CN108395228B - 烧成不油浸铬镁铝无碳质滑板砖及其制备方法 - Google Patents
烧成不油浸铬镁铝无碳质滑板砖及其制备方法 Download PDFInfo
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Abstract
本发明公开了烧成不油浸铬镁铝无碳质滑板砖,按重量百分含量计,包含以下组分:棕刚玉37%~38%、85矾土3%~5%、铬刚玉14%~18%、熔融石英4%~7%、板状刚玉8%~11%、镁橄榄石5%~8%、烧结莫来石5%~6%、活性α‑Al2O3微粉5%~7%、铝片2%~3%、金属硅粉2%~3%、高温促烧粉4%~6%,上述配方中所有组分重量之和为100%,外加热塑性树脂4~5%,六次甲基四胺(乌洛托品)0.4~0.5%。本发明的目的在于提供了一种生产周期短、节约大量能源(如水电气)、工序减少、生产和使用对环境无污染、有良好的抗侵蚀性和抗冲刷性的烧成不油浸铬镁铝无碳质滑板砖及其制备方法。
Description
技术领域
本发明涉及以氧化铝、氧化镁、碳为基料的无机非金属耐火材料领域,更具体涉及烧成不油浸铬镁铝无碳质滑板砖及其制备方法。
背景技术
随着冶炼新技术的发展,冶炼钢种增加,对连铸用滑板材料的要求也不断的提高。因此,迫切需要开发新型滑板或进一步提高原有滑板的品质。
由于世界各国在国防、交通、石油及汽车等行业的发展与技术进步,对钢材性能的要求日益苛刻。实践证明,钢材的纯净度越高,其性能越高,使用寿命也越长。钢中杂质含量降到一定水平时,钢材的性能将发生质变。如钢中碳含量从40×10-6降至10×10-6时,深冲钢的伸长率可增加7%;对汽车工业而言,汽车钢板的超深冲成形性主要通过降碳和提高钢的纯净度。近几年来,钢中含碳量的国际先进水平已经降到了10~20ppm。
目前连铸用耐火材料主要还是含碳材料。碳的存在显然对高纯净钢的浇铸是不利的。因此,通过材质的改进,开发无碳或低碳连铸用耐火材质体系,以尽可能降低碳对钢水的污染,同时也达到提高其使用寿命的目的。
随着科技的进步,技术的更新换代,国内外各大炼钢厂的钢种也在不断的升级创新,我公司的滑板砖为了满足钢厂钢种变化的需求,材质也在做调整来适应各钢厂的冶炼的需求。因现在各大钢厂低碳钢、高氧钢较多,如果滑板中C含量较高,会导致钢水二次污染,均不利于冶炼低碳钢、洁净钢,也会导致钢坯增C的风险;同样高氧钢中的O含量较高,如果滑板中的C含量同样高,在使用过程中C与O反应生成CO2,因氧化失碳形成变质层增多,滑板易氧化发白,结构组织疏松,抗氧化性减弱,导致滑板不耐侵蚀和抗冲刷,从而影响滑板使用寿命或存在浇钢不安全因素。
滑板烧成之后,目前国内外厂家一般要进行油浸,油浸中一般采用立式或卧式真空-加压油浸装置。滑板预热后放入油浸罐内,并抽真空至真空度 650mmHg柱以上,引入加热了的焦油或沥青,并对油加压至8-16kgf/cm2 或更高的压力,使焦油或沥青被吸入滑板的开口气孔中。但油浸中沥青碳挥发,对环境污染和人体健康均不利。
由于世界各国重视环保节能,尤其我国更加重视,所以采用一种烧成不油浸铬镁铝无碳质滑板砖势在必行,即环保又节能,对生产和使用不会造成环境污染。
发明内容
为了解决上述问题,本发明的目的在于提供了一种生产周期短、节约大量能源(如水电气)、工序减少、生产和使用对环境无污染、有良好的抗侵蚀性和抗冲刷性的烧成不油浸铬镁铝无碳质滑板砖及其制备方法。
本发明的目的可以通过以下技术方案实现:
烧成不油浸铬镁铝无碳质滑板砖,按重量百分含量计,包含以下组分:棕刚玉37%~38%、85矾土3%~5%、铬刚玉14%~18%、熔融石英4%~ 7%、板状刚玉8%~11%、镁橄榄石5%~8%、烧结莫来石5%~6%、活性α-Al2O3微粉5%~7%、铝片2%~3%、金属硅粉2%~3%、高温促烧粉4%~6%,上述配方中所有组分重量之和为100%,外加热塑性树脂4~ 5%,六次甲基四胺(乌洛托品)0.4~0.5%。
其各组分的颗粒级配为:棕刚玉的颗粒直径为3~1以及1~0mm,85 矾土颗粒直径为1~0mm,铬刚玉颗粒直径为0.5~0mm,熔融石英颗粒直径为1~0mm,板状刚玉为325目,镁橄榄石为180目,烧结莫来石为200目,活性α-Al2O3微粉为1μm,铝片为320目,金属硅粉为240目,高温促烧粉为 320目,所述的热塑性树脂为液体。
棕刚玉颗粒级配按重量百分含量为:
3~1mm 18%~22%
1~0mm 16%~19%;
棕刚玉的颗粒级配重量百分含量之和为37%~38%。
按重量百分含量计,所述的棕刚玉:Al2O3含量≥95%、Fe2O3含量≤ 1.8%、SiO2含量<1.2%,所述的85矾土:Al2O3含量≥85%、Fe2O3含量<1%、TiO2含量<4.0%;所述的铬刚玉:Al2O3含量≥85%、Cr2O3含量≥13%;所述的熔融石英:SiO2含量≥98%;所述的板状刚玉:Al2O3含量≥ 99%、Fe2O3含量≤0.2%;所述的镁橄榄石:MgO含量≥45%,SiO2含量≥ 40%;Fe2O3含量≤10%;所述的烧结莫来石:Al2O3含量≥99%、Fe2O3含量≤0.6%;所述的活性α-Al2O3微粉:Al2O3含量≥72%、Fe2O3≤含量0.3%;所述的铝片:活性铝Al≥97%;所述的金属硅粉:Si含量≥97%、Fe2O3含量≤1.0%;所述的高温促烧粉:Al2O3含量≥70%,SiO2含量≤25%;所述的热塑性树脂:残碳量45±4%、固含量75~80%、粘度15000~18000mpa。
烧成不油浸铬镁铝无碳质滑板砖的制备方法,采用以下方法制备:按比例将棕刚玉、85矾土、铬刚玉、熔融石英、板状刚玉、镁橄榄石、烧结莫来石、活性α-Al2O3微粉、铝片、金属硅粉、高温促烧粉、六次甲基四按(乌洛托品)和热塑性酚醛树脂搅拌混合,然后成型并自然干燥,再放入干燥窑中缓慢升温干燥40~60小时,干燥窑温度不超过180~190℃为宜,然后推入中高温隧道窑均匀升温到580℃±20℃,保温15-20小时,最后匀速降温16-25小时即可。
烧成不油浸铬镁铝无碳质滑板砖的制备方法,1小时内将干燥窑温度均匀升温到80℃,且在80℃保温12小时,然后24小时内将温度从80℃均匀上升到190℃,并在190℃下保温20时。
烧成不油浸铬镁铝无碳质滑板砖的制备方法,在15-20小时内将温度均匀升温到580℃±20℃,最后匀速降温20小时。
烧成铝锆碳材质是目前滑板普遍采用的一种材质。一般在铝锆碳滑板生产过程中引入金属硅粉,使之在高温下原位生成SiC晶须,提高强度,提高滑板的抗氧化性。但在高温使用过程中SiC最终生成SiO2,SiO2过多,与钢水中的[Fe]、[Mn]等元素反应,使得制品的抗侵蚀性能下降。所以,烧成不油浸铬镁铝无碳质滑板砖中加入少量铝片、降低Si的引入量,这不仅可以提高材料强度和抗侵蚀性,并且还能降低制品的烧成温度,其主要原因是在烧成过程中Al反应生成Al4C3和AlN。在烧成不油浸铬镁铝无碳质滑板砖中,不仅有机结合剂在烧成中碳化结焦,在砖中形成碳结合,而且加入物,加入金属硅,在<1300℃还原烧成时,能与碳素化合生成SiC,而在砖体内形成陶瓷结合。所以,烧成不油浸铬镁铝无碳质滑板砖中存在着陶瓷结合和碳结合的双重结合系统,使滑板强度明显提高。
铬刚玉:该产品是用铝热法生产金属铬的副产品,由高纯的氧化铬与金属铝粉经过充分混合,在反应炉点燃,金属铝粉燃烧产生的大量热量,使炉内物料熔融,同时金属铝夺取氧化铬中的氧原子时被氧化,氧化铬被还原生成金属铬,在高温激烈的化学反应过程中,氧化铝变成高温溶液与部份未被还原的氧化铬形成固熔体,此种方法生成的铬刚玉原料纯度高、结晶发育好,是一种抗侵蚀性能优秀的耐火原料。
高温促烧粉:该产品主要应用在定型耐火材料基质中,其耐火度大于 1800℃,砖坯在180~250℃干燥后,易促进制品内部结构形成碳结合,在保持制品原有的常温耐压强度、体密和气孔的条件下:砖坯具有优良的抗热震性、抗剥落性和抗氧化性,制品韧性增强,能有效提高砖坯在使用过程中受极冷极热的影响,导致砖坯开裂、剥落而影响使用,从而达到提高使用寿命的目的。
烧成不油浸铬镁铝无碳质滑板砖生产过程要求:
(1)配料要严密按比率称量,细粉要混平均,配混合粉时,添加剂要加在物料之间,经混合机搅动的混合粉要抽察其化工成份是否平均;
(2)经湿碾机或者高速混练机混合的物料要操纵其气温,以提防物料温渡过高或者过低影响混料成效和成型性。冬节需采纳保温举措,夏天要尽力下降室气温,最好能保持在25℃前后。
(3)成型时压力要先轻后重,之间排气,免除层裂;常常检查底盖板的弯曲度,提防滑板变形造成废品;
(4)严密控制烧成流程中的升温曲线,降温时必需匀速缓慢提防出现裂纹;
(5)滑板磨制时必需严密操纵平行度和平整度;
(6)滑板在搬运或者抛光流程中要轻拿轻放,在固定或者打箍时要以木捶或者橡皮捶轻小扣打,禁止用铁捶。
具体实施方式
原料规格如下:
棕刚玉:Al2O3含量≥95%、Fe2O3含量≤1.8%、SiO2含量<1.2%,
85矾土:Al2O3含量≥85%、Fe2O3含量<1%、TiO2含量<4.0%;
铬刚玉:Al2O3含量≥85%、Cr2O3含量≥13%;
熔融石英:SiO2含量≥98%;
板状刚玉:Al2O3含量≥99%、Fe2O3含量≤0.2%;
镁橄榄石:MgO含量≥45%,SiO2含量≥40%;Fe2O3含量≤10%;
烧结莫来石:Al2O3含量≥99%、Fe2O3含量≤0.6%;
活性α-Al2O3微粉:Al2O3含量≥72%、Fe2O3≤含量0.3%;
铝片:活性铝Al≥97%;所述的金属硅粉:Si含量≥97%、Fe2O3含量≤ 1.0%;
高温促烧粉:Al2O3含量≥70%,SiO2含量25≤%;
热塑性树脂:残碳量45±4%、固含量75~80%、粘度15000~ 18000mpa。
发明产品基本生产工艺是:按表1中的配方,棕刚玉、85矾土、铬刚玉、熔融石英经破碎筛分后按表1中的配方进行配料,加入湿碾机或高速混练机中混合3~6分钟,加入热塑性酚醛树脂结合剂,混匀后再加入如下细粉:板状刚玉、镁橄榄石、烧结莫来石、活性α-Al2O3微粉、铝片、金属硅粉、高温促烧粉、六次甲基四按(乌洛托品),混合10~30分钟出料。成型采用1250吨以上螺旋压砖机,按照砖的形状、尺寸,精确称量物料,称量好的料加入到模具内,成型到规定尺寸,每块砖要测量外形尺寸、平整度、对角线尺寸,每班要抽查10%的单重,每一车砖要检测气孔率、体积密度,凡发现不合格现象必须报废并查找原因。成型后的砖坯一般需经自然干燥后才能入干燥窑,砖坯在干燥器中,1小时内将干燥窑温度均匀升温到80℃,且在80℃保温12小时,然后24小时内将温度从80℃均匀上升到190℃,再在190℃下保温20小时,然后推入中高温隧道窑烧成均匀升温580℃± 20℃,匀速升温18小时,保温15小时即可,最后匀速降温20小时。为了提高滑板的使用性,防止裂纹的产生和扩大,要用钢带对滑板周边打箍,在滑板周围用薄铁皮包扎,它可以预防滑板在使用中的碎裂,并由于这种金属箍包扎得十分紧,因此限制滑板砖内裂纹扩展,特别是防止裂纹张开扩大的作用。为了提高滑板在开拉过程中的灵活性,防止从滑动面之间漏钢,滑动面要在磨床上进行加工,要求平整度小于0.05mm。磨制后的滑板经检验合格后,要在背面粘贴石棉垫和马口铁或套铁壳,其作用主要是减少通过滑板砖传递到滑动机构上热量,防止机构在高温下变形而影响使用寿命。
表1本发明产品试验的3个配方中各组分的百分含量铬镁铝无碳质烧成不油浸滑板砖
表2按照表1中3个配方所制得的产品的理化测试指标对照表
根据表2中的检验结果可知:以上3个配方都能正常使用,配方2效果最佳。烧成不油浸铬镁铝无碳质滑板砖在各大中型钢厂钢包、中包成熟使用,比C含量高的滑板砖具有更好的抗侵蚀性和安全性。今年该发明产品已成功在永联钢厂,花山钢厂,首秦钢厂、宝钢、太钢使用。能缓解钢包热周转压力,进一步降低生产成本,减轻工人劳动强度,在不同吨位钢包实施多炉连用技术,从以前的2~3炉提高到4~5炉,吨钢成本降低约2元,其使用性能总结如下:
耐腐蚀性:产品纵向扩径较小,孔径规则,有效行程未出现严重拉毛现象,说明产品的抗侵蚀性较好。
耐磨损性:滑板在高侵蚀性钢种使用后,没出现严重的拉毛,粗糙现象,证明耐磨损性良好。
耐热震性:孔径处无严重剥落现象,其它产品裂纹很少且很小,孔口处无损落现象,外侧也无剥落现象,说明滑板耐热震性良好。
耐氧化性:使用后未发现因氧化而导至滑板严重的组织脆弱,呈发白现象,抗氧化性良好。
热膨胀性:滑板在使用中未出现因受热膨胀过大导致滑板拆卸困难情况,并且能来回自如的滑动,说明试用滑板的膨胀性适中。
环保性:免烧滑板不用沥青油浸,使用时不产生有毒有害的气味,对环境、人体不会产生影响。
本发明产品对社会有益效果:
1、生产周期短,加快了供货时间;
2、节约大量能源(如水电气);
3、工序减少,操作工较少;
4、不油浸,生产和使用对环境无污染;
5、对冶炼洁净钢、低碳钢提供了保障;
6、有良好的抗侵蚀性和抗冲刷性。
7、发明产品使用寿命比原烧成铝碳锆、铝碳质滑板提高35%以上;
8、发明产品能为钢铁行业实现节能降耗,冶炼精品钢、优质钢,增加效益发挥了不可替代的作用;
节能环保优势:由于传统的烧成滑板砖采用1400℃~1600℃碳保护高温烧成,经浸渍焦油、沥青后,再进行干馏及清焦。这种生产工艺不仅能耗高,天然气消耗高达1800立方米/吨产品,而且焦油、沥青在浸渍、干馏和清焦时产生大量的有害物质,对环境、人类健康产生很大的影响;本发明的生产周期从原来的30天缩短到15天,天然气消耗降低至35立方米/吨产品,一种烧成不油浸铬镁铝无碳质滑板砖真正属于环保、节能的绿色耐材产品。
以上所述的仅是发明的一些实施方式,应当指出,对于本领域的普通技术人员来说,在不脱离本发明 的创造构思的前提下,还可以做出其它变形和改进,这些都属于本发明 的保护范围。
Claims (7)
1.烧成不油浸铬镁铝无碳质滑板砖,其特征在于按重量百分含量计,包含以下组分:棕刚玉37%~38%、85矾土3%~5%、铬刚玉14%~18%、熔融石英4%~7%、板状刚玉8%~11%、镁橄榄石5%~8%、烧结莫来石5%~6%、活性α-Al2O3微粉5%~7%、铝片2%~3%、金属硅粉2%~3%、高温促烧粉4%~6%,上述配方中所有组分重量之和为100%,外加热塑性树脂4~5%,六次甲基四胺(乌洛托品)0.4~0.5%。
2.根据权利要求1所述的烧成不油浸铬镁铝无碳质滑板砖,其特征在于,其各组分的颗粒级配为:棕刚玉的颗粒直径为3~1mm以及1~0mm,85矾土颗粒直径为1~0mm,铬刚玉颗粒直径为0.5~0mm,熔融石英颗粒直径为1~0mm,板状刚玉为325目,镁橄榄石为180目,烧结莫来石为200目,活性α-Al2O3微粉为1μm,铝片为320目,金属硅粉为240目,高温促烧粉为320目,所述的热塑性树脂为液体。
3.根据权利要求2所述的烧成不油浸铬镁铝无碳质滑板砖,其特征在于,所述的棕刚玉颗粒级配按重量百分含量为:
3~1mm 18%~22%
1~0mm 16%~19%;
所述的棕刚玉的颗粒级配重量百分含量之和为37%~38%。
4.根据权利要求1所述的烧成不油浸铬镁铝无碳质滑板砖,其特征在于按重量百分含量计,所述的棕刚玉:Al2O3含量≥95%、Fe2O3含量≤1.8%、SiO2含量<1.2%,所述的85矾土:Al2O3含量≥85%、Fe2O3含量<1%、TiO2含量<4.0%;所述的铬刚玉:Al2O3含量≥85%、Cr2O3含量≥13%;所述的熔融石英:SiO2含量≥98%;所述的板状刚玉:Al2O3含量≥99%、Fe2O3含量≤0.2%;所述的镁橄榄石:MgO含量≥45%,SiO2含量≥40%;Fe2O3含量≤10%;所述的烧结莫来石:Al2O3含量≥99%、Fe2O3含量≤0.6%;所述的活性α-Al2O3微粉:Al2O3含量≥72%、Fe2O3≤含量0.3%;所述的铝片:活性铝Al≥97%;所述的金属硅粉:Si含量≥97%、Fe2O3含量≤1.0%;所述的高温促烧粉:Al2O3含量≥70%,SiO2含量≤25%;所述的热塑性树脂:残碳量45±4%、固含量75~80%、粘度15000~18000mpa。
5.根据权利要求1所述的烧成不油浸铬镁铝无碳质滑板砖的制备方法,其特征在于采用以下方法制备:按比例将棕刚玉、85矾土、铬刚玉、熔融石英、板状刚玉、镁橄榄石、烧结莫来石、活性α-Al2O3微粉、铝片、金属硅粉、高温促烧粉、六次甲基四按(乌洛托品)和热塑性酚醛树脂搅拌混合,然后成型并自然干燥,再放入干燥窑中缓慢升温干燥40~60小时,干燥窑温度不超过180~190℃为宜,然后推入中高温隧道窑均匀升温到580℃±20℃,保温15-20小时,最后匀速降温16-25小时即可。
6.根据权利要求5所述的烧成不油浸铬镁铝无碳质滑板砖的制备方法,其特征在于,1小时内将干燥窑温度均匀升温到80℃,且在80℃保温12小时,然后24小时内将温度从80℃均匀上升到190℃,并在190℃下保温20时。
7.根据权利要求6所述的烧成不油浸铬镁铝无碳质滑板砖的制备方法,其特征在于,在15-20小时内将温度均匀升温到580℃±20℃,最后匀速降温20小时。
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