WO2018121292A1 - 一种纳米孔轻量刚玉耐火骨料及其制备方法 - Google Patents

一种纳米孔轻量刚玉耐火骨料及其制备方法 Download PDF

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WO2018121292A1
WO2018121292A1 PCT/CN2017/116577 CN2017116577W WO2018121292A1 WO 2018121292 A1 WO2018121292 A1 WO 2018121292A1 CN 2017116577 W CN2017116577 W CN 2017116577W WO 2018121292 A1 WO2018121292 A1 WO 2018121292A1
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refractory aggregate
nanoporous
corundum refractory
water
lightweight corundum
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PCT/CN2017/116577
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English (en)
French (fr)
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顾华志
付绿平
黄奥
张美杰
李正坤
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武汉科技大学
江苏晶鑫新材料股份有限公司
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Publication of WO2018121292A1 publication Critical patent/WO2018121292A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/0051—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof characterised by the pore size, pore shape or kind of porosity
    • C04B38/0054—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof characterised by the pore size, pore shape or kind of porosity the pores being microsized or nanosized

Definitions

  • the invention belongs to the technical field of lightweight corundum refractory aggregates. Specifically, it relates to a nanoporous lightweight corundum refractory aggregate and a preparation method thereof.
  • the light weight of the working lining refractory material can effectively reduce the heat loss of the thermal kiln; on the other hand, it has more light refractory materials.
  • the pores can effectively accommodate thermal stress during temperature changes and improve the thermal peeling resistance of the material.
  • research findings (LPFu, HZGu, A. Huang, et al. Slag resistance mechanism of lightweight microporous corundum aggregates. J. Am. Ceram. Soc. 95 (5) (2015) 1658-1663), suitable stomata
  • the pore size has little effect on the slag resistance of lightweight refractories, and even increases. However, it has a great relationship with the composition and viscosity of the slag. Therefore, the key to realizing the weight reduction of the working layer refractory material is to prepare a lightweight aggregate having a small pore size and a low apparent porosity.
  • porous corundum-mullite aggregates SJLi, N. Li, Effects of composition and temperature on porosity and pore size distribution of porous ceramics prepared from Al(OH) 3 and kaolinite gangue, Ceram. Int. 33(4) (2007) 551-556
  • the average pore size of the prepared aggregate is Small, however, the apparent porosity is as high as 40%; R.
  • the porous corundum-spinel aggregate (R.) was prepared by in situ decomposition of hydrotalcite.
  • MV VCPandolfellia Porous alumina-spinel ceramics for high temperature applications, Ceram. Int. 37(4) (2011) 1393-1399
  • the aggregates prepared can not meet production requirements in terms of apparent porosity and pore size.
  • the invention aims to overcome the defects of the prior art, and the task is to provide a preparation method of a nanoporous lightweight corundum refractory aggregate with low cost and simple process; the nanoporous lightweight corundum refractory aggregate prepared by the method has low porosity It contains a large number of nano-scale intracrystalline closed pores, low thermal conductivity and strong resistance to slag erosion.
  • the technical scheme adopted by the present invention is: using 85 to 99 wt% of industrial alumina fine powder and 1 to 15 wt% of water-soluble salt as raw materials; and dissolving the water-soluble salt in the raw material 15 to 25wt% of water, obtaining a mixed solution; placing the industrial alumina fine powder in a rotary ball machine, then spraying the mixed solution under rotating conditions, rotating to form all spherical particles; and then the spherical particles are at 110-200 Dry at °C for 12 to 36 hours, and hold at 1750 to 1950 °C for 1 to 8 hours to obtain nanoporous lightweight corundum refractory aggregate.
  • the industrial alumina fine powder has an Al 2 O 3 content of >97% by weight and a particle diameter D 50 of 1 to 8 ⁇ m.
  • the water-soluble salt is one or more selected from the group consisting of aluminum chloride, aluminum nitrate, magnesium chloride, magnesium nitrate, magnesium sulfate, zirconium tetrachloride, zirconium oxychloride, zirconyl nitrate, zirconium sulfate, zirconium nitrate and titanium chloride.
  • the present invention has the following positive effects compared with the prior art:
  • the present invention introduces a water-soluble salt which, when dissolved in water, hydrolyzes to form a hydrated cation, exists in the form of a tetramer or a dimer, and the aggregate has a bridging hydroxyl group which can be connected to each other to be in situ A network structure having nanopores is formed; in addition, by introducing different water-soluble salts, the pore size of the nanopores can be controlled within a certain range.
  • the oxide particles produced by the decomposition of tetramer or dimer are all nanometer grade, which forms a misaligned sintering with the industrial alumina micropowder. Due to the difference in sintering properties, the above nanopores are quickly closed. Inside the grains, nanometer-sized intragranular pores are formed.
  • the nanoporous lightweight corundum refractory aggregate prepared by the invention has been tested to have a bulk density of 2.85-3.15 g/cm 3 , a apparent porosity of 1 to 10%, and an average pore diameter of 100-350 nm.
  • the invention has the advantages of low cost and simple process, and the prepared nanoporous lightweight corundum refractory aggregate has the characteristics of low porosity, large number of nano-scale closed pores, low thermal conductivity and strong resistance to slag erosion. .
  • the industrial alumina fine powder has an Al 2 O 3 content of >97% by weight and a particle diameter D 50 of 1 to 8 ⁇ m.
  • Nano hole lightweight corundum refractory aggregate and preparation method thereof 85 to 88 wt% of industrial alumina fine powder and 12 to 15 wt% of water-soluble salt as raw materials; the water-soluble salt is dissolved in 15-20% by weight of the raw material to obtain a mixed solution; industrial alumina fine powder Put it into a ball machine, then spray the mixed solution under rotating conditions, rotate to all to form spherical particles; then dry the spherical particles at 110-200 ° C for 12-24 hours, at 1750 ⁇ 1850 ° C Under the condition of 4 to 8 hours of heat preservation, the nanoporous lightweight corundum refractory aggregate is obtained.
  • the water soluble salt is aluminum chloride.
  • the nanoporous lightweight corundum refractory aggregate prepared in this example was tested to have a bulk density of 3.05 to 3.15 g/cm 3 , a apparent porosity of 1 to 5%, and an average pore diameter of 100 to 200 nm.
  • Nano hole lightweight corundum refractory aggregate and preparation method thereof Except for the water-soluble salt, the same as in the first embodiment:
  • the water soluble salt is zirconium oxychloride.
  • the nanoporous lightweight corundum refractory aggregate prepared in this embodiment has been tested to have a bulk density of 3.0 to 3.1 g/cm 3 , a apparent porosity of 2 to 6%, and an average pore diameter of 100 to 200 nm.
  • Nano hole lightweight corundum refractory aggregate and preparation method thereof 85 to 88 wt% of industrial alumina fine powder and 12 to 15 wt% of water-soluble salt as raw materials; the water-soluble salt is dissolved in 20 to 25 wt% of water of the raw material to obtain a mixed solution; industrial alumina fine powder Put it into a ball machine, then spray the mixed solution under rotating conditions, rotate to all to form spherical particles; then dry the spherical particles at 110-200 ° C for 24-36 hours, at 1850 ⁇ 1950 ° C Under the condition of 1 to 5 hours of heat preservation, the nanoporous lightweight corundum refractory aggregate is obtained.
  • the water soluble salt is a mixture of magnesium chloride and titanium chloride.
  • the nanoporous lightweight corundum refractory aggregate prepared in this embodiment has been tested to have a bulk density of 3.05 to 3.15 g/cm 3 , a apparent porosity of 2 to 7%, and an average pore diameter of 100 to 200 nm.
  • Nano hole lightweight corundum refractory aggregate and preparation method thereof Except for the water-soluble salt, the same as in the third embodiment:
  • the water soluble salt is a mixture of aluminum nitrate and zirconium nitrate.
  • the nanoporous lightweight corundum refractory aggregate prepared in this example was tested to have a bulk density of 3.05 to 3.15 g/cm 3 , a apparent porosity of 2 to 6%, and an average pore diameter of 100 to 200 nm.
  • Nano hole lightweight corundum refractory aggregate and preparation method thereof 88-92 wt% of industrial alumina fine powder and 8-12 wt% of water-soluble salt as raw materials; the water-soluble salt is dissolved in 15-20 wt% of water of the raw material to obtain a mixed solution; industrial alumina fine powder Put it into a ball machine, then spray the mixed solution under rotating conditions, rotate to all to form spherical particles; then dry the spherical particles at 110-200 ° C for 12-24 hours, at 1750 ⁇ 1850 ° C Under the condition of 4 to 8 hours of heat preservation, the nanoporous lightweight corundum refractory aggregate is obtained.
  • the water soluble salt is a mixture of magnesium nitrate, zirconium tetrachloride and titanium chloride.
  • the nanoporous lightweight corundum refractory aggregate prepared in this example was tested to have a bulk density of 2.95-3.05 g/cm 3 , a apparent porosity of 4 to 7%, and an average pore diameter of 150 to 250 nm.
  • Nano hole lightweight corundum refractory aggregate and preparation method thereof Except for the water-soluble salt, the same as in the example 5:
  • the water soluble salt is a mixture of aluminum chloride, magnesium sulfate and zirconyl nitrate.
  • the nanoporous lightweight corundum refractory aggregate prepared in this embodiment has been tested to have a bulk density of 3.0 to 3.1 g/cm 3 , a apparent porosity of 3 to 6%, and an average pore diameter of 150 to 300 nm.
  • Nano hole lightweight corundum refractory aggregate and preparation method thereof 88 to 92 wt% of industrial alumina fine powder and 8 to 12 wt% of water-soluble salt as raw materials; the water-soluble salt is dissolved in 20 to 25 wt% of water of the raw material to obtain a mixed solution; industrial alumina fine powder Put it into a ball machine, then spray the mixed solution under rotating conditions, rotate to all to form spherical particles; then dry the spherical particles at 110-200 ° C for 24-36 hours, at 1850 ⁇ 1950 ° C Under the condition of 1 to 5 hours of heat preservation, the nanoporous lightweight corundum refractory aggregate is obtained.
  • the water soluble salt is a mixture of aluminum nitrate, magnesium chloride, zirconium sulfate and titanium chloride.
  • the nanoporous lightweight corundum refractory aggregate prepared in this example was tested to have a bulk density of 2.95-3.1 g/cm 3 , a apparent porosity of 3 to 7%, and an average pore diameter of 150-250 nm.
  • Nano hole lightweight corundum refractory aggregate and preparation method thereof Except for the water soluble salt, the same as in the seventh embodiment:
  • the water soluble salt is a mixture of aluminum chloride, magnesium nitrate, zirconium tetrachloride and titanium chloride.
  • the nanoporous lightweight corundum refractory aggregate prepared in this example was tested to have a bulk density of 3.0 to 3.15 g/cm 3 , a apparent porosity of 3 to 6%, and an average pore diameter of 150 to 300 nm.
  • Nano hole lightweight corundum refractory aggregate and preparation method thereof 92-96 wt% of industrial alumina fine powder and 4-8 wt% of water-soluble salt as raw materials; the water-soluble salt is dissolved in 15-20 wt% of water of the raw material to obtain a mixed solution; industrial alumina fine powder Put it into a ball machine, then spray the mixed solution under rotating conditions, rotate to all to form spherical particles; then dry the spherical particles at 110-200 ° C for 12-24 hours, at 1750 ⁇ 1850 ° C Under the condition of 4 to 8 hours of heat preservation, the nanoporous lightweight corundum refractory aggregate is obtained.
  • the water-soluble salt is a mixture of aluminum nitrate, magnesium chloride, magnesium sulfate, zirconium nitrate and titanium chloride.
  • the nanoporous lightweight corundum refractory aggregate prepared in this example was tested to have a bulk density of 2.9 to 3.05 g/cm 3 , a apparent porosity of 5 to 9%, and an average pore diameter of 200 to 300 nm.
  • Nano hole lightweight corundum refractory aggregate and preparation method thereof Except for the water-soluble salt, the same as in Example 9:
  • the water-soluble salt is a mixture of aluminum chloride, aluminum nitrate, magnesium sulfate, zirconyl nitrate and titanium chloride.
  • the nanoporous lightweight corundum refractory aggregate prepared in this example was tested to have a bulk density of 2.9 to 3.15 g/cm 3 , a apparent porosity of 6 to 9%, and an average pore diameter of 150 to 300 nm.
  • Nano hole lightweight corundum refractory aggregate and preparation method thereof 92 to 96 wt% of industrial alumina fine powder and 4 to 8 wt% of water-soluble salt are used as raw materials; the water-soluble salt is dissolved in 20 to 25 wt% of water of the raw material to obtain a mixed solution; Put it into a ball machine, then spray the mixed solution under rotating conditions, rotate to all to form spherical particles; then dry the spherical particles at 110-200 ° C for 24-36 hours, at 1850 ⁇ 1950 ° C Under the condition of 1 to 5 hours of heat preservation, the nanoporous lightweight corundum refractory aggregate is obtained.
  • the water soluble salt is a mixture of aluminum chloride, magnesium chloride, magnesium nitrate, zirconium oxychloride, zirconium nitrate and titanium chloride.
  • the nanoporous lightweight corundum refractory aggregate prepared in this example was tested to have a bulk density of 2.95-3.1 g/cm 3 , a apparent porosity of 5 to 8%, and an average pore diameter of 200-300 nm.
  • Nano hole lightweight corundum refractory aggregate and preparation method thereof Except for the water-soluble salt, the same as in the same embodiment 11:
  • the water-soluble salts are a mixture of aluminum nitrate, magnesium chloride, magnesium nitrate, zirconium tetrachloride, zirconyl nitrate, zirconium sulfate and titanium chloride.
  • the nanoporous lightweight corundum refractory aggregate prepared in this example was tested to have a bulk density of 2.95-3.1 g/cm 3 , a apparent porosity of 6-8%, and an average pore diameter of 200-300 nm.
  • Nano hole lightweight corundum refractory aggregate and preparation method thereof 96 to 99 wt% of industrial alumina fine powder and 1-4 wt% of water-soluble salt as raw materials; the water-soluble salt is dissolved in 15-20% by weight of the raw material to obtain a mixed solution; industrial alumina fine powder Put it into a ball machine, then spray the mixed solution under rotating conditions, rotate to all to form spherical particles; then dry the spherical particles at 110-200 ° C for 12-24 hours, at 1750 ⁇ 1850 ° C Under the condition of 4 to 8 hours of heat preservation, the nanoporous lightweight corundum refractory aggregate is obtained.
  • the water-soluble salt is a mixture of aluminum chloride, magnesium chloride, magnesium nitrate, zirconium tetrachloride, zirconium oxychloride, zirconium sulfate, zirconium nitrate and titanium chloride.
  • the nanoporous lightweight corundum refractory aggregate prepared in this example was tested to have a bulk density of 2.85-3.0 g/cm 3 , a apparent porosity of 6-10%, and an average pore diameter of 200-350 nm.
  • Nano hole lightweight corundum refractory aggregate and preparation method thereof Except for the water-soluble salt, the same as the same Example 13:
  • the water-soluble salts are a mixture of aluminum chloride, aluminum nitrate, magnesium chloride, magnesium sulfate, zirconium oxychloride, zirconyl nitrate, zirconium sulfate, zirconium nitrate and titanium chloride.
  • the nanoporous lightweight corundum refractory aggregate prepared in the present embodiment was tested to have a bulk density of 2.85 to 2.95 g/cm 3 , a apparent porosity of 7 to 10%, and an average pore diameter of 200 to 350 nm.
  • Nano hole lightweight corundum refractory aggregate and preparation method thereof 96 to 99 wt% of industrial alumina fine powder and 1-4 wt% of water-soluble salt as raw materials; the water-soluble salt is dissolved in 20 to 25 wt% of water of the raw material to obtain a mixed solution; industrial alumina fine powder Put it into a ball machine, then spray the mixed solution under rotating conditions, rotate to all to form spherical particles; then dry the spherical particles at 110-200 ° C for 24-36 hours, at 1850 ⁇ 1950 ° C Under the condition of 1 to 5 hours of heat preservation, the nanoporous lightweight corundum refractory aggregate is obtained.
  • the water-soluble salts are a mixture of aluminum chloride, aluminum nitrate, magnesium chloride, magnesium nitrate, magnesium sulfate, zirconium tetrachloride, zirconium oxychloride, zirconyl nitrate, zirconium sulfate and zirconium nitrate.
  • the nanoporous lightweight corundum refractory aggregate prepared in this example was tested to have a bulk density of 2.9-3.0 g/cm 3 , a apparent porosity of 7-10%, and an average pore diameter of 250-350 nm.
  • Nano hole lightweight corundum refractory aggregate and preparation method thereof Except for the water-soluble salt, the same as Example 15:
  • the water-soluble salts are a mixture of aluminum chloride, aluminum nitrate, magnesium chloride, magnesium nitrate, magnesium sulfate, zirconium tetrachloride, zirconium oxychloride, zirconyl nitrate, zirconium sulfate, zirconium nitrate and titanium chloride.
  • the nanoporous lightweight corundum refractory aggregate prepared in this example was tested to have a bulk density of 2.9 to 2.95 g/cm 3 , a apparent porosity of 6 to 10%, and an average pore diameter of 250 to 350 nm.
  • the present invention introduces a water-soluble salt which, when dissolved in water, hydrolyzes to form a hydrated cation, exists in the form of a tetramer or a dimer, and the aggregate has a bridging hydroxyl group which can be connected to each other to be in situ A network structure having nanopores is formed; in addition, by introducing different water-soluble salts, the pore size of the nanopores can be controlled within a certain range.
  • the oxide particles produced by the decomposition of tetramer or dimer are all nanometer grade, which forms a misaligned sintering with the industrial alumina micropowder. Due to the difference in sintering properties, the above nanopores are quickly closed. Inside the grains, nanometer-sized intragranular pores are formed.
  • the nanoporous lightweight corundum refractory aggregate prepared by the specific embodiment has been tested to have a bulk density of 2.85-3.15 g/cm 3 , a apparent porosity of 1 to 10%, and an average pore diameter of 100-350 nm. Therefore, the specific embodiment has low cost and simple process, and the prepared nanoporous lightweight corundum refractory aggregate has low apparent porosity, contains a large number of nano-scale intracrystalline closed pores, low thermal conductivity and strong resistance to slag erosion. specialty.

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Abstract

一种纳米孔轻量刚玉耐火骨料及其制备方法。其制备方法是：以85～99wt％的工业氧化铝微粉和1～15wt％的水溶性盐为原料；将水溶性盐溶解在占原料15～25wt％的水中，获得混合溶液；将工业氧化铝微粉置于旋转成球机中，然后在旋转条件下喷洒该混合溶液，旋转至全部形成球形颗粒；再将球形颗粒在110～200℃条件下干燥12～36小时，然后在1750～1950℃条件下保温1～8小时，即得纳米孔轻量刚玉耐火骨料。

Description

一种纳米孔轻量刚玉耐火骨料及其制备方法 技术领域
本发明属于轻量刚玉耐火骨料技术领域。具体涉及一种纳米孔轻量刚玉耐火骨料及其制备方法。
背景技术
近年来，随着炉外精炼技术的快速发展，钢包在冶金过程中担任着越来越重要的角色，其工作层耐火材料的服役条件也更加苛刻，要求耐火材料既具有优异的机械强度、抗热剥落和冲刷性能及抗渣性能，又具有良好的隔热保温性能。工作层耐火材料轻量化被认为是有可能实现耐火材料具有高品质、多功能的有效途径。一方面，隔热耐火材料越靠近工作面，其隔热节能效果越好，工作衬耐火材料轻量化能有效降低热工炉窑热量散失；另一方面，由于轻量耐火材料中具有较多的气孔，在温度剧变时能够有效容纳热应力，提升材料抗热剥落性能。并且，研究发现(L.P.Fu,H.Z.Gu,A.Huang,et al.Slag resistance mechanism of lightweight microporous corundum aggregates.J.Am.Ceram.Soc.95(5)(2015)1658-1663)，合适的气孔孔径，对轻量耐火材料的抗渣性能影响不大，甚至反而提升。但是，跟渣的组成、黏度等性质关系较大。因此，实现工作层耐火材料轻量化的关键在于制备具有小孔径及低显气孔率的轻量骨料。
近年来，世界各地开展了许多关于轻量骨料及其相应的工作衬用轻量耐火材料的研究，并报道了许多制备轻量耐火骨料的方法，例如有机物分解法，原位成孔技术及氢氧化物/碳酸盐分解法等。O. Lyckfeldt等人采用淀粉作为结合剂及发泡剂，制备了多孔氧化铝(O.Lyckfeldt,J.M.F.Ferreira,Processing of porous ceramics by starch consolidation,J.Eur.Ceram.Soc.18(2)(1998)131–140)，所制备骨料体积密度明显降低，然而显气孔率及孔径较大；S.J.Li等人采用高岭石作为发泡剂，制备了多孔刚玉-莫来石骨料(S.J.Li,N.Li,Effects of composition and temperature on porosity and pore size distribution of porous ceramics prepared from Al(OH) 3and kaolinite gangue,Ceram.Int.33(4)(2007)551-556)，所制备骨料平均孔径较小，然而显气孔率高达40％；R.
Figure PCTCN2017116577-appb-000001
等人利用水滑石的原位分解，制备了多孔刚玉-尖晶石骨料(R.
Figure PCTCN2017116577-appb-000002
M.V.
Figure PCTCN2017116577-appb-000003
V.C.Pandolfellia,Porous alumina-spinel ceramics for high temperature applications,Ceram.Int.37(4)(2011)1393-1399)，所制备骨料在显气孔率及孔径方面也无法达到生产要求。
“一种微闭孔轻量刚玉耐火骨料及其制备方法”(ZL 201410405108.9)专利技术和“一种轻质微闭孔含镁刚玉耐火骨料及其制备方法”(ZL 201410688444.9)专利技术，采用湿法虽然分别制得了显气孔率低且含有大量微闭气孔的轻量刚玉耐火骨料和轻质含镁刚玉耐火骨料，但所采用的原料中纳米粉体成本较高，且湿法制备工艺相对较为复杂，较难实现工业化生产。
发明内容
本发明旨在克服现有技术缺陷，任务是提供一种成本低和工艺简单的纳米孔轻量刚玉耐火骨料的制备方法；用该方法制备的纳米孔轻 量刚玉耐火骨料显气孔率低、含大量纳米级晶内闭口气孔、热导率较低和抗熔渣侵蚀能力强。
为实现上述任务，本发明所采用的技术方案是：以85～99wt％的工业氧化铝微粉和1～15wt％的水溶性盐为原料；将所述水溶性盐溶解在占所述原料15～25wt％的水中，获得混合溶液；将工业氧化铝微粉置于旋转成球机中，然后在旋转条件下喷洒所述混合溶液，旋转至全部形成球形颗粒；再将所述球形颗粒在110～200℃条件下干燥12～36小时，在1750～1950℃条件下保温1～8小时，即得纳米孔轻量刚玉耐火骨料。
所述工业氧化铝微粉的Al 2O 3含量>97wt％，粒径D 50为1～8μm。
所述水溶性盐为氯化铝、硝酸铝、氯化镁、硝酸镁、硫酸镁、四氯化锆、氯氧化锆、硝酸氧锆、硫酸锆、硝酸锆和氯化钛中的一种以上。
由于采用上述技术方案，本发明与现有技术相比具有如下积极效果：
(1)本发明引入水溶性盐，该盐溶解于水中时发生水解可以形成水合阳离子，以四聚体或者二聚体的形式存在，该聚体具有的架桥羟基能够相互连接，从而原位形成具有纳米孔隙的网络结构；此外，通过引入不同的水溶性盐，可以对纳米孔隙的孔径在一定范围内进行调控。
(2)在热处理过程中，四聚体或者二聚体分解产生的氧化物粒子均为纳米级别，与工业氧化铝微粉形成错位烧结，由于两者烧结性能的差异，使得上述纳米孔隙被快速封闭在晶粒内部，从而形成纳米尺寸的晶内气孔。
本发明所制备的纳米孔轻量刚玉耐火骨料经检测：体积密度为2.85～3.15g/cm 3；显气孔率为1～10％；平均孔径为100～350nm。
因此，本发明成本低和工艺简单，所制备的纳米孔轻量刚玉耐火骨料具有显气孔率低、含大量纳米级晶内闭口气孔、热导率较低和抗 熔渣侵蚀能力强的特点。
具体实施方式
下面结合具体实施方式对本发明作进一步的描述，并非对保护范围的限制：
为避免重复，先将本具体实施方式所涉及的原料统一描述如下，实施例中不再赘述：
所述工业氧化铝微粉的Al 2O 3含量>97wt％，粒径D 50为1～8μm。
实施例1
一种纳米孔轻量刚玉耐火骨料及其制备方法。以85～88wt％的工业氧化铝微粉和12～15wt％的水溶性盐为原料；将所述水溶性盐溶解在占所述原料15～20wt％的水中，获得混合溶液；将工业氧化铝微粉置于旋转成球机中，然后在旋转条件下喷洒所述混合溶液，旋转至全部形成球形颗粒；再将所述球形颗粒在110～200℃条件下干燥12～24小时，在1750～1850℃条件下保温4～8小时，即得纳米孔轻量刚玉耐火骨料。
所述水溶性盐为氯化铝。
本实施例所制备的纳米孔轻量刚玉耐火骨料经检测：体积密度为3.05～3.15g/cm 3；显气孔率为1～5％；平均孔径为100～200nm。
实施例2
一种纳米孔轻量刚玉耐火骨料及其制备方法。除水溶性盐外，其余同实施例1：
所述水溶性盐为氯氧化锆。
本实施例所制备的纳米孔轻量刚玉耐火骨料经检测：体积密度为3.0～3.1g/cm 3；显气孔率为2～6％；平均孔径为100～200nm。
实施例3
一种纳米孔轻量刚玉耐火骨料及其制备方法。以85～88wt％的工业氧化铝微粉和12～15wt％的水溶性盐为原料；将所述水溶性盐溶解在占所述原料20～25wt％的水中，获得混合溶液；将工业氧化铝微粉 置于旋转成球机中，然后在旋转条件下喷洒所述混合溶液，旋转至全部形成球形颗粒；再将所述球形颗粒在110～200℃条件下干燥24～36小时，在1850～1950℃条件下保温1～5小时，即得纳米孔轻量刚玉耐火骨料。
所述水溶性盐为氯化镁和氯化钛的混合物。
本实施例所制备的纳米孔轻量刚玉耐火骨料经检测：体积密度为3.05～3.15g/cm 3；显气孔率为2～7％；平均孔径为100～200nm。
实施例4
一种纳米孔轻量刚玉耐火骨料及其制备方法。除水溶性盐外，其余同实施例3：
所述水溶性盐为硝酸铝和硝酸锆的混合物。
本实施例所制备的纳米孔轻量刚玉耐火骨料经检测：体积密度为3.05～3.15g/cm 3；显气孔率为2～6％；平均孔径为100～200nm。
实施例5
一种纳米孔轻量刚玉耐火骨料及其制备方法。以88～92wt％的工业氧化铝微粉和8～12wt％的水溶性盐为原料；将所述水溶性盐溶解在占所述原料15～20wt％的水中，获得混合溶液；将工业氧化铝微粉置于旋转成球机中，然后在旋转条件下喷洒所述混合溶液，旋转至全部形成球形颗粒；再将所述球形颗粒在110～200℃条件下干燥12～24小时，在1750～1850℃条件下保温4～8小时，即得纳米孔轻量刚玉耐火骨料。
所述水溶性盐为硝酸镁、四氯化锆和氯化钛的混合物。
本实施例所制备的纳米孔轻量刚玉耐火骨料经检测：体积密度为2.95～3.05g/cm 3；显气孔率为4～7％；平均孔径为150～250nm。
实施例6
一种纳米孔轻量刚玉耐火骨料及其制备方法。除水溶性盐外，其余同实施例5：
所述水溶性盐为氯化铝、硫酸镁和硝酸氧锆的混合物。
本实施例所制备的纳米孔轻量刚玉耐火骨料经检测：体积密度为3.0～3.1g/cm 3；显气孔率为3～6％；平均孔径为150～300nm。
实施例7
一种纳米孔轻量刚玉耐火骨料及其制备方法。以88～92wt％的工业氧化铝微粉和8～12wt％的水溶性盐为原料；将所述水溶性盐溶解在占所述原料20～25wt％的水中，获得混合溶液；将工业氧化铝微粉置于旋转成球机中，然后在旋转条件下喷洒所述混合溶液，旋转至全部形成球形颗粒；再将所述球形颗粒在110～200℃条件下干燥24～36小时，在1850～1950℃条件下保温1～5小时，即得纳米孔轻量刚玉耐火骨料。
所述水溶性盐为硝酸铝、氯化镁、硫酸锆和氯化钛的混合物。
本实施例所制备的纳米孔轻量刚玉耐火骨料经检测：体积密度为2.95～3.1g/cm 3；显气孔率为3～7％；平均孔径为150～250nm。
实施例8
一种纳米孔轻量刚玉耐火骨料及其制备方法。除水溶性盐外，其余同实施例7：
所述水溶性盐为氯化铝、硝酸镁、四氯化锆和氯化钛的混合物。
本实施例所制备的纳米孔轻量刚玉耐火骨料经检测：体积密度为3.0～3.15g/cm 3；显气孔率为3～6％；平均孔径为150～300nm。
实施例9
一种纳米孔轻量刚玉耐火骨料及其制备方法。以92～96wt％的工业氧化铝微粉和4～8wt％的水溶性盐为原料；将所述水溶性盐溶解在占所述原料15～20wt％的水中，获得混合溶液；将工业氧化铝微粉置于旋转成球机中，然后在旋转条件下喷洒所述混合溶液，旋转至全部形成球形颗粒；再将所述球形颗粒在110～200℃条件下干燥12～24小时，在1750～1850℃条件下保温4～8小时，即得纳米孔轻量刚玉耐火骨料。
所述水溶性盐为硝酸铝、氯化镁、硫酸镁、硝酸锆和氯化钛的混 合物。
本实施例所制备的纳米孔轻量刚玉耐火骨料经检测：体积密度为2.9～3.05g/cm 3；显气孔率为5～9％；平均孔径为200～300nm。
实施例10
一种纳米孔轻量刚玉耐火骨料及其制备方法。除水溶性盐外，其余同实施例9：
所述水溶性盐为氯化铝、硝酸铝、硫酸镁、硝酸氧锆和氯化钛的混合物。
本实施例所制备的纳米孔轻量刚玉耐火骨料经检测：体积密度为2.9～3.15g/cm 3；显气孔率为6～9％；平均孔径为150～300nm。
实施例11
一种纳米孔轻量刚玉耐火骨料及其制备方法。以92～96wt％的工业氧化铝微粉和4～8wt％的水溶性盐为原料；将所述水溶性盐溶解在占所述原料20～25wt％的水中，获得混合溶液；将工业氧化铝微粉置于旋转成球机中，然后在旋转条件下喷洒所述混合溶液，旋转至全部形成球形颗粒；再将所述球形颗粒在110～200℃条件下干燥24～36小时，在1850～1950℃条件下保温1～5小时，即得纳米孔轻量刚玉耐火骨料。
所述水溶性盐为氯化铝、氯化镁、硝酸镁、氯氧化锆、硝酸锆和氯化钛的混合物。
本实施例所制备的纳米孔轻量刚玉耐火骨料经检测：体积密度为2.95～3.1g/cm 3；显气孔率为5～8％；平均孔径为200～300nm。
实施例12
一种纳米孔轻量刚玉耐火骨料及其制备方法。除水溶性盐外，其余同实施例11：
所述水溶性盐为硝酸铝、氯化镁、硝酸镁、四氯化锆、硝酸氧锆、硫酸锆和氯化钛的混合物。
本实施例所制备的纳米孔轻量刚玉耐火骨料经检测：体积密度为 2.95～3.1g/cm 3；显气孔率为6～8％；平均孔径为200～300nm。
实施例13
一种纳米孔轻量刚玉耐火骨料及其制备方法。以96～99wt％的工业氧化铝微粉和1～4wt％的水溶性盐为原料；将所述水溶性盐溶解在占所述原料15～20wt％的水中，获得混合溶液；将工业氧化铝微粉置于旋转成球机中，然后在旋转条件下喷洒所述混合溶液，旋转至全部形成球形颗粒；再将所述球形颗粒在110～200℃条件下干燥12～24小时，在1750～1850℃条件下保温4～8小时，即得纳米孔轻量刚玉耐火骨料。
所述水溶性盐为氯化铝、氯化镁、硝酸镁、四氯化锆、氯氧化锆、硫酸锆、硝酸锆和氯化钛的混合物。
本实施例所制备的纳米孔轻量刚玉耐火骨料经检测：体积密度为2.85～3.0g/cm 3；显气孔率为6～10％；平均孔径为200～350nm。
实施例14
一种纳米孔轻量刚玉耐火骨料及其制备方法。除水溶性盐外，其余同实施例13：
所述水溶性盐为氯化铝、硝酸铝、氯化镁、硫酸镁、氯氧化锆、硝酸氧锆、硫酸锆、硝酸锆和氯化钛的混合物。
本实施例所制备的纳米孔轻量刚玉耐火骨料经检测：体积密度为2.85～2.95g/cm 3；显气孔率为7～10％；平均孔径为200～350nm。
实施例15
一种纳米孔轻量刚玉耐火骨料及其制备方法。以96～99wt％的工业氧化铝微粉和1～4wt％的水溶性盐为原料；将所述水溶性盐溶解在占所述原料20～25wt％的水中，获得混合溶液；将工业氧化铝微粉置于旋转成球机中，然后在旋转条件下喷洒所述混合溶液，旋转至全部形成球形颗粒；再将所述球形颗粒在110～200℃条件下干燥24～36小时，在1850～1950℃条件下保温1～5小时，即得纳米孔轻量刚玉耐火骨料。
所述水溶性盐为氯化铝、硝酸铝、氯化镁、硝酸镁、硫酸镁、四氯化锆、氯氧化锆、硝酸氧锆、硫酸锆和硝酸锆的混合物。
本实施例所制备的纳米孔轻量刚玉耐火骨料经检测：体积密度为2.9～3.0g/cm 3；显气孔率为7～10％；平均孔径为250～350nm。
实施例16
一种纳米孔轻量刚玉耐火骨料及其制备方法。除水溶性盐外，其余同实施例15：
所述水溶性盐为氯化铝、硝酸铝、氯化镁、硝酸镁、硫酸镁、四氯化锆、氯氧化锆、硝酸氧锆、硫酸锆、硝酸锆和氯化钛的混合物。
本实施例所制备的纳米孔轻量刚玉耐火骨料经检测：体积密度为2.9～2.95g/cm 3；显气孔率为6～10％；平均孔径为250～350nm。
本具体实施方式与现有技术相比具有如下积极效果：
(1)本发明引入水溶性盐，该盐溶解于水中时发生水解可以形成水合阳离子，以四聚体或者二聚体的形式存在，该聚体具有的架桥羟基能够相互连接，从而原位形成具有纳米孔隙的网络结构；此外，通过引入不同的水溶性盐，可以对纳米孔隙的孔径在一定范围内进行调控。
(2)在热处理过程中，四聚体或者二聚体分解产生的氧化物粒子均为纳米级别，与工业氧化铝微粉形成错位烧结，由于两者烧结性能的差异，使得上述纳米孔隙被快速封闭在晶粒内部，从而形成纳米尺寸的晶内气孔。
本具体实施方式所制备的纳米孔轻量刚玉耐火骨料经检测：体积密度为2.85～3.15g/cm 3；显气孔率为1～10％；平均孔径为100～350nm。因此，本具体实施方式成本低和工艺简单，所制备的纳米孔轻量刚玉耐火骨料具有显气孔率低、含大量纳米级晶内闭口气孔、热导率较低和抗熔渣侵蚀能力强的特点。

Claims (4)

  1. 一种纳米孔轻量刚玉耐火骨料的制备方法，其特征在于以85～99wt％的工业氧化铝微粉和1～15wt％的水溶性盐为原料；将所述水溶性盐溶解在占所述原料15～25wt％的水中，获得混合溶液；将工业氧化铝微粉置于旋转成球机中，然后在旋转条件下喷洒所述混合溶液，旋转至全部形成球形颗粒；再将所述球形颗粒在110～200℃条件下干燥12～36小时，在1750～1950℃条件下保温1～8小时，即得纳米孔轻量刚玉耐火骨料。
  2. 根据权利要求1所述的纳米孔轻量刚玉耐火骨料的制备方法，其特征在于所述工业氧化铝微粉的Al 2O 3含量>97wt％，粒径D 50为1～8μm。
  3. 根据权利要求1所述的纳米孔轻量刚玉耐火骨料的制备方法，其特征在于所述水溶性盐为氯化铝、硝酸铝、氯化镁、硝酸镁、硫酸镁、四氯化锆、氯氧化锆、硝酸氧锆、硫酸锆、硝酸锆和氯化钛中的一种以上。
  4. 一种纳米孔轻量刚玉耐火骨料，其特征在于所述的纳米孔轻量刚玉耐火骨料是根据权利要求书1～3项中任一项所述的纳米孔轻量刚玉耐火骨料的制备方法所制备的纳米孔轻量刚玉耐火骨料。
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