。这种脱硫方法是以一个外衬耐火材料的搅拌桨浸入铁水罐内进行旋转搅动铁水,使铁水产生旋涡,经过称量的脱硫剂由给料器加入到铁水表面,并被旋涡卷入铁水中,与高温铁水混合、反应,达到脱硫的目的。KR脱硫方法具有脱硫效率高,脱硫剂消耗少,作业时间短,金属耗损低以及耐火材料消耗低等特点。许多钢厂越来越多地采用KR脱硫工艺。
搅拌桨是KR脱硫装置中的重要部件，是由旋转轴与十字叶片组成。所以搅拌桨也称搅拌器或搅拌头。搅拌桨芯为金属材料铸造而成，工作衬为耐火浇注料整体浇注成型。一般搅拌桨是4个桨叶，钢结构也是4叶，钢结构表面设置锚固件。
KR搅拌脱硫工艺诞生后，刚开始的推广应用较慢，主要原因是搅拌桨的寿命较低，制抑了该脱硫工艺的发展。通过长期的应用和研究，搅拌桨的寿命有了很大提高。为了KR脱硫搅拌工艺的顺行和降低脱硫成本，持续提高搅拌桨的使用寿命是永恒的课题。
现有技术，CN101857446A公开了“脱硫搅拌桨浇注料”的发明，烧结锆莫来石26-33％，普通电熔莫来石26-35％，焦宝石5-9％，蓝晶石4-7％，特级高铝矾土熟料5-10％，硅微粉3-5％，α-Al 2O 3微粉 3-5％，ρ-Al 2O 3 5-8％，纯铝酸钙水泥1.5-3.5％，致密刚玉细粉1.5-3.5％。该发明采用了烧结锆莫来石、致密刚玉细粉，成本较高，加入蓝晶石，浇注料膨胀较大，对抗热震性不利。采用特级高铝矾土熟料和致密刚玉细粉，对抗热震性不利。CN200510019721.8公开了“铁水脱硫搅拌器用耐火浇注料”的发明，除了采用电容莫来石和焦宝石，还加入了蓝晶石、特级高铝和致密刚玉细粉，后3种组分的不利因素同前面发明。CN101337821A公开了“KR搅拌桨用低密度耐火浇注料”的发明。颗粒以特级焦宝石、硅石、碳化硅为主要原料，浇注料还含有小于0.074mm的氧化铝粉、碳化硅、二氧化硅微粉和氧化铝水泥。该发明主原料中的焦宝石和硅石虽然密度低，但抗侵蚀性不好，以碳化硅为主原料，不仅成本高，而且对抗热震性不利。CN104311071A公开了“铁水脱硫搅拌器用耐火浇注料”的发明，硅石30-35份，碳化硅20-25份，镁砂细粉30-40份，氧化铝微粉40-45份，镁铝尖晶石20-25份。其中，硅石、碳化硅的不利因素上面已说明，镁砂细粉和镁铝尖晶石的膨胀较大，高温下镁砂细粉和氧化铝微粉反应形成尖晶石，也要膨胀，主要，浇注料高温下膨胀较大，抗热震性和抗剥落性较差。CN201310059252.7公开了“一种转炉铁水脱硫搅拌桨的浇铸生产方法”的发明，原料采用电容莫来石、白刚玉、碳化硅和红柱石，碳化硅的不利因素前面已说明，加入白刚玉对抗热震性不利，且白刚玉成本较高。
发明内容
研究表明，搅拌桨为间隙式使用，要求浇注料具有良好的抗热震性；搅拌桨在高温铁水中高速旋转，受到铁水的冲刷磨损，要求浇注料具有良好的抗冲刷性；脱硫剂是含有一定萤石的石灰，对浇注料有侵蚀作用，要求浇注料具有良好的抗侵蚀性。
使用表明，搅拌桨的损毁形式，主要是三方面：
1)搅拌桨开裂，裂纹扩大，局部剥落；
2)受到高温铁水和渣的冲刷磨损、侵蚀，桨叶变小；
3)钢结构膨胀，使搅拌桨纵向拉伸，出现竹节状凹陷，常常在桨叶中部形成横向裂纹，成为铁水容易渗入的薄弱环节。
搅拌桨下线主要是二种情况，一是桨叶开裂剥落较多，继续使用可能会烧穿钢结构；二是桨叶磨损侵蚀较多，浇注料残厚较薄，不能起到较好的搅拌脱硫效果。
因此，根据搅拌桨的使用特点，浇注料必须兼顾抗热震性、抗冲刷性和抗侵蚀性。
为实现上述技术目的，本发明提供了一种KR脱硫搅拌桨浇注料及其制备方法，改进和提高搅拌桨浇注料的综合性能，既具有优良的抗热震性，又具有良好的抗钢水冲刷性和抗脱硫剂的侵蚀性，从而提高搅拌桨的使用寿命。
本发明的技术方案为：
一种KR脱硫搅拌桨浇注料，其由浇注料基料和添加剂组成；
所述浇注料基料由如下重量百分比的原料组成：M70烧结莫来石60～80％、焦宝石5～20％、微粉5～20％、纯铝酸钙水泥1～5％；
所述添加剂的各组分占浇注料基料重量的百分比为：减水剂0.05～0.2％、耐热不锈钢纤维1～5％。
优选地，本发明的浇注料基料中Al 2O 3含量百分比为60～70％。
本发明中，
主要原料采用M70烧结莫来石(M70烧结莫来石中Al 2O 3含量占比大于等于70％)，重量百分比占浇注料基料的60％以上，确保具有良好的抗热震性，中温强度和高温强度均控制在100-180MPa，确保具有良好的抗铁水冲刷性能，浇注料的Al 2O 3含量60-70％，确保具有良好的抗侵蚀性。使高温强度和中温强度之比控制在1-1.2，进一步提高 浇注料的抗热震性。
焦宝石优选为Al 2O 3含量占比大于等于43％的焦宝石。
微粉采用硅微粉(SiO 2含量百分比大于等于92％，粒度≦1μm)和/或氧化铝微粉(Al 2O 3含量百分比大于等于99％，粒度≦3μm)。
纯铝酸钙水泥优选为Al 2O 3含量占比大于等于70％的纯铝酸钙水泥。
耐热不锈钢纤维可以为446#耐热不锈钢纤维等。
现有技术，除了莫来石，往往加入高铝矾土、红柱石、蓝晶石和SiC。本发明认为，加入高铝矾土，虽然搅拌桨的Al 2O 3含量较高，但含高铝矾土的浇注料抗热震性较差。在加入耐热不锈钢纤维的情况下，浇注料在高温下呈现膨胀特征，如果再加入蓝晶石、红柱石，使浇注料膨胀更大，对抗热震性不利。加入碳化硅，尽管SiC耐磨性较好，对抗冲刷性有利，但试验研究表明，加入碳化硅使浇注料的抗热震性明显变差。并且，SiC的导热系数很高，使用时铁水温度容易传热到里面的钢结构，使钢结构温度较高，钢结构膨胀较大。特别是搅拌桨使用到中后期，桨叶侵蚀变小，里面钢结构的温度更高。钢结构膨胀大，容易造成浇注料开裂。另外，碳化硅不利于浇注料的烧结，而且原料成本较高。
本发明，如果M70烧结莫来石含量低于60％，对抗热震性不利。如果强度低于100MPa，浇注料抗冲刷性不够，高于180MPa，强度过高对抗热震性不利。浇注料的Al 2O 3含量低于60％，抗侵蚀性不够，高于70％，烧结莫来石含量不足，对抗热震性不利。如果高温强度和中温强度之比低于1，说明浇注料的高温烧结强度不够，对抗冲刷性不利，高于1.2，高温强度和中温强度相差较大，对抗热震性和抗剥落性不利。
本发明还提供了所述KR脱硫搅拌桨浇注料的制备方法，即按配 比称取浇注料基料和添加剂，混合均匀。
有益效果
本发明改善了搅拌桨浇注料的综合性能，既具有优良的抗热震性，又具有良好的抗钢水冲刷性和抗脱硫剂的侵蚀性，从而有利于提高搅拌桨的使用寿命。
具体实施方式
按照表1中的配比称取各原料得到实施例1-3和对比例1-5的浇注料基料；再分别向实施例1-3和对比例1-5中加入占浇注料基料重量0.12％的减水剂(三聚磷酸钠)和3％的446#耐热不锈钢纤维，混合均匀，分别得到实施例1-3和对比例1-5的KR脱硫搅拌桨浇注料。
表1浇注料基料的成分配比(wt％)
Figure PCTCN2018104508-appb-000001
表1中，
M70烧结莫来石中Al 2O 3含量约为70％。
焦宝石中Al 2O 3含量约为43％。
微粉为硅微粉(SiO 2含量约92％，粒度≦1μm)和氧化铝微粉(Al 2O 3含量约99％，粒度≦3μm)按质量比1:1的混合物。
纯铝酸钙水泥中Al 2O 3含量约为70％。
耐热不锈钢纤维可以为446#耐热不锈钢纤维等。
本发明中的Al 2O 3含量是指Al 2O 3所占的重量百分比。
对实施例1-3和对比例1-5的KR脱硫搅拌桨浇注料进行性能测试，测试结果见表2。
表2浇注料的性能测试结果
Figure PCTCN2018104508-appb-000002
表2列出了实施例和对比例的性能，中温强度和高温强度分别是1000℃烧3h后的耐压强度(检验标准GB/T 5072.1-1998)和1400℃烧3h后的耐压强度。强度比是1400℃烧3h后耐压强度与1000℃烧3h后耐压强度之比。抗热震性(检验标准YB/T 2206.2-1998)为1100℃→水冷35次后观察试样的裂纹情况。抗侵蚀性指数，以实施例2为基准，数值越大，抗侵蚀性越差。
可以看出，实施例的综合性能较好。对比例中，对比例1的中温强度和高温强度比较低，对比例2因焦宝石加入较多，抗侵蚀性较差， 对比例3因含有较多的特级矾土，抗热震性较差，对比例4因含有较多SiC，抗热震性较差，对比例5因强度比太大，抗热震性也较差。
本发明实施例1-3改善了搅拌桨浇注料的综合性能，既具有优良的抗热震性，又具有良好的抗钢水冲刷性和抗脱硫剂的侵蚀性，从而有利于提高搅拌桨的使用寿命。
实施例2与对比例2的使用效果进行对比，结果见表3。
表3实炉使用效果
项目 实施例2 对比例2
浇注料成本 降低了8％ /
桨叶开裂、剥落 较少 较多
搅拌桨底部侵蚀 较少 较多
桨叶修补次数 较少 较多
搅拌桨寿命 提高了12％ /
实施例2的浇注料成本较对比例2降低了8％，搅拌桨寿命提高了12％。

Claims (7)

  1. 一种KR脱硫搅拌桨浇注料，由浇注料基料和添加剂组成，其特征在于：
    所述浇注料基料由如下重量百分比的原料组成：M70烧结莫来石60～80％、焦宝石5～20％、微粉5～20％、纯铝酸钙水泥1～5％；
    所述添加剂的各组分占浇注料基料重量的百分比为：减水剂0.05～0.2％、耐热不锈钢纤维1～5％。
  2. 根据权利要求1所述的KR脱硫搅拌桨浇注料，其特征在于：浇注料基料中Al 2O 3含量百分比为60～70％。
  3. 根据权利要求1所述的KR脱硫搅拌桨浇注料，其特征在于：M70烧结莫来石中Al 2O 3含量占比大于等于70％。
  4. 根据权利要求1所述的KR脱硫搅拌桨浇注料，其特征在于：焦宝石中Al 2O 3含量占比大于等于43％。
  5. 根据权利要求1所述的KR脱硫搅拌桨浇注料，其特征在于：微粉为硅微粉/或氧化铝微粉。
  6. 根据权利要求1所述的KR脱硫搅拌桨浇注料，其特征在于：纯铝酸钙水泥中Al 2O 3含量占比大于等于70％。
  7. 权利要求1-6中任一项所述KR脱硫搅拌桨浇注料的制备方法：按配比称取浇注料基料和添加剂，混合均匀。
PCT/CN2018/104508 2017-09-21 2018-09-07 一种kr脱硫搅拌桨浇注料及其制备方法 WO2019056952A1 (zh)

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