CN112125692A - 一种燃烧原位形成镁尖晶石-氧化锆弥散式透气砖及其制备工艺 - Google Patents
一种燃烧原位形成镁尖晶石-氧化锆弥散式透气砖及其制备工艺 Download PDFInfo
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- CN112125692A CN112125692A CN202011027880.3A CN202011027880A CN112125692A CN 112125692 A CN112125692 A CN 112125692A CN 202011027880 A CN202011027880 A CN 202011027880A CN 112125692 A CN112125692 A CN 112125692A
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- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 239000011449 brick Substances 0.000 title claims abstract description 60
- 239000000395 magnesium oxide Substances 0.000 title claims abstract description 58
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000002485 combustion reaction Methods 0.000 title claims abstract description 12
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 27
- 239000011029 spinel Substances 0.000 claims abstract description 26
- 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 21
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 238000005245 sintering Methods 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 13
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 22
- 239000011777 magnesium Substances 0.000 claims description 20
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 18
- 229910052749 magnesium Inorganic materials 0.000 claims description 17
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- -1 magnesium aluminate Chemical class 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 12
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 12
- 239000001569 carbon dioxide Substances 0.000 claims description 9
- 238000010304 firing Methods 0.000 claims description 7
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 7
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 7
- 239000004615 ingredient Substances 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 5
- 239000007767 bonding agent Substances 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 2
- 238000003483 aging Methods 0.000 claims description 2
- 238000009740 moulding (composite fabrication) Methods 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 238000007580 dry-mixing Methods 0.000 claims 1
- 238000005303 weighing Methods 0.000 claims 1
- 235000012245 magnesium oxide Nutrition 0.000 abstract description 48
- 230000035939 shock Effects 0.000 abstract description 15
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 229910052593 corundum Inorganic materials 0.000 abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052799 carbon Inorganic materials 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 8
- 230000003628 erosive effect Effects 0.000 abstract description 8
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 230000035699 permeability Effects 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 3
- 229910000831 Steel Inorganic materials 0.000 description 61
- 239000010959 steel Substances 0.000 description 61
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 34
- 239000007789 gas Substances 0.000 description 22
- 229910052786 argon Inorganic materials 0.000 description 17
- 239000002245 particle Substances 0.000 description 17
- 238000007664 blowing Methods 0.000 description 15
- 229940091250 magnesium supplement Drugs 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 238000007670 refining Methods 0.000 description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 9
- 229910052791 calcium Inorganic materials 0.000 description 9
- 239000011575 calcium Substances 0.000 description 9
- 239000013078 crystal Substances 0.000 description 7
- 239000010431 corundum Substances 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 5
- QRNPTSGPQSOPQK-UHFFFAOYSA-N magnesium zirconium Chemical compound [Mg].[Zr] QRNPTSGPQSOPQK-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
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- 229960000869 magnesium oxide Drugs 0.000 description 4
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- 239000011148 porous material Substances 0.000 description 4
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- 238000009423 ventilation Methods 0.000 description 4
- QQHSIRTYSFLSRM-UHFFFAOYSA-N alumanylidynechromium Chemical compound [Al].[Cr] QQHSIRTYSFLSRM-UHFFFAOYSA-N 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000011819 refractory material Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 229910000655 Killed steel Inorganic materials 0.000 description 2
- 229910001336 Semi-killed steel Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000009991 scouring Methods 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- 229910026161 MgAl2O4 Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000005049 combustion synthesis Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000004200 deflagration Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000000156 glass melt Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 229910001338 liquidmetal Inorganic materials 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002436 steel type Substances 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
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- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
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- C04B38/0025—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof obtained by a chemical conversion or reaction other than those relating to the setting or hardening of cement-like material or to the formation of a sol or a gel, e.g. by carbonising or pyrolysing preformed cellular materials based on polymers, organo-metallic or organo-silicon precursors starting from inorganic materials only, e.g. metal foam; Lanxide type 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
- C04B35/44—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 aluminates
- C04B35/443—Magnesium aluminate spinel
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- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
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Abstract
本发明涉及一种燃烧原位形成镁尖晶石‑氧化锆弥散式透气砖及其制备工艺。以方镁石、尖晶石、氧化锆为主原料,添加金属Mg粉和活性Al2O3,利用Mg在CO2中粉燃烧生成MgO和碳,同时局部产生大于2000℃高温,生成的MgO具有高反应活性,和活性Al2O3原位反应形成尖晶石促进烧结,使透气砖获得高强度和耐磨性。同时,燃烧的高温使MgO部分固溶于ZrO2,提高了透气砖的抗侵蚀性和抗热震性;碳在后续氧化中烧失,遗留弥散式孔道赋予良好的通气性。
Description
技术领域
本发明涉及一种燃烧合成镁尖晶石-氧化锆弥散式透气砖及其制备工艺,属于无机非金属材料学科高温陶瓷和耐火材料领域。
技术背景
炉外精炼是制备特种钢、高等级钢种不可或缺的冶炼工艺,在精炼中利用钢包底部透气砖进行吹氩搅拌,以实现均化钢水成分,均化钢水温度,促进夹杂物、渣、气体上浮去除非金属夹杂,促进合金冶金反应进行,洁净钢水、提高钢水质量,达到精炼目的。透气砖必须具有优良的透气性,同时,在钢水的高温环境下服役必须具有优异的抗侵蚀性,在吹气时钢水搅动和气体冲刷要求其具有优良的高温耐磨性、抗热震性。
目前广泛使用的透气砖主要有狭缝式、弥散式两大类型。其中,弥散式透气砖是通过颗粒堆积,在颗粒之间产生弥散连通气孔,这些弥散的贯通气孔成为吹气的通道。透气砖中的基质细粉和微粉加入量欠缺,不达到致密堆积效果,基质仅在高温作用下烧结为透气砖提供结合强度。由于弥散式透气砖的弥散结构,吹气时产生大量的弥散小气泡,这些细小气泡具有较大的比表面积,更易捕捉钢液中的夹杂物,更有效的去除钢水有害夹杂、更有效的均匀钢水成分和温度。与狭缝型透气砖相比,弥散式透气砖上气快,吹通率高、使用安全、有效避免狭缝夹钢、砖芯断裂等优点。但弥散式透气砖的气孔率较高(气孔率为25~30%),且气孔尺寸较大,导致弥散式透气砖强度较低,抗冲刷能力差;在使用中钢液、钢渣通过气孔渗入工作层,导致气孔堵塞或形成致密变质层,需要通过吹氧轻烧,加速了弥散式透气砖的损毁。
钢包透气砖的常用材质主要有刚玉质的材质,刚玉质或刚玉和其它材料复合的透气砖(刚玉-尖晶石质、铬刚玉质和铬刚玉-尖晶石质)因为其强度高、膨胀系数小而广泛应用,但钢包精炼钢种或使用条件的不同,透气砖的损毁机制也不尽相同。由于氧化铝的两性氧化物特性,刚玉在高温下易和碱反应,导致刚玉质透气砖抗碱侵蚀能力很差,难以适应钙处理钢、高氧钢、优质钢、沸腾钢、镇静钢、半镇静钢等特种钢炉外精炼的要求,精炼以上这些特种钢种的钢包透气砖成为制约炉外精炼钢包寿命的关键因素。
发明内容
本发明采用抗碱侵蚀好的氧化镁、镁铝尖晶石、氧化锆为主要原料,通过燃烧合成制备具有优异的通气性、抗侵蚀性、耐磨性、抗热震性、且成本低廉、使用安全稳定的镁铝尖晶石-氧化锆质弥散式透气砖,满足钙处理钢、高氧钢、洁净钢精炼的使用条件及安全要求。
一种燃烧原位形成镁尖晶石-氧化锆弥散式透气砖,按照质量百分比计,原料配方如下:
(1)粒度4~2mm的电熔镁砂,26~44%;
(2)粒度2~1mm的电熔镁砂,38~45%;
(3)粒度1~0.088mm的氧化锆,5~11%;
(4)粒度1~0.088mm的镁铝尖晶石,2~5%;
(5)粒度1~0.088mm的活性氧化铝,3~6%;
(6)粒度1~0.088mm的金属镁粉,5~10%;
(7)二氧化碳气体;
(8)外加添加剂,聚甲基丙烯酸甲酯(PMMA)粉,+6~12%;
(9)外加结合剂,液体焦油,+2~3%;
本发明以电熔镁砂、尖晶石、氧化锆为主原料。电熔镁砂的结晶相为方镁石,属等轴晶系NaCl型结构,负离子O2-作立方最紧密堆积,构成立方面心格子,正离子Mg2+填充在O2-最紧密堆积形成的八面体空隙中,Mg2+与O2-以离子键结合,其静电强度相等,晶格能为3933.0KJ/mol,晶体结构稳定,熔点2800℃。方镁石化学性能稳定,在高温时(1540℃)氧化镁和各种耐火材料之间不起反应或弱反应(硅质除外),对含CaO和FeO的碱性渣有极好的抵抗能力,因此特别适用于钙处理钢、高氧钢、优质钢、沸腾钢、镇静钢、半镇静钢等特种钢炉外精炼的要求。但方镁石热膨胀系数大(0~1500℃,α=14~15×10-6/℃),并随温度升高而增大,而导热系数随温度升高而下降(100℃时,λ=123.5KJ/m·℃;1000℃时,λ=24.1KJ/m·℃),因此,单纯采用的方镁石为原料的镁砖抗热震性较差,常常与其它材料复合,比如炼钢工艺广泛使用的镁碳砖,通过方镁石复合石墨改善抗热震性。本发明是通过在镁质耐火材料中添加ZrO2提高抗热震性和抗侵蚀性,同时,方镁石晶内的氧化锆细晶颗粒起到钉扎效应,减少了材料的高温蠕变滑移,提高了材料的高温强度和抗折性能。氧化锆熔点约2700℃,莫氏硬度超过7,高温强度大,抗热震性好,荷重软化温度高(0.2MPa荷重时在2000℃保持0.5-1h才产生变形)。在20-1080℃时氧化锆热膨胀系数为8.0×10-6。ZrO2中的Zr与7个以上O配位,氧化锆具有很高的化学稳定性,无论对酸或碱或玻璃熔体都有很强的化学惰性,不易被液态金属润湿。由于氧化锆和氧化镁的熔点都很高,且在MgO-ZrO2二元系中没有二元化合物,最低共熔点高达2070℃。因此,即使加入其它助烧剂,镁锆砖的烧结温度仍然很高,如,CN102145995A,公布了烧成工艺为1680~1840℃保温3~5h,若采用较低温度烧成的镁锆砖,必然引入氧化硅等组分,如,CN103964873B采用锆英砂的方式引入氧化硅、CN102320844B直接加入二氧化硅细粉原料。根据MgO-ZrO2-SiO2三元相图,加入二氧化硅导致镁锆砖的共熔点温度降低,必然降低其高温性能。
本发明是在不引入二氧化硅的情况下,降低镁锆砖烧成的环境温度,通过添加金属Mg粉和活性Al2O3,利用Mg在CO2中粉燃烧生成MgO和碳,同时局部产生大于2000℃高温,生成的MgO具有高反应活性,和活性Al2O3原位反应形成尖晶石促进透气砖烧结,获得高强度和耐磨性。同时,燃烧的高温使MgO部分固溶于ZrO2,提高了透气砖的抗侵蚀性和抗热震性;碳在后续氧化中烧失,遗留弥散式孔道赋予良好的通气性。
涉及的化学反应包括前期和后期:
(1)前期有燃烧反应和原位生成尖晶石反应:
2Mg+CO2=2MgO+C,强放热反应,产生大于2000℃高温;
MgO +Al2O3=MgAl2O4,原位形成尖晶石,烧结透气砖;
(2)后期碳氧化反应:
C + O2= CO2,逸出CO2气体,遗留孔道。
加入的镁铝尖晶石作为晶种,引导镁和二氧化碳反应生成的高活性氧化镁和活性氧化铝发生反应,原位形成尖晶石达到烧结透气砖的作用。
颗粒级配采用粒度4~2mm、2~1mm、1~0.088mm的三级配料方式,利用颗粒的非致密堆积效果的百分比例,以形成弥散的贯通孔隙。原料(8)、(9)另外加入,不计入原料总质量百分比内。外加的聚甲基丙烯酸甲酯(PMMA)膨胀系数大,在高温时烧失,为原位反应形成的尖晶石体积膨胀预留体积,也为弥散的贯通孔隙预留体积。液体焦油为有机结合剂,同时覆盖金属镁粉,防止镁粉在研磨和搅拌时接触空气或氧气产生爆燃,液体焦油在高温下烧失。
本发明制备工艺技术特征包括以下步骤:
(1)配料混碾:按比例称量粒度4~2mm的电熔镁砂、粒度2~1mm的电熔镁砂干混2~3min,然后加入液体焦油,混合2~3min。再加入1~0.088mm的氧化锆、粒度1~0.088mm的镁铝尖晶石、粒度1~0.088mm的活性氧化铝、粒度1~0.088mm金属镁粉,强力混碾15~20min;
(2)成形:经密闭困料24~36h后,倒入模具中,压制成形;
(3)干燥:自然干燥24~48h后,再在160~220℃干燥24~48h;
(4)烧成:装入气氛炉内烧成,通入0.2~0.3MPa压力的CO2气体,在1500~1600℃保温3~5h。然后,通入空气,保温1~2小时。
本发明技术特点有:(1)主要原料为电熔镁砂和氧化锆,通过氧化锆改善透气砖的抗热震性和抗侵蚀性;(2)作为原料加入的镁铝尖晶石起到晶种作用,引导CO2和Mg粉燃烧反应新生成的具有高反应活性MgO和活性Al2O3原位反应形成尖晶石,促进透气砖烧结,获得高的强度和耐磨性;(3)镁和二氧化碳反应还有碳副产物,碳在后续高温时氧化烧失,遗留弥散式贯通孔隙,增多细小孔隙而获得优良的通气性。显著的优点为:通过辅助燃烧局部放热的瞬态高温,在较低环境温度下烧结,原位形成的镁铝尖晶石-氧化锆质弥散式透气砖具有优异的通气性、抗侵蚀性、耐磨性、抗热震性。其体密约为2.9g/cm3;常温耐压强度≥80MPa;1450℃高温抗折强度≥10MPa;抗热震性(1100℃×0.5h~水循环)10次以上断裂;0.3MPa氩气气流量≥380L/min。本发明制备成本低廉、使用安全稳定的,满足钙处理钢、高氧钢、洁净钢精炼的使用条件及安全要求。在新某钢厂LF精炼钢包使用,精炼钢种钙处理钢,钢包容量70T,装有2支透气砖,安装在耳轴连线成30°,钢包底1/3处,避开冲击区。每炉吹氩时间150~220分钟,吹氩压力0.2~0.4MPa,钢水温度1580~1650℃,使用了30炉后下线,残余长度160mm以上,残砖无夹钢、无渗钢,表现出优异的抗侵蚀性能。
具体实施实例
实施例一
原料规格和配方(重量百分含量)如下:
(1)粒度4~2mm的电熔镁砂,26%;
(2)粒度2~1mm的电熔镁砂,45%;
(3)粒度1~0.088mm的氧化锆,11%;
(4)粒度1~0.088mm的镁铝尖晶石,2%;
(5)粒度1~0.088mm的活性氧化铝,6%;
(6)粒度1~0.088mm的金属镁粉,10%;
(7)二氧化碳气体;
(8)外加添加剂,聚甲基丙烯酸甲酯(PMMA)粉,+18%;
(9)外加结合剂,液体焦油,+3%;
制备工艺技术包括以下步骤:
(1)配料混碾:按比例称量粒度4~2mm的电熔镁砂、粒度2~1mm的电熔镁砂干混2min,然后加入液体焦油,混合3min。再加入1~0.088mm的氧化锆、粒度1~0.088mm的镁铝尖晶石、粒度1~0.088mm的活性氧化铝、粒度1~0.088mm金属镁粉,强力混碾20min;
(2)成形:经密闭困料36h后,倒入模具中,压制成形;
(3)干燥:自然干燥48h后,再在220℃干燥24h;
(4)烧成:装入气氛炉内烧成,通0.3MPa压力的CO2气体,在1500℃保温5h。然后,通入空气,2小时。
表1列出了本发明的镁尖晶石-氧化锆弥散式透气砖实施例一的原料规格和配方及其性能。体密2.91g/cm3,具有良好的强度,其常温耐压强度82MPa、尤其是高温强度表现突出,1450℃,高温抗折强度11MPa。同时具有很高的气体流量0.3MPa氩气气流量382L/min,大于常用的铝铬系透气砖通气量350L/min。且抗热震性优良,1100℃×0.5h~水循环10次断裂。应用于新某钢厂精炼钢种钙处理钢,吹氩时间200分钟,吹氩压力0.3MPa,钢水温度1620℃,使用30炉后下线,残余长度170mm,残砖无夹钢、无渗钢,表现优异的抗侵蚀性能。
实施例二
原料规格和配方(重量百分含量)如下:
(1)粒度4~2mm的电熔镁砂,35%;
(2)粒度2~1mm的电熔镁砂,42%;
(3)粒度1~0.088mm的氧化锆,8%;
(4)粒度1~0.088mm的镁铝尖晶石,4%;
(5)粒度1~0.088mm的活性氧化铝,4%;
(6)粒度1~0.088mm的金属镁粉,7%;
(7)二氧化碳气体;
(8)外加添加剂,聚甲基丙烯酸甲酯(PMMA)粉,+12%;
(9)外加结合剂,液体焦油,+2%;
制备工艺技术包括以下步骤:
(1)配料混碾:按比例称量粒度4~2mm的电熔镁砂、粒度2~1mm的电熔镁砂干混3min,然后加入液体焦油,混合2min。再加入1~0.088mm的氧化锆、粒度1~0.088mm的镁铝尖晶石、粒度1~0.088mm的活性氧化铝、粒度1~0.088mm金属镁粉,强力混碾20min;
(2)成形:经密闭困料30h后,倒入模具中,压制成形;
(3)干燥:自然干燥36h后,再在200℃干燥36h;
(4)烧成:装入气氛炉内烧成,通0.3MPa压力的CO2气体,在1550℃保温4h。然后,通入空气,保温1.5小时。
表1列出了本发明的镁尖晶石-氧化锆弥散式透气砖实施例二的原料规格和配方及其性能。体密2.90g/cm3,具有良好的强度,其常温耐压强度82MPa、尤其是高温强度表现突出,1450℃,高温抗折强度11MPa。同时具有很高的气体流量0.3MPa氩气气流量383L/min,大于常用的铝铬系透气砖通气量350L/min。且抗热震性优良,1100℃×0.5h~水循环11次断裂。应用于新某钢厂精炼钢种钙处理钢,吹氩时间200分钟,吹氩压力0.3MPa,钢水温度1620℃,使用30炉后下线,残余长度166mm,残砖无夹钢、无渗钢,表现优异的抗侵蚀性能。
实施例三
原料规格和配方(重量百分含量)如下:
(1)粒度4~2mm的电熔镁砂,44%;
(2)粒度2~1mm的电熔镁砂,38%;
(3)粒度1~0.088mm的氧化锆,5%;
(4)粒度1~0.088mm的镁铝尖晶石,5%;
(5)粒度1~0.088mm的活性氧化铝,3%;
(6)粒度1~0.088mm的金属镁粉,5%;
(7)二氧化碳气体;
(8)外加添加剂,聚甲基丙烯酸甲酯(PMMA)粉,+6%;
(9)外加结合剂,液体焦油,+2%;
制备工艺技术包括以下步骤:
(1)配料混碾:按比例称量粒度4~2mm的电熔镁砂、粒度2~1mm的电熔镁砂干混2min,然后加入液体焦油,混合2min。再加入1~0.088mm的氧化锆、粒度1~0.088mm的镁铝尖晶石、粒度1~0.088mm的活性氧化铝、粒度1~0.088mm金属镁粉,强力混碾15min;
(2)成形:经密闭困料24h后,倒入模具中,压制成形;
(3)干燥:自然干燥24h后,再在160℃干燥48h;
(4)烧成:装入气氛炉内烧成,通0.2MPa压力的CO2气体,在1600℃保温3h。然后,通入空气,保温1小时。
表1列出了本发明的镁尖晶石-氧化锆弥散式透气砖实施例三的原料规格和配方及其性能。体密2.88g/cm3,具有良好的强度,其常温耐压强度80MPa、尤其是高温强度表现突出,1450℃,高温抗折强度10MPa。同时具有很高的气体流量0.3MPa氩气气流量390L/min,大于常用的铝铬系透气砖通气量350L/min。且抗热震性优良,1100℃×0.5h~水循环11次出现大裂纹。应用于新某钢厂精炼钢种钙处理钢,吹氩时间200分钟,吹氩压力0.3MPa,钢水温度1620℃,使用30炉后下线,残余长度161mm,残砖无夹钢、无渗钢,表现优异的抗侵蚀性能。
对比例一
原料规格和配方(重量百分含量)如下:
(1)粒度4~2mm的电熔镁砂,36%;
(2)粒度2~1mm的电熔镁砂,45%;
(3)粒度1~0.088mm的氧化锆,11%;
(4)粒度1~0.088mm的镁铝尖晶石,2%;
(5)粒度1~0.088mm的活性氧化铝,6%;
(6)粒度1~0.088mm的金属镁粉,10%;
(7)外加结合剂,木质素磺酸镁水溶液(浓度8%),+3%;
制备工艺技术包括以下步骤:
(1)配料混碾:按比例称量粒度4~2mm的电熔镁砂、粒度2~1mm的电熔镁砂干混2min,然后加入结合剂,混合3min。再加入1~0.088mm的氧化锆、粒度1~0.088mm的镁铝尖晶石、粒度1~0.088mm的活性氧化铝,强力混碾20min;
(2)成形:经密闭困料36h后,倒入模具中,压制成形;
(3)干燥:自然干燥48h后,再在220℃干燥24h;
(4)烧成:装入高温炉内烧成,在1750℃保温3h。
表1列出了对比例一的原料规格和配方及其性能。对比例一没有加入金属镁粉原料,因为没有金属镁粉和二氧化碳燃烧产生的局部2000℃以上的高温,即使经过炉内环境温度1750℃保温3h超高温烧成后,其体密(2.90g/cm3)、常温耐压强度(75MPa)、高温抗折强度(1450℃,9MPa)等物理性能能仍低于本发明采用较低温度烧成的性能。同时,因为没有碳氧化逸出二氧化碳气体遗留的孔道,透气砖的气流量(0.3MPa氩气气流量350L/min)低于本发明透气砖气流量(380L/min以上)。抗热震性(1100℃×0.5h~水循环10次断裂)和本发明相当。但使用性能显著低于比本发明实施例(对比例一:高度380mm透气砖应用于新某钢厂精炼钢种钙处理钢,吹氩时间200分钟,吹氩压力0.3MPa,钢水温度1620℃,使用28炉后下线,残余长度仅有155mm,残砖无夹钢、无渗钢。而实施例使用30炉后下线,残余长度仍超过160mm)。
表1 镁尖晶石-氧化锆弥散式透气砖的原料规格、配方及其性能对照表
Claims (2)
1.一种燃烧原位形成镁尖晶石-氧化锆弥散式透气砖及其制备工艺,原料以重量百分含量计为:
粒度4~2mm的电熔镁砂,26~44%;
粒度2~1mm的电熔镁砂,38~45%;
粒度1~0.088mm的氧化锆,5~11%;
粒度1~0.088mm的镁铝尖晶石,2~5%;
粒度1~0.088mm的活性氧化铝,3~6%;
粒度1~0.088mm的金属镁粉,5~10%;
二氧化碳气体;
外加添加剂,聚甲基丙烯酸甲酯(PMMA)粉,+6~18%;
外加结合剂,液体焦油,+2~3%。
2.制备工艺技术特征,包括以下步骤:
配料混碾:按比例称量粒度4~2mm的电熔镁砂、粒度2~1mm的电熔镁砂干混2~3min,然后加入液体焦油,混合2~3min;再加入1~0.088mm的氧化锆、粒度1~0.088mm的镁铝尖晶石、粒度1~0.088mm的活性氧化铝、粒度1~0.088mm金属镁粉,强力混碾15~20min;
成形:经密闭困料24~36h后,倒入模具中,压制成形;
干燥:自然干燥24~48h后,再在160~220℃干燥24~48h;
烧成:装入气氛炉内烧成,通入0.2~0.3MPa压力的CO2气体,在1500~1600℃保温3~5h;然后,通入空气,保温1~2小时。
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