CN115448700B - 精炼炉炉底用镁质捣打料及其制备工艺 - Google Patents
精炼炉炉底用镁质捣打料及其制备工艺 Download PDFInfo
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- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 44
- 239000011777 magnesium Substances 0.000 title claims abstract description 44
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000007670 refining Methods 0.000 title claims abstract description 33
- 239000000463 material Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 193
- 239000002245 particle Substances 0.000 claims abstract description 125
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 98
- 239000002699 waste material Substances 0.000 claims abstract description 75
- 239000011449 brick Substances 0.000 claims abstract description 74
- 239000000843 powder Substances 0.000 claims abstract description 63
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 43
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000001095 magnesium carbonate Substances 0.000 claims abstract description 37
- 235000014380 magnesium carbonate Nutrition 0.000 claims abstract description 37
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims abstract description 37
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims abstract description 37
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 36
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000010457 zeolite Substances 0.000 claims abstract description 36
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 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 29
- 239000004576 sand Substances 0.000 claims abstract description 24
- 229910052845 zircon Inorganic materials 0.000 claims abstract description 24
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 20
- 239000011029 spinel Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 7
- 239000011230 binding agent Substances 0.000 claims abstract description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 72
- 229910052751 metal Inorganic materials 0.000 claims description 63
- 239000002184 metal Substances 0.000 claims description 63
- 238000001354 calcination Methods 0.000 claims description 27
- 238000000498 ball milling Methods 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 18
- 229920002545 silicone oil Polymers 0.000 claims description 18
- 239000011268 mixed slurry Substances 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 15
- -1 magnesium aluminate Chemical class 0.000 claims description 14
- 239000011812 mixed powder Substances 0.000 claims description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 239000000853 adhesive Substances 0.000 claims description 4
- 230000001070 adhesive effect Effects 0.000 claims description 4
- HIHIPCDUFKZOSL-UHFFFAOYSA-N ethenyl(methyl)silicon Chemical compound C[Si]C=C HIHIPCDUFKZOSL-UHFFFAOYSA-N 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 39
- 239000000377 silicon dioxide Substances 0.000 abstract description 8
- 238000002386 leaching Methods 0.000 abstract description 6
- 230000003628 erosive effect Effects 0.000 abstract description 5
- 230000001988 toxicity Effects 0.000 abstract description 4
- 231100000419 toxicity Toxicity 0.000 abstract description 4
- 239000011819 refractory material Substances 0.000 abstract description 2
- 239000011651 chromium Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 238000011056 performance test Methods 0.000 description 7
- 238000005245 sintering Methods 0.000 description 7
- 238000003828 vacuum filtration Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000006378 damage Effects 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052839 forsterite Inorganic materials 0.000 description 2
- 238000011534 incubation Methods 0.000 description 2
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- NACUKFIFISCLOQ-UHFFFAOYSA-N [Mg].[Cr] Chemical compound [Mg].[Cr] NACUKFIFISCLOQ-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 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 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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Abstract
本发明属于耐火材料技术领域,具体涉及精炼炉炉底用镁质捣打料及其制备工艺。所述精炼炉炉底用镁质捣打料,包括主体原料和粘结剂,主体原料由以下质量份数的物质组成:废弃镁碳砖颗粒12‑22份,废弃镁铬砖颗粒10‑20份,电熔镁砂细粉22‑35份,镁铝尖晶石颗粒12‑18份,硅微粉8‑15份,菱镁矿8‑15份,沸石粉1‑3份,金属铝粉结合物1‑5份,锆英砂3‑5份。本发明的镁质捣打料,解决了废弃耐火砖的堆积处理问题以及废弃料中Cr6+的浸出毒性问题,绿色环保,同时提高了捣打料的力学性能、高温性能和抗侵蚀性。
Description
技术领域
本发明属于耐火材料技术领域,具体涉及精炼炉炉底用镁质捣打料及其制备工艺。
背景技术
精炼炉底部由环流管组成,其中两个圆形的环流管与定形的炉底电熔再结合镁铬砖之间有较大的空隙,在砌筑炉底时,需要将捣打料均匀的填充在这些空隙中,然后捣打密实,构成一个封闭的炉底结构。
传统炉底捣打料通常以刚玉、氧化镁为主要材质,制得的捣打料成本较高,且中低温强度低,容易出现垮炉现象,同时还存在高温烧结困难、烧结温度高和保温时间长的问题。此外,镁质捣打料的原材料开采困难,成本较高,长期无序的开采、制备技术水平的不足和资源利用水平低,都对自然资源造成了严重的浪费。
使用镁铬质捣打料,可以吸收环流管受热膨胀的热应力,防止环流管膨胀起拱而损坏。但是镁铬砖中的Cr2O3容易发生变价,在生产和使用过程中,会产生对人体有毒、环境有害的Cr6+。因此,需要研究一种成本较低、节约自然资源、绿色环保且力学性能优异的镁质捣打料。
发明内容
本发明要解决的技术问题是:提供一种精炼炉炉底用镁质捣打料,解决了废弃耐火砖的堆积处理问题以及废弃料中Cr6+的浸出毒性问题,绿色环保,同时提高了捣打料的力学性能、高温性能和抗侵蚀性;本发明还提供其制备工艺。
本发明所述的精炼炉炉底用镁质捣打料,包括主体原料和粘结剂,主体原料由以下质量份数的物质组成:
废弃镁碳砖颗粒 12-22份,
废弃镁铬砖颗粒 10-20份,
电熔镁砂细粉 22-35份,
镁铝尖晶石颗粒 12-18份,
硅微粉 8-15份,
菱镁矿 8-15份,
沸石粉 1-3份,
金属铝粉结合物 1-5份,
锆英砂 3-5份。
本发明中,所述废弃镁碳砖颗粒的粒径为3-6mm,MgO含量≥82wt.%,C含量为10-18wt.%。
本发明中,所述废弃镁铬砖颗粒的粒径为3-6mm,MgO含量≥55wt.%,Cr2O3含量为3-5wt.%。
本发明中,所述电熔镁砂细粉的粒径为40-70μm,MgO含量≥95wt.%。
本发明中,所述镁铝尖晶石颗粒的粒径为0.4-2.8mm,MgO含量≥79wt.%,Al2O3含量≥20wt.%。
优选的,镁铝尖晶石颗粒的粒径分布如下:
1.8mm≤粒径≤2.8mm 25-30wt.%;
1.0mm≤粒径<1.8mm 35-40wt.%;
0.4mm≤粒径<1.0mm 30-40wt.%。
本发明中,所述硅微粉的粒径为0.005-0.01mm,SiO2含量≥93wt.%。
本发明中,所述菱镁矿的粒径为2.5-4.0mm,MgO含量≥80wt.%。
优选的,菱镁矿颗粒在使用前进行煅烧,煅烧温度为800-900℃,煅烧时间为3-6h,煅烧后在球磨机中球磨10-20min。
本发明中,所述沸石粉的粒径为150-200目,SiO2含量≥50wt.%。
优选的,沸石粉在使用前放置于球磨机中球磨10-20min,以增加其表面活性。
本发明中,所述锆英砂的粒径为60-80目,ZrO2含量≥66wt.%,SiO2含量≥33wt.%。
本发明中,所述金属铝粉结合物的制备方法如下:
将金属铝粉球磨后,置于水蒸气氛围中保持8-20min,然后干燥,再置于含氢硅油中,超声混合,得到混合料浆;将得到的混合料浆真空抽滤,抽滤物干燥后,在250-400℃条件下煅烧3-10h,得到金属铝粉结合物。
在一种实施方式中,所述金属铝粉结合物的制备方法具体如下:
将金属铝粉在无水乙醇保护下,球磨20-30min,置于水蒸气氛围中保持8-20min,然后在100-110℃条件下干燥4-6h,再置于含氢硅油中,超声混合30-80min,得到混合料浆;将得到的混合料浆真空抽滤,抽滤物在105-130℃条件下干燥至恒重后,在250-400℃条件下煅烧3-10h,得到金属铝粉结合物。
优选的,所采用的含氢硅油为甲基含氢硅油、乙基含氢硅油、甲基乙烯基硅油中的一种或多种;含氢硅油与金属铝粉的质量比为(4-8):1。
本发明中,所述粘结剂为铝溶胶,铝溶胶的胶粒粒径为20-80nm,Al2O3含量为20-30wt.%;粘结剂的用量为主体原料总质量的5-9%。
本发明的主体原料组成中,加入的沸石是一种价格低廉、呈架状结构的多孔性物质,其比表面积高,具有很强的吸附性。在镁质捣打料中,沸石可以吸附原料中的Cr6+,降低Cr(Ⅵ)的浸出毒性,在镁质捣打料升温至500℃以上时,Cr(Ⅵ)含量达到最高值,沸石可以吸附这些Cr(Ⅵ),降低镁质捣打料对环境造成的污染和对人体的损害。
菱镁矿具有不水化的特点,克服了现有镁质浇注料在成型和养护过程中出现裂纹和剥落的缺点,高温下菱镁矿分解形成的氧化镁和材料中的氧化硅微粉发生反应形成镁橄榄石,提高了捣打料的力学性能和抗侵蚀性。
锆英砂在高温下可以进行烧结,进而提高材料的耐高温性和抗热震稳定性,但烧结速度很慢,因此,需要烧结助剂,原料中含有的MgO可充当烧结助剂,促进锆英砂的烧结,防止锆英砂的分解,从而提高材料的体积稳定性。
硅微粉可以与镁铝尖晶石颗粒发生反应,生成镁-硅-铝系合金,铝溶胶分解产生的纳米氧化铝能够加入分子间的碰撞,降低反应所需要的温度,促使捣打料在较低温度的烧结,提高材料的中低温强度,提高烧结效率,避免烘烤过程中出现垮炉的现象。
此外,碳的氧化是导致镁质捣打料损坏的主要原因之一,为了解决捣打料中碳的氧化问题,常规做法是引入金属铝粉,基于铝粉对氧气的亲和力高于碳,能够防止碳的氧化,但是铝粉易于发生水化,影响捣打料的性能。本发明针对这一问题,将铝粉处理后得到的金属铝粉结合物作为抗氧化剂,避免了直接加入铝粉发生水化对材料产生的影响。金属铝粉结合物在400-600℃时开始发生破裂,这时,铝粉会裸露出来,铝粉与氧气结合原位生成Al2O3,起到防止碳氧化的作用,生成的Al2O3受热后膨胀填充了基体中的气孔,降低了气孔率。当温度升高到1000℃时,生成的Al2O3与SiO2反应生成莫来石相,莫来石相在基质中构成网络结构,进一步提高捣打料的抗侵蚀性和高温力学性能。
本发明所述的精炼炉炉底用镁质捣打料的制备工艺,包括以下步骤:
(1)将废弃镁碳砖颗粒、废弃镁铬砖颗粒分别在700-900℃下煅烧4-7h;
(2)将菱镁矿在800-900℃下煅烧3-6h,然后球磨10-20min;
(3)将沸石粉球磨10-20min;
(4)将处理后的废弃镁碳砖颗粒、废弃镁铬砖颗粒、菱镁矿、沸石粉以及电熔镁砂细粉、镁铝尖晶石颗粒、硅微粉、金属铝粉结合物和锆英砂按比例混合均匀,得到混合粉料;
(5)在混合粉料中加入粘结剂,混合均匀,得到精炼炉炉底用镁质捣打料。
其中,将废弃镁碳砖颗粒和废弃镁铬砖颗粒在700-900℃下煅烧,目的是去除其中的可挥发物和杂质。
与现有技术相比,本发明的有益效果如下:
(1)本发明采用废弃镁碳砖、废弃镁铬砖,不仅解决了废弃耐火砖的堆积处理问题,而且进一步节约了自然资源,具有较大的工业应用价值;
(2)本发明在原料中加入处理后的沸石粉,利用物理的方式解决Cr6+的浸出毒性问题,绿色环保,降低对人体损伤;
(3)本发明对金属铝粉进行改性处理,以金属铝粉结合物的方式加入到捣打料中,有效的解决了捣打料中碳的氧化损坏问题,在循环利用废弃镁碳砖颗粒节约资源的同时大大提高了材料的力学性能和高温性能;
(4)本发明采用的菱镁矿具有不水化的特点,克服了现有镁质浇注料在成型和养护过程中出现裂纹和剥落的缺点,高温下菱镁矿分解形成的氧化镁和材料中的氧化硅微粉发生反应形成镁橄榄石,提高了捣打料的力学性能和抗侵蚀性。
具体实施方式
下面结合实施例对本发明作进一步说明,实施例中所使用的原料,如无特别说明,均为市售常规原料;实施例中所使用的工艺方法,如无特别说明,均为本领域常规方法。
实施例中所采用的部分原料指标如下:
废弃镁碳砖颗粒:粒径范围3-6mm,MgO含量85.6wt.%,C含量13.2wt.%;
废弃镁铬砖颗粒:粒径范围3-6mm,MgO含量65.8wt.%,Cr2O3含量4.3wt.%;
电熔镁砂细粉:粒径范围40-70μm,MgO含量97.2wt.%;
镁铝尖晶石颗粒:MgO含量79.6wt.%,Al2O3含量20.2wt.%;
硅微粉:粒径范围0.005-0.01mm,SiO2含量94.3wt.%;
菱镁矿:粒径范围2.5-4.0mm,MgO含量83.8wt.%;
沸石粉:粒径范围150-200目,SiO2含量52.4wt.%;
锆英砂;粒径范围60-80目,ZrO2含量66.5wt.%,SiO2含量33.2wt.%;
铝溶胶:胶粒粒径范围20-80nm,Al2O3含量25.5wt.%。
实施例1
一种精炼炉炉底用镁质捣打料,以质量份数计,由7份铝溶胶和以下主体原料组成:
废弃镁碳砖颗粒18份,废弃镁铬砖颗粒15份,电熔镁砂细粉29份,镁铝尖晶石颗粒(1.8mm≤粒径≤2.8mm占比27wt.%、1.0mm≤粒径<1.8mm占比38wt.%,0.4mm≤粒径<1.0mm占比35wt.%)15份,硅微粉12份,菱镁矿12份,沸石粉2份,金属铝粉结合物3份,锆英砂4份。
其中,金属铝粉结合物的制备方法如下:
将金属铝粉在无水乙醇保护下,球磨25min,置于水蒸气氛围中保持15min,然后在100℃条件下干燥5h,再置于质量为金属铝粉7倍的甲基含氢硅油中,超声混合50min,得到混合料浆;将得到的混合料浆真空抽滤,抽滤物在110℃条件下干燥至恒重后,在320℃条件下煅烧6h,得到金属铝粉结合物。
所述精炼炉炉底用镁质捣打料的制备步骤如下:
(1)将废弃镁碳砖颗粒、废弃镁铬砖颗粒分别在800℃下煅烧6h,去除其中的可挥发物和杂质;
(2)将菱镁矿在850℃下煅烧5h,然后球磨15min;
(3)将沸石粉球磨15min;
(4)将处理后的废弃镁碳砖颗粒、废弃镁铬砖颗粒、菱镁矿、沸石粉以及电熔镁砂细粉、镁铝尖晶石颗粒、硅微粉、金属铝粉结合物和锆英砂按比例混合均匀,得到混合粉料;
(5)在混合粉料中加入7份铝溶胶混合均匀,得到精炼炉炉底用镁质捣打料。
实施例2
一种精炼炉炉底用镁质捣打料,以质量份数计,由5份铝溶胶和以下主体原料组成:
废弃镁碳砖颗粒12份,废弃镁铬砖颗粒10份,电熔镁砂细粉22份,镁铝尖晶石颗粒(1.8mm≤粒径≤2.8mm占比25wt.%、1.0mm≤粒径<1.8mm占比35wt.%,0.4mm≤粒径<1.0mm占比40wt.%)12份,硅微粉8份,菱镁矿8份,沸石粉1份,金属铝粉结合物1份,锆英砂3份。
其中,金属铝粉结合物的制备方法如下:
将金属铝粉在无水乙醇保护下,球磨20min,置于水蒸气氛围中保持8min,然后在100℃条件下干燥4h,再置于质量为金属铝粉4倍的乙基含氢硅油中,超声混合30min,得到混合料浆;将得到的混合料浆真空抽滤,抽滤物在105℃条件下干燥至恒重后,在250℃条件下煅烧3h,得到金属铝粉结合物。
所述精炼炉炉底用镁质捣打料的制备步骤如下:
(1)将废弃镁碳砖颗粒、废弃镁铬砖颗粒分别在700℃下煅烧4h,去除其中的可挥发物和杂质;
(2)将菱镁矿在800℃下煅烧3h,然后球磨10min;
(3)将沸石粉球磨10min;
(4)将处理后的废弃镁碳砖颗粒、废弃镁铬砖颗粒、菱镁矿、沸石粉以及电熔镁砂细粉、镁铝尖晶石颗粒、硅微粉、金属铝粉结合物和锆英砂按比例混合均匀,得到混合粉料;
(5)在混合粉料中加入5份铝溶胶混合均匀,得到精炼炉炉底用镁质捣打料。
实施例3
一种精炼炉炉底用镁质捣打料,以质量份数计,由9份铝溶胶和以下主体原料组成:
废弃镁碳砖颗粒22份,废弃镁铬砖颗粒20份,电熔镁砂细粉35份,镁铝尖晶石颗粒(1.8mm≤粒径≤2.8mm占比30wt.%、1.0mm≤粒径<1.8mm占比40wt.%,0.4mm≤粒径<1.0mm占比30wt.%)18份,硅微粉15份,菱镁矿15份,沸石粉3份,金属铝粉结合物5份,锆英砂粒径为5份。
其中,金属铝粉结合物的制备方法如下:
将金属铝粉在无水乙醇保护下,球磨30min,置于水蒸气氛围中保持20min,然后在110℃条件下干燥6h,再置于质量为金属铝粉5倍的甲基乙烯基硅油中,超声混合80min,得到混合料浆;将得到的混合料浆真空抽滤,抽滤物在130℃条件下干燥至恒重后,在400℃条件下煅烧10h,得到金属铝粉结合物。
所述精炼炉炉底用镁质捣打料的制备步骤如下:
(1)将废弃镁碳砖颗粒、废弃镁铬砖颗粒分别在900℃下煅烧7h,去除其中的可挥发物和杂质;
(2)将菱镁矿在900℃下煅烧6h,然后球磨20min;
(3)将沸石粉球磨20min;
(4)将处理后的废弃镁碳砖颗粒、废弃镁铬砖颗粒、菱镁矿、沸石粉以及电熔镁砂细粉、镁铝尖晶石颗粒、硅微粉、金属铝粉结合物和锆英砂按比例混合均匀,得到混合粉料;
(5)在混合粉料中加入9份铝溶胶混合均匀,得到精炼炉炉底用镁质捣打料。
实施例4
一种精炼炉炉底用镁质捣打料,以质量份数计,由8份铝溶胶和以下主体原料组成:
废弃镁碳砖颗粒20份,废弃镁铬砖颗粒18份,电熔镁砂细粉32份,镁铝尖晶石颗粒(1.8mm≤粒径≤2.8mm占比28wt.%、1.0mm≤粒径<1.8mm占比38wt.%,0.4mm≤粒径<1.0mm占比34wt.%)16份,硅微粉14份,菱镁矿14份,沸石粉3份,金属铝粉结合物4份,锆英砂4份。
其中,金属铝粉结合物的制备方法如下:
将金属铝粉在无水乙醇保护下,球磨27min,置于水蒸气氛围中保持18min,然后在107℃条件下干燥5h,再置于质量为金属铝粉6倍的甲基含氢硅油中,超声混合70min,得到混合料浆;将得到的混合料浆真空抽滤,抽滤物在125℃条件下干燥至恒重后,在350℃条件下煅烧8h,得到金属铝粉结合物。
所述精炼炉炉底用镁质捣打料的制备步骤如下:
(1)将废弃镁碳砖颗粒、废弃镁铬砖颗粒分别在850℃下煅烧6h,去除其中的可挥发物和杂质;
(2)将菱镁矿在880℃下煅烧5h,然后球磨18min;
(3)将沸石粉球磨16min;
(4)将处理后的废弃镁碳砖颗粒、废弃镁铬砖颗粒、菱镁矿、沸石粉,以及电熔镁砂细粉、镁铝尖晶石颗粒、硅微粉、金属铝粉结合物锆英砂按比例混合均匀,得到混合粉料;
(5)在混合粉料中加入8份铝溶胶混合均匀,得到精炼炉炉底用镁质捣打料。
实施例5
一种精炼炉炉底用镁质捣打料,以质量份数计,由6份铝溶胶和以下主体原料组成:
废弃镁碳砖颗粒13份,废弃镁铬砖颗粒11份,电熔镁砂细粉(粒径40μm)24份,镁铝尖晶石颗粒(1.8mm≤粒径≤2.8mm占比26wt.%、1.0mm≤粒径<1.8mm占比36wt.%,0.4mm≤粒径<1.0mm占比38wt.%)13份,硅微粉10份,菱镁矿10份,沸石粉2份,金属铝粉结合物2份,锆英砂4份。
其中,金属铝粉结合物的制备方法如下:
将金属铝粉在无水乙醇保护下,球磨25min,置于水蒸气氛围中保持12min,然后在100℃条件下干燥4h,再置于质量为金属铝粉8倍的乙基含氢硅油中,超声混合40min,得到混合料浆;将得到的混合料浆真空抽滤,抽滤物在110℃条件下干燥至恒重后,在280℃条件下煅烧4h,得到金属铝粉结合物。
所述精炼炉炉底用镁质捣打料的制备步骤如下:
(1)将废弃镁碳砖颗粒、废弃镁铬砖颗粒分别在750℃下煅烧5h,去除其中的可挥发物和杂质;
(2)将菱镁矿在850℃下煅烧4h,然后球磨15min;
(3)将沸石粉球磨15min;
(4)将处理后的废弃镁碳砖颗粒、废弃镁铬砖颗粒、菱镁矿、沸石粉,以及电熔镁砂细粉、镁铝尖晶石颗粒、硅微粉、金属铝粉结合物和锆英砂按比例混合均匀,得到混合粉料;
(5)在混合粉料中加入6份铝溶胶混合均匀,得到精炼炉炉底用镁质捣打料。
对比例1
本对比例与实施例1的不同之处仅在于,采用等质量的金属铝粉替换金属铝粉结合物,以考察金属铝粉处理前后对产品的性能影响。
对比例2
本对比例与实施例1的不同之处仅在于,原料中不加入菱镁矿,以考察菱镁矿加入前后对产品的性能影响。
对比例3
本对比例与实施例1的不同之处仅在于,原料中不加入沸石粉,以考察沸石粉加入前后对产品的性能影响。
对比例4
本对比例与实施例1的不同之处仅在于,原料中不加入锆英砂,以考察锆英砂加入前后对产品的性能影响。
将实施例和对比例制备的捣打料依次在110℃下干燥24h,在815℃下保温3h,在1400℃下保温3h,并分别进行性能测试,其中,体积密度参照YB/T 5200-1993标准进行测试,耐压强度参照标准GB/T 5072-2008进行测试,加热永久线变化参照GB/T 5988-2007进行测试,抗渣性参照GB/T8931-2007进行测试,Cr(Ⅵ)浸出量参照GB/T 16400-2015进行测试。
测试结果如表1-3所示,其中表1为110℃下干燥24h后的性能测试结果,表2为815℃保温3h后的性能测试结果,表3为1400℃下保温3h后的性能测试结果。
表1 110℃下干燥24h后的性能测试结果
表2 815℃下保温3h后的性能测试结果
表3 1400℃下保温3h后的性能测试结果
从表1-3可以看出,金属铝粉结合物的加入大大提高了捣打料的耐压强度和抗渣性,菱镁矿的加入同样提高了捣打料的耐压强度和抗渣性能,沸石粉能够吸附掉捣打料中Cr(Ⅵ)的浸出,降低材料对环境和人体的伤害,锆英砂的加入提高了捣打料的体积稳定性,有利于延长材料在高温中的使用寿命。
Claims (7)
1.一种精炼炉炉底用镁质捣打料,其特征在于:由主体原料和粘结剂组成,主体原料由以下质量份数的物质组成:
废弃镁碳砖颗粒 12-22份,
废弃镁铬砖颗粒 10-20份,
电熔镁砂细粉 22-35份,
镁铝尖晶石颗粒 12-18份,
硅微粉 8-15份,
菱镁矿 8-15份,
沸石粉 1-3份,
金属铝粉结合物 1-5份,
锆英砂 3-5份;
所述粘结剂为铝溶胶,铝溶胶的胶粒粒径为20-80nm,Al2O3含量为20-30wt.%;粘结剂的用量为主体原料总质量的5-9%;
所述金属铝粉结合物的制备方法如下:
将金属铝粉球磨后,置于水蒸气氛围中保持8-20min,然后干燥,再置于含氢硅油中,超声混合,得到混合料浆;将得到的混合料浆真空抽滤,抽滤物干燥后,在250-400℃条件下煅烧3-10h,得到金属铝粉结合物;
所采用的含氢硅油为甲基含氢硅油、乙基含氢硅油、甲基乙烯基硅油中的一种或多种;含氢硅油与金属铝粉的质量比为(4-8):1。
2.根据权利要求1所述的精炼炉炉底用镁质捣打料,其特征在于:所述废弃镁碳砖颗粒的粒径为3-6mm,MgO含量≥82wt.%,C含量为10-18wt.%;
所述废弃镁铬砖颗粒的粒径为3-6mm,MgO含量≥55wt.%,Cr2O3含量为3-5wt.%;
所述电熔镁砂细粉的粒径为40-70μm,MgO含量≥95wt.%。
3.根据权利要求1所述的精炼炉炉底用镁质捣打料,其特征在于:所述镁铝尖晶石颗粒的粒径为0.4-2.8mm,MgO含量≥79wt.%,Al2O3含量≥20wt.%;粒径分布如下:
1.8mm≤粒径≤2.8mm 25-30wt.%,
1.0mm≤粒径<1.8mm 35-40wt.%,
0.4mm≤粒径<1.0mm 30-40wt.%。
4.根据权利要求1所述的精炼炉炉底用镁质捣打料,其特征在于:所述硅微粉的粒径为0.005-0.01mm,SiO2含量≥93wt.%;
所述菱镁矿的粒径为2.5-4.0mm,MgO含量≥80wt.%;
所述沸石粉的粒径为150-200目,SiO2含量≥50wt.%;
所述锆英砂的粒径为60-80目,ZrO2含量≥66wt.%,SiO2含量≥33wt.%。
5.根据权利要求1所述的精炼炉炉底用镁质捣打料,其特征在于:所述菱镁矿在使用前进行煅烧,煅烧温度为800-900℃,煅烧时间为3-6h,煅烧后在球磨机中球磨10-20min。
6.根据权利要求1所述的精炼炉炉底用镁质捣打料,其特征在于:所述沸石粉在使用前放置于球磨机中球磨10-20min。
7.一种权利要求1-6任一项所述的精炼炉炉底用镁质捣打料的制备工艺,其特征在于:包括以下步骤:
(1)将废弃镁碳砖颗粒、废弃镁铬砖颗粒分别在700-900℃下煅烧4-7h;
(2)将菱镁矿在800-900℃下煅烧3-6h,然后球磨10-20min;
(3)将沸石粉球磨10-20min;
(4)将处理后的废弃镁碳砖颗粒、废弃镁铬砖颗粒、菱镁矿、沸石粉以及电熔镁砂细粉、镁铝尖晶石颗粒、硅微粉、金属铝粉结合物和锆英砂按比例混合均匀,得到混合粉料;
(5)在混合粉料中加入粘结剂,混合均匀,得到精炼炉炉底用镁质捣打料。
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