CN107266085B - 一种锆酸铁钡蓄热材料、制备方法及其应用 - Google Patents
一种锆酸铁钡蓄热材料、制备方法及其应用 Download PDFInfo
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- 238000005338 heat storage Methods 0.000 title claims abstract description 74
- 239000011232 storage material Substances 0.000 title claims abstract description 57
- 229910021523 barium zirconate Inorganic materials 0.000 title claims abstract description 29
- YADLKQDEUNZTLC-UHFFFAOYSA-N [Fe].[Ba] Chemical compound [Fe].[Ba] YADLKQDEUNZTLC-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims abstract description 32
- 239000002994 raw material Substances 0.000 claims abstract description 29
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 23
- 239000011707 mineral Substances 0.000 claims abstract description 23
- 229910052845 zircon Inorganic materials 0.000 claims abstract description 22
- 239000004576 sand Substances 0.000 claims abstract description 21
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims abstract description 21
- DQBAOWPVHRWLJC-UHFFFAOYSA-N barium(2+);dioxido(oxo)zirconium Chemical compound [Ba+2].[O-][Zr]([O-])=O DQBAOWPVHRWLJC-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 16
- 239000010959 steel Substances 0.000 claims abstract description 16
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000010428 baryte Substances 0.000 claims abstract description 6
- 229910052601 baryte Inorganic materials 0.000 claims abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 65
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 61
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 60
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 26
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 25
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 24
- 239000012535 impurity Substances 0.000 claims description 19
- 239000012141 concentrate Substances 0.000 claims description 16
- 229910052840 fayalite Inorganic materials 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 9
- 238000010304 firing Methods 0.000 claims description 8
- 230000001172 regenerating effect Effects 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 3
- 239000008187 granular material Substances 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
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- 239000007921 spray Substances 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 27
- 238000005245 sintering Methods 0.000 abstract description 23
- 239000004615 ingredient Substances 0.000 abstract description 14
- 229910052742 iron Inorganic materials 0.000 abstract description 14
- 239000000203 mixture Substances 0.000 abstract description 14
- 239000000126 substance Substances 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 239000000919 ceramic Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000002440 industrial waste Substances 0.000 abstract 1
- 230000004584 weight gain Effects 0.000 abstract 1
- 235000019786 weight gain Nutrition 0.000 abstract 1
- 239000011449 brick Substances 0.000 description 19
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 15
- 239000000047 product Substances 0.000 description 14
- 239000000377 silicon dioxide Substances 0.000 description 11
- 239000004927 clay Substances 0.000 description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 238000002485 combustion reaction Methods 0.000 description 8
- 238000005096 rolling process Methods 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 229910052681 coesite Inorganic materials 0.000 description 5
- 229910052906 cristobalite Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 229910052682 stishovite Inorganic materials 0.000 description 5
- 229910052905 tridymite Inorganic materials 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 229910006501 ZrSiO Inorganic materials 0.000 description 4
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000010431 corundum Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 229910052609 olivine Inorganic materials 0.000 description 3
- 239000010450 olivine Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000010606 normalization Methods 0.000 description 2
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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Abstract
本发明公开了一种锆酸铁钡蓄热材料、制备方法及其应用,该蓄热材料主要由锆酸钡和硅酸铁组成;该蓄热材料以锆英石砂、轧钢铁皮(铁鳞)为原料,添加铅锌尾矿中精选的重晶石为增重原料,通过配料、化学组成、矿物组成和烧成温度、气氛的控制,制备出导热性能好、体积密度大、蓄热量大、软化温度高、表面致密瓷化抗侵蚀性能优良的换热材料。一种蓄热材料的制备方法包括以下步骤:步骤一、原料的选取及化学、矿物组成控制;步骤二、蓄热材料的配料计算;步骤三、蓄热材料成型坯料制备、成型;步骤四、干燥和烧成。高导热高蓄热材料的制备方法简单,蓄热量大、换热快、热风温度高、使用寿命长,生产成本低。可综合利用工业废渣,环保效果显著。
Description
技术领域
本发明属于高温结构材料行业,是热工设备中用于高温烟气热能回收换热装置中使用的一种锆酸铁钡蓄热材料、制备方法及其应用。
背景技术
蓄热式换热器在很多工业过程中都有应用,燃烧中助燃空气的预热就是一个典型的应用领域,例如:焦炉、玻璃熔窑、热风炉等。蓄热式换热器的原理是利用燃烧后排放烟气中的热能,用于预热助燃空气,从而达到燃烧低品位燃料、提高燃烧过程的热效率、实现更高的燃烧反应温度等目的。
蓄热式换热器通过多通道高温结构材料的短暂能量储存,将热量从一种流体传递给另外一种流体。首先,在习惯上称为加热周期的时间内,下部被预热气体进气阀关闭,热气流从蓄热式换热器中的蓄热材料上部的不同通道流过,热量从气流传递到蓄热材料,气流温度降低,蓄热材料温度升高,温度降低的热气流从蓄热式换热器下部进入烟道排放。加热周期结束时,蓄热式换热器上部热气流进气阀关闭,下部被预热气体进气阀打开,气体流动方向进行切换,冷流体(助燃空气)流经蓄热体。在冷却周期,流体从蓄热式换热器的蓄热材料吸收热量,供燃烧的助燃空气被加热。因此,对于常规的流向变换,蓄热体内的蓄热材料交替性的与冷热流体进行换热。重复上述过程,有两套并列设备或同一设备中具有两套并列蓄热体通道同时工作就能使换热连续进行。
蓄热式换热器中的蓄热材料多为耐火材料,如:高炉热风炉中选用的有硅质、高铝质和粘土质六孔或八孔格子砖,玻璃熔窑蓄热室使用的电熔锆刚玉十字型格子砖、致密粘土砖等蓄热材料。蓄热式换热器中的蓄热材料要求是:一是导热性能好,即被加热和放热速度快,热气流从底部排除温度低,顶部被加热助燃空气温度高,能源利用率高;二是热容量大,即比热容大,体积密度高;三是热震稳定性好,抗腐蚀,不软化变形。
目前应用的硅质、高铝质、电熔锆刚玉和粘土质蓄热材料存在问题是导热系数低,换热慢;体积密度低,蓄热量小。硅质蓄热材料的体积密度不超过1.95g/cm3,1000℃导热系数约为1.74w/m.k;高铝制品体积密度不超过2.85g/cm3,1000℃导热系数约为2.30w/m.k;高致密粘土砖体积密度不超过2.30g/cm3,1000℃导热系数约为1.28w/m.k;电熔锆刚玉蓄热材料生产成本极高。高导热高蓄热材料的发明提高了蓄热式换热器的换热效率,提高了能源利用率。
发明内容
针对现有技术中的缺陷和不足,本发明目的在于利用尾矿提取物,提供一种锆酸铁钡蓄热材料、制备方法及其应用,取代目前的耐火蓄热材料。
为了实现上述任务,本发明采取如下的技术解决方案:
一种锆酸铁钡蓄热材料,包括氧化硅、氧化亚铁、氧化钡和氧化锆。
具体的,按质量分数计,氧化硅为12%~14%,氧化亚铁为28%~30%,氧化钡为30%~32%,氧化锆为24%~26%。
或者,氧化硅和氧化亚铁以铁橄榄石矿物相的形式存在,铁橄榄石矿物相含量为38%~42%;所述的氧化钡和氧化锆以锆酸钡矿物相的形式存在,锆酸钡矿物相含量为52%~56%。
还可以,按质量百分比计,铁橄榄石矿物相中氧化硅为29%~30%,氧化亚铁为70%~71%,两者百分比之和为100%;
按质量百分比计,锆酸钡矿物相中氧化钡为55%~56%,氧化锆为44%~45%,两者百分比之和为100%。
另外,还包括杂质,杂质的含量为1%~4%。
所述的锆酸铁钡蓄热材料的制备方法,其特征在于,制备原料包括锆英石砂、铅锌尾矿选出的重晶石精矿和轧钢铁皮,控制原料中成分氧化钡、氧化硅、氧化亚铁和氧化锆含量总和为96%~99%,杂质成分为1~4%;
制备原料经喷雾增湿造粒制成坯料,坯料经陈化、干燥及干燥压制成坯体后烧制即得锆酸铁钡蓄热材料,烧制温度为1550~1580℃。
具体的,制备原料在喷雾增湿造粒前球磨成颗粒,颗粒的粒径为筛余量250目<1.0wt%和325目<4.0wt%。
所述的锆酸铁钡蓄热材料作为蓄热式换热器中蓄热材料的应用。
所述的锆酸铁钡蓄热材料的制备方法制备得到的锆酸铁钡蓄热材料作为蓄热式换热器中蓄热材料的应用。
与现有技术相比,本发明的优点在于:
本发明的一种锆酸铁钡蓄热材料与目前广泛应用的硅质、高铝质、粘土质蓄热格子砖相比,主晶相为铁橄榄石和锆酸钡,耐火度大于1650℃,硬度7左右,密度大于4.67-4.86g/cm3,蓄热量大;由于原料中含有30%左右的高导热性成分氧化亚铁,其1000℃导热系数约为黏土砖、高铝砖的2.5倍,硅砖的3.5倍,蓄热量为黏土砖、高铝砖的1.5倍,硅砖的2.2倍。与炼铜废渣制备的硅酸铁蓄热材料相比,体积密度平均提高了16.5%(硅酸铁蓄热材料体积密度4.08g/cm3-4.10g/cm3,锆酸铁钡蓄热材料体积密度4.67g/cm3-4.86g/cm3),蓄热量提高了20%左右,耐火度由1350℃提高至1650℃。本发明的一种蓄热材料表面结构致密,抗渣性能、抗粉尘侵蚀性能优良。
具体实施方式
2010年,西安建筑科技大学承担了陕西省“13115”科技创新工程重大科技专项“陕南铅锌尾矿砂及废渣梯级综合利用示范”项目,研究开发铅锌尾矿砂及废渣综合利用。其中宁强山坪铅锌选矿厂的铅锌尾矿硫酸钡含量高达50%左右,具有选取工业价值。硫酸钡经煅烧分解后可得到氧化钡,氧化钡密度大、导热性好,将其与高密度的氧化锆材料结合,应用于高导热高蓄热材料的制备,使用效果远优于目前使用的粘土质、硅质、高铝质等硅酸盐类蓄热材料。
本发明的一种锆酸铁钡蓄热材料导热性能和蓄热量远高于目前使用的蓄热室用耐火砖。通过成分调节和过程控制制备蓄热材料,实现了资源的综合利用。
一种锆酸铁钡蓄热材料,包括氧化硅、氧化钡、氧化亚铁和氧化锆。
具体的,按质量分数计,氧化钡为30%~32%,氧化硅为12%~14%,氧化亚铁为28%~30%,氧化锆为24%~26%。上述为蓄热材料的有效成分的含量,还包括杂质,杂质的含量为1%~4%,有效成分和杂质的含量总和为100%,杂质或引入的烧结剂与少量氧化钡、氧化亚铁和氧化锆形成玻璃相,促进烧结,起到了陶瓷结合作用,降低了产品的气孔率,提高了强度。
更具体的,氧化硅和氧化亚铁以铁橄榄石(密度4.34g/cm3)矿物相的形式存在,铁橄榄石矿物相含量为40%~44%;按质量百分比计,铁橄榄石矿物相中氧化硅为29%~30%,氧化亚铁为70%~71%,两者百分比之和为100%。所述的氧化钡和氧化锆以锆酸钡(熔点2500℃,密度5.52g/cm3)矿物相的形式存在,锆酸钡矿物相含量为54%~58%;按质量百分比计,锆酸钡矿物相中氧化钡为55%~56%,氧化锆为44%~45%,两者百分比之和为100%。氧化硅与氧化亚铁完全形成铁橄榄石、氧化锆与氧化钡完全形成锆酸钡产品性能更稳定。铁橄榄石的形成使产品抗氧化性能大大提高,锆酸钡的形成提高了产品的体积密度和蓄热量
锆酸铁钡蓄热材料的制备方法,包括原料的选取、配料计算和制备工艺。
原料采用锆英石砂(ZrSiO4)、铅锌尾矿选出的重晶石精矿(BaSO4)和轧钢铁皮(FeO)。采用锆英石砂的生产成本远低于采用脱硅氧化锆,但对锆酸铁钡体系的密度和导热、蓄热性能影响不大,毕竟氧化硅的带入量只有12%左右,氧化硅的引入可以减少烧成后冷却过程中的开裂。为了满足氧化硅与氧化亚铁完全形成铁橄榄石、氧化锆与氧化钡完全形成锆酸钡的要求,锆英石砂(ZrSiO4)、碳酸钡精矿(BaSO4)和铁精矿粉(FeO)的理论计算配比如下:
本发明中采用的锆英石砂(ZrSiO4)、铅锌尾矿选出的重晶石精矿(BaSO4)和轧钢铁皮(FeO)的化学组成见表1,锆英石砂、重晶石精矿均为矿产品原料,轧钢铁皮为轧钢厂轧钢过程副产品。其化学组成应满足如下条件:wt%:
表1
原料 | ZrO<sub>2</sub> | SiO<sub>2</sub> | BaO | TFeO | TiO<sub>2</sub> | 其他杂质总量 | 灼减 |
锆英石砂 | 65-66 | 33-34 | -- | <0.25 | <0.40 | <2.0 | <0.25 |
硫酸钡精矿 | -- | 0.2-0.5 | 65-66 | 0.1-2.0 | -- | <2.5 | 33-35 |
轧钢铁皮 | -- | 2.0-3.0 | -- | 95-98 | -- | <1.5 | <0.50 |
锆英石砂(ZrSiO4)的组成:ZrSiO4 ZrO2 SiO2
摩尔质量依次为(占比%):183.3(100%) 123.2(67.2%) 60.1(32.8%)
锆英石中的氧化硅全部生成铁橄榄石需要氧化亚铁数量:
SiO2+2FeO→2FeO·SiO2
60.1 143.7 203.8(摩尔质量(占比%))需氧化亚铁143.7;
锆英石中的氧化锆全部生成锆酸钡需要氧化钡数量:
ZrO2+BaO→BaZrO3
123.2 153.3 276.5(摩尔质量(占比%))需氧化钡153.3;
BaSO4→BaO+SO3↑
233.4 53.3(摩尔质量(占比%))需硫酸钡233.4;
以锆英石砂、轧钢铁皮和硫酸钡精矿为原料制备高蓄热材料,氧化硅和氧化亚铁以铁橄榄石矿物相的形式存在,氧化钡和氧化锆以锆酸钡矿物相的形式存在,理论上原料的配比为:
锆英石砂:轧钢铁皮:碳酸钡精矿=183.3:143.7:233.4,即理论配比为:锆英石砂占32.7%,轧钢铁皮占25.7%,硫酸钡精矿占41.6%。按质量分数计,氧化钡:氧化硅:氧化亚铁:氧化锆=153.3:60.1:143.7:123.2,即理论配比为:氧化钡占31.8%,氧化硅为12.5%,氧化亚铁为29.9%,氧化锆为25.6%。
锆酸铁钡蓄热材料的制备,包括原料选取、配料、细磨制粉、造粒、成型和烧成。
控制原料中主成分氧化钡、氧化硅、氧化亚铁、氧化锆含量不少于96%,杂质成分为1~4%。原料按确定的比例准确称量后,入球磨机共磨12h,保证共磨粉筛余量250目<1.0wt%、325目<4.0wt%。以浓度为1.5%的羧甲基纤维素溶液为结合剂,经喷雾增湿造粒,控制临界粒度为2mm即为合格坯料。坯料陈化24h以上,采用液压成型工艺,成形圧力为65MPa。成型后的坯体经干燥,残余水分小于0.7%,即可入窑烧成。烧成温度为1550~1580℃,强还原气氛烧成。原料纯度较高(杂质总量≤1.25%)、烧成温度偏高时可加入碳酸钠烧结剂(原料杂质种类、数量对烧结温度影响复杂,基本判断依据为烧成温度上限设定为1580℃,锆酸铁钡蓄热材料的显气孔率>7.0%时,需加入碳酸钠烧结剂)。
具体的,本发明的锆酸铁钡蓄热材料的制备方法包括下列步骤:
步骤一、原料的选取和成分的控制。选用的原料化学组成见表2.
表2原料的化学组成(wt%)
原料 | ZrO<sub>2</sub> | SiO<sub>2</sub> | BaO | TFeO | TiO<sub>2</sub> | CaO | MgO | Al<sub>2</sub>O<sub>3</sub> | Na<sub>2</sub>O | K<sub>2</sub>O | 灼减 |
锆英石砂 | 65.13 | 33.38 | -- | 0.21 | 0.38 | 0.01 | 0.02 | 0.63 | 0.02 | 0.05 | 0.17 |
硫酸钡精矿 | -- | 0.21 | 65.35 | 0.03 | -- | 0.02 | 0.01 | 0.19 | -- | -- | 34.19 |
轧钢铁皮 | -- | 2.57 | -- | 95.32 | 0.01 | 0.32 | 0.12 | 1.24 | 0.02 | 0.01 | 0.39 |
硫酸钡精矿以硫酸盐形式存在,灼减量高达34.19%,配料按烧后组成计算,锆英石砂、轧钢铁皮灼减量较小,配料时不考虑灼减量。
配料控制氧化钡为30~32%,氧化硅为12%~14%,氧化亚铁为28%~30%,氧化铁小于2%,氧化锆为24%~26%(参照理论配比:锆英石砂占32.7%,轧钢铁皮占25.7%,硫酸钡精矿占41.6%,反算配料的化学组成)。
控制杂质的含量为1%~4%。杂质含量高荷重软化温度下降,杂质含量太低,烧结困难。
步骤二、配料与共磨。按计算配比,准确称量配料,入球磨机共磨12h,保证共磨粉筛余量250目<1.0wt%、325目<4.0wt%。
步骤三、坯料的制备与成型。以浓度为1.5%的羧甲基纤维素溶液为结合剂,经喷雾增湿造粒,控制临界粒度为2mm即为合格坯料。坯料陈化24h以上,采用液压成型工艺,成型圧力为65MPa。
步骤四、干燥与烧成。成型后的坯体经干燥,残余水分小于0.7%,即可入窑烧成。烧成温度为1550~1580℃,强还原气氛烧成。烧成后的制品经冷却后,表面温度低于120℃才能出窑。
以下结合具体实施例对本发明进行具体的说明。
实施例一:
步骤一、按锆英石砂占32.7%,轧钢铁皮占25.7%,硫酸钡精矿占41.6%配比计算如下:
由配料计算结果可知:配料满足氧化钡、氧化硅、氧化亚铁和氧化锆含量要求。归一化后杂质总含量为1.21%,原料纯度较高。
步骤二、按锆英石砂占32.7%,轧钢铁皮占25.7%,硫酸钡精矿占41.6%准确称量配料,入球磨机共磨12h,实测共磨粉筛余量250目<0.84wt%、325目<3.66wt%。
步骤三、以浓度为1.5%的羧甲基纤维素溶液为结合剂,经喷雾增湿造粒,造粒料过2mm筛,即为合格坯料。坯料陈化27h,采用液压成型工艺,成型压力为65MPa。
步骤四、成型后的坯体经自然干燥48h后入窑烧成。烧成温度为1580℃,保温4h,强还原气氛烧成。烧成后的制品经自然冷却至仪表显示温度为90℃出窑。
检测产品的理化指标如下:体积密度4.67g/cm3,1000℃导热系数5.42w/m.k,显气孔率7.20%,耐压强度201MPa,耐火度1670℃。1000℃导热系数为高铝质的2.35倍,硅砖的3.11倍,高致密粘土砖的4.23倍;蓄热量为高铝砖的1.64倍,硅砖的2.40倍,高致密粘土砖的2.03倍。最高使用温度可达1500℃。
实施例二:
本实施例与实施例一的不同之处在于:
针对实例一中氧化亚铁和氧化锆含量略偏低,烧结温度偏高,产品显气孔率偏高问题,对配料组成进行了调整。原料配比如下:
由配料计算结果可知:配料满足氧化钡、氧化硅、氧化亚铁和氧化锆含量要求。引入1%碳酸钠烧结剂,归一化后杂质总含量为1.59%,其中强熔剂氧化钾、氧化钠含量为0.5%,可降低烧结温度。
检测产品的理化指标如下:体积密度4.86g/cm3,1000℃导热系数5.51w/m.k,显气孔率3.09%,耐压强度222MPa,耐火度1610℃。蓄热量、导热系数均高于实施例一的指标。最高使用温度略有下降,但仍远高于蓄热材料的使用温度。
实施例三:
本实施例与实施例二的不同之处在于:
步骤四、成型后的坯体经自然干燥48h后入窑烧成。烧成温度为1550℃,保温4h,强还原气氛烧成。
检测产品的理化指标如下:体积密度4.72g/cm3,1000℃导热系数5.45w/m.k,显气孔率4.98%,耐压强度209MPa,耐火度1610℃。产品理化指标介于实施例一和实施例二之间,但烧结温度降低了30℃。
Claims (6)
1.一种锆酸铁钡蓄热材料,其特征在于,包括氧化硅、氧化亚铁、氧化钡和氧化锆;
按质量分数计,氧化硅为12%~14%,氧化亚铁为28%~30%,氧化钡为30%~32%,氧化锆为24%~26%;
氧化硅和氧化亚铁以铁橄榄石矿物相的形式存在,铁橄榄石矿物相含量为38%~42%;所述的氧化钡和氧化锆以锆酸钡矿物相的形式存在,锆酸钡矿物相含量为52%~56%;
按质量百分比计,铁橄榄石矿物相中氧化硅为29%~30%,氧化亚铁为70%~71%,两者百分比之和为100%;
按质量百分比计,锆酸钡矿物相中氧化钡为55%~56%,氧化锆为44%~45%,两者百分比之和为100%。
2.如权利要求1所述的锆酸铁钡蓄热材料,其特征在于,还包括杂质,杂质的含量为1%~4%。
3.权利要求1-2任一权利要求所述的锆酸铁钡蓄热材料的制备方法,其特征在于,制备原料包括锆英石砂、铅锌尾矿选出的重晶石精矿和轧钢铁皮,控制原料中成分氧化钡、氧化硅、氧化亚铁和氧化锆含量总和为96%~99%,杂质成分为1~4%;
制备原料经喷雾增湿造粒制成坯料,坯料经陈化、干燥及干燥压制成坯体后烧制即得锆酸铁钡蓄热材料,烧制温度为1550~1580℃。
4.如权利要求3所述的锆酸铁钡蓄热材料的制备方法,其特征在于,制备原料在喷雾增湿造粒前球磨成颗粒,颗粒的粒径为筛余量250目<1.0wt%和325目<4.0wt%。
5.权利要求1-2任一权利要求所述的锆酸铁钡蓄热材料作为蓄热式换热器中蓄热材料的应用。
6.权利要求3或4所述的锆酸铁钡蓄热材料的制备方法制备得到的锆酸铁钡蓄热材料作为蓄热式换热器中蓄热材料的应用。
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