CN108503371B - 一种利用高炉渣和高铝粉煤灰制备发泡陶瓷材料的方法 - Google Patents
一种利用高炉渣和高铝粉煤灰制备发泡陶瓷材料的方法 Download PDFInfo
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- 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 44
- 239000010881 fly ash Substances 0.000 title claims abstract description 42
- 239000002893 slag Substances 0.000 title claims abstract description 39
- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 63
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000000463 material Substances 0.000 claims abstract description 30
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 25
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 25
- 239000000654 additive Substances 0.000 claims abstract description 16
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- 239000000377 silicon dioxide Substances 0.000 claims abstract description 15
- 239000002002 slurry Substances 0.000 claims abstract description 15
- MOMKYJPSVWEWPM-UHFFFAOYSA-N 4-(chloromethyl)-2-(4-methylphenyl)-1,3-thiazole Chemical compound C1=CC(C)=CC=C1C1=NC(CCl)=CS1 MOMKYJPSVWEWPM-UHFFFAOYSA-N 0.000 claims abstract description 13
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- 238000002156 mixing Methods 0.000 claims abstract description 13
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 13
- 235000019983 sodium metaphosphate Nutrition 0.000 claims abstract description 13
- 239000004328 sodium tetraborate Substances 0.000 claims abstract description 13
- 235000010339 sodium tetraborate Nutrition 0.000 claims abstract description 13
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 230000000996 additive effect Effects 0.000 claims description 8
- 229910052593 corundum Inorganic materials 0.000 claims description 8
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 8
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 6
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Abstract
一种利用高炉渣和高铝粉煤灰制备发泡陶瓷材料的方法，按以下步骤进行：(1)将高炉渣、高铝粉煤灰和硅砂均磨细后混合作为原料；(2)准备硼砂、碳酸钠、碳酸钙、偏磷酸钠和粘土作为添加剂；(3)将原料和添加剂混合形成混合物料，湿磨混合制成料浆；(4)喷雾造粒制成粉体颗粒；(5)填充到模具中进行焙烧发泡造孔；(6)随炉冷却至常温，获得发泡陶瓷材料。本发明的方法制备工艺简洁，实现了固体废弃物的资源化利用，产品主要为物相为晶体矿物，材料强度高、隔热性好、防火、体积密度低，性能优异。
Description
技术领域
本发明属于材料技术领域，特别涉及一种利用高炉渣和高铝粉煤灰制备发泡陶瓷材料的方法。
背景技术
发泡陶瓷是一种多孔陶瓷材料，气孔率高达50％以上，具有轻质、隔热、防火、吸音等优良性能；发泡陶瓷材料因为其原料在烧制过程中由于界面诱导析晶和一些金属氧化物作为晶核剂引发析晶，导致材料中主要物相以晶体形式存在，从而区别于泡沫玻璃材料，相较于泡沫玻璃材料，发泡陶瓷拥有较高的强度和更好的隔热性和稳定性；高温发泡陶瓷的制备主要是在原料中加入适量的高温发泡剂、稳泡剂、助熔剂等助剂，混匀后物料在高温下熔融，形成具有适宜粘度的熔体，发泡剂在高温下发生分解反应，产生挥发气体，此时高粘度的熔体使气体无法逸散，封闭在材料内部，引起材料发泡膨胀，而随着温度降低，熔体逐渐冷却凝固，封闭在熔体中的气体在材料内部形成闭合气孔，得到发泡陶瓷材料。
近年来，发泡陶瓷材料，因其具备轻质、强度高、耐高温、耐化学腐蚀、防火隔热、隔音等优良特性，在建筑节能材料、热交换材料、催化剂载体、污水处理等领域得到广泛应用。其制备工艺对原料的要求并不十分苛刻，使用工业固体废弃物制备发泡陶瓷材料不仅符合国家所倡导的节能减排政策，还能够对废渣进行资源化利用，得到高附加值得材料产品，因此利用工业废渣制备发泡陶瓷材料成为了当下研究的热门。
高炉渣是在高炉炼铁过程中，由矿石中的脉石、燃料中的灰分和石灰石熔剂中的非挥发组分形成的固体废渣，是冶金行业产量最大的一种废渣之一；高炉渣根据处理方式的不同分为气冷渣、水淬渣、膨胀矿渣和矿渣棉。气冷渣和膨胀渣可代替天然砂石，作为混凝土的骨料而得到资源化利用，矿渣棉是用压缩空气或高压蒸汽喷吹渣流得到的，可作为保温防火材料，水淬渣则作为水泥混合混合料，生产矿渣硅酸盐水泥；我国的高炉渣主要以水淬渣为主，水淬渣是熔渣直接用大量的水淬冷后得到的以非晶态玻璃体味主要物相的细颗粒渣，具有潜在的水硬性，可作为水泥原料。当前我国的高炉渣利用率约为85％，主要的应用生产为水泥和混凝土等低附加值产品。
粉煤灰是燃煤经过高温燃烧后，其中的无机组分在高温环境下发生熔融、聚合等不同程度的物理和化学反应后形成的微细粉煤灰粒子，经过炉尾的除尘设备分离和收集得到的固体废弃物。粉煤灰中主要为晶体矿物和玻璃态矿物，高铝粉煤灰是产自我国山西北部及内蒙中部地区的一种特色煤炭，其燃烧生产电能后的粉煤灰中Al2O3含量超过40％，与普通粉煤灰的化学成分含量差别较大。我国高铝粉煤灰产量很大，资源化利用率低，据统计，当前堆存总量已经超过1.7亿吨；高铝粉煤灰的大量堆存会造成当地土壤的碱化，破坏生态，污染大气，威胁人体健康，因此发展对高炉粉煤灰的资源化利用技术十分紧迫。
发明内容
本发明的目的是提供一种利用高炉渣和高铝粉煤灰制备发泡陶瓷材料的方法，采用的原料高炉渣，高铝粉煤灰和硅砂，添加硼砂、碳酸钠、碳酸钙、偏磷酸钠和粘土等添加剂，在中温炉中一次焙烧，发泡成型，实现高炉渣和高铝粉煤灰资源化利用的同时，制得性能优良的发泡陶瓷材料。
本发明的方法包括以下步骤：
1、将高炉渣、高铝粉煤灰和硅砂均磨细至粒径≤0.124mm，然后混合作为原料；原料中按质量百分比高炉渣占42～51％，高铝粉煤灰占15～24％，硅砂占30～40％；
2、准备硼砂、碳酸钠、碳酸钙、偏磷酸钠和粘土作为添加剂；添加剂中硼砂占原料总质量的1～3％，碳酸钠占原料总质量的2～7％，碳酸钙占原料总质量的1～5％，偏磷酸钠占原料总质量的0.5～1.5％，粘土占原料总质量的4～8％；
3、将原料和添加剂混合形成混合物料，然后用球磨机进行湿磨，混合均匀并制成料浆；料浆中水的重量百分比为30～40％；
4、将料浆注入喷雾造粒器中进行喷雾造粒，制成粉体颗粒；粉体颗粒的粒径≤0.5mm；
5、将粉体颗粒填充到模具中，然后置于加热炉内，进行焙烧发泡造孔；焙烧发泡造孔过程中的温度制度为：炉温从室温以7～10℃/min的速率升到800～950℃，保温至少20min，然后以2～4℃/min的升温速率升到1100～1200℃，保温50～90min；
6、焙烧发泡造孔完成后随炉冷却至常温，获得发泡陶瓷材料。
上述的高炉渣按质量百分比含SiO2 32～33％，Al2O3 10～11％，Fe2O3 0.9～1.0％，CaO 45～46％，Na2O 0.9～1.2％，TiO2 0.6～0.7％，MgO 6～7％，K2O 0.3～0.4％，其余为杂质。
上述的高铝粉煤灰按质量百分比含SiO2 39～40％，Al2O3 46～47％，Fe2O3 4～5％，CaO 3～4％，Na2O 0.3～0.5％，TiO2 1～2％，MgO 0.5～0.8％，K2O 0.7～0.9％，其余为杂质。
上述的发泡陶瓷材料的体积密度为0.4～0.65g/cm3，抗压强度为1.5～3.5MPa，导热系数为0.1～0.25W/(m·K)。
上述方法中，湿磨时水、混合物料和磨球的质量比为0.5:1:4。
上述方法中，为保证料浆成分均匀，将料浆搅拌均匀化至少30min，然后进行喷雾造粒。
高炉渣中的主要成分组成为CaO、SiO2、Al2O3和MgO，其中前三者的含量最高，冷态高炉渣的熔融温度较高，很难直接制备发泡陶瓷材料；根据CaO-SiO2-Al2O3三元相图，找到了三组元的低共熔点成分比例，计算表明，通过向水淬渣中添加一定量的高铝粉煤灰和硅砂，即可使原料在较低的温度下共熔，从而达到制备发泡陶瓷的条件；本发明的方法得到的粉体配合料经过一次焙烧，即可得到填满闭合气孔，体积密度小，强度高，隔热性能好的高性能发泡陶瓷材料。
本发明的方法具有以下优点：1)制备工艺简洁，没有复杂的操作过程；2)所用原料为高炉渣和高铝粉煤灰等工业废渣，实现了固体废弃物的资源化利用，得到的产品价值高，为两种工业废渣的利用提供行思路；3)制备得到的发泡陶瓷材料基本完全瓷化，主要为物相为晶体矿物，材料强度高、隔热性好、防火、体积密度低，性能优异；通过实验验证，多孔陶瓷材料完全瓷化，达到国家A级防火材料标准。
本发明提供的方法便于实现工业化，且得到的发泡陶瓷材料各方面性能优异，使用固体废弃物为原料，符合国家节能减排的发展要求，可在隧道窑中实现大面积一次烧成，按照要求任意切割，能够在保温隔热材料，防火材料，建筑材料等领域得到广泛应用。
具体实施方式
下面结合具体的实施方式对本发明的内容进一步说明和补充。
本发明实施例中的高炉渣按质量百分比含SiO2 32.05％，Al2O3 10.01％，Fe2O30.902％，CaO 45.37％，Na2O 0.998％，TiO2 0.680％，MgO 6.35％，K2O 0.352％。
本发明实施例中的高铝粉煤灰按质量百分比含SiO2 39.37％，Al2O3 46.88％，Fe2O3 4.86％，CaO 3.03％，Na2O 0.302％，TiO2 1.65％，MgO 0.541％，K2O 0.760％。
本发明实施例中采用的粘土的粒径<0.074mm。
本发明实施例中采用的硼砂(Na2B4O7·10H2O)、偏磷酸钠、Na2CO3和CaCO3为市购产品。
本发明实施例中的粉体颗粒的粒径≤0.5mm。
本发明实施例中采用的模具为拼装式耐火砖窑具。
本发明实施例中采用的加热炉为中温炉。
本发明实施例中料浆中水的重量百分比为30～40％。
本发明实施例中的高炉渣、高铝粉煤灰和硅砂在使用前先在90±2℃条件下烘干至少2h，去除水分。
实施例1
将高炉渣、高铝粉煤灰和硅砂均磨细至粒径≤0.124mm，然后混合作为原料；原料中按质量百分比高炉渣占45.6％，高铝粉煤灰占17.4％，硅砂占37％；
准备硼砂、碳酸钠、碳酸钙、偏磷酸钠和粘土作为添加剂；添加剂中硼砂占原料总质量的2％，碳酸钠占原料总质量的6％，碳酸钙占原料总质量的4％，偏磷酸钠占原料总质量的1％，粘土占原料总质量的7％；
将全部原料和添加剂混合形成混合物料，然后用球磨机进行湿磨，混合均匀并制成料浆；湿磨时水、混合物料和磨球的质量比为0.5:1:4；
将料浆注入喷雾造粒器中进行喷雾造粒，制成粉体颗粒；
将粉体颗粒填充到模具中，然后置于加热炉内，进行焙烧发泡造孔；焙烧发泡造孔过程中的温度制度为：炉温从室温以8℃/min的速率升到840℃，保温20min，然后以3℃/min的升温速率升到1135℃，保温60min；
焙烧发泡造孔完成后随炉冷却至常温，获得发泡陶瓷材料；发泡陶瓷材料的体积密度为0.447g/cm3，抗压强度为1.87MPa，导热系数为0.1W/(m·K)。
实施例2
方法同实施例1，不同点在于：
(1)原料中按质量百分比高炉渣占44.4％，高铝粉煤灰占16.7％，硅砂占38.9％；添加剂中硼砂占原料总质量的2％，碳酸钠占原料总质量的3％，碳酸钙占原料总质量的2％，偏磷酸钠占原料总质量的1％，粘土占原料总质量的5％；
(2)以8℃/min的速率升到880℃，保温20min，以3℃/min的速率升到1150℃，保温75min；
(3)发泡陶瓷材料的体积密度为0.564g/cm3，抗压强度为2.74MPa，导热系数为0.15W/(m·K)。
实施例3
方法同实施例1，不同点在于：
(1)原料中按质量百分比高炉渣占48.5％，高铝粉煤灰占20％，硅砂占31.5％；添加剂中硼砂占原料总质量的2％，碳酸钠占原料总质量的3％，碳酸钙占原料总质量的2％，偏磷酸钠占原料总质量的1％，粘土占原料总质量的5％；
(2)以8℃/min的速率升到920℃，保温20min，以3℃/min的速率升到1170℃，保温85min；
(3)发泡陶瓷材料的体积密度为0.603g/cm3，抗压强度为3.1MPa，导热系数为0.20W/(m·K)。
实施例4
方法同实施例1，不同点在于：
(1)原料中按质量百分比高炉渣占42％，高铝粉煤灰占24％，硅砂占34％；添加剂中硼砂占原料总质量的1％，碳酸钠占原料总质量的7％，碳酸钙占原料总质量的1％，偏磷酸钠占原料总质量的1.5％，粘土占原料总质量的4％；
(2)将料浆用磁力搅拌器进行搅拌均匀化，时间30min，
(3)以7℃/min的速率升到800℃，保温30min，以2℃/min的速率升到1100℃，保温90min；
(4)发泡陶瓷材料的体积密度为0.42g/cm3，抗压强度为3.44MPa，导热系数为0.19W/(m·K)。
实施例5
方法同实施例1，不同点在于：
(1)原料中按质量百分比高炉渣占51％，高铝粉煤灰占19％，硅砂占30％；添加剂中硼砂占原料总质量的3％，碳酸钠占原料总质量的2％，碳酸钙占原料总质量的5％，偏磷酸钠占原料总质量的0.5％，粘土占原料总质量的8％；
(2)将料浆用磁力搅拌器进行搅拌均匀化，时间35min，
(3)以9℃/min的速率升到900℃，保温25min，以3℃/min的速率升到1150℃，保温70min；
(4)发泡陶瓷材料的体积密度为0.55g/cm3，抗压强度为2.2MPa，导热系数为0.18W/(m·K)。
实施例6
方法同实施例1，不同点在于：
(1)原料中按质量百分比高炉渣占45％，高铝粉煤灰占15％，硅砂占40％；添加剂中硼砂占原料总质量的1～3％，碳酸钠占原料总质量的6％，碳酸钙占原料总质量的4％，偏磷酸钠占原料总质量的1.5％，粘土占原料总质量的6％；
(2)将料浆用磁力搅拌器进行搅拌均匀化，时间40min，
(3)以10℃/min的速率升到950℃，保温20min，以4℃/min的速率升到1200℃，保温50min；
(4)发泡陶瓷材料的体积密度为0.65g/cm3，抗压强度为1.5MPa，导热系数为0.25W/(m·K)。
Claims (2)
1.一种利用高炉渣和高铝粉煤灰制备发泡陶瓷材料的方法，其特征在于按以下步骤进行：
（1）将高炉渣、高铝粉煤灰和硅砂均磨细至粒径≤0.124mm，然后混合作为原料；原料中按质量百分比高炉渣占42~51%，高铝粉煤灰占15~24%，硅砂占30~40%；所述的高炉渣按质量百分比含SiO2 32~33%，Al2O3 10~11%，Fe2O3 0.9~1.0%， CaO 45~46%，Na2O 0.9~1.2%，TiO2 0.6~0.7%，MgO 6~7%，K2O 0.3~0.4%，其余为杂质；所述的高铝粉煤灰按质量百分比含SiO2 39~40%，Al2O3 46~47%，Fe2O3 4~5%， CaO 3~4%，Na2O 0.3~0.5%，TiO2 1~2%，MgO 0.5~0.8%，K2O 0.7~0.9%，其余为杂质；
（2）准备硼砂、碳酸钠、碳酸钙、偏磷酸钠和粘土作为添加剂；添加剂中硼砂占原料总质量的1~3%，碳酸钠占原料总质量的2~7%，碳酸钙占原料总质量的1~5%，偏磷酸钠占原料总质量的0.5~1.5%，粘土占原料总质量的4~8%；
（3）将原料和添加剂混合形成混合物料，然后用球磨机进行湿磨，混合均匀并制成料浆；料浆中水的重量百分比为30~40%；
（4）将料浆注入喷雾造粒器中进行喷雾造粒，制成粉体颗粒；粉体颗粒的粒径≤0.5mm；
（5）将粉体颗粒填充到模具中，然后置于加热炉内，进行焙烧发泡造孔；焙烧发泡造孔过程中的温度制度为：炉温从室温以7~10℃/min的速率升到800~950℃，保温至少20min，然后以2~4℃/min的升温速率升到1100~1200℃，保温50~90min；
（6）焙烧发泡造孔完成后随炉冷却至常温，获得发泡陶瓷材料。
2.根据权利要求1所述的一种利用高炉渣和高铝粉煤灰制备发泡陶瓷材料的方法，其特征在于所述的发泡陶瓷材料的体积密度为0.4~0.65g/cm3，抗压强度为1.5~3.5MPa，导热系数为0.1~0.25W/(m·K)。
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| CN111470879B (zh) * | 2020-03-24 | 2021-08-20 | 北京科技大学 | 一种常温发泡高温烧制的发泡陶瓷的制备方法 |
| CN111548189A (zh) * | 2020-06-06 | 2020-08-18 | 清远职业技术学院 | 一种用陶瓷抛磨废料和高炉矿渣制备发泡陶瓷材料的方法 |
| CN112723905B (zh) * | 2021-02-02 | 2021-09-14 | 波尔玛(辛集)保温材料有限公司 | 一种建筑节能保温材料及其制备方法 |
| CN112979277B (zh) * | 2021-03-03 | 2022-03-18 | 东北大学 | 一种自析晶构筑吸附位点的多孔功能材料制备方法 |
| CN112898045A (zh) * | 2021-03-31 | 2021-06-04 | 成渝钒钛科技有限公司 | 一种高钛高炉渣多孔吸声陶瓷及其制备方法 |
| CN113072391A (zh) * | 2021-04-22 | 2021-07-06 | 四川双铁科技有限公司 | 一种全固废基多孔陶瓷吸音材料及其制备方法 |
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| CN104744070A (zh) * | 2015-03-25 | 2015-07-01 | 北京大学包头创新研究院 | 粉煤灰轻质隔热发泡陶瓷保温板及其制法和应用 |
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