CN108484187A - 一种改性钛铝酸钙耐火原料及其制备方法 - Google Patents

一种改性钛铝酸钙耐火原料及其制备方法 Download PDF

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CN108484187A
CN108484187A CN201810330874.1A CN201810330874A CN108484187A CN 108484187 A CN108484187 A CN 108484187A CN 201810330874 A CN201810330874 A CN 201810330874A CN 108484187 A CN108484187 A CN 108484187A
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calcium aluminate
titanium calcium
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赵惠忠
陈建威
张寒
余俊
王相辉
范润东
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JINZHOU GUOTAI INDUSTRIAL Co Ltd
Wuhan University of Science and Engineering WUSE
Wuhan University of Science and Technology WHUST
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Wuhan University of Science and Engineering WUSE
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Abstract

本发明涉及一种改性钛铝酸钙耐火原料及其制备方法。其技术方案是:先将钛铝酸钙熔块于1400~1450℃条件下保温3~4小时,随炉冷却,破碎,研磨至粒度≤0.058mm,得到钛铝酸钙微粉;再按所述钛铝酸钙微粉∶硅微粉∶五氧化二钒微粉的质量比为1∶(0.15~0.20)∶(0.01~0.03),将所述钛铝酸钙微粉、所述硅微粉和所述五氧化二钒微粉混合,球磨2~3小时,得到混合料;然后将所述混合料于160~180MPa条件下机压成型,在1450~1500℃条件下保温2~4小时,随炉冷却后,破碎,制得改性钛铝酸钙耐火原料。本发明具有资源综合利用和节能环保的特点,所制备的改性钛铝酸钙耐火原料导热系数小、化学稳定性好和易烧结。

Description

一种改性钛铝酸钙耐火原料及其制备方法
技术领域
本发明属于钛铝酸钙技术领域。具体涉及一种改性钛铝酸钙耐火原料及其制备方法。
背景技术
钛铝酸钙以导热系数较小、耐磨性高和耐火度高等特点被广泛应用在铁水包内衬、中间包永久层、水泥回转窑过渡带和炼钒反射炉内衬。但是,目前的报道主要是将钛铝酸钙直接应用到其他复相材料中,往往忽略了钛铝酸钙在不同材料体系中的物相变化对复相材料性能的不利影响。如“一种钛铝酸钙-高铝矾土改性耐火材料及其制备方法”(CN104609872A)和“一种炼钒反射炉内衬用钛铝酸钙预制件及其制备方法”(CN105036774A)专利技术,都是将钛铝酸钙直接与其他原料复合使用,没有考虑到钛铝酸钙中的CA2向CA6转变和微量金属钛和铁的氧化对材料烧结行为的影响。此外,“以钛铁渣为主要原料的再生高铝耐火材料及其制备方法”(CN103922772A)专利技术,虽然对钛铝酸钙进行了研磨、煅烧和酸浸处理,但是煅烧温度较低,不利于CA2向CA6的完全转变,且酸浸不能消除钛铝酸钙中的金红石相,导致生成的高铝耐火原料中的杂质含量太高,限制了应用范围。
发明内容
本发明旨在克服现有技术缺陷,目的在于提供一种资源综合利用和节能环保的改性钛铝酸钙耐火原料的制备方法,用该方法制备的改性钛铝酸钙耐火原料导热系数小、化学稳定性好和易烧结。
为实现上述目的,本发明采用的技术方案是:
先将钛铝酸钙熔块于1400~1450℃条件下保温3~4小时,随炉冷却,破碎,研磨至粒度≤0.058mm,得到钛铝酸钙微粉。
再按所述钛铝酸钙微粉∶硅微粉∶五氧化二钒微粉的质量比为1∶(0.15~0.20)∶(0.01~0.03),将所述钛铝酸钙微粉、所述硅微粉和所述五氧化二钒微粉混合,球磨2~3小时,得到混合料。
然后将所述混合料于160~180MPa条件下机压成型,在1450~1500℃条件下保温2~4小时,随炉冷却后,破碎,制得改性钛铝酸钙耐火原料。
所述钛铝酸钙熔块的主要化学成分是:Al2O3≥74.18wt%,CaO≥11.69wt%,TiO2≥11.08wt%;所述钛铝酸钙熔块的粒度≤30mm。
所述硅微粉的SiO2含量≥94.8wt%;所述硅微粉的粒度≤0.058mm。
所述五氧化二钒微粉的V2O5含量≥99.9wt%;所述五氧化二钒微粉的粒度≤0.058mm。
由于采用上述技术方案,本发明与现有技术相比具有以下积极效果:
1、本发明以钛铝酸钙为主要原料,具有资源综合利用和节能环保的特点。
2、本发明中的钛铝酸钙与硅微粉反应生成钙长石物相,并伴随着新的刚玉相的生成;钙长石具有导热系数小的特点,刚玉与试样中多余的硅微粉在五氧化二钒微粉做催化剂的情况下,原位反应生成莫来石,有利于提高改性钛铝酸钙耐火原料的化学稳定性。
3、本发明制备的改性钛铝酸钙耐火原料从以CA6、Ca((Al0.84Ti0.16)2)6O19、CA2、CaTiO3、金红石和刚玉为晶相的六相材料变成了以刚玉、钙长石、金红石和莫来石为晶相的四相材料,且转变后的改性钛铝酸钙耐火原料的物相的化学稳定性更优。
4、本发明制备的改性钛铝酸钙耐火原料中的金红石物相,一方面可以作为催化剂促进刚玉与硅微粉反应生成莫来石;另一方面可以作为助烧剂,促进产品的烧结,因此,改性钛铝酸钙耐火原料易烧结。
本发明所制备的改性钛铝酸钙耐火原料经检测:导热系数为1.8~2.0W·m-1·K-1(1000℃);体积密度为2.8~2.85g·cm-3
因此,本发明具有资源综合利用和节能环保的特点,所制备的改性钛铝酸钙耐火原料导热系数小、化学稳定性好和易烧结。
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,并非对其保护范围的限制。
为避免重复,先将本具体实施方式所涉及的物料统一描述如下,实施例中不再赘述:
所述钛铝酸钙熔块的主要化学成分是:Al2O3≥74.18wt%,CaO≥11.69wt%,TiO2≥11.08wt%;所述钛铝酸钙熔块的粒度≤30mm。
所述硅微粉的SiO2含量≥94.8wt%;所述硅微粉的粒度≤0.058mm。
所述五氧化二钒微粉的V2O5含量≥99.9wt%;所述五氧化二钒微粉的粒度≤0.058mm。
实施例1
一种改性钛铝酸钙耐火原料及其制备方法。本实施例所述制备方法是:
先将钛铝酸钙熔块于1400~1430℃条件下保温3~4小时,随炉冷却,破碎,研磨至粒度≤0.058mm,得到钛铝酸钙微粉。
再按所述钛铝酸钙微粉∶硅微粉∶五氧化二钒微粉的质量比为1∶(0.15~0.17)∶(0.025~0.03),将所述钛铝酸钙微粉、所述硅微粉和所述五氧化二钒微粉混合,球磨2~3小时,得到混合料。
然后将所述混合料于160~180MPa条件下机压成型,在1450~1480℃条件下保温2~2.6小时,随炉冷却后,破碎,制得改性钛铝酸钙耐火原料。
本实施例所制备的改性钛铝酸钙耐火原料经检测:导热系数为1.8~1.86W·m-1·K-1(1000℃);体积密度为2.80~2.82g·cm-3
实施例2
一种改性钛铝酸钙耐火原料及其制备方法。本实施例所述制备方法是:
先将钛铝酸钙熔块于1420~1450℃条件下保温3~4小时,随炉冷却,破碎,研磨至粒度≤0.058mm,得到钛铝酸钙微粉。
再按所述钛铝酸钙微粉∶硅微粉∶五氧化二钒微粉的质量比为1∶(0.16~0.18)∶(0.02~0.026),将所述钛铝酸钙微粉、所述硅微粉和所述五氧化二钒微粉混合,球磨2~3小时,得到混合料。
然后将所述混合料于160~180MPa条件下机压成型,在1470~1500℃条件下保温2.5~3.1小时,随炉冷却后,破碎,制得改性钛铝酸钙耐火原料。
本实施例所制备的改性钛铝酸钙耐火原料经检测:导热系数为1.90~1.96W·m-1·K-1(1000℃);体积密度为2.82~2.84g·cm-3
实施例3
一种改性钛铝酸钙耐火原料及其制备方法。本实施例所述制备方法是:
先将钛铝酸钙熔块于1400~1430℃条件下保温3~4小时,随炉冷却,破碎,研磨至粒度≤0.058mm,得到钛铝酸钙微粉。
再按所述钛铝酸钙微粉∶硅微粉∶五氧化二钒微粉的质量比为1∶(0.17~0.19)∶(0.015~0.021),将所述钛铝酸钙微粉、所述硅微粉和所述五氧化二钒微粉混合,球磨2~3小时,得到混合料。
然后将所述混合料于160~180MPa条件下机压成型,在1450~1480℃条件下保温3~3.6小时,随炉冷却后,破碎,制得改性钛铝酸钙耐火原料。
本实施例所制备的改性钛铝酸钙耐火原料经检测:导热系数为1.95~2.0W·m-1·K-1(1000℃);体积密度为2.83~2.85g·cm-3
实施例4
一种改性钛铝酸钙耐火原料及其制备方法。本实施例所述制备方法是:
先将钛铝酸钙熔块于1420~1450℃条件下保温3~4小时,随炉冷却,破碎,研磨至粒度≤0.058mm,得到钛铝酸钙微粉。
再按所述钛铝酸钙微粉∶硅微粉∶五氧化二钒微粉的质量比为1∶(0.18~0.20)∶(0.01~0.016),将所述钛铝酸钙微粉、所述硅微粉和所述五氧化二钒微粉混合,球磨2~3小时,得到混合料。
然后将所述混合料于160~180MPa条件下机压成型,在1470~1500℃条件下保温3.5~4小时,随炉冷却后,破碎,制得改性钛铝酸钙耐火原料。
本实施例所制备的改性钛铝酸钙耐火原料经检测:导热系数为1.85~1.91W·m-1·K-1(1000℃);体积密度为2.81~2.83g·cm-3
本具体实施方式与现有技术相比具有以下积极效果:
1、本具体实施方式以钛铝酸钙为主要原料,具有资源综合利用和节能环保的特点。
2、本具体实施方式钛铝酸钙与硅微粉反应生成钙长石物相,并伴随着新的刚玉相的生成;钙长石具有导热系数小的特点,刚玉与试样中多余的硅微粉在五氧化二钒微粉做催化剂的情况下,原位反应生成莫来石,有利于提高改性钛铝酸钙耐火原料的化学稳定性。
3、本具体实施方式制备的的改性钛铝酸钙耐火原料从以CA6、Ca((Al0.84Ti0.16)2)6O19、CA2、CaTiO3、金红石和刚玉为晶相的六相材料变成了以刚玉、钙长石、金红石和莫来石为晶相的四相材料,且转变后的改性钛铝酸钙耐火原料的物相的化学稳定性更优。
4、本具体实施方式制备的改性钛铝酸钙耐火原料中的金红石物相,一方面可以作为催化剂促进刚玉与硅微粉反应生成莫来石;另一方面可以作为助烧剂,促进产品的烧结,因此,改性钛铝酸钙耐火原料易烧结。
本具体实施方式所制备的改性钛铝酸钙耐火原料经检测:导热系数为1.8~2.0W·m-1·K-1(1000℃);体积密度为2.8~2.85g·cm-3
因此,本具体实施方式具有资源综合利用和节能环保的特点,所制备的改性钛铝酸钙耐火原料导热系数小、化学稳定性好和易烧结。

Claims (5)

1.一种改性钛铝酸钙耐火原料的制备方法,其特征在于:先将钛铝酸钙熔块于1400~1450℃条件下保温3~4小时,随炉冷却,破碎,研磨至粒度≤0.058mm,得到钛铝酸钙微粉;
再按所述钛铝酸钙微粉∶硅微粉∶五氧化二钒微粉的质量比为1∶(0.15~0.20)∶(0.01~0.03),将所述钛铝酸钙微粉、所述硅微粉和所述五氧化二钒微粉混合,球磨2~3小时,得到混合料;
然后将所述混合料于160~180MPa条件下机压成型,在1450~1500℃条件下保温2~4小时,随炉冷却后,破碎,制得改性钛铝酸钙耐火原料。
2.根据权利要求1所述的改性钛铝酸钙耐火原料的制备方法,其特征在于所述钛铝酸钙熔块的主要化学成分是:Al2O3≥74.18wt%,CaO≥11.69wt%,TiO2≥11.08wt%;所述钛铝酸钙熔块的粒度≤30mm。
3.根据权利要求1所述的改性钛铝酸钙耐火原料的制备方法,其特征在于所述硅微粉的SiO2含量≥94.8wt%;所述硅微粉的粒度≤0.058mm。
4.根据权利要求1所述的改性钛铝酸钙耐火原料的制备方法,其特征在于所述五氧化二钒微粉的V2O5含量≥99.9wt%;所述五氧化二钒微粉的粒度≤0.058mm。
5.一种改性钛铝酸钙耐火原料,其特征在于所述改性钛铝酸钙耐火原料是根据权利要求1~4项中任一项所述的改性钛铝酸钙耐火原料的制备方法所制备的改性钛铝酸钙耐火原料。
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