CN108546086A - 一种利用赤泥制备高强度多孔陶瓷材料的方法 - Google Patents
一种利用赤泥制备高强度多孔陶瓷材料的方法 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 31
- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000000463 material Substances 0.000 claims abstract description 45
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000005187 foaming Methods 0.000 claims abstract description 19
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 18
- 239000002002 slurry Substances 0.000 claims abstract description 18
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 17
- 239000004576 sand Substances 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 239000004927 clay Substances 0.000 claims abstract description 14
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 13
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 13
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 13
- 229910021538 borax Inorganic materials 0.000 claims abstract description 11
- 239000004328 sodium tetraborate Substances 0.000 claims abstract description 11
- 235000010339 sodium tetraborate Nutrition 0.000 claims abstract description 11
- 239000000654 additive Substances 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 9
- 230000000996 additive effect Effects 0.000 claims abstract description 8
- 239000008187 granular material Substances 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 238000001238 wet grinding Methods 0.000 claims abstract description 7
- 239000003595 mist Substances 0.000 claims abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 13
- 230000006835 compression Effects 0.000 claims description 8
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- 239000012535 impurity Substances 0.000 claims description 4
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052681 coesite Inorganic materials 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- 239000002689 soil Substances 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- 229910052682 stishovite Inorganic materials 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052905 tridymite Inorganic materials 0.000 claims description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 3
- 239000003292 glue Substances 0.000 claims 1
- 238000001816 cooling Methods 0.000 abstract 1
- 239000011148 porous material Substances 0.000 description 11
- 239000000919 ceramic Substances 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 4
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- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
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- 238000004131 Bayer process Methods 0.000 description 1
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- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
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Abstract
一种利用赤泥制备高强度多孔陶瓷材料的方法,按以下步骤进行:(1)准备赤泥作为原料;(2)准备硅砂和粘土作为辅料;准备MgO、硼砂、Na2CO3和CaCO3作为添加剂;将原料、辅料和添加剂混合制成混合物料;(3)将混合物料用球磨机进行湿磨制成料浆;(4)喷雾造粒;(5)将粉体颗粒填充到模具内,于加热炉中进行焙烧发泡造孔;(6)随炉冷却。本发明的方法工艺流程简短,成本低,赤泥的利用率高,产品导热系数低,防火防潮性能良好。
Description
技术领域
本发明属于建筑材料技术领域,特别涉及一种利用赤泥制备高强度多孔陶瓷材料的方法。
背景技术
随着环境问题的日益严重和自然资源的逐渐减少,人们对大宗工业固体废弃物资源化利用技术的渴望也愈发迫切。赤泥是氧化铝提取过程中产生的污染性固体废弃物,是铝工业中产生的主要废渣,按照不同的生产工艺分为拜耳法赤泥、烧结法赤泥和联合法赤泥。当前的铝土矿品位和生产技术条件下,平均每生产1吨氧化铝产生1~2吨赤泥,我国的氧化铝产量居世界之最,截止2015年,我国氧化铝产能已达6800万吨,占全球总产能的50.2%,这意味着我国的赤泥产能约为6800~13600万吨。
目前,我国的赤泥处理主要依靠露天筑坝堆存,大量的赤泥不能得到无害化处理和资源化利用,会导致如下危害:(1)容易造成严重的环境污染。赤泥作为一种强碱性(10<pH),且含有重金属的微细颗粒废渣,大量露天存放,其中的污染物随雨水渗漏,污染土壤和水体,而干燥状态下,赤泥粉尘随风飘散,造成大气污染;(2)存在安全隐患。使用大面积的土地长期堆存赤泥,不仅占用大量的土地资源,还存在着溃坝的危险,一旦赤泥尾矿溃坝,对当地生态***的打击是灾难性的;(3)造成资源的浪费。赤泥成分与性质复杂,但其中金属氧化物含量丰富,自身颗粒的分散性好,是极具潜力的固废资源,但目前仍不能进行大规模的资源化利用;因此,探索出能够直接大量消耗赤泥,并得到高价值产品的资源化利用技术,已经十分紧迫。
发明内容
本发明的目的是提供一种利用赤泥制备高强度多孔陶瓷材料的方法,采用赤泥作为原料,使用粘土和硅砂作为辅料,添加氧化镁等添加剂,经中温焙烧发泡成型,大规模资源化利用赤泥的同时,制得高强度多孔陶瓷材料。
本发明的方法按以下步骤进行:
1、准备赤泥作为原料;
2、准备硅砂和粘土作为辅料;准备MgO、硼砂、Na2CO3和CaCO3作为添加剂;将原料、辅料和添加剂混合制成混合物料,混合物料按质量百分比赤泥占43~68%,硅砂占10~22%,粘土占13~27%,MgO占0.5~2.5%,硼砂占3~6%,Na2CO3占2~5%,CaCO3占2~5%;
3、将混合物料用球磨机进行湿磨,将物料混合均匀并制成料浆;湿磨时水、全部原料和磨球的质量比为0.8:1:4;
4、将料浆注入喷雾造粒器中进行喷雾造粒,制成粉体颗粒;
5、将粉体颗粒填充到模具内,再置于加热炉中,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8~13℃/min的速率升到800~900℃,保温至少10min,然后以3.5~7.5℃/min的升温速率升到1000~1200℃,保温40~90min,完成焙烧发泡造孔;
6、焙烧发泡造孔后的物料随炉冷却至常温,获得高强度多孔陶瓷材料。
上述的赤泥按质量百分比含Fe2O3 28~29%,Al2O3 19~20%,SiO2 10~11%,CaO15~16%,Na2O 5~6%,TiO2 6~7%,MgO 0.5~0.8%,K2O 0.1~0.2%,其余为杂质。
上述的高强度多孔陶瓷材料的体积密度为0.5~0.75g/cm3,抗压强度为5~15MPa,导热系数为0.10~0.30W/(m·K)。
上述的料浆中水的重量百分比为30~40%。
上述方法中,为保证料浆各组分混合均匀并控制料浆中的水含量,将料浆从球磨机中取出后在80±5℃搅拌30~40min。
多孔陶瓷材料是骨架中存在有大量孔结构的无机非金属材料,依靠其中孔洞结构和材料本身性质来实现所需要的隔热、轻质、隔音等物理和化学性能;按孔结构,多孔陶瓷可分为开口气孔型、闭口气孔型和贯通气孔型;闭口气孔型多孔陶瓷可通过在原料中添加造孔剂,采用高温熔融发泡造孔的方式制备;造孔剂在高温下发生化学反应产生气体,在具有一定粘度的熔体中形成气孔,冷凝后保存在材料中得到孔结构,该过程需要碱金属或碱土金属元素的存在,造孔剂才能持续反应产生气体;而赤泥中恰好具有较高的碱含量,并且其主要组分与陶瓷原料的组分类似,通过配方设计,适当添加辅料,在中温炉中烧制,即可得到强度高、孔结构均匀、体积密度低、隔热性能好的多孔陶瓷材料。
本发明的方法具有以下优点:1)工艺流程简短,没有复杂的操作过程;2)所用原料赤泥、粘土、硅砂均为微细颗粒粉料,不需要破碎,球磨混匀的成本低;3)赤泥的利用率高,赤泥添加量高达43~68%;4)由于赤泥中的铁含量较高,熔体中大量碱金属和碱土金属存在,促使了铁与硅与碱金属和碱土金属反应生成铁硅酸盐,极大的提高了多孔陶瓷材料强度,同时由于材料中闭合气孔的大量存在,使得材料导热系数低,防火防潮性能良好。
通过实验验证,使用赤泥制备多孔陶瓷隔热材料的方法得到的样品本发明提供的方法得到的多孔陶瓷材料各方面性能优异,可以作为隔热材料,在工业和建筑领域得到应用。
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。
本发明实施例中的赤泥在使用前,先在80±2℃条件下烘干至少2h去除水分。
本发明实施例中采用的赤泥的干粉料粒径≤0.074mm。
本发明实施例中赤泥在适用前先筛分去除杂物,采用筛子筛分出粒径≤0.074mm的部分作为原料。
本发明实施例中采用的硅砂粒径<0.124mm。
本发明实施例中采用的粘土粒径<0.074mm。
本发明实施例中采用的MgO、硼砂(Na2B4O7·10H2O)、Na2CO3和CaCO3为市购产品。
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。
本发明实施例中的粉体颗粒的粒径≤0.5mm。
本发明实施例中料浆中水的重量百分比为30~40%。
本发明实施例中所使用的赤泥来自广西,主要成分按质量百分比含Fe2O328.84%,Al2O319.85%,SiO2 10.65%,CaO 15.66%,Na2O 5.09%,TiO2 6.12%,MgO0.528%,K2O 0.138%,其余为杂质。
实施例1
准备赤泥作为原料;
准备硅砂和粘土作为辅料;准备MgO、硼砂、Na2CO3和CaCO3作为添加剂;将原料、辅料和添加剂混合制成混合物料,混合物料准中按质量百分比赤泥占45%,硅砂占20%,粘土占25%,MgO占1%,硼砂占4%,Na2CO3占2.5%,CaCO3占2.5%;
将全部原料用球磨机进行湿磨,将物料混合均匀并制成料浆;湿磨时水、全部原料和磨球的质量比为0.8:1:4;
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内,再置于加热炉中,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10℃/min的速率升到850℃,保温10min,然后以3.5℃/min的升温速率升到1000℃,保温90min,完成焙烧发泡造孔;
焙烧发泡造孔后的物料随炉冷却至常温,获得高强度多孔陶瓷材料;高强度多孔陶瓷材料的体积密度为0.527g/cm3,抗压强度为6.5MPa,导热系数为0.17W/(m·K)。
实施例2
方法同实施例1,不同点在于:
(1)混合物料中按质量百分比赤泥占50%,硅砂占20%,粘土占20%,MgO占2.5%,硼砂占3.5%,Na2CO3占3%,CaCO3占4%;
(2)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800℃,保温15min,;以4℃/min的速率升到1050℃,保温80min;
(3)高强度多孔陶瓷材料的体积密度为0.603g/cm3,抗压强度为7.2MPa,导热系数为0.20W/(m·K)。
实施例3
方法同实施例1,不同点在于:
(1)混合物料中按质量百分比赤泥占62%,硅砂占13%,粘土占14%,MgO占0.5%,硼砂占4.5%,Na2CO3占2.5%,CaCO3占3.5%;
(2)焙烧发泡造孔过程中的温度制度为:炉温从室温以13℃/min的速率升到900℃,保温20min,;以4.5℃/min的速率升到1100℃,保温70min;
(3)高强度多孔陶瓷材料的体积密度为0.722g/cm3,抗压强度为10.6MPa,导热系数为0.28W/(m·K)。
实施例4
方法同实施例1,不同点在于:
(1)混合物料中按质量百分比赤泥占43%,硅砂占22%,粘土占27%,MgO占1%,硼砂占3%,Na2CO3占2%,CaCO3占2%;
(2)料浆从球磨机中取出后在80±5℃搅拌35min
(3)焙烧发泡造孔过程中的温度制度为:炉温从室温以9℃/min的速率升到850℃,保温15min,;以5℃/min的速率升到1150℃,保温60min;
(4)高强度多孔陶瓷材料的体积密度为0.63g/cm3,抗压强度为12.5MPa,导热系数为0.14W/(m·K)。
实施例5
方法同实施例1,不同点在于:
(1)混合物料中按质量百分比赤泥占68%,硅砂占10%,粘土占13%,MgO占1.5%,硼砂占3.5%,Na2CO3占2%,CaCO3占2%;
(2)料浆从球磨机中取出后在80±5℃搅拌30min
(3)焙烧发泡造孔过程中的温度制度为:炉温从室温以12℃/min的速率升到900℃,保温15min,;以6℃/min的速率升到1150℃,保温50min;
(4)高强度多孔陶瓷材料的体积密度为0.71g/cm3,抗压强度为6.9MPa,导热系数为0.26W/(m·K)。
实施例6
方法同实施例1,不同点在于:
(1)混合物料中按质量百分比赤泥占52%,硅砂占14%,粘土占16%,MgO占2%,硼砂占6%,Na2CO3占5%,CaCO3占5%;
(2)料浆从球磨机中取出后在80±5℃搅拌40min
(3)焙烧发泡造孔过程中的温度制度为:炉温从室温以11℃/min的速率升到880℃,保温15min,;以7.5℃/min的速率升到1200℃,保温40min;
(4)高强度多孔陶瓷材料的体积密度为0.65g/cm3,抗压强度为8.3MPa,导热系数为0.29W/(m·K)。
Claims (4)
1.一种利用赤泥制备高强度多孔陶瓷材料的方法,其特征在于按以下步骤进行:
(1)准备赤泥作为原料;
(2)准备硅砂和粘土作为辅料;准备MgO、硼砂、Na2CO3和CaCO3作为添加剂;将原料、辅料和添加剂混合制成混合物料,混合物料按质量百分比赤泥占43~68%,硅砂占10~22%,粘土占13~27%,MgO占0.5~2.5%,硼砂占3~6%,Na2CO3占2~5%,CaCO3占2~5%;
(3)将混合物料用球磨机进行湿磨,将物料混合均匀并制成料浆;湿磨时水、全部原料和磨球的质量比为0.8:1:4;
(4)将料浆注入喷雾造粒器中进行喷雾造粒,制成粉体颗粒;
(5)将粉体颗粒填充到模具内,再置于加热炉中,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8~13℃/min的速率升到800~900℃,保温至少10min,然后以3.5~7.5℃/min的升温速率升到1000~1200℃,保温40~90min,完成焙烧发泡造孔;
(6)焙烧发泡造孔后的物料随炉冷却至常温,获得高强度多孔陶瓷材料。
2.根据权利要求1所述的一种利用赤泥制备高强度多孔陶瓷材料的方法,其特征在于所述的赤泥按质量百分比含Fe2O3 28~29%,Al2O3 19~20%,SiO2 10~11%,CaO 15~16%,Na2O 5~6%,TiO2 6~7%,MgO 0.5~0.8%,K2O 0.1~0.2%,其余为杂质。
3.根据权利要求1所述的一种利用赤泥制备高强度多孔陶瓷材料的方法,其特征在于所述的高强度多孔陶瓷材料的体积密度为0.5~0.75g/cm3,抗压强度为5~15MPa,导热系数为0.10~0.30W/(m·K)。
4.根据权利要求1所述的一种利用赤泥制备高强度多孔陶瓷材料的方法,其特征在于步骤(3)中,为保证料浆各组分混合均匀并控制料浆中的水含量,将料浆从球磨机中取出后在80±5℃搅拌30~40min。
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