CN113716948A - 一种高温管道系统用低导热耐火材料及其制备方法 - Google Patents
一种高温管道系统用低导热耐火材料及其制备方法 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229910052849 andalusite Inorganic materials 0.000 claims abstract description 46
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 34
- 239000010431 corundum Substances 0.000 claims abstract description 33
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052863 mullite Inorganic materials 0.000 claims abstract description 23
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 16
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- 239000002245 particle Substances 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 9
- RGPUVZXXZFNFBF-UHFFFAOYSA-K diphosphonooxyalumanyl dihydrogen phosphate Chemical compound [Al+3].OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O RGPUVZXXZFNFBF-UHFFFAOYSA-K 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
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- 238000007580 dry-mixing Methods 0.000 claims description 2
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- 229910052782 aluminium Inorganic materials 0.000 claims 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 1
- 229910001845 yogo sapphire Inorganic materials 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 20
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 description 9
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- KMWBBMXGHHLDKL-UHFFFAOYSA-N [AlH3].[Si] Chemical class [AlH3].[Si] KMWBBMXGHHLDKL-UHFFFAOYSA-N 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
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- 239000000155 melt Substances 0.000 description 1
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- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052851 sillimanite Inorganic materials 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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Abstract
本发明涉及一种高温管道系统用低导热耐火材料及其制备方法，所述耐火材料可选自包括以质量分数计的如下组分：10％～30％的微孔烧结刚玉、10％～15％的莫来石、10％～45％的红柱石、30％～36％的红柱石粉、4％～10％的氢氧化铝。该耐火材料以红柱石作为主材料，充分利用红柱石是网状的莫来石中间夹杂高纯石英相的微观结构，有利于降低导热；此外采用具有微孔结构的微孔烧结刚玉为部分原料，并搭配微米级氢氧化铝，利用氢氧化铝高温气相挥发留下空隙，营造微孔效果，从而降低耐火材料的导热性并提高抗热震稳定性。
Description
技术领域
本发明涉及耐火材料制备技术领域，尤其涉及一种高温管道系统用低导热耐火材料及其制备方法。
背景技术
常见的高温管道，如高炉热风炉管道，一般均采用重质铝硅系耐火材料，如刚玉莫来石砖、莫来石砖、刚玉红柱石砖、硅线石砖等，这些材料在设计和质量控制时要求气孔率越低越好、体密越大越好。低气孔率、高致密性虽然有利于耐受高温性能，但不具备低导热性能，不利于保温；温度越高，导热率对温降的影响越明显，所以，在不降低高温性能的前提下降低工作衬的导热率意义重大。
耐火材料的导热性能与其组成、气孔率等密切相关。分布在高炉和热风炉之间的无抗渣要求的管道，管道长约50米至80米，荷载不高，但远距离输送热风，因此需要具有很好的保温性能，正常工况时会发生温度波动，因此需要具有一定的抗热震稳定性。
本发明基于高温管道对耐火材料的特殊要求，提供一种适用于该工况下的具备低导热性、高抗热震稳定性的耐火材料，也适用于不接触熔体的高温炉衬。
发明内容
为解决现有技术的不足，本发明提出一种高温管道系统用低导热耐火材料及其制备方法。
为实现以上目的，本发明所采用的技术方案包括：
根据本发明的第一个方面，公开了一种高温管道系统用低导热耐火材料，所述耐火材料可选自包括以质量分数计的如下组分：10％～30％的微孔烧结刚玉、10％～15％的莫来石、10％～45％的红柱石、30％～36％的红柱石粉、4％～10％的氢氧化铝。
进一步地，所述微孔烧结刚玉优选为包括质量含量不低于99％的Al2O3和质量含量不高于0.1％的Fe2O3，所述微孔烧结刚玉的显气孔率小于等于5％且闭气孔率大于等于6％。
进一步地，所述莫来石优选为包括质量含量不低于72％的Al2O3和质量含量不高于0.5％的Fe2O3，所述莫来石的莫来石相质量含量大于等于92％。
进一步地，所述红柱石和红柱石粉分别优选为包括质量含量不低于57％的Al2O3和质量含量不高于1％的Fe2O3。
进一步地，所述10％～30％的微孔烧结刚玉优选为包括10％～20％粒度分布为1～3mm的微孔烧结刚玉和0％～10％粒度小于等于1mm的微孔烧结刚玉。
进一步地，所述莫来石的粒度分布优选为1～3mm。
进一步地，所述10％～45％的红柱石优选为包括10％～30％粒度分布为1～3mm的红柱石和0％～15％粒度小于等于1mm的红柱石，所述红柱石粉的粒度优选为小于等于0.08mm。
进一步地，所述氢氧化铝的粒度优选为小于等于5微米。
根据本发明的第二个方面，公开了一种如上所述的一种高温管道系统用低导热耐火材料的制备方法，包括加料、干混、外加质量分数为4％～6％的磷酸二氢铝、混匀、冲压成型、干燥、烧成的工艺过程。
进一步地，所述干燥工艺优选为包括在80～120℃的温度区间内干燥24～48h,所述烧成工艺优选为包括在1450℃下保温12h。
本发明的有益效果为：
采用本发明所述的一种高温管道系统用低导热耐火材料，以红柱石作为主材料，采用同系多相复合、充分利用红柱石是网状的莫来石中间夹杂高纯石英相的微观结构，有利于降低导热；此外采用具有微孔结构的微孔烧结刚玉为部分原料，并搭配微米级氢氧化铝，利用氢氧化铝高温气相挥发留下空隙，营造微孔效果，从而降低耐火材料的导热性并提高抗热震稳定性。
具体实施方式
研究表明耐火材料并不是越致密性能越优，材料的有些性能之间是相克的，例如材料的气孔率越低、材料越致密，材料的抗热震性能就越差、导热率越高。本发明首先在选材上选择根据导热原理，选择低导热率材料，然后在材料基体内营造微孔，使材料在不改变材质、不降低高温性能的情况下，提高材料的抗热震稳定性、降低材料的导热率，从而提高节能效果。
本发明的技术原理：材料的导热率与相组成、相分布，特别是气孔密切相关。对于铝硅系耐材来说，硅含量越高、气孔率越高、导热率越低，这和材料的结构有关。材料的导热率，一般是单晶的导热率小于多晶的导热率；材料的结构越复杂、材料的导热率越低；空气的导热率相对固体来说，导热率很低，因此，气孔率可明显降低材料的导热率。根据这些原理，本发明首先选择红柱石作为主材料，因为红柱石的微观结构是网状的莫来石中间夹杂高纯石英相，有利于降低导热；另外采用微孔结构的微孔烧结刚玉为部分原料，在配料过程中，基质和骨料均不采用单相材料，采用同系多相混合原料；最重要的是添加微米氢氧化铝，利用其高温气相挥发留下空隙，营造微孔，从而降低导热、提高热震稳定性。
为了更清楚的理解本发明的内容，将结合实施例详细说明。
实施例1
一种高温管道系统用低导热耐火材料，选自包括以质量分数计的如下组分：10％的微孔烧结刚玉、10％的莫来石、40％的红柱石、36％的红柱石粉、4％的氢氧化铝。其中所述微孔烧结刚玉的粒度分布为1～3mm且包括质量含量不低于99％的Al2O3和质量含量不高于0.1％的Fe2O3，所述微孔烧结刚玉的显气孔率小于等于5％且闭气孔率大于等于6％；所述莫来石的粒度分布为1～3mm且包括质量含量不低于72％的Al2O3和质量含量不高于0.5％的Fe2O3，且所述莫来石的质量含量大于等于92％；所述红柱石包括25％粒度分布为1～3mm的红柱石和15％粒度小于等于1mm的红柱石，所述红柱石粉的粒度小于等于0.08mm，且所述红柱石和红柱石粉分别包括质量含量不低于57％的Al2O3和质量含量不高于1％的Fe2O3；所述氢氧化铝的粒度小于等于5微米。
优选的，一种高温管道系统用低导热耐火材料的制备方法包括将上述原料配料，干混3～5分钟，外加质量分数为4％～6％的磷酸二氢铝，在混炼机中混合15分钟，混合后按照2～3锤/公斤单重进行冲压成型，然后在80～120℃干燥器内干燥24～48小时至水分小于0.5％后进行烧成，烧成为在1450℃下保温12小时。
实施例2
一种高温管道系统用低导热耐火材料，选自包括以质量分数计的如下组分：20％的微孔烧结刚玉、12％的莫来石、28％的红柱石、34％的红柱石粉、6％的氢氧化铝。其中所述微孔烧结刚玉包括15％粒度分布为1～3mm的微孔烧结刚玉和5％粒度小于等于1mm的微孔烧结刚玉，且所述微孔烧结刚玉包括质量含量不低于99％的Al2O3和质量含量不高于0.1％的Fe2O3，所述微孔烧结刚玉的显气孔率小于等于5％且闭气孔率大于等于6％；所述莫来石的粒度分布为1～3mm且包括质量含量不低于72％的Al2O3和质量含量不高于0.5％的Fe2O3，且所述莫来石的质量含量大于等于92％；所述红柱石包括18％粒度分布为1～3mm的红柱石和10％粒度小于等于1mm的红柱石，所述红柱石粉的粒度小于等于0.08mm，且所述红柱石和红柱石粉分别包括质量含量不低于57％的Al2O3和质量含量不高于1％的Fe2O3；所述氢氧化铝的粒度小于等于5微米。
优选的，一种高温管道系统用低导热耐火材料的制备方法包括将上述原料配料，干混3～5分钟，外加质量分数为4％～6％的磷酸二氢铝，在混炼机中混合15分钟，混合后按照2～3锤/公斤单重进行冲压成型，然后在80～120℃干燥器内干燥24～48小时至水分小于0.5％后进行烧成，烧成为在1450℃下保温12小时。
实施例3
一种高温管道系统用低导热耐火材料，选自包括以质量分数计的如下组分：30％的微孔烧结刚玉、10％的莫来石、20％的红柱石、30％的红柱石粉、10％的氢氧化铝。其中所述微孔烧结刚玉包括20％粒度分布为1～3mm的微孔烧结刚玉和10％粒度小于等于1mm的微孔烧结刚玉，且所述微孔烧结刚玉包括质量含量不低于99％的Al2O3和质量含量不高于0.1％的Fe2O3，所述微孔烧结刚玉的显气孔率小于等于5％且闭气孔率大于等于6％；所述莫来石的粒度分布为1～3mm且包括质量含量不低于72％的Al2O3和质量含量不高于0.5％的Fe2O3，且所述莫来石的质量含量大于等于92％；所述红柱石包括15％粒度分布为1～3mm的红柱石和5％粒度小于等于1mm的红柱石，所述红柱石粉的粒度小于等于0.08mm，且所述红柱石和红柱石粉分别包括质量含量不低于57％的Al2O3和质量含量不高于1％的Fe2O3；所述氢氧化铝的粒度小于等于5微米。
优选的，一种高温管道系统用低导热耐火材料的制备方法包括将上述原料配料，干混3～5分钟，外加质量分数为4％～6％的磷酸二氢铝，在混炼机中混合15分钟，混合后按照2～3锤/公斤单重进行冲压成型，然后在80～120℃干燥器内干燥24～48小时至水分小于0.5％后进行烧成，烧成为在1450℃下保温12小时。
上述实施例1至3得到的耐火材料制品，经过测试，均满足显气孔率≤20％，荷重软化开始温度≥1650℃，热震、1100℃水冷≥20次，导热率1200℃≤2.1w/mk，完全符合高温管道的使用要求。上述实施例1至3得到的耐火材料制品的理化检测结果如表1所示。
表1一种高温管道系统用低导热耐火材料的性能指标
| 显气率，％ | 荷重软化开始温度，℃ | 导热率，1200℃，w/mk | 热震，1100℃水冷 | |
| 实施例1 | 18.9 | 1670 | 2.01 | ≥20次 |
| 实施例2 | 19.4 | 1660 | 2.03 | ≥20次 |
| 实施例3 | 19.5 | 1660 | 1.97 | ≥20次 |
以上所述仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到的变化或替换等都应涵盖在本发明的保护范围之内。因此，本发明的保护范围应该以权利要求书的保护范围为准。
Claims (10)
1.一种高温管道系统用低导热耐火材料，其特征在于，可选自包括以质量分数计的如下组分：10％～30％的微孔烧结刚玉、10％～15％的莫来石、10％～45％的红柱石、30％～36％的红柱石粉、4％～10％的氢氧化铝。
2.如权利要求1所述的耐火材料，其特征在于，所述微孔烧结刚玉包括质量含量不低于99％的Al2O3和质量含量不高于0.1％的Fe2O3，所述微孔烧结刚玉的显气孔率小于等于5％且闭气孔率大于等于6％。
3.如权利要求1所述的耐火材料，其特征在于，所述莫来石包括质量含量不低于72％的Al2O3和质量含量不高于0.5％的Fe2O3，所述莫来石的质量含量大于等于92％。
4.如权利要求1所述的耐火材料，其特征在于，所述红柱石和红柱石粉分别包括质量含量不低于57％的Al2O3和质量含量不高于1％的Fe2O3。
5.如权利要求2所述的耐火材料，其特征在于，所述10％～30％的微孔烧结刚玉包括10％～20％粒度分布为1～3mm的微孔烧结刚玉和0％～10％粒度小于等于1mm的微孔烧结刚玉。
6.如权利要求3所述的耐火材料，其特征在于，所述莫来石的粒度分布为1～3mm。
7.如权利要求4所述的耐火材料，其特征在于，所述10％～45％的红柱石包括10％～30％粒度分布为1～3mm的红柱石和0％～15％粒度小于等于1mm的红柱石，所述红柱石粉的粒度小于等于0.08mm。
8.如权利要求1至7任一项所述的耐火材料，其特征在于，所述氢氧化铝的粒度小于等于5微米。
9.如权利要求1至8任一项所述的高温管道系统用低导热耐火材料的制备方法，其特征在于，包括加料、干混、外加质量分数为4％～6％的磷酸二氢铝、混匀、冲压成型、干燥、烧成的工艺过程。
10.如权利要求9所述的制备方法，其特征在于，所述干燥工艺包括在80～120℃的温度区间内干燥24～48h,所述烧成工艺包括在1450℃下保温12h。
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