CN101863672B - 一种矾土基刚玉空心球的制备方法 - Google Patents
一种矾土基刚玉空心球的制备方法 Download PDFInfo
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- 229910052593 corundum Inorganic materials 0.000 title claims abstract description 44
- 239000010431 corundum Substances 0.000 title claims abstract description 44
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 45
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 238000010891 electric arc Methods 0.000 claims abstract description 10
- 238000003723 Smelting Methods 0.000 claims abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 56
- HIGRAKVNKLCVCA-UHFFFAOYSA-N alumine Chemical compound C1=CC=[Al]C=C1 HIGRAKVNKLCVCA-UHFFFAOYSA-N 0.000 claims description 29
- 229910052742 iron Inorganic materials 0.000 claims description 25
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000003575 carbonaceous material Substances 0.000 claims description 17
- 238000002844 melting Methods 0.000 claims description 17
- 230000008018 melting Effects 0.000 claims description 16
- 239000000571 coke Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000003610 charcoal Substances 0.000 claims description 8
- 238000007670 refining Methods 0.000 claims description 7
- 229910000831 Steel Inorganic materials 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000003245 coal Substances 0.000 claims description 4
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 239000011295 pitch Substances 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- 239000010959 steel Substances 0.000 claims description 4
- -1 forge in back Jiao Substances 0.000 claims description 2
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- 239000006260 foam Substances 0.000 abstract 1
- 230000002068 genetic effect Effects 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 20
- 239000000377 silicon dioxide Substances 0.000 description 10
- 238000006722 reduction reaction Methods 0.000 description 9
- 239000012535 impurity Substances 0.000 description 8
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- 150000001875 compounds Chemical class 0.000 description 5
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- 238000002156 mixing Methods 0.000 description 5
- 238000012216 screening Methods 0.000 description 5
- 229960001866 silicon dioxide Drugs 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
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- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 2
- 229910001950 potassium oxide Inorganic materials 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- 229910001948 sodium oxide Inorganic materials 0.000 description 2
- 229910000519 Ferrosilicon Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
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Abstract
本发明公开了一种矾土基刚玉空心球的制备方法。是以高铝矾土为原料，并引入脱硅材料，在三相交流电弧矿热炉或直流电弧矿热炉中熔炼提纯，用压缩空气喷吹，然后经过筛分得到0.2～5mm的刚玉空心球。采用价格低廉的矾土为原料，通过添加脱硅材料在熔炼过程中实现对矾土的提纯，然后喷吹熔融氧化铝制备刚玉空心球，能够大幅降低刚玉空心球的生产成本，而且所制备的刚玉空心球的使用温度与氧化铝空心球相接近，耐压强度高，与采用燃尽物加入法、泡沫法、气体发生法生产的氧化铝隔热材料相比具有更高的力学强度和更高的使用温度。适合做轻质浇注料的骨料，施工过程中破损率低。
Description
技术领域
本发明涉及耐火材料的制备方法，尤其是涉及一种矾土基刚玉空心球的制备方法。
背景技术
在传统能源日益枯竭而新能源发展缓慢的今天，当前最迫切的任务是开发轻质、高强、热震稳定性好、使用温度高能满足轻质结构高温炉所需的内衬材料，改变传统的超高温窑炉由于采用重质结构而存在的热容量大、升温速率低、能耗大、使用寿命短、中期维修量大等缺点，节约能源，降低能耗，为建设资源节约型社会和人类可持续发展服务。
由于轻质保温材料是通过引入气孔的方式获得低热导率，引入大量气孔会导致轻质材料的重烧线收缩率提高、荷重软化温度降低、高温蠕变严重、耐压强度降低，从而使隔热材料的使用温度很难提高，并使应用范围受到限制，因此寻找新的方法制备新的高温隔热材料一直是各国专家的工作重点。在现有的隔热材料中，氧化铝隔热材料品种最多，使用温度高，隔热节能效果好，是当今重点发展的隔热材料，其中轻质氧化铝空心球陶瓷的应用是隔热材料技术进步的一个标志，它克服了原有泡沫氧化铝产品强度低、高温抗蠕变性能差的缺点，可直接接触火焰，也可作为高温内衬结构材料使用，能够推动传统高温窑炉结构改造，为设计新型窑炉结构奠定基础。但是目前的氧化铝空心球一般多采用γ-Al2O3粉体生产，原料价格相对较高，限制了氧化铝空心球作为隔热材料在许多领域中的应用。高铝矾土价格低廉，以高铝矾土为原料制备刚玉空心球能够大幅度降低刚玉空心球的生产成本，具有广阔的市场前景。然而高铝矾土中含有一定量的杂质如SiO2、TiO2、Fe2O3等，会对生产氧化铝含量较高的刚玉空心球产生不利影响，必须予以除去。高铝矾土中脱硅的方法有磨矿浮选和焙烧溶出等工艺，但这些生产工艺需要涉及液相制备，工艺过程比较复杂，不适合作为原料提纯方法应用于电熔法制备刚玉空心球。
发明内容
本发明的目的在于提供一种矾土基刚玉空心球的制备方法，是以高铝矾土为主要原料，同时引入一定量的脱硅材料，熔炼过程中在高温条件下脱硅材料与高铝矾土中的SiO2发生反应，从而脱除SiO2。
如单一采用碳素材料作为脱硅剂，则碳素材料与SiO2反应生成气态挥发物质SiO，从而使矾土中的SiO2脱除，从熔体中排出的SiO与空气中的氧结合形成硅灰(SiO2)通过除尘系统被收集。同时熔液中铁、钛杂质还可发生还原反应而生成的比重较大的物质如铁、钛，与还原反应生成的一部分硅形成硅铁合金沉降于炉底，从而与熔融氧化铝产生分离，此外一些低熔点氧化物如氧化钠、氧化钾等在受热的条件下挥发排出，氧化铝得以富集，之后通过喷吹熔融氧化铝而制得刚玉空心球。如采用碳素材料与含铁成分物质的混合物作为脱硅剂，SiO2被还原生成金属硅，硅和铁生成铁合金沉于熔池底部，杂质钛也会被还原和生成铁合金沉于底部，低熔点的氧化钾和氧化钠则在高温下变成蒸气挥发，从而使矾土中氧化铝得以富集，之后通过喷吹熔融氧化铝而制得刚玉空心球。
本发明采用的技术方案如下：
本发明以高铝矾土为原料，并加入脱硅材料，在三相交流或直流电弧矿热炉中加热熔炼，料液温度达到2100～2400℃完成脱硅后，精炼10～50分钟，然后倾炉用压缩空气喷吹成空心球。
所述的脱硅材料为碳素材料或碳素材料和含铁成分物质的混合物。
所述的碳素材料为石墨、石油焦、煅后焦、煤、焦炭、沥青、木炭中的一种或几种，含铁成分物质为铁屑、铁矿石、铁红、氧化铁黑、废铁、废钢中的一种或几种。
所述的加入脱硅材料采用单一碳素材料作为脱硅材料时，其用量保证碳素材料中的碳摩尔数为高铝矾土中SiO2摩尔百分含量的1.2～4倍。
所述的加入脱硅材料采用碳素材料和含铁成分物质的混合物时，其用量保证碳素材料中的碳摩尔数为高铝矾土中SiO2摩尔百分含量的0.8～3倍，含铁成分物质中Fe的摩尔数为高铝矾土中SiO2摩尔百分含量的2～5倍。
所述的高铝矾土中质量百分含量Al2O3％＞80％。
所述的矾土基刚玉空心球中Al2O3的质量百分含量为92～98％。
所述的倾炉用压缩空气喷吹成空心球中，选取0.2～5mm的空心球作为产品。
在制备矾土基刚玉空心球时，三相交流或直流电弧矿热炉顶部有抽风装置；炉底部含铁熔融料不能用于喷吹刚玉空心球，可倾倒冷却作为棕刚玉。
本发明具有的有益效果是：
采用价格低廉的矾土为原料，通过添加脱硅材料在熔炼过程中实现对矾土的提纯，然后喷吹熔融氧化铝制备刚玉空心球，能够大幅降低刚玉空心球的生
产成本，而且所制备的刚玉空心球的使用温度与氧化铝空心球相接近，耐压强度高，与采用燃尽物加入法、泡沫法、气体发生法生产的氧化铝隔热材料相比具有更高的力学强度和更高的使用温度。
本发明适合做轻质浇注料的骨料，施工过程中破损率低。
具体实施方式
实施例1：
所采用的高铝矾土中氧化铝含量为88％，氧化硅含量为7％，氧化铁含量为2％，脱硅材料采用石墨，其用量保证石墨中的C摩尔数为高铝矾土中SiO2摩尔数的1.2倍，将上述原料按比例配好混匀备用，电弧炉熔炼准备工作完成后加入炉中熔炼，在料温达到1500℃后开启电弧炉顶部抽风装置，混合料熔炼过程中发生还原反应，逐渐脱除矾土中的二氧化硅和杂质，原料完全熔融后调整电流精炼30分钟，温度达到2100℃后提起电极棒，立即倾炉喷吹制备刚玉空心球，炉底部料不能够用于制备刚玉空心球，但可用于制备棕刚玉。经筛分得到的粒度为0.2～5mm之间的统球作为最终产品，所得刚玉空心球中Al2O3％≥96％。
实施例2：
所采用的高铝矾土中氧化铝含量为83％，氧化硅含量为7％，氧化铁含量为2％，脱硅材料采用焦炭和木炭，其用量保证焦炭和木炭中的C摩尔数为高铝矾土中SiO2摩尔数的4倍，将上述原料按比例配好混匀备用，电弧炉熔炼准备工作完成后加入炉中熔炼，在料温达到1500℃后开启电弧炉顶部抽风装置，混合料熔炼过程中发生还原反应，逐渐脱除矾土中的二氧化硅和杂质，原料完全熔融后调整电流精炼30分钟，温度达到2100℃后提起电极棒，立即倾炉喷吹制备刚玉空心球，炉底部料不能够用于制备刚玉空心球，但可用于制备棕刚玉。经筛分得到的粒度为0.2～5mm之间的统球作为最终产品，所得刚玉空心球中Al2O3％≥93％。
实施例3：
所采用的高铝矾土中氧化铝含量为80％，氧化硅含量为11％，氧化铁含量为1％，脱硅材料由石油焦、煅后焦、煤和铁屑混合而成，石油焦、煅后焦、煤的总共用量保证其中的C摩尔数为高铝矾土中SiO2摩尔数的0.8倍，铁屑用量保证其中的Fe摩尔数为高铝矾土中SiO2摩尔数的5倍，将上述原料按比例配好混匀备用，电弧炉熔炼准备工作完成后加入炉中熔炼，在料温达到1500℃后开启电弧炉顶部抽风装置，混合料熔炼过程中发生还原反应，逐渐脱除矾土中的二氧化硅和杂质，原料完全熔融后调整电流精炼30分钟，温度达到2400℃后提起电极棒，立即倾炉喷吹制备刚玉空心球，炉底部料不能够用于制备刚玉空心球，但可用于制备棕刚玉。喷吹后有部分原料没有成球或破损，可在下次继续加到炉中进行熔炼，经筛分得到的粒度为0.2～5mm之间的统球作为最终产品，所得刚玉空心球中Al2O3％≥92％。
实施例4：
所采用的高铝矾土中氧化铝含量为88％，氧化硅含量为6％，氧化铁含量为0.5％，脱硅材料由焦炭、沥青、木炭和铁矿石、铁红、氧化铁黑混合而成，焦炭、沥青、木炭的总共用量保证其中的C摩尔数为高铝矾土中SiO2摩尔数的1.5倍，铁矿石、铁红、氧化铁黑的总共用量保证其中的Fe摩尔数为高铝矾土中SiO2摩尔数的2倍，将上述原料按比例配好混匀备用，电弧炉熔炼准备工作完成后加入炉中熔炼，在料温达到1500℃后开启电弧炉顶部抽风装置，混合料熔炼过程中发生还原反应，逐渐脱除矾土中的二氧化硅和杂质，原料完全熔融后调整电流精炼30分钟，温度达到2200℃后提起电极棒，立即倾炉喷吹制备刚玉空心球，炉底部料不能够用于制备刚玉空心球，但可用于制备棕刚玉。喷吹后有部分原料没有成球或破损，可在下次继续加到炉中进行熔炼，经筛分得到的粒度为0.2～5mm之间的统球作为最终产品，所得刚玉空心球中Al2O3％≥98％。
实施例5：
所采用的高铝矾土中氧化铝含量为86％，氧化硅含量为8％，氧化铁含量为1％，脱硅材料由焦炭、木炭和铁红、废铁、废钢混合而成，焦炭、木炭的总共用量保证其中的C摩尔数为高铝矾土中SiO2摩尔数的3倍，铁红、废铁、废钢的总共用量保证其中的Fe摩尔数为高铝矾土中SiO2摩尔数的3倍，将上述原料按比例配好混匀备用，电弧炉熔炼准备工作完成后加入炉中熔炼，在料温达到1500℃后开启电弧炉顶部抽风装置，混合料熔炼过程中发生还原反应，逐渐脱除矾土中的二氧化硅和杂质，原料完全熔融后调整电流精炼30分钟，温度达到2300℃后提起电极棒，立即倾炉喷吹制备刚玉空心球，炉底部料不能够用于制备刚玉空心球，但可用于制备棕刚玉。经筛分得到的粒度为0.2～5mm之间的统球作为最终产品，所得刚玉空心球中Al2O3％≥95％。
Claims (1)
1.一种矾土基刚玉空心球的制备方法，其特征在于：以高铝矾土为原料，并加入脱硅材料，在三相交流或直流电弧矿热炉中加热熔炼，料液温度达到2100～2400℃完成脱硅后，精炼10～50分钟，然后倾炉用压缩空气喷吹成空心球；
所述的脱硅材料为碳素材料或碳素材料和含铁成分物质的混合物；
所述的碳素材料为石墨、石油焦、煅后焦、煤、焦炭、沥青、木炭中的一种或几种，含铁成分物质为铁屑、铁矿石、铁红、氧化铁黑、废铁、废钢中的一种或几种；
所述的加入脱硅材料采用单一碳素材料作为脱硅材料时，其用量保证碳素材料中的碳摩尔数为高铝矾土中SiO2摩尔数的1.2～4倍；
所述的加入脱硅材料采用碳素材料和含铁成分物质的混合物时，其用量保证碳素材料中的碳摩尔数为高铝矾土中SiO2摩尔数的0.8～3倍，含铁成分物质中Fe的摩尔数为高铝矾土中SiO2摩尔数的2～5倍；
所述的高铝矾土中质量百分含量Al2O3％＞80％；
所述的矾土基刚玉空心球中Al2O3的质量百分含量为92～98％；
所述的倾炉用压缩空气喷吹成空心球中，选取0.2～5mm的空心球作为产品。
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| PCT/CN2011/074768 WO2011150771A1 (zh) | 2010-06-01 | 2011-05-27 | 一种矾土基刚玉空心球的制备方法 |
| US13/698,816 US20130106024A1 (en) | 2010-06-01 | 2011-05-27 | Method for producing bauxite-based hollow corundum sphere |
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| CN101863672B (zh) * | 2010-06-01 | 2012-11-07 | 江苏晶邦新型材料有限公司 | 一种矾土基刚玉空心球的制备方法 |
| WO2012122745A1 (zh) * | 2011-03-11 | 2012-09-20 | 浙江大学 | 一种耐高温空心球及其制备方法 |
| CN102180687A (zh) * | 2011-03-11 | 2011-09-14 | 浙江大学 | 一种矾土基镁铝空心球及其制备方法 |
| CN102180689A (zh) * | 2011-03-11 | 2011-09-14 | 傅晓云 | 一种镁铝空心球及其制备方法 |
| CN102180686A (zh) * | 2011-03-11 | 2011-09-14 | 浙江大学 | 一种矾土基铝钙空心球及其制备方法 |
| CN102249715A (zh) * | 2011-05-31 | 2011-11-23 | 浙江大学 | 一种铬刚玉空心球及其制备方法 |
| CN102295463A (zh) * | 2011-05-31 | 2011-12-28 | 浙江大学 | 一种锆刚玉空心球及其制备方法 |
| CN102249714A (zh) * | 2011-05-31 | 2011-11-23 | 浙江大学 | 一种铝钛空心球及其制备方法 |
| CN102249716A (zh) * | 2011-05-31 | 2011-11-23 | 傅晓云 | 一种耐高温空心球及其制备方法 |
| CN102295462A (zh) * | 2011-05-31 | 2011-12-28 | 浙江大学 | 一种镁铬空心球及其制备方法 |
| CN102249713A (zh) * | 2011-05-31 | 2011-11-23 | 浙江大学 | 一种镁钛空心球及其制备方法 |
| CN102249717A (zh) * | 2011-05-31 | 2011-11-23 | 浙江大学 | 一种镁铝钙空心球及其制备方法 |
| CN102249712A (zh) * | 2011-05-31 | 2011-11-23 | 浙江大学 | 一种镁钙空心球及其制备方法 |
| CN102826860A (zh) * | 2012-08-27 | 2012-12-19 | 苏州罗卡节能科技有限公司 | 低成本空心球及其制备方法和应用 |
| JP6316153B2 (ja) * | 2013-09-19 | 2018-04-25 | 太平洋セメント株式会社 | 微小アルミナ中空粒子 |
| CN105837072B (zh) * | 2016-03-30 | 2018-08-10 | 长安大学 | 一种路面抗滑磨耗层用集料及制备方法 |
| CN107698249A (zh) * | 2017-09-15 | 2018-02-16 | 浙江嘉吉石化工程有限公司 | 一种丙烯腈装置废水焚烧炉用低气孔莫来石砖的生产方法 |
| CN112939041A (zh) * | 2021-02-11 | 2021-06-11 | 贵州大学 | 一种利用棕刚玉除尘灰强化低品位铝土矿脱硅的方法 |
| CN114012613A (zh) * | 2021-11-19 | 2022-02-08 | 白鸽磨料磨具有限公司 | 一种磨凸轮轴用多组合砂轮及其制备方法 |
| CN114394840A (zh) * | 2021-12-31 | 2022-04-26 | 江苏新时高温材料股份有限公司 | 高纯度堆积密度石化填料用板状刚玉球 |
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| CN1789197A (zh) * | 2005-10-28 | 2006-06-21 | 王家邦 | 刚玉空心球的制备方法 |
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| US4744831A (en) * | 1984-07-30 | 1988-05-17 | Minnesota Mining And Manufacturing Company | Hollow inorganic spheres and methods for making such spheres |
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| US7309446B1 (en) * | 2004-02-25 | 2007-12-18 | Metadigm Llc | Methods of manufacturing diamond capsules |
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| CN101863672B (zh) * | 2010-06-01 | 2012-11-07 | 江苏晶邦新型材料有限公司 | 一种矾土基刚玉空心球的制备方法 |
| US20130077731A1 (en) * | 2011-03-28 | 2013-03-28 | Torxx Group Inc. | Ceramic encapsulations for nuclear materials and systems and methods of production and use |
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