CN117430435B - 赤泥回收熔分炉底用的铝铬镁锆复合材料及其制法与应用 - Google Patents
赤泥回收熔分炉底用的铝铬镁锆复合材料及其制法与应用 Download PDFInfo
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- CN117430435B CN117430435B CN202311757133.9A CN202311757133A CN117430435B CN 117430435 B CN117430435 B CN 117430435B CN 202311757133 A CN202311757133 A CN 202311757133A CN 117430435 B CN117430435 B CN 117430435B
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- aluminum
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- magnesium
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- 238000002844 melting Methods 0.000 title claims abstract description 40
- 230000008018 melting Effects 0.000 title claims abstract description 40
- -1 Aluminum-chromium-magnesium-zirconium Chemical compound 0.000 title claims abstract description 33
- 239000002131 composite material Substances 0.000 title claims abstract description 24
- 238000011084 recovery Methods 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 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 60
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 42
- 239000011029 spinel Substances 0.000 claims abstract description 42
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000011230 binding agent Substances 0.000 claims abstract description 31
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910000423 chromium oxide Inorganic materials 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 20
- QRRWWGNBSQSBAM-UHFFFAOYSA-N alumane;chromium Chemical compound [AlH3].[Cr] QRRWWGNBSQSBAM-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims description 54
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 33
- 239000002245 particle Substances 0.000 claims description 31
- 239000000843 powder Substances 0.000 claims description 31
- 238000005245 sintering Methods 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 18
- 238000009826 distribution Methods 0.000 claims description 17
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 239000011651 chromium Substances 0.000 claims description 11
- 239000012768 molten material Substances 0.000 claims description 11
- 239000011159 matrix material Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 229910001593 boehmite Inorganic materials 0.000 claims description 8
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 8
- QQHSIRTYSFLSRM-UHFFFAOYSA-N alumanylidynechromium Chemical compound [Al].[Cr] QQHSIRTYSFLSRM-UHFFFAOYSA-N 0.000 claims description 6
- 230000005496 eutectics Effects 0.000 claims description 6
- 238000009740 moulding (composite fabrication) Methods 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 2
- 239000008187 granular material Substances 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 56
- 239000011819 refractory material Substances 0.000 abstract description 28
- 229910052742 iron Inorganic materials 0.000 abstract description 27
- 230000003628 erosive effect Effects 0.000 abstract description 13
- 239000002893 slag Substances 0.000 abstract description 13
- 239000002253 acid Substances 0.000 abstract description 6
- 239000003513 alkali Substances 0.000 abstract description 6
- 230000006378 damage Effects 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 27
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 10
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 238000003723 Smelting Methods 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 239000000395 magnesium oxide Substances 0.000 description 6
- 239000011449 brick Substances 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000004131 Bayer process Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 238000009991 scouring Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000004375 Dextrin Substances 0.000 description 3
- 229920001353 Dextrin Polymers 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 235000019425 dextrin Nutrition 0.000 description 3
- RGPUVZXXZFNFBF-UHFFFAOYSA-K diphosphonooxyalumanyl dihydrogen phosphate Chemical compound [Al+3].OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O RGPUVZXXZFNFBF-UHFFFAOYSA-K 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000003077 lignite Substances 0.000 description 2
- 238000009766 low-temperature sintering Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 2
- 229910001950 potassium oxide Inorganic materials 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 229910021487 silica fume Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- 229910001948 sodium oxide Inorganic materials 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000009628 steelmaking Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- KMWBBMXGHHLDKL-UHFFFAOYSA-N [AlH3].[Si] Chemical class [AlH3].[Si] KMWBBMXGHHLDKL-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011490 mineral wool Substances 0.000 description 1
- 230000001089 mineralizing effect Effects 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/12—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on chromium oxide
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
- F27D1/00—Casings; Linings; Walls; Roofs
- F27D1/0043—Floors, hearths
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Abstract
本发明公开了一种赤泥回收熔分炉底用的铝铬镁锆复合材料及其制法与应用,属于耐火材料技术领域。本发明提供的铝铬镁锆复合材料的原料包括:20‑30重量份的铝镁尖晶石;40‑50重量份的电熔氧化铬;15‑20重量份的重熔料;3‑5重量份的氧化锆微粉;5‑7重量份的氧化铝微粉;2‑3重量份的氧化铝溶胶结合剂;1‑3重量份的铬铝凝胶。本发明提供的铝铬镁锆复合材料,气孔率极低,达到10%‑13%,体积密度大,耐压强度大,在应用于熔分炉池底部位,用于回收赤泥中的有用成分的过程中,耐酸耐碱,抗渣性强,尤其是抗铁水侵蚀能力强,不易发生烧穿、熔化或损毁。
Description
技术领域
本发明属于耐火材料技术领域,尤其涉及一种赤泥回收熔分炉底用的铝铬镁锆复合材料及其制法与应用。
背景技术
赤泥是氧化铝生产过程中排出的废渣,因技术、成本等原因,利用率极低,巨量的赤泥堆放问题成为世界性难题。因强碱性、高盐度的赤泥废液造成水体、土壤碱化,污染地下水源,导致环保压力剧增,严重制约着我国氧化铝工业的可持续发展。但拜耳法赤泥含有较高的氧化铁,Fe2O3含量一般在30%-40%以上,是可以用作炼铁的原料,世界各国都在努力寻求综合利用方法,从赤泥中回收利用其中的铁资源,对补充我国的铁矿石资源有重要意义。
目前,我国已有稳定成熟的综合利用技术,可以实现赤泥的完全利用——“吃干榨净”,采用煤基直接还原烧成-渣铁磁选分离-母液溶出的新工艺流程。利用煤矿采完后大量存在的褐煤(一种劣质煤,不能发电,也无法利用的资源),将拜耳法溶出提炼后的高铁赤泥添加褐煤(含碳、二氧化硅、氧化铝、氧化镁等成分),作为还原剂,加入膨润土,高压压制成球,经过转底炉矿化,催化还原成单质铁或者是一氧化铁,形成非常好的球团,再加入少量的石灰、焦炭粉,在熔分炉里进行融熔化,强融熔化后,通过控制液固比等参数对熟料进行碱液溶出。铁的比重比较大,铁水就沉到下层炉底,富含大量二氧化硅的熔渣浮到这个铁水的上层,出现熔渣和铁水分离,得到高铝碱液和富铁残渣,上层含有氧化铁、氧化铝、氧化钙、氧化镁、氧化钾、氧化钠等成分,是生产矿棉的主要原料。下层炉底的铁水,经过出铁口排出生产出优质的铁水,该产品可作电炉炼钢的”半钢”原料。这种技术既实现了拜耳法赤泥金属铁元素的提取利用又可实现拜耳法赤泥的全面综合利用。
在熔分炉熔融过程中,因为碱性成分非常高,碱性熔渣侵蚀非常严重。下层非铁非钢工况环境,若是按照炼铁的工况,那么炉衬材料用铝硅系材料加含碳材料最佳;若是炼钢的工况,是碱性的含碳材料最优。而赤泥冶炼工况为酸、碱熔渣侵蚀,又酸又碱,又超高温(1600-1800℃),且冶炼过程中温度变化非常剧烈,整个熔池的上下部工况差异很大:变化又非常大,熔融液上部是酸性的熔融液,熔融液熔融液下部又是碱性的熔融液,因此,熔分炉熔池用耐火材料成为制约熔分技术发展的问题。原用高铝质制、镁系(镁铬、镁尖晶石、镁铝尖晶石)、铝尖晶石、镁碳砖、铝镁碳砖、复合材料、铬刚玉等,分别出现炉衬材料全部熔化堵塞出铁口、高温熔炼中炉体变红炉体烧穿、炉膛使用1-3炉全部熔化损毁等问题。
高温熔融液熔化后,铁水聚积到池底,池底材料抵抗高温铁水的冲刷、侵蚀,炉缸内实现渣和金属熔融液分离,聚积到一定量后,从渣铁口排出,等铁水从出铁口流出,富硅的酸性溶液从上部流下,池底抵抗酸性的熔融液侵蚀,环境非常复杂。因此,研究开发一种应用于熔分炉不同部位的耐火材料,对赤泥的回收具有重要意义。
公开于该背景技术部分的信息仅仅旨在增加对本发明的总体背景的理解,而不应当被视为承认或以任何形式暗示该信息为本领域一般技术人员所公知的现有技术。
发明内容
本发明的目的在于解决现有技术中,由于赤泥回收环境苛刻,现有的耐火材料容易发生熔化、烧穿等问题,提供赤泥回收熔分炉底用的铝铬镁锆复合材料及其制法与应用。
本发明第一方面提供一种赤泥回收熔分炉底用的铝铬镁锆复合材料,所述铝铬镁锆复合材料的原料包括:
20-30重量份的铝镁尖晶石;
40-50重量份的电熔氧化铬;
15-20重量份的重熔料;
3-5重量份的氧化锆微粉;
5-7重量份的氧化铝微粉;
2-3重量份的氧化铝溶胶结合剂;
1-3重量份的铬铝凝胶。
在一些实施方式中,所述铝镁尖晶石的粒度为3-1mm;
和/或,所述电熔氧化铬的粒度分布及重量比为(5-3mm):(3-1mm):(1-0mm)=1:1.5:2;
和/或,所述重熔料的粒度分布及重量比为(5-3mm):(3-1mm)=1:1;
和/或,所述氧化锆微粉的粒度为<5μm,所述氧化锆微粉的纯度为99%以上;
和/或,所述氧化铝微粉的粒度分布及重量比为(1<5μm):(1<1μm)=1:1。
控制原材料的颗粒分布范围,使得各原料混合后形成骨架的整体抗侵蚀趋势,提升抗热震稳定性,铝镁尖晶石颗粒与电熔氧化铬颗粒、重熔料颗粒配比间形成合理配伍,紧密堆积,提升材料是性能。
在一些实施方式中,所述铝镁尖晶石为富铝铝镁尖晶石,包括90wt%以上的Al2O3,和5wt%-7wt%的MgO。
富铝铝镁尖晶石抗K2O、Na2O的侵蚀性好,抗化学侵蚀能力强,热震稳定性好,由于富铝铝镁尖晶石能在很大范围内固溶Al2O3,发生3Mg2+→2Al3+非等价置换,导致晶面间距减小,即尖晶石愈富铝,缺陷愈多,其晶格常数也愈小,试样的体积密度就愈大,材料越致密,抗侵蚀抗渗透性能越好。
氧化铝微粉起烧结作用,在高温状态下和<5μm、<1μm氧化铬形成细小的铝铬共熔体。该铝铬共熔体具有良好的活性,中低温条件下能够促进烧结,高温条件下使产品致密化,既能抵抗高温酸性熔渣,更能抵抗强碱性熔渣侵蚀。
在一些实施方式中,所述重熔料为铝铬共熔体,具体的,重熔料是铝铬渣经过高温重新熔化,去掉CaO、MgO、Fe2O3、K2O、Na2O等杂质,形成高品质的铝铬共熔体。所述重熔料中Al2O3和Cr2O3的总量≥94wt%,所述重熔料中SiO2的含量≤1.0wt%。
在一些实施方式中,所述氧化铝溶胶结合剂为ρ-Al2O3微粉和α-Al2O3微粉加水后形成的勃姆石凝胶,所述ρ-Al2O3微粉与α-Al2O3微粉的粒度小于1μm。
在一些实施方式中,所述ρ-Al2O3微粉与α-Al2O3微粉的用量重量比为1:1。
﹤1μm超细ρ-Al2O3和﹤1μm超细α-Al2O3微粉加水,ρ-Al2O3和水形成勃姆石凝胶能够大大的增加材料的氧化铝含量,还能够提升材料的耐高温化学组分的含量。同时勃姆石凝胶形成以后,有﹤1μm超细α-Al2O3粉存在,α-Al2O3能够随着结合剂充分的均匀的分布到材料的任何一个部位,促进材料烧结,形成陶瓷相结合,不但能够提高材料的初期强度,又能够提高材料后期的烧结性能,同时在高温应用状态下,因为耐高温的化学主分相对较高,比如氧化铝的含量提升,所以它的耐高温性能相应更优异。
本发明富铝铝镁尖晶石等材料是脊性料,不具备粘性和可塑性,必须要加入结合剂增加材料的可塑性,普通的结合剂,比如粘土、硅微粉等,会带来不可逆的二氧化硅的含量和其他杂质成分,比如说氧化铁、氧化钠、氧化钾等杂质,尤其最可怕的是二氧化硅,会破坏材料的抗碱性渣的能力;如果用糊精、羧甲基纤维素钠等有机结合剂,中高温烧成后会留下微细的气孔,提高材料的气孔率,导致材料的抗侵蚀和抗渗能力下降;一般的磷酸和磷酸二氢铝,塑性和粘度达不到本发明的要求。
在一些实施方式中,铬铝凝胶包括40重量份的Cr2O3,35重量份的P2O5,8重量份的Al2O3,12重量份的H2O;
和/或,所述铬铝凝胶的pH值为1.5-2.5。
铬铝凝胶用于促进形成共晶,生成大量铝铬固熔体,以提高初期粘结性能,中温强度,高温烧结性能等。
本发明第二方面提供一种铝铬镁锆复合材料的制备方法,包括:
S1将所述铝镁尖晶石、电熔氧化铬、重熔料混合均匀,得到预混合颗粒料;
S2将所述氧化锆微粉、氧化铝微粉混合均匀,得到预混合基质细粉;
S3向所述预混合颗粒中加入氧化铝溶胶结合剂,混合均匀后,得到泥料;
S4困料、加压成型,干燥后烧成,得到所述铬铝锆耐火材料。
在一些实施方式中,所述困料的时间为24-72小时;
和/或,所述加压的压力为600T-1000T;
和/或,所述干燥的温度为150℃-180℃,干燥的时间为24-48小时;
和/或,所述烧成的温度为1550℃-1600℃,保温16小时。
本发明第三方面提供上述铬铝镁锆复合材料或上述制备方法制备得到的铬铝镁锆复合材料在赤泥回收熔分炉底的应用。
本发明的技术原理在于:
赤泥回收熔分炉池底工况环境更为复杂,在投料熔炼的起始阶段,池底的工况环境与池壁处相似,需要具备优异的耐酸、碱侵蚀性能;在熔化冶炼后期,池底后期熔化完后,似于盛铁容器,需要具有优异的抗铁侵蚀性能,因此,池底耐材中添加富铝铝镁尖晶石,用以抵抗熔渣(FeO)侵蚀、大比重的铁水冲刷与渗透。
富铝铝镁尖晶石颗粒与基质中的氧化铬微粉、氧化铝微粉以及结合剂铝溶胶均可在高温下发生互相固熔与二次尖晶石化反应,实现低温烧成条件下的二次尖晶石化及烧结,提高材料颗粒与基质间的结合程度,提高材料致密性,以达到提高材料抗熔液侵蚀与铁水渗透和冲刷性能,适用于池底炉衬材料。
相比现有技术,本发明达到的技术效果如下:
(1)本发明提供的铝铬镁锆复合材料,气孔率极低,达到10%-13%,体积密度大,耐压强度大,在应用于熔分炉池底部位,用于回收赤泥中的有用成分的过程中,耐酸耐碱,抗渣性强,尤其是抗铁水侵蚀能力强,不易发生烧穿、熔化或损毁。
(2)本发明采用富铝铝镁尖晶石,结合电熔氧化铬,添加重熔料、氧化锆微粉、氧化铝微粉,以合理的颗粒级配,控制原材料的颗粒分布范围,使得各原料混合后形成骨架的整体抗侵蚀趋势,提升抗热震稳定性,富铝铝镁尖晶石颗粒与电熔氧化铬颗粒、重熔料颗粒等配比间形成合理配伍,紧密堆积,提升材料性能。
(3)富铝铝镁尖晶石颗粒与基质中的氧化铬微粉、氧化铝微粉以及结合剂铝溶胶均可在高温下发生互相固熔与二次尖晶石化反应,实现低温烧成条件下的二次尖晶石化及烧结,提高材料颗粒与基质间的结合程度,提高材料致密性,以达到提高材料抗熔液侵蚀与铁水渗透和冲刷性能,适用于池底炉衬材料。
(4)本发明采用氧化铝溶胶作为结合剂,不仅能够大大的增加材料的氧化铝含量,还能够提升材料的耐高温化学组分的含量,α-Al2O3能够随着结合剂充分的均匀的分布到材料的任何一个部位,促进材料烧结,形成陶瓷相结合,不但能够提高材料的初期强度,又能够提高材料后期的烧结性能,同时在高温应用状态下,因为耐高温的化学主分相对较高,比如氧化铝的含量提升,所以它的耐高温性能相应更优异。
具体实施方式
以下通过具体实施例说明本发明的技术方案。应该理解,本发明提到的一个或者多个步骤不排斥在组合步骤前后还存在其他方法和步骤,或者这些明确提及的步骤间还可以插入其他方法和步骤。还应理解,这些实例仅用于说明本发明而不用于限制本发明的范围。除非另有说明,各方法步骤的编号仅为鉴别各方法步骤的目的,而非限制每个方法的排列次序或限定本发明的实施范围,其相对关系的改变或调整,在无实质技术内容变更的条件下,亦可视为本发明可实施的范畴。
实施例中所采用的原料和仪器,对其来源没有特定限制,在市场购买或者按照本领域内技术人员熟知的常规方法制备即可。
实施例中原料铝镁尖晶石均使用富铝铝镁尖晶石,所述富铝铝镁尖晶石包括90wt%以上的Al2O3,和5wt%-7wt%的MgO。
实施例1
一种赤泥回收熔分炉底用的铝铬镁锆复合材料,其原料包括:
25重量份的铝镁尖晶石,铝镁尖晶石的粒度以3-1mm为主;
45重量份的电熔氧化铬,电熔氧化铬的粒度分布及比例为(5-3mm):(3-1mm):(1-0mm)=1:1.5:2;
18重量份的重熔料,所述重熔料中Al2O3和Cr2O3的总量≥94wt%,所述重熔料中SiO2的含量≤1.0wt%,重熔料的粒度分布及比例为(5-3mm):(3-1mm)=1:1;
4重量份的氧化锆微粉,氧化锆微粉的粒度为<5μm,氧化锆微粉的纯度为99%;
6重量份的氧化铝微粉,氧化铝微粉的粒度分布及比例为(<5μm):(<1μm)=1:1;
2.5重量份的氧化铝溶胶结合剂,氧化铝溶胶结合剂的制备方法为:ρ-Al2O3和﹤1μ超细α-Al2O3微粉加水形成勃姆石凝胶即为氧化铝溶胶;
2重量份的铬铝凝胶,铬铝凝胶包括40重量份的Cr2O3,35重量份的P2O5,8重量份的Al2O3,12重量份的H2O,混合后常温下搅拌即形成铬铝凝胶,所述铬铝凝胶的pH值为2.0。
上述铝铬镁锆复合材料的制备方法如下:
S1:将所述富铝铝镁尖晶石、电熔氧化铬、重熔料混合均匀,得到预混合颗粒料;
S2:将所述氧化锆微粉、氧化铝微粉混合均匀,得到预混合基质细粉;
S3:向所述预混合颗粒中加入氧化铝溶胶结合剂,混合均匀后,得到泥料;
S4:困料,所述困料的时间为24-72小时;
S5:困过的泥料再次碾压搅拌5分钟后,在600T-1000T多面加压压砖机成型;
S6:步骤S5获得的成型胚料在150℃-180℃下干燥24-48小时,干燥后烧成,烧成温度1550℃,保温16小时,得到用于赤泥回收熔分炉底的铬铝镁锆耐火材料。
制得的铬铝镁锆耐火材料经检测,达到以下指标:
将上述铬铝镁锆耐火材料应用于熔分炉池底部位,用于回收赤泥中的有用成分,实践证明,重复使用10炉,熔分炉底部耐火材料完整,没有剥落侵蚀和渗透,未出现熔化、损毁的迹象。
实施例2
一种赤泥回收熔分炉底用的铝铬镁锆复合材料,其原料包括:
20重量份的铝镁尖晶石,铝镁尖晶石的粒度以3-1mm为主;
40重量份的电熔氧化铬,电熔氧化铬的粒度分布及比例为(5-3mm):(3-1mm):(1-0mm)=1:1.5:2;
15重量份的重熔料,所述重熔料中Al2O3和Cr2O3的总量≥94wt%,所述重熔料中SiO2的含量≤1.0wt%,重熔料的粒度分布及比例为(5-3mm):(3-1mm)=1:1;
3重量份的氧化锆微粉,氧化锆微粉的粒度为<5μm,氧化锆微粉的纯度为99%;
5重量份的氧化铝微粉,氧化铝微粉的粒度分布及比例为(<5μm):(<1μm)=1:1;
2重量份的氧化铝溶胶结合剂,氧化铝溶胶结合剂的制备方法为:ρ-Al2O3和﹤1μ超细α-Al2O3微粉加水形成勃姆石凝胶即为氧化铝溶胶;
1重量份的铬铝凝胶,铬铝凝胶包括40重量份的Cr2O3,35重量份的P2O5,8重量份的Al2O3,12重量份的H2O,混合后常温下搅拌即形成铬铝凝胶,所述铬铝凝胶的pH值为1.8。
上述铝铬镁锆复合材料的制备方法如下:
S1:将所述铝镁尖晶石、电熔氧化铬、重熔料混合均匀,得到预混合颗粒料;
S2:将所述氧化锆微粉、氧化铝微粉混合均匀,得到预混合基质细粉;
S3:向所述预混合颗粒中加入氧化铝溶胶结合剂,混合均匀后,得到泥料;
S4:困料,所述困料的时间为24-72小时;
S5:困过的泥料再次碾压搅拌5分钟后,在600T-1000T多面加压压砖机成型;
S6:步骤S5获得的成型胚料在150℃-180℃下干燥24-48小时,干燥后烧成,烧成温度1550℃,保温16小时,得到用于赤泥回收熔分炉底的铬铝镁锆耐火材料。
制得的铬铝镁锆耐火材料经检测、使用,结果与实施例1一致,此处不再赘述。
制得的铬铝镁锆耐火材料经检测,达到以下指标:
实施例3
一种赤泥回收熔分炉底用的铝铬镁锆复合材料,其原料包括:
30重量份的铝镁尖晶石,铝镁尖晶石的粒度以3-1mm为主;
50重量份的电熔氧化铬,电熔氧化铬的粒度分布及比例为(5-3mm):(3-1mm):(1-0mm)=1:1.5:2;
20重量份的重熔料,所述重熔料中Al2O3和Cr2O3的总量≥94wt%,所述重熔料中SiO2的含量≤1.0wt%,重熔料的粒度分布及比例为(5-3mm):(3-1mm)=1:1;
5重量份的氧化锆微粉,氧化锆微粉的粒度为<5μm,氧化锆微粉的纯度为99%;
7重量份的氧化铝微粉,氧化铝微粉的粒度分布及比例为(<5μm):(<1μm)=1:1;
3重量份的氧化铝溶胶结合剂,氧化铝溶胶结合剂的制备方法为:ρ-Al2O3和﹤1μ超细α-Al2O3微粉加水形成勃姆石凝胶即为氧化铝溶胶;
3重量份的铬铝凝胶,铬铝凝胶包括40重量份的Cr2O3,35重量份的P2O5,8重量份的Al2O3,12重量份的H2O,混合后常温下搅拌即形成铬铝凝胶,所述铬铝凝胶的pH值为2.5。
上述铝铬镁锆复合材料的制备方法如下:
S1:将所述铝镁尖晶石、电熔氧化铬、重熔料混合均匀,得到预混合颗粒料;
S2:将所述氧化锆微粉、氧化铝微粉混合均匀,得到预混合基质细粉;
S3:向所述预混合颗粒中加入氧化铝溶胶结合剂,混合均匀后,得到泥料;
S4:困料,所述困料的时间为24-72小时;
S5:困过的泥料再次碾压搅拌5分钟后,在600T-1000T多面加压压砖机成型;
S6:步骤S5获得的成型胚料在150℃-180℃下干燥24-48小时,干燥后烧成,烧成温度1600℃,保温16小时,得到用于赤泥回收熔分炉底的铬铝镁锆耐火材料。
制得的铬铝镁锆耐火材料经检测、使用,结果与实施例1一致,此处不再赘述。
制得的铬铝镁锆耐火材料经检测,达到以下指标:
对比例1
本对比例与实施例1不同在于,使用硅微粉结合剂代替实施例1中的氧化铝溶胶结合剂,硅微粉结合剂用量与实施例1中氧化铝凝胶的重量份一致。
对比例1制得的耐火材料,经测试,SiO2含量超标,达2.3%。将对比例1制得的耐火材料应用于熔分炉池底部位,用于回收赤泥中的有用成分,结果仅使用2炉,炉体就发生烧穿现象。
对比例2
本对比例与实施例1不同在于,使用糊精有机结合剂代替实施例1中的氧化铝溶胶结合剂,糊精结合剂用量与实施例1中氧化铝凝胶的重量份一致。
对比例2制得的耐火材料,经测试,该耐火材料气孔率较高,达15%。将对比例1制得的耐火材料应用于熔分炉池底部位,用于回收赤泥中的有用成分,结果仅使用1炉,炉体就发生烧穿现象,与现有耐火材料在赤泥回收应用现状相同。
对比例3
本对比例与实施例1不同在于,使用1:1的磷酸和磷酸二氢铝结合剂代替实施例1中的氧化铝溶胶结合剂,磷酸和磷酸二氢铝总量与实施例1中氧化铝凝胶的重量份一致。
该对比例制得的耐火材料的性能参数如下表:
对比例4
本对比例与实施例1不同在于,铝镁尖晶石为富镁尖晶石,加入量与实施例1相同。
该对比例制得的耐火材料的性能参数如下表:
对比例5
本对比例与实施例1不同在于,原料不添加铬铝凝胶,其他与实施例1相同。
该对比例制得的耐火材料的性能参数如下表:
对比例6
本对比例与实施例1不同在于,原料不添加氧化锆微粉,其他与实施例1相同。
该对比例制得的耐火材料的性能参数如下表:
对比例7
本对比例与实施例1不同在于,原料不添加氧化铝微粉,其他与实施例1相同。
该对比例制得的耐火材料的性能参数如下表:
对比例8
本对比例与实施例1不同在于,原料不添加重熔料,其他与实施例1相同。
该对比例制得的耐火材料的性能参数如下表:
对比例3-8的各项指标均有下降,不添加铬铝凝胶,使材料的气孔率提高,体积密度下降,使材料的抗渗透、抗侵蚀性能下降;原料不添加氧化锆微粉,主要突出在热证稳定性下降严重,必然导致使用过程中产生剥落;不添加氧化铝微粉和不添加重熔料均导致各项指标下降。
前述对本发明的具体示例性实施方案的描述是为了说明和例证的目的。这些描述并非想将本发明限定为所公开的精确形式,并且很显然,根据上述教导,可以进行很多改变和变化。对示例性实施例进行选择和描述的目的在于解释本发明的特定原理及其实际应用,从而使得本领域的技术人员能够实现并利用本发明的各种不同的示例性实施方案以及各种不同的选择和改变。本发明的范围意在由权利要求书及其等同形式所限定。
Claims (7)
1.一种赤泥回收熔分炉底用的铝铬镁锆复合材料,其特征在于,所述铝铬镁锆复合材料的原料包括:
20-30重量份的铝镁尖晶石;
40-50重量份的电熔氧化铬;
15-20重量份的重熔料;
3-5重量份的氧化锆微粉;
5-7重量份的氧化铝微粉;
2-3重量份的氧化铝溶胶结合剂;
1-3重量份的铬铝凝胶;
所述铝镁尖晶石的粒度为3-1mm;
所述电熔氧化铬的粒度分布及重量比为(5-3mm):(3-1mm):(1-0mm)=1:1.5:2;
所述重熔料的粒度分布及重量比为(5-3mm):(3-1mm)=1:1;
所述氧化锆微粉的粒度为<5μm,所述氧化锆微粉的纯度为99%以上;
所述氧化铝微粉的粒度分布及重量比为(<5μm):(<1μm)=1:1;
所述铝镁尖晶石为富铝铝镁尖晶石,包括90wt%以上的Al2O3,和5wt%-7wt%的MgO;
所述重熔料为铝铬共熔体,所述重熔料中Al2O3和Cr2O3的总量≥94wt%,所述重熔料中SiO2的含量≤1.0wt%;
所述氧化铝溶胶结合剂为ρ-Al2O3微粉和α-Al2O3微粉加水后形成的勃姆石凝胶,所述ρ-Al2O3微粉与α-Al2O3微粉的粒度小于1μm,所述ρ-Al2O3微粉与α-Al2O3微粉的用量重量比为1:1;
所述铬铝凝胶包括40重量份的Cr2O3,35重量份的P2O5,8重量份的Al2O3,12重量份的H2O;
所述铬铝凝胶的pH值为1.5-2.5。
2.根据权利要求1所述的铝铬镁锆复合材料的制备方法,其特征在于,包括:
S1将所述铝镁尖晶石、电熔氧化铬、重熔料混合均匀,得到预混合颗粒料;
S2将所述氧化锆微粉、氧化铝微粉混合均匀,得到预混合基质细粉;
S3向所述预混合颗粒中加入氧化铝溶胶结合剂,混合均匀后,得到泥料;
S4困料、加压成型,干燥后烧成,得到所述铝铬镁锆复合材料。
3.根据权利要求2所述的制备方法,其特征在于,所述困料的时间为24-72小时。
4.根据权利要求2所述的制备方法,其特征在于,所述加压的压力为600T-1000T。
5.根据权利要求2所述的制备方法,其特征在于,所述干燥的温度为150℃-180℃,干燥的时间为24-48小时。
6.根据权利要求2所述的制备方法,其特征在于,所述烧成的温度为1550℃-1600℃,保温16小时。
7.根据权利要求1所述的铝铬镁锆复合材料或权利要求2-6任一项所述制备方法制备得到的铝铬镁锆复合材料在赤泥回收熔分炉底的应用。
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