WO2021238029A1 - 高导热铁水沟浇注料 - Google Patents

高导热铁水沟浇注料 Download PDF

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WO2021238029A1
WO2021238029A1 PCT/CN2020/122096 CN2020122096W WO2021238029A1 WO 2021238029 A1 WO2021238029 A1 WO 2021238029A1 CN 2020122096 W CN2020122096 W CN 2020122096W WO 2021238029 A1 WO2021238029 A1 WO 2021238029A1
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parts
powder
castable
thermal conductivity
iron
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French (fr)
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丁丰收
晁尚奎
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郑州市瑞沃耐火材料有限公司
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
    • C04B35/101—Refractories from grain sized mixtures
    • C04B35/103—Refractories from grain sized mixtures containing non-oxide refractory materials, e.g. carbon
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B7/00—Blast furnaces
    • C21B7/04—Blast furnaces with special refractories
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B7/00—Blast furnaces
    • C21B7/14—Discharging devices, e.g. for slag
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    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • C04B2235/3222—Aluminates other than alumino-silicates, e.g. spinel (MgAl2O4)
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Definitions

  • the invention relates to a castable for a blast furnace iron ditch, in particular to a high thermal conductivity iron ditch castable.
  • the iron-making blast furnace is one of the important equipment used in iron and steel smelting
  • the blast furnace iron tapping ditch (iron ditch) is an important facility in front of the blast furnace, and its function is to realize the separation of liquid slag and iron and to divert molten iron.
  • the molten iron ditch not only has to withstand the high pressure impact of blast furnace tapping and the high temperature above 1400°C, but also withstand the thermal erosion from the complex chemical composition in the slag, resulting in the short life of the refractory lining of the molten iron ditch, frequent maintenance, and labor intensity Large, high maintenance costs, so to improve the life of the iron ditch, reduce the cost of use of the iron ditch has always been the direction of research and development in the industry.
  • Cooling media such as water, nitrogen or compressed air are passed into the cooling device, which can take away the excess heat in the molten iron ditch through effective heat conduction, stabilize the temperature in the molten iron ditch and form a semi-solidified slag iron layer in the side wall of the molten iron ditch. Protect the ditch wall, thereby greatly improving the service life of the iron water ditch.
  • the castable for the molten iron ditch In order to ensure that the cooling device can take away the excess heat in the molten iron ditch in time, the castable for the molten iron ditch must be required to have good thermal conductivity.
  • the castable for the molten iron ditch currently used in blast furnaces is mainly made of Al 2 O 3 -SiC-C
  • the composition, the thermal conductivity is lower than 3.0w/(m ⁇ k), this kind of castable cannot meet the heat conduction requirements of the molten iron ditch after the water cooling device is installed. Therefore, it is one of the technical problems that need to be solved urgently to develop a castable for hot metal ditch that can meet the requirements of installing a cooling device.
  • the purpose of the present invention is to provide a high thermal conductivity castable for iron ditch, which can not only meet the oxidation resistance and strength of the iron ditch during operation, but also has higher thermal conductivity.
  • the high thermal conductivity iron runner castable of the present invention is made of raw materials fused brown corundum, fused dense corundum, special grade bauxite, silicon carbide, pure calcium aluminate cement, silica powder, bimodal activated alumina powder, spherical Pitch, nano carbon black powder, carbon resin powder, carbon dispersant, antioxidant, organic fiber, anti-explosion agent and superplasticizer are prepared in the following parts by weight:
  • the silicon carbide used in the present invention SiC ⁇ 97%; microsilica in the SiO 2 ⁇ 94%.
  • the softening temperature of the spherical pitch used in the present invention is 105-125°C, where C ⁇ 48%.
  • the carbon black powder used in the present invention has C ⁇ 95%; the carbon resin powder has C ⁇ 80%.
  • the carbon dispersant used in the present invention is nickel fluoroborate (commodity number N1055).
  • the antioxidant used in the present invention is prepared from metal silicon powder and boron carbide in a weight ratio of 1.5-2:0.3-0.5.
  • the organic fiber used in the present invention is a low-melting organic fiber, and its melting temperature is 70-100°C.
  • the explosion-proof agent used in the present invention is metal aluminum powder with a particle size of 80-120 mesh, in which Al ⁇ 98%.
  • the water reducing agent used in the present invention is prepared by sodium tripolyphosphate and sodium hexametaphosphate in weight parts of 0.04 ⁇ 0.1:0.08 ⁇ 0.13; or HDS and FDN are prepared by weight parts of 0.08 ⁇ 0.13:0.02 ⁇ 0.05 Or it is made by the weight parts of the German BASF FS10 and FS20 water reducing agents at 0.04 ⁇ 0.08:0.08 ⁇ 0.12 parts by weight.
  • the advantage of the present invention is that in view of the poor thermal conductivity of traditional castables, on the basis of the original Al 2 O 3 -SiC-C castable for iron ditch, the ratio of each basic raw material is scientifically adjusted, and nano carbon black is introduced.
  • the reasonable gradation of powder, carbon resin powder and spherical pitch, supplemented by carbon dispersant and composite antioxidant (made of metal silicon powder and boron carbide in a certain proportion), solves the problem of easy oxidation of carbon materials and carbon composition due to light specific gravity during construction
  • the problem of floating when adding water and stirring ensures that the carbon component can be well combined with other materials, so that the carbon component can give full play to the heat conduction effect, and greatly improve the thermal conductivity of the castable for the iron trough;
  • the present invention adds special grade aluminum to the raw material Although bauxite slightly reduces the strength, it significantly improves the thermal shock stability of the castable.
  • the finished high thermal conductivity castable for iron ditch has good oxidation resistance, high temperature strength, volume stability and Anti-scouring performance, combined with the use of a cooling device, greatly improves the service life of the molten iron ditch, increases the tapping capacity, improves the tapping yard environment, and improves the economic and environmental benefits of blast furnace ironmaking.
  • Figure 1 shows the newly built iron ditch with cooling device.
  • Figure 2 shows the transformed iron water ditch.
  • the raw materials used in the present invention are all commercially available products, which can be purchased according to the purity described in the text.
  • the raw material ratio is:
  • the user can make appropriate adjustments according to the actual batch number of the raw materials purchased, and the components of the raw materials used within the scope disclosed in the text, and the effect can be guaranteed.
  • the prepared finished castable has been inspected and tested, and its technical indicators are as follows:
  • Figure 1 shows the newly built iron storage ditch with a total width of 2900mm, which is used in conjunction with large and medium-sized ironmaking blast furnaces (volume 1080m 3 and above).
  • the working layer 1 adopts the castable prepared in Example 1, and the thickness is 900mm; the carbon-containing refractory brick layer 3 (thermal conductivity 15w/(m ⁇ k)) is built between the steel shell 2 and the working layer 1, and the outer steel shell 2
  • a water-cooled plate 4 is installed, and a temperature measuring thermocouple 5 is arranged in the working layer 1 close to the carbon-containing refractory brick layer 3.
  • Figure 2 shows the iron storage ditch transformed from an ordinary iron ditch.
  • the total width is the same as that in Figure 1.
  • the original refractory material Al 2 O 3 -SiC-C Is the main component of the castable
  • the steel shell 2a is internally retracted, leaving the installation position of the water-cooled plate 4a in the steel shell
  • the same carbon-containing refractory brick layer 3a as in Fig. 1 is built between 2a and the working layer 1a, and a temperature measuring thermocouple 5a is arranged in the working layer 1a close to the carbon-containing refractory brick layer 3a.
  • thermocouples in Figure 1 and Figure 2 are 300°C respectively. And 350°C, it proves that the thermal conductivity of the castable used in the working layer in Figure 1 is slightly better than that of the castable in Figure 2, but both are better than the castable for the iron runner used in the current blast furnace.

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Abstract

一种高导热铁水沟浇注料，是由原料电熔棕刚玉、电熔致密刚玉、特级铝矾土、碳化硅、纯铝酸钙水泥、硅微粉、双峰活性氧化铝微粉、球状沥青、纳米碳黑粉、碳树脂粉、碳分散剂、抗氧化剂、有机纤维、防爆剂和高效减水剂按一定重量份配制而成；针对传统浇注料导热性能差的问题，科学调整了各基础原料的配比，引入了纳米碳黑粉、碳树脂粉与球状沥青合理级配，辅以碳分散剂和复合抗氧化剂，大大提高了铁水沟浇注料的导热性；同时成品高导热铁水沟浇注料具有很好的抗氧化性能、高温强度、体积稳定性和抗冲刷性能，配合冷却装置，可大大提高铁水沟的使用寿命，提高了高炉炼铁的经济效益和环保效益。

Description

高导热铁水沟浇注料 技术领域
本发明涉及高炉铁水沟用浇注料，尤其是涉及一种高导热铁水沟浇注料。
背景技术
炼铁高炉是钢铁冶炼所用的重要设备之一，而高炉出铁水沟(铁水沟)则是高炉炉前的重要设施，其功能是实现液态渣和铁的分离并导流铁水。铁水沟在工作时不但要承受高炉出铁的高压冲击和1400℃以上的高温，还要承受来自渣子中复杂化学成分的热侵蚀作用，导致铁水沟内衬耐火材料寿命短、维修频繁，劳动强度大、维修成本高，故提高铁水沟的寿命、降低铁水沟的使用成本一直是行业内的研发方向。
研究发现，如果能有效降低铁水沟侧壁的工作温度，不仅可延长铁水沟内衬的使用寿命，还能提高使用的安全性，而为铁水沟加装冷却装置则是一种简单有效的方法。冷却装置中通入水、氮气或压缩空气等冷却介质，能通过有效的热传导作用带走铁水沟内的富余热量，使铁水沟内温度稳定并在铁水沟侧壁内形成半凝固的渣铁层来保护沟壁，进而大幅提高铁水沟的使用寿命。
为保证冷却装置及时将铁水沟内的富余热量带走，就必须要求铁水沟浇注料具有较好的导热性，但是目前高炉所用的铁水沟浇注料主要以Al 2O 3-SiC-C为主要成分，导热率低于3.0w/(m·k)，此种浇注料满足不了加装水冷装置后铁水沟的热传导要求。所以研发一种能满足加装冷却装置后的铁水沟用浇注料是目前亟待解决的技术问题之一。
发明内容
本发明的目的在于提供一种高导热铁水沟浇注料，既能满足铁水沟工作时的抗氧化性和强度，还具有较高的导热性能。
为实现上述目的，本发明可采取下述技术方案：
本发明所述的高导热铁水沟浇注料，是由原料电熔棕刚玉、电熔致密刚玉、 特级铝矾土、碳化硅、纯铝酸钙水泥、硅微粉、双峰活性氧化铝微粉、球状沥青、纳米碳黑粉、碳树脂粉、碳分散剂、抗氧化剂、有机纤维、防爆剂和高效减水剂按下述重量份配制而成：
粒度1～8mm的电熔棕刚玉40～50份；
电熔致密刚玉8～13份，其中粒度0～1mm的颗粒料5～8份，325目的粉料3～5份；
粒度3～8mm的特级铝矾土1～10份；
碳化硅20～35份，其中粒度0～1mm的颗粒料10～20份，200目的粉料10～15份；
纯铝酸钙水泥1～4份；
粒度1μm的硅微粉1～4份；
粒度3～5μm的双峰活性氧化铝微粉4～8份；
粒度0.2～0.5mm的球状沥青2～5份；
纳米碳黑粉0.3～1份；
碳树脂粉0.3～1份；
碳分散剂0.2～0.8份；
抗氧化剂1.5～3.5份；
有机纤维0.04～0.1份；
防爆剂0.06～0.12份；
高效减水剂0.1～0.3份。
为保证成品浇注料的质量，本发明所用电熔棕刚玉中Al 2O 3≥95％，特级铝矾土中Al 2O 3≥85％，电熔致密刚玉中Al 2O 3≥99％，纯铝酸钙水泥中Al 2O 3≥70％，双峰活性氧化铝微粉中Al 2O 3≥99％。
本发明所用的碳化硅中SiC≥97％；所述硅微粉中SiO 2≥94％。
本发明所用的球状沥青的软化温度为105～125℃，其中C≥48％。
本发明所用的碳黑粉中C≥95％；所述碳树脂粉中C≥80％。
本发明所用的碳分散剂为氟硼酸镍(商品货号N1055)。
本发明所用的抗氧化剂由金属硅粉和碳化硼按1.5～2:0.3～0.5之重量份配比配制而成。
本发明所用的有机纤维为低熔点有机纤维，其熔化温度为70～100℃。
本发明所用的防爆剂为粒度80～120目的金属铝粉，其中Al≥98％。
本发明所用的减水剂为三聚磷酸钠和六偏磷酸钠按照0.04～0.1:0.08～0.13之重量份配制而成；或者为HDS和FDN按照0.08～0.13:0.02～0.05之重量份配制而成；或者为德国巴斯夫FS10型和FS20型减水剂按0.04～0.08:0.08～0.12之重量份配制而成。
配制时，将所有原料准确称量后混合均匀，装入防潮防晒的吨袋储存即可。
现场施工时加入物料总重5～6％的自来水，搅拌均匀后直接施工，经常规烘烤(800℃保温4小时)，即可出铁使用。
经测试，本发明配制的铁水沟浇注料的技术指标如下表所示：
Figure PCTCN2020122096-appb-000001
从表中数据可以看出，本发明配制的浇注料的各项指标均符合铁水沟的工作 要求，且导热率得以大幅度提高。
本发明的优点在于针对传统浇注料导热性能差的问题，在原Al 2O 3-SiC-C为主要成分的铁水沟浇注料基础上，科学调整了各基础原料的配比，引入了纳米碳黑粉、碳树脂粉与球状沥青合理级配，辅以碳分散剂和复合抗氧化剂(由金属硅粉和碳化硼按一定比例配成)，解决了碳材料容易氧化和由于比重轻施工时碳成分在加水搅拌时的漂浮问题，保证了碳成分能与其他材料很好的结合，使碳成分充分发挥了导热作用，大大提高了铁水沟浇注料的导热性；本发明在原料中加入了特级铝矾土，虽略微降低了强度，但显著提高了浇注料的热震稳定性；同时通过配方优化，保证了成品高导热铁水沟浇注料具有很好的抗氧化性能、高温强度、体积稳定性和抗冲刷性能，配合采用冷却装置，大大提高了铁水沟的使用寿命，增大了出铁量，改善了出铁场环境，提高了高炉炼铁的经济效益和环保效益。
附图说明
图1为新砌筑的带有冷却装置的铁水沟。
图2为经过改造的铁水沟。
具体实施方式
下面通过具体实施例对本发明做更加详细的说明，以便于本领域技术人员的理解。
本发明所用原料均为市售产品，按文中记载的纯度购买即可。
实施例1配制储铁式铁水沟用工作衬浇注料
其原料配比为：
粒度1～8mm的电熔棕刚玉45份；
电熔致密刚玉10份，其中粒度0～1mm的颗粒料7份，325目的粉料3份；
粒度3～8mm的特级铝矾土8份；
碳化硅30份，其中粒度0～1mm的颗粒料18份，200目的粉料12份；
纯铝酸钙水泥2份；
粒度1μm的硅微粉3份；
粒度3～5μm的双峰活性氧化铝微粉8份；
粒度0.2～0.5mm的球状沥青4份；
纳米碳黑粉1份；
碳树脂粉1份；
碳分散剂0.8份；
抗氧化剂3份；
有机纤维0.1份；
防爆剂0.12份；
高效减水剂0.3份。
将以上原料准确称量后，加入搅拌机中混合均匀，装入防潮防晒的吨袋储存。
在实际配制时，使用者可根据实际购买的原料批号，所用原料的组分在文中公开的范围内进行适当调整，效果均能得以保证。
配制的成品浇注料经检验测试，其技术指标如下：
Figure PCTCN2020122096-appb-000002
实施例2使用效果对比
图1为新砌筑的总宽度2900mm的储铁式铁水沟，与大中型炼铁高炉(容积1080m 3及以上)配套使用。其工作层1采用实施例1配制的浇注料，厚度为900mm；钢壳2和工作层1之间砌筑含碳耐火砖层3(导热率15w/(m·k))，钢壳2外安装有水冷板4，在靠近含碳耐火砖层3的工作层1内排布测温热电偶5。
图2为由普通铁水沟改造而成的储铁式铁水沟，总宽度与图1相同，为节约资源并降低改造成本，仅将需要改造部位的原耐火材料(Al 2O 3-SiC-C为主要成分的浇注料)挖出，保留铁水沟内60％的原有材料作为工作层1a，厚度为800mm；然后将钢壳2a内收，留出水冷板4a的安装位置，并在钢壳2a和工作层1a之间砌筑与图1中相同的含碳耐火砖层3a，在靠近含碳耐火砖层3a的工作层1a内排布测温热电偶5a。
当高温窑炉工作时，温度在1450℃的高温铁水从铁水沟中流过，此时将水冷板的工作温度调整至40°，经测量，图1和图2中热电偶的温度分别为300℃和350℃，证明图1中工作层所用的浇注料的导热性能较图2中工作层浇注料的导热性能略好，但均优于目前高炉所用的铁水沟浇注料。

Claims (10)

  1. 一种高导热铁水沟浇注料，其特征在于：是由原料电熔棕刚玉、电熔致密刚玉、特级铝矾土、碳化硅、纯铝酸钙水泥、硅微粉、双峰活性氧化铝微粉、球状沥青、纳米碳黑粉、碳树脂粉、碳分散剂、抗氧化剂、有机纤维、防爆剂和高效减水剂按下述重量份配制而成：
    粒度1～8mm的电熔棕刚玉40～50份；
    电熔致密刚玉8～13份，其中粒度0～1mm的颗粒料5～8份，325目的粉料3～5份；
    粒度3～8mm的特级铝矾土1～10份；
    碳化硅20～35份，其中粒度0～1mm的颗粒料10～20份，200目的粉料10～15份；
    纯铝酸钙水泥1～4份；
    粒度1μm的硅微粉1～4份；
    粒度3～5μm的双峰活性氧化铝微粉4～8份；
    粒度0.2～0.5mm的球状沥青2～5份；
    纳米碳黑粉0.3～1份；
    碳树脂粉0.3～1份；
    碳分散剂0.2～0.8份；
    抗氧化剂1.5～3.5份；
    有机纤维0.04～0.1份；
    防爆剂0.06～0.12份；
    高效减水剂0.1～0.3份。
  2. 根据权利要求1所述的高导热铁水沟浇注料，其特征在于：所述电熔棕刚玉中Al 2O 3≥95％，所述特级铝矾土中Al 2O 3≥85％，所述电熔致密刚玉中Al 2O 3≥99％，所述纯铝酸钙水泥中Al 2O 3≥70％，所述双峰活性氧化铝微粉中Al 2O 3≥99％。
  3. 根据权利要求1所述的高导热铁水沟浇注料，其特征在于：所述碳化硅中 SiC≥97％；所述硅微粉中SiO 2≥94％。
  4. 根据权利要求1所述的高导热铁水沟浇注料，其特征在于：所述球状沥青的软化温度为105～125℃，其中C≥48％。
  5. 根据权利要求1所述的高导热铁水沟浇注料，其特征在于：所述碳黑粉中C≥95％；所述碳树脂粉中C≥80％。
  6. 根据权利要求1所述的高导热铁水沟浇注料，其特征在于：所述碳分散剂为氟硼酸镍。
  7. 根据权利要求1所述的高导热铁水沟浇注料，其特征在于：所述抗氧化剂由金属硅粉和碳化硼按1.5～2:0.3～0.5之重量份配比配制而成。
  8. 根据权利要求1所述的高导热铁水沟浇注料，其特征在于：所述有机纤维为低熔点有机纤维，其熔化温度为70～100℃。
  9. 根据权利要求1所述的高导热铁水沟浇注料，其特征在于：所述防爆剂为粒度80～120目的金属铝粉，其中Al≥98％。
  10. 根据权利要求1所述的高导热铁水沟浇注料，其特征在于：所述减水剂为三聚磷酸钠和六偏磷酸钠按照0.04～0.1:0.08～0.13之重量份配制而成；或者为HDS和FDN按照0.08～0.13:0.02～0.05之重量份配制而成；或者为德国巴斯夫FS10型和FS20型减水剂按0.04～0.08:0.08～0.12之重量份配制而成。
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