CN107963898B - 莫来石结合钛铝酸钙空心球隔热耐火材料及其制备方法 - Google Patents
莫来石结合钛铝酸钙空心球隔热耐火材料及其制备方法 Download PDFInfo
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- 239000011819 refractory material Substances 0.000 title claims abstract description 42
- -1 calcium titanium aluminate Chemical class 0.000 title claims abstract description 35
- 229910052863 mullite Inorganic materials 0.000 title claims abstract description 34
- 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 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 67
- 239000002994 raw material Substances 0.000 claims abstract description 29
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 22
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 19
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 19
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 19
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 19
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 17
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011575 calcium Substances 0.000 claims abstract description 15
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 15
- 239000002270 dispersing agent Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 238000000465 moulding Methods 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000009413 insulation Methods 0.000 claims description 4
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 4
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical group [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 4
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 4
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 4
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 230000035939 shock Effects 0.000 abstract description 12
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 abstract description 10
- 238000001035 drying Methods 0.000 abstract description 6
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 3
- 229910000423 chromium oxide Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- QQHSIRTYSFLSRM-UHFFFAOYSA-N alumanylidynechromium Chemical compound [Al].[Cr] QQHSIRTYSFLSRM-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
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Abstract
本发明涉及一种莫来石结合钛铝酸钙空心球隔热耐火材料及其制备方法。其技术方案是：以11～16wt％的α‑Al2O3粉体、5～10wt％的SiO2粉体、1～3wt％的V2O5粉体、70～75wt％的钛铝酸钙空心球和5～6wt％的硅溶胶为原料；按所述原料及其含量，先将所述α‑Al2O3粉体、所述SiO2粉体和所述V2O5粉体在行星球磨机中预混1～2小时，即得混合料；再将所述混合料、所述钛铝酸钙空心球、所述硅溶胶和所述原料0.05～0.2wt％的分散剂混合，搅拌，成型，养护，干燥；然后在1300～1400℃条件下保温3～4h，制得莫来石结合钛铝酸钙空心球隔热耐火材料。本发明成本低廉、工艺简单和成品率高；所制备制品体积密小、抗折与耐压强度大、导热系数小和抗热震性能优良。
Description
技术领域
本发明属于钛铝酸钙空心球隔热耐火材料技术领域。具体涉及一种莫来石结合钛铝酸钙空心球隔热耐火材料及其制备方法。
背景技术
隔热耐火材料作为热工设备的主要炉衬材料，其高效隔热保温对提高热工设备的能源利用率、产品质量和高效安全生产具有重要的作用。因此，隔热耐火材料和空心球隔热材料的研制受到本领域技术人员的关注：“轻质隔热耐火浇注料”(CN104341168A)专利技术，采用粉煤灰、莫来石、氧化铝空心球、氧化铝微粉和碳酸镁作为原料制备轻质隔热耐火浇注料，碳酸镁在高温下的分解可以提高材料的气孔率，虽能导致材料的导热系数减小，但是基质中镁铝尖晶石结合相的完整发育需要很高的烧成温度，且材料中高的气孔率会导致强度的降低；另外“一种含氧化铬的氧化铝空心球隔热制品”(CN104478452A)专利技术，采用氧化铝空心球、α-Al2O3粉和氧化铬粉作为原料制备含氧化铬的氧化铝空心球制品，在基质中可以生成铝铬固溶体，虽然能提高材料的抗热震性、耐磨性和强度，但是材料需要经较高的烧成温度和较长的保温时间处理。
发明内容
本发明旨在克服现有技术缺陷，目的在于提供一种成本低廉、工艺简单和成品率高的莫来石结合钛铝酸钙空心球隔热耐火材料的制备方法，用该方法制备的莫来石结合钛铝酸钙空心球隔热耐火材料体积密度较小、抗折与耐压强度大、导热系数小和抗热震性能优良。
为实现上述目的，本发明采用的技术方案是：
以11～16wt％的α-Al2O3粉体、5～10wt％的SiO2粉体、1～3wt％的V2O5粉体、70～75wt％的钛铝酸钙空心球和5～6wt％的硅溶胶为原料。按所述原料及其含量，先将所述α-Al2O3粉体、所述SiO2粉体和所述V2O5粉体在行星球磨机中预混1～2小时，即得混合料A；再将所述混合料A、所述钛铝酸钙空心球、所述硅溶胶和所述原料0.05～0.2wt％的分散剂混合，搅拌5～8min，振动成型，室温条件下养护20～28h；然后于90～115℃条件下干燥20～24h，在1300～1400℃条件下保温3～4h，制得莫来石结合钛铝酸钙空心球隔热耐火材料。
所述α-Al2O3粉体的Al2O3含量≥98.7wt％；α-Al2O3粉体的粒度为≤0.058mm。
所述SiO2粉体的SiO2含量≥97.9wt％；SiO2粉体的粒度为≤0.058mm。
所述V2O5粉体的V2O5含量≥99.2wt％；V2O5粉体的粒度为≤0.058mm。
所述钛铝酸钙空心球的主要化学成分是：Al2O3≥74.18wt％，CaO≥11.69wt％，TiO2≥11.08wt％；所述钛铝酸钙空心球的密度为0.8g/cm3，粒度为≤3mm。
所述硅溶胶的固含量为30wt％。
所述分散剂为六偏磷酸钠或为聚丙烯酸钠。
由于采用上述技术方案，本发明与现有技术相比具有以下优点：
1、本发明所采用的主要原料钛铝酸钙空心球原料来源丰富，成本低廉，且制备该原料的工艺简单，故莫来石结合钛铝酸钙空心球隔热耐火材料成本低廉，工艺简单。
2、本发明采用的钛铝酸钙空心球含有板片状晶形和封闭微孔结构的CA6物相，具有较低的热导率，故所制备的莫来石结合钛铝酸钙空心球隔热耐火材料导热系数小。
3、本发明采用的α-Al2O3粉体和SiO2粉体，在V2O5粉体的催化作用下生成莫来石晶须，莫来石晶须环绕在钛铝酸钙空心球的周围，显著提高了莫来石结合钛铝酸钙空心球隔热耐火材料的抗热震性和强度。
本发明所制备的莫来石结合钛铝酸钙空心球隔热耐火材料经检测：成品率为99.2～99.7％；体积密度为0.7～1.2g·cm-3；抗折强度为4～9MPa；耐压强度为13～20MPa；导热系数为0.4～0.9W·m-1·K-1(1000℃)；1100℃水冷试验条件下，抗热震次数为13～18次。
因此，本发明具有成本低廉、工艺简单和成品率高的特点；所制备的莫来石结合钛铝酸钙空心球隔热耐火材料体积密小、抗折与耐压强度大、导热系数小和抗热震性能优良。
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α-Al2O3粉体的Al2O3含量≥98.7wt％；α-Al2O3粉体的粒度为≤0.058mm。
所述SiO2粉体的SiO2含量≥97.9wt％；SiO2粉体的粒度为≤0.058mm。
所述V2O5粉体的V2O5含量≥99.2wt％；V2O5粉体的粒度为≤0.058mm。
所述钛铝酸钙空心球的主要化学成分是：Al2O3≥74.18wt％，CaO≥11.69wt％，TiO2≥11.08wt％；所述钛铝酸钙空心球的密度为0.8g/cm3，粒度为≤3mm。
所述硅溶胶的固含量为30wt％。
实施例1
一种莫来石结合钛铝酸钙空心球隔热耐火材料及其制备方法。本实施例所述制备方法是：
以14～16wt％的α-Al2O3粉体、5～7wt％的SiO2粉体、1～3wt％的V2O5粉体、70～72wt％的钛铝酸钙空心球和5～6wt％的硅溶胶为原料。按所述原料及其含量，先将所述α-Al2O3粉体、所述SiO2粉体和所述V2O5粉体在行星球磨机中预混1～2小时，即得混合料A；再将所述混合料A、所述钛铝酸钙空心球、所述硅溶胶和所述原料0.05～0.2wt％的分散剂混合，搅拌5～8min，振动成型，室温条件下养护20～28h；然后于90～115℃条件下干燥20～24h，在1300～1400℃条件下保温3～4h，制得莫来石结合钛铝酸钙空心球隔热耐火材料。
所述分散剂为六偏磷酸钠。
本实施例所制备的莫来石结合钛铝酸钙空心球隔热耐火材料经检测：成品率为99.2～99.7％；体积密度为0.7～0.9g·cm-3；抗折强度为4～6MPa；耐压强度为13～16MPa；导热系数为0.4～0.6W·m-1·K-1(1000℃)；1100℃水冷试验条件下，抗热震次数为13～15次。
实施例2
一种莫来石结合钛铝酸钙空心球隔热耐火材料及其制备方法。本实施例所述制备方法是：
以13～15wt％的α-Al2O3粉体、8～10wt％的SiO2粉体、1～3wt％的V2O5粉体、71～73wt％的钛铝酸钙空心球和5～6wt％的硅溶胶为原料。按所述原料及其含量，先将所述α-Al2O3粉体、所述SiO2粉体和所述V2O5粉体在行星球磨机中预混1～2小时，即得混合料A；再将所述混合料A、所述钛铝酸钙空心球、所述硅溶胶和所述原料0.05～0.2wt％的分散剂混合，搅拌5～8min，振动成型，室温条件下养护20～28h；然后于90～115℃条件下干燥20～24h，在1300～1400℃条件下保温3～4h，制得莫来石结合钛铝酸钙空心球隔热耐火材料。
所述分散剂为聚丙烯酸钠。
本实施例所制备的莫来石结合钛铝酸钙空心球隔热耐火材料经检测：成品率为99.2～99.7％；体积密度为1.0～1.2g·cm-3；抗折强度为7～9MPa；耐压强度为17～20MPa；导热系数为0.7～0.9W·m-1·K-1(1000℃)；1100℃水冷试验条件下，抗热震次数为16～18次。
实施例3
一种莫来石结合钛铝酸钙空心球隔热耐火材料及其制备方法。本实施例所述制备方法是：
以12～14wt％的α-Al2O3粉体、7～9wt％的SiO2粉体、1～3wt％的V2O5粉体、72～74wt％的钛铝酸钙空心球和5～6wt％的硅溶胶为原料。按所述原料及其含量，先将所述α-Al2O3粉体、所述SiO2粉体和所述V2O5粉体在行星球磨机中预混1～2小时，即得混合料A；再将所述混合料A、所述钛铝酸钙空心球、所述硅溶胶和所述原料0.05～0.2wt％的分散剂混合，搅拌5～8min，振动成型，室温条件下养护20～28h；然后于90～115℃条件下干燥20～24h，在1300～1400℃条件下保温3～4h，制得莫来石结合钛铝酸钙空心球隔热耐火材料。
所述分散剂为六偏磷酸钠。
本实施例所制备的莫来石结合钛铝酸钙空心球隔热耐火材料经检测：成品率为99.2～99.7％；体积密度为0.9～1.1g·cm-3；抗折强度为5～7MPa；耐压强度为16～19MPa；导热系数为0.6～0.8W·m-1·K-1(1000℃)；1100℃水冷试验条件下，抗热震次数为15～17次。
实施例4
一种莫来石结合钛铝酸钙空心球隔热耐火材料及其制备方法。本实施例所述制备方法是：
以11～13wt％的α-Al2O3粉体、6～8wt％的SiO2粉体、1～3wt％的V2O5粉体、73～75wt％的钛铝酸钙空心球和5～6wt％的硅溶胶为原料。按所述原料及其含量，先将所述α-Al2O3粉体、所述SiO2粉体和所述V2O5粉体在行星球磨机中预混1～2小时，即得混合料A；再将所述混合料A、所述钛铝酸钙空心球、所述硅溶胶和所述原料0.05～0.2wt％的分散剂混合，搅拌5～8min，振动成型，室温条件下养护20～28h；然后于90～115℃条件下干燥20～24h，在1300～1400℃条件下保温3～4h，制得莫来石结合钛铝酸钙空心球隔热耐火材料。
所述分散剂为聚丙烯酸钠。
本实施例所制备的莫来石结合钛铝酸钙空心球隔热耐火材料经检测：成品率为99.2～99.7％；体积密度为0.8～1.0g·cm-3；抗折强度为6～8MPa；耐压强度为14～17MPa；导热系数为0.5～0.7W·m-1·K-1(1000℃)；1100℃水冷试验条件下，抗热震次数为14～16次。
本具体实施方式与现有技术相比具有以下优点：
1、本具体实施方式所采用的主要原料钛铝酸钙空心球原料来源丰富，成本低廉，且制备该原料的工艺简单，故莫来石结合钛铝酸钙空心球隔热耐火材料成本低廉，工艺简单。
2、本具体实施方式采用的钛铝酸钙空心球含有板片状晶形和封闭微孔结构的CA6物相，具有较低的热导率，故所制备的莫来石结合钛铝酸钙空心球隔热耐火材料导热系数小。
3、本具体实施方式采用的α-Al2O3粉体和SiO2粉体，在V2O5粉体的催化作用下生成莫来石晶须，莫来石晶须环绕在钛铝酸钙空心球的周围，显著提高了莫来石结合钛铝酸钙空心球隔热耐火材料的抗热震性和强度。
本具体实施方式所制备的莫来石结合钛铝酸钙空心球隔热耐火材料经检测：成品率为99.2～99.7％；体积密度为0.7～1.2g·cm-3；抗折强度为4～9MPa；耐压强度为13～20MPa；导热系数为0.4～0.9W·m-1·K-1(1000℃)；1100℃水冷试验条件下，抗热震次数为13～18次。
因此，本具体实施方式具有成本低廉、工艺简单和成品率高的特点；所制备的莫来石结合钛铝酸钙空心球隔热耐火材料体积密小、抗折与耐压强度大、导热系数小和抗热震性能优良。
Claims (8)
1.一种莫来石结合钛铝酸钙空心球隔热耐火材料的制备方法，其特征在于：以11～16wt％的α-Al2O3粉体、5～10wt％的SiO2粉体、1～3wt％的V2O5粉体、70～75wt％的钛铝酸钙空心球和5～6wt％的硅溶胶为原料；按所述原料及其含量，先将所述α-Al2O3粉体、所述SiO2粉体和所述V2O5粉体在行星球磨机中预混1～2小时，即得混合料；再将所述混合料、所述钛铝酸钙空心球、所述硅溶胶和所述原料0.05～0.2wt％的分散剂混合，搅拌5～8min，振动成型，室温条件下养护20～28h；然后于90～115℃条件下干燥20～24h，在1300～1400℃条件下保温3～4h，制得莫来石结合钛铝酸钙空心球隔热耐火材料；
所述α-Al2O3粉体的粒度为≤0.058mm；
所述SiO2粉体的粒度为≤0.058mm；
所述V2O5粉体的粒度为≤0.058mm；
所述钛铝酸钙空心球的密度为0.8g/cm3，粒度为≤3mm。
2.根据权利要求1所述的莫来石结合钛铝酸钙空心球隔热耐火材料的制备方法，其特征在于所述α-Al2O3粉体的Al2O3含量≥98.7wt％。
3.根据权利要求1所述的莫来石结合钛铝酸钙空心球隔热耐火材料的制备方法，其特征在于所述SiO2粉体的SiO2含量≥97.9wt％。
4.根据权利要求1所述的莫来石结合钛铝酸钙空心球隔热耐火材料的制备方法，其特征在于所述V2O5粉体的V2O5含量≥99.2wt％。
5.根据权利要求1所述的莫来石结合钛铝酸钙空心球隔热耐火材料的制备方法，其特征在于所述钛铝酸钙空心球的主要化学成分是：Al2O3≥74.18wt％，CaO≥11.69wt％，TiO2≥11.08wt％。
6.根据权利要求1所述的莫来石结合钛铝酸钙空心球隔热耐火材料的制备方法，其特征在于所述硅溶胶的固含量为30wt％。
7.根据权利要求1所述的莫来石结合钛铝酸钙空心球隔热耐火材料的制备方法，其特征在于所述分散剂为六偏磷酸钠或为聚丙烯酸钠。
8.一种莫来石结合钛铝酸钙空心球隔热耐火材料，其特征在于所述莫来石结合钛铝酸钙空心球隔热耐火材料是根据权利要求1～7项中任一项所述的莫来石结合钛铝酸钙空心球隔热耐火材料的制备方法所制备的莫来石结合钛铝酸钙空心球隔热耐火材料。
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