WO2003035574A1 - Materiau refractaire constitue de spinelle de chrome-aluminium - Google Patents

Materiau refractaire constitue de spinelle de chrome-aluminium Download PDF

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Publication number
WO2003035574A1
WO2003035574A1 PCT/CN2001/001484 CN0101484W WO03035574A1 WO 2003035574 A1 WO2003035574 A1 WO 2003035574A1 CN 0101484 W CN0101484 W CN 0101484W WO 03035574 A1 WO03035574 A1 WO 03035574A1
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corundum
chromite
chrome
refractory material
aluminum spinel
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PCT/CN2001/001484
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French (fr)
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Wenhou Zhao
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Wenhou Zhao
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    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/10Shaped 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
    • C04B35/101Refractories from grain sized mixtures
    • C04B35/105Refractories from grain sized mixtures containing chromium oxide or chrome ore
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/327Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3272Iron oxides or oxide forming salts thereof, e.g. hematite, magnetite

Definitions

  • the invention belongs to the field of refractory production, and particularly relates to a chrome-aluminum spinel refractory. Background technique
  • the AL 2 0 3 as a main component and corundum in some industrial smelting furnace is widely used, which comprises a fused corundum, sintered corundum and various corundum.
  • These corundum refractory materials have the advantages of high temperature resistance, corrosion resistance, high hardness, good abrasion resistance, strong impact resistance, high compressive strength at room temperature, and high softening temperature under load.
  • AL 2 0 3 has a stable crystal structure and resistance to slag invasion. Stronger, its insulation and air tightness are better, and the refractory products made are very dense.
  • the above-mentioned corundum refractories also have the following disadvantages. 1.
  • the corundum refractories are The strength at high temperatures is rather low. 2. Compared with other refractory materials, corundum products have larger elastic modulus, so their thermal shock resistance is relatively poor. 3. At high temperature, AL 2 0 3 in the corundum forms a low melting point substance in the strong alkaline slag, and because of its high content of AL 2 0 3 , it will shrink at high temperature, and the alkaline slag is extremely easy to penetrate. As a result, a metamorphic layer is formed under temperature changes, so its resistance to alkaline slag erosion is poor.
  • Aluminum complex chromium slag smelting output byproduct because of its rich AL 2 0 3 and Cr 2 0 3 is provided with a number of excellent properties so that the refractory, the refractory material having good high temperature chemical stability, The effect is better in acidic slag and neutral slag.
  • the use of decomposition in alkaline and low alkaline slags results in the formation of low melting point materials, which has a reduced resistance to slag erosion and is not ideal in use.
  • the density of aluminum chromium slag itself is not as good as that of corundum, and the compactness of its products is worse than that of corundum.
  • aluminum chromium slag has worse thermal shock stability. It is often used in locations with temperature fluctuations and often has spalling and cracking.
  • aluminum chromium slag is a by-product of smelting metal chromium, its resources are also greatly limited. Object of the invention
  • the purpose of the present invention is to overcome the shortcomings of the above-mentioned refractory materials, to solve the problems existing in the use of the above-mentioned refractory materials, to improve the technical performance of refractories, and to expand the source of raw materials of chrome-aluminum refractories. Reduce production costs and provide a chrome-aluminum spinel refractory. After adding additional zirconium dioxide, the strength of the product is further increased, and the product's impermeability, corrosion resistance, and thermal shock resistance are improved. Technical solution of the present invention
  • the invention is a material formula including (by weight percentage):
  • the amount of binder used for the above materials is: 0.5 ⁇ 14% of the total weight of the above materials;
  • corundum requires the composition of alumina:
  • Chromite requires chromium trioxide as:
  • the above-mentioned binding agents include organic binding agents and inorganic binding agents.
  • an admixture of 0.5-8% of the total weight of the material composed of corundum and chromite can be added, and the admixture contains 85% of zirconium dioxide.
  • Corundum and chromite that meet the requirements are magnetically treated separately, and then the required particle size is separately selected, and the mixture is mixed with the binder uniformly according to the above proportion, and it becomes a scattered chrome-aluminum spinel refractory material. After being shaped, dried, and then sintered at high temperature, the refractory material becomes a chromium-aluminum spinel molded product.
  • the present invention uses corundum as the main component, and after adding chromite and a binder, and then through magnetic separation, particle size sieving, mixing and other manufacturing processes, it becomes a new chrome-aluminum spinel refractory material.
  • Cr 2 0 3 in chromite and AL 2 0 3 in corundum generate material migration during high temperature sintering, which promotes the compactness of the bond between AL 2 0 3 and Cr 2 0 3 and forms a dense continuous Solid solution and high melting point compounds increase the viscosity of the liquid phase, allowing the slag to infiltrate only the shallow surface of the material, thereby reducing the phenomenon of structural spalling. Therefore, it has more obvious advantages than simple corundum and aluminum chromium slag. Increase It has resistance to slag erosion and impermeability.
  • the alumina requires alumina in the example: AL 2 0 3 ⁇ 78% ; the chromite requires a chromium trioxide composition: Cr 2 0 3 ⁇ 35 ; additive contains 85% zirconium dioxide):
  • Corundum with a composition that meets the requirements and a particle size of 0 to 15 mm, and chromite with a composition that meets the requirements and a particle size of 0 to 8 mm are subjected to magnetic separation treatment to remove the ferromagnetic substances therefrom;
  • To screen out corundum and chromite of the required particle size take 200kg (20%) of corundum, 800kg (80%) of chromite, 140kg of organic binder resin (14% of the total weight of the material), mix and stir well It becomes a chrome-aluminum spinel refractory.
  • Corundum with a composition that meets the requirements and a particle size of 0 to 15 mm, and chromite with a composition that meets the requirements and a particle size of 0 to 8 mm are subjected to magnetic separation treatment to remove the ferromagnetic substances therefrom;
  • To screen out corundum and chromite of the required particle size take 980kg (98%) of corundum, 20kg (2%) of chromite, 5kg of organic binder paper paddle (5% of the total weight of the material), mix and stir Uniformity becomes the grid aluminum spinel refractories.
  • corundum whose composition meets the requirements and has a particle size of 0 to 15 mm, and the chromite, which meets the requirements and has a particle size of 0 to 8 mm, are separately subjected to magnetic separation treatment to remove the ferromagnetic substances; According to the needs of screening, select corundum and chromite of the required particle size; take 550kg (55%) of corundum, 450kg (45%) of chromite, 65kg of inorganic binder boric acid (6.5% of the total weight of the material) After mixing, stir evenly to become chrome-aluminum spinel refractories.
  • Corundum with a composition that meets the requirements and a particle size of 0 to 15 mm, and chromite with a composition that meets the requirements and a particle size of 0 to 8 mm are separately subjected to magnetic separation treatment to remove the ferromagnetic substances therefrom; Screening to select corundum and chromite of the required particle size; 800 kg (80%) of corundum, 200 kg (20%) of chromite, 90 kg of inorganic binder phosphoric acid or aluminum phosphate (total weight of material. Percentage 9% ) Mix and stir to become chrome-aluminum spinel refractories.
  • Corundum with a composition that meets the requirements and a particle size of 0 to 15 mm, and chromite with a composition that meets the requirements and a particle size of 0 to 8 mm are separately magnetically treated, and then the dioxo zirconia with a particle size of 0 to 6 mm that meets the requirements , Respectively, to remove the ferromagnetic substances; then, according to the needs of the screening, the corundum, vermiculite and zirconium dioxide of the required particle size level were selected; 780 kg (78%) of corundum, 2Q0 kg of chromite (20 ° 20% (2%) of zirconium dioxide admixture, 90kg of phosphoric acid (9% of the total weight of the material) are mixed, and evenly mixed to become a chrome-aluminum-zirconium spinel refractory.
  • chrome-aluminum spinel refractories After the above-mentioned chrome-aluminum spinel refractories are formed, dried, and then sintered at high temperature, various shaped products of chrome-aluminum spinel refractories can be obtained.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Ceramic Products (AREA)

Description

一种铬铝尖晶石耐火材料 抟术领域
本发明属于耐火材料生产领域, 特别涉及一种铬铝尖晶石耐火材料。 背景技术
现有技术中的耐火材料有许多种,其中以 AL203为主要成份的刚玉在冶炼 和一些工业窑炉上应用非常广泛, 它包括电熔刚玉、 烧结刚玉及各种刚玉。 这些刚玉耐火材料具有耐高温、 耐腐蚀、 硬度大、 耐磨性好、 抗冲击能力强、 常温耐压强度高、 荷重软化温度高等优点, 而且, AL203晶体结构稳定, 抗 渣侵能力较强, 其绝缘性、 气密性也比较好, 制成的耐火材料制品十分致密。 但上述刚玉耐火材料同时又具有以下的缺点, 1、由于刚玉物料颗粒表面光滑, 且必需在超高温下烧结, 否则, 颗粒与基质之间很难牢固的结合在一起, 因 此, 刚玉耐火材料在高温下的强度反而较低。 2、 与其他耐火材料相比刚玉制 品的弹性模量较大, 故而其抗热震稳定性相对较差。 3、 在高温状态下, 刚玉 中的 AL203在强碱性熔渣中形成低熔点物质, 又因其 AL203含量高, 高温时 会产生收縮, 碱性熔渣又极易浸透, 致使在温度变化情况下, 形成变质层, 故其抗碱性熔渣侵蚀的性能较差。
铝络渣是冶炼金属铬产出的副产品, 因其富含 AL203和 Cr203故具备了许 多耐火材料的优良性能, 该物质耐高温, 具有较好的高温化学稳定性, 在酸 性熔渣和中性熔渣中使用效果较好。 但在碱性与低碱性熔渣中使用分解形成 低熔点物质, 其抗渣侵蚀性能下降, 使用效果不理想, 而且, 铝铬渣本身的 密度不如刚玉, 其制品的致密性比刚玉差, 另外铝铬渣的热震稳定性更差, 在温度波动的部位使用, 常有剥落和开裂现象, 还有, 由于铝铬渣是冶炼金 属铬的副产品, 其资源也受到很大的限制。 发明目的
本发明的目的是克服上述耐火材料存在的不足,解决上述耐火材料在使用 中存在的问题, 改善耐火材料的技术性能, 扩大铬铝质耐火材料的原料来源, 降低生产成本, 提供一种铬铝尖晶石耐火材料。 在加入外加济二氧化锆后, 至使产品又进一步的强度增加, 提高了制品的抗渗透性, 抗腐蚀性, 抗热震 性。 本发明的技术方案
本发明是材料配方包括 (按重量百分比计):
刚玉: 20〜98 %
铬铁矿: 2〜80%
上述材料采用结合剂的量为: 上述材料总重量的 0.5~14%;
其中, 刚玉要求三氧化二铝成份为:
AL203^78 ;
铬铁矿要求三氧化二铬成份为:
Cr203^35% ;
上述所说的结合剂包括有机结合剂和无机结合剂。
本发明还可以 ¾入由刚玉和铬铁矿构成的材料总重量 0.5~8%的外加剂, 外加剂含二氧化锆 85 %。
将粒度符合要求的刚玉和铬铁矿分别进行磁选处理后, 再分别筛选出所 需的粒度, 按照上述配比与结合剂混合均匀, 既成为散状铬铝尖晶石耐火材 料, 该散状耐火材料经成型、 干燥后, 再经过高温烧结, 即成为铬铝尖晶石 成型制品。 本发明的效果
本发明的优点在于:
1、 本发明以刚玉作为主要成份, 在其中加入铬铁矿和结合剂, 再经过磁 选、 粒度分筛、 混料等制作工艺后, 便成为一种新的铬铝尖晶石耐火材料, 其中, 铬铁矿中的 Cr203与刚玉中的 AL203在高温烧结的过程中产生物质迁 移, 促进了 AL203与 Cr203间结合的致密性, 形成致密的连续固熔体和高熔 点化合物, 增加了液相粘度, 使熔渣仅仅渗入材料的浅表, 从而减少了结构 剥落的现象, 所以, 它比单质的刚玉和铝铬渣具有更为明显的优越性, 提高 了抗渣侵蚀和抗渗透性能。
2、在刚玉中加入铬铁矿后, 提高了 AL203在高温下出现液相的温度, 并 使液相浓度增大, 使形成的铬铝质耐火材料具有很好的抗渣熔蚀的能力和很 强的抗玻璃熔体侵蚀的能力。
3、 在刚玉中加入铬铁矿后, 在高温下可促使铝铬结合强度增大, 提高原 物质在高温下的抗折强度, 降低烧结温度, 而且, 使原物料在高温下的收縮 现象得到改善, 提高了材料的热震稳定性。
4、 刚玉和铬铁矿来源广泛, 不受资源限制, 为冶炼金属铬的副产品一一 铝铬渣找到了一种性能更为优越的替代产品。 本发明的实施例 '
下面提供本发明的实施例 (百分比除另有说明外为材料重量百分比, 实 施例中刚玉要求成份三氧化二铝为: AL203^78% ;铬铁矿要求三氧化二铬成 份为: Cr203^35 ; 外加剂含二氧化锆 85 % ):
实施例 1:
将成份符合要求、 粒度为 0〜15毫米的刚玉, 以及成份符合要求、 粒度 为 0〜8毫米的铬铁矿分别进行磁选处理, 去除其中的铁磁性物质; 然后, 再 根据需要分别进行筛选,筛选出所需粒度级别的刚玉和铬铁矿;取刚玉 200kg (20%)、 铬铁矿 800kg ( 80%)、 有机结合剂树脂 140kg (材料总重量的百分 比 14%) 进行混合, 搅拌均匀即成为铬铝尖晶石耐火材料。
实施例 2:
将成份符合要求、 粒度为 0〜15毫米的刚玉, 以及成份符合要求、 粒度 为 0〜8毫米的铬铁矿分别进行磁选处理, 去除其中的铁磁性物质; 然后, 再 根据需要分别进行筛选,筛选出所需粒度级别的刚玉和铬铁矿,取刚玉 980kg (98%)、铬铁矿 20kg (2%)、有机结合剂纸桨 5kg (材料总重量的百分比 5%) 进行混合, 搅拌均匀即成为格铝尖晶石耐火材料。 将成份符合要求、 粒度为 0〜15毫米的刚玉, 以及成份符合要求、 粒度 为 0〜8毫米的铬铁矿分别进行磁选处理, 去除其中的铁磁性物质; 然后, 再 根据需要分别进行筛选,筛选出所需粒度级别的刚玉和铬铁矿;取刚玉 550kg ( 55%)、 铬铁矿 450kg (45%)、 无机结合剂硼酸 65kg (材料总重量的百分比 6.5%) 进行混合, 搅拌均匀即成为铬铝尖晶石耐火材料。
实施例 4:
将成份符合要求、 粒度为 0〜15毫米的刚玉, 以及成份符合要求、 粒度 为 0〜8毫米的铬铁矿分别进行磁选处理, 去除其中的铁磁性物质; 然后, 再 才艮据需要分别进行筛选,筛选出所需粒度级别的刚玉和铬铁矿;取刚玉 800kg ( 80%)、 铬铁矿 200kg (20%)、 无机结合剂磷酸或磷酸铝 90kg (材料总重量 的.百分比 9%) 进行混合, 搅拌均匀即成为铬铝尖晶石耐火材料。
实施例 5:
将成份符合要求、 粒度为 0〜15毫米的刚玉, 以及成份符合要求、 粒度 为 0〜8毫米的铬铁矿分别进行磁选处理, 再将符合要求粒度为 0〜6毫米的 二氧代锆, 分别去除其中的铁磁性物质; 然后, 再根据需要分别进行筛选, 筛选出所需粒度级别的刚玉、 袼铁矿及二氧化锆; 取刚玉 780kg (78%)、 铬 铁矿 2Q0kg (20°/。)、 外加剂二氧化锆 20 kg (2%)、 结合剂磷酸 90kg (材料总 重量的百分比 9%) 进行混合, 搅拌均匀即成为铬铝锆尖晶石耐火材料。
上述铬铝尖晶石耐火材料经成型、 干燥后, 再经过高温烧结, 即可得到 铬铝尖晶石耐火材料的各种成型制品。

Claims

权利要求
1、 一种铬铝尖晶石耐火材料, 其特征在于材料配方包括 (按重量百分比 计):
刚玉: 20〜98 %
铬铁矿: 2〜80%
上述材料采用结合剂的量为: 上述材料总重量的 0.5~14%;
其中, 刚玉要求成份三氧化二铝为:
AL203^78 % ;
铬铁矿要求三氧化二铬成份为:
Cr203 ^35 ;
上述所说的结合剂包括有机结合剂和无机结合剂。
2、根据权利要求 1所述的铬铝尖晶石耐火材料, 其特征在于加入由刚玉 和铬铁矿构成的材料总重量 0.5~8%的外加剂, 外加剂含二氧化锆 85 %。
3、 根据权利要求 1所述的铬铝尖晶石耐火材料, 其特征在于材料配方包 括 (按重量百分比计): 刚玉: 20 %, 铬铁矿: 80%; 上述材料釆用树脂结合 剂的量为: 上述材料总重量的 14%。
4、 根据权利要求 1所述的铬铝尖晶石耐火材料, 其特征在于材料配方包 括 (按重量百分比计): 刚玉: 98 %, 铬铁矿: 2% ; 上述材料采用纸浆结合 剂的量为: 上述材料总重量的 5%。
5、 根据权利要求 1所述的铬铝尖晶石耐火材料, 其特征在于材料配方包 括 (按重量百分比计): 刚玉: 55 %, 铬铁矿: 45 %; 上述材料采用硼酸结合 剂的量为: 上述材料总重量的 6.5%。
6、 根据权利要求 1所述的铬铝尖晶石耐火材料, 其特征在于材料配方包 括 (按重量百分比计): 刚玉: 80 %, 铬铁矿: 20% ; 上述材料釆用磷酸或磷 酸铝结合剂的量为: 上述材料总重量的 9%。
7、根据权利要求 1至 6中任一项所述的铬铝尖晶石耐火材料, 其特征在 于刚玉的粒度为 0-15毫米, 铬铁矿的粒度为 0-8毫米。
PCT/CN2001/001484 2000-11-03 2001-10-17 Materiau refractaire constitue de spinelle de chrome-aluminium WO2003035574A1 (fr)

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