CN111423222A - 一种抗还原反应、抗热震的有色金属冶炼烟化炉或侧吹炉用铬刚玉砖的生产方法 - Google Patents
一种抗还原反应、抗热震的有色金属冶炼烟化炉或侧吹炉用铬刚玉砖的生产方法 Download PDFInfo
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Abstract
一种抗还原反应、抗热震的有色金属冶炼烟化炉或侧吹炉用铬刚玉砖的生产方法,将破碎后的铬渣、烧结刚玉和铬精矿混合均匀,加入到三相电弧炉中冶炼,进行冶炼得到铬刚玉料,铬刚玉料经破碎、粉磨、筛分分级得到粒度分别为5‑3mm、3‑1mm和1‑0mm的颗粒料以及180目和325目的粉料,并加入3‑1mm的电熔锆莫来石,得到混合预混料,加入结合剂磷酸,搅拌均匀,放置≥48h;加入结合剂磷酸二氢铝,进行混练,压制成型,经高温烧成,得到铬刚玉砖。优点是:原料成本低廉,性价比高,生产的铬刚玉砖不仅具有抗冲刷、抗侵蚀、抗高温性,同时还具有抗还原反应、抗热震性,可用于炼铅、锌、锡等有色金属窑炉渣线部位、底部及反应带。
Description
技术领域
本发明属于耐火材料领域,特别涉及一种铬刚玉砖的生产方法,特别涉及一种抗还原反应、抗热震的有色金属冶炼烟化炉或侧吹炉用铬刚玉砖的生产方法。
背景技术
有色金属窑炉用耐火材料工作环境恶劣,尤其是一些领域的窑炉,如炼铅、锌、锡的烟化炉、侧吹炉,对耐火材料的要求更高,要求有高的常温耐压强度,高抗冲刷能力,高抗还原能力,高抗热震性能,高的性价比。这些都原耐火材料—镁铬质耐火材料不预备的。而现有的普通铬渣耐火材料均存在抗还原反应及热震稳定性较差的问题,无法满足这些窑炉的使用要求。
铬刚玉是用工业氧化铝与氧化铬绿电熔生产的,或是用铝热法生产金属铬的副产品铝铬渣,经过高温处理,氧化铝变成高温溶液与部分未被还原的氧化铬形成的固熔体,即为铬刚玉。铬渣主要矿物组成为α-Al2O3和Cr2O3的固熔体,其中Al2O3+Cr2O3质量百分含量一般≥90%,是一种抗侵蚀性能优秀的耐火材料。
发明内容
本发明要解决的技术问题是提供了一种不仅具有抗冲刷、抗侵蚀、抗高温性,同时还具有抗还原反应、抗热震的有色金属冶炼烟化炉或侧吹炉用铬刚玉砖的生产方法,可用于炼铅、锌、锡等有色金属窑炉渣线部位、底部及反应带。
本发明的技术解决方案是:
一种抗还原反应、抗热震的有色金属冶炼烟化炉或侧吹炉用铬刚玉砖的生产方法,具体步骤如下:
a.原料称取
按重量份数计称取以下原料:
b.原料加工
将铬渣进行破碎至粒度≤5mm;将板状刚玉或烧结刚玉破碎至粒度为≤5mm;将铬精矿破碎至粒度为40目~200目;将电熔锆莫来石破碎至粒度至3-1mm;
c.高温冶炼
将破碎后的铬渣、烧结刚玉和铬精矿混合均匀,得到混合料;先将碳质引弧剂放到炉底,与石墨电极正对摆放,将石墨电极下降使之接触到引弧剂,给电起弧后,将混合料加入到三相电弧炉中冶炼,温度控制在2100~2300℃,冶炼时间控制到8~12小时,冶炼完成后,铬渣中含的金属铬沉降至炉缸底部形成铬的碳化物,铬渣中中间价态氧化铬转化成三价铬,铬渣中氧化钠低熔点杂质挥发掉,铬精矿中的氧化铁沉降至炉缸底部进入铬的碳化物,铬渣、烧结刚玉、铬精矿三者中的Al2O3、Cr2O3经高温熔炼成铬刚玉相在炉缸上部,降温冷却固化,将炉缸上部的铬刚玉料进行砸选,去除渣皮得到铬刚玉料;
d.铬刚玉材料加工
将步骤c获得的铬刚玉料经破碎、粉磨、筛分分级得到粒度分别为5-3mm、3-1mm和1-0mm的颗粒料以及180目和325目的粉料;
e.困料
按重量份数计取80份~95份的经筛分分级为粒度5-3mm、3-1mm、1-0mm、180目和325目的铬刚玉料,加入5份~20份的3-1mm的电熔锆莫来石,得到混合预混料,最后再加入占混合预混料总质量3%~4%的结合剂磷酸,搅拌均匀,放置≥48h;
f.二次混练
加入占混合预混料总质量1.5%~2%的结合剂磷酸二氢铝,进行混练;
g.成型与制砖
将经混练的混合预混料进行压制成型,经1500℃~1650℃高温烧成,保温22h~30h,得到铬刚玉砖。
进一步的,所述铬刚玉砖的Cr2O3质量含量为10%~23%、Al2O3质量含量为57%~80%、ZrO2质量含量为1.5%~6%、SiO2质量含量为1.0%~3.5%,显气孔率为12%~15%,体积密度为3.35g/cm3~3.45g/cm3。
进一步的,所述铬渣中Al2O3质量百分比含量为78%~86%、Cr2O3质量百分比含量为5%~13%、Al2O3和Cr2O3总量的质量百分比含量≥92%。
进一步的,所述板状刚玉中Al2O3质量百分比含量≥99.0%;所述烧结刚玉中Al2O3质量百分比含量≥99.0%。
进一步的,所述铬精矿中Al2O3质量百分比含量为15%~26%、Cr2O3质量百分比含量为43%~56%。
进一步的,所述电熔锆莫来石中Al2O3质量百分比含量43%~48%,SiO2质量百分比含量16%~20%,ZrO2质量百分比含量≥30.0%。
进一步的,步骤e的混合预混料配料时,按重量份数计,粒度为5mm-3mm的料为28份~32份、粒度为3mm-1mm的料为28份~31份、粒度为1mm-0mm的料为9份~11份、粒度为180目的粉料为20份~27份、粒度为325目的粉料为3份~10份。
进一步的,压制成型时,压制压力为630Mpa~1000Mpa。
进一步的,所述磷酸的质量浓度为65%~70%。
本发明的有益效果:
1、以铬渣、板状刚玉(烧结刚玉)、铬精矿、电熔锆莫来石为主要原料,先将原料进行预处理,将铬渣、板状刚玉、铬精矿三种材料采用电熔合成法得到铬刚玉材料,在高温熔炼的过程中形成铝铬连续固熔体,促进制品致密化,提高抗熔渣的侵蚀性能,而且将有害杂质元素去除,在高温熔炼的条件下,碱性氧化物挥发掉,铬渣中残留的金属铬和铬精矿中的氧化铁会因比重较大沉降在炉缸底部形成铬的碳化物,使铬刚玉材料纯净化、致密化,且因使用固体废渣—冶炼铬渣,成本低廉,性价比高;
2、同时引入电熔锆莫来石,可以有效提高制品热震稳定性和抗剥落性能,因经过高温冶炼后产品氧化铁含量低,制品的抗还原效果好;制得的铬刚玉砖热震稳定性(风冷)≥50次,能满足有色冶金炉窑特殊部位的使用要求,可以用于炼铅、锌、锡等有色金属窑炉渣线部位、底部及反应带。制得的铬刚玉砖的化学成分和理化指标如表1所示:
表1本发明铬刚玉砖的化学成分和理化指标表
具体实施方式
实施例1
原料选择:铬渣中Al2O3质量百分比含量为78%~86%、Cr2O3质量百分比含量为5%~13%、Al2O3和Cr2O3总量的质量百分比含量≥92%;所述板状刚玉中Al2O3质量百分比含量≥99.0%;所述铬精矿中Al2O3质量百分比含量为15%~26%、Cr2O3质量百分比含量为43%~56%;所述电熔锆莫来石中Al2O3质量百分比含量43%~48%,SiO2质量百分比含量16%~20%,ZrO2质量百分比含量≥30.0%。
具体制备步骤如下:
a.原材料及加工
将铬渣进行破碎至粒度≤5mm;将板状刚玉进行破碎至粒度≤5mm;将铬精矿粉磨至粒度为40目;将电熔锆莫来石破碎至≤3mm;
b.混合均匀
将破碎至粒度≤5mm的铬渣8.4吨、粒度≤5mm烧结刚玉9.5吨、粒度为40目铬精矿2.1吨混合均匀,得到混合料;
c.高温冶炼
将6300KVA三相电弧炉冷却水打开,将碳质引弧剂放到炉底,与石墨电极正对摆放,将石墨电极下降使之接触到引弧剂,给电起弧后,将步骤b混合料加入到三相电弧炉中冶炼,埋弧冶炼至熔融状态,温度控制在2100~2300℃,冶炼时间控制到8小时;高温冶炼完成后,铬渣中含的残余金属铬沉降至炉缸底部与石墨电极中的C形成铬的碳化物,中间价态氧化铬转化成三价铬,氧化钠、氧化钾等低熔点杂质挥发掉,进入收尘系统,铬精矿中的氧化铁沉降至炉缸底部进入铬的碳化物;混合料中的Al2O3、Cr2O3经高温熔炼成铬刚玉相在炉缸上部,降温冷却固化;经取样检验,铬刚玉材料中的Al2O3含量达到81.68%,Cr2O3含量达到11.24%。
d.铬刚玉材料的加工
将炉缸上部的铬刚玉料进行砸选,去除渣皮得到纯净且致密的铬刚玉料,经破碎、粉磨、筛分分级得到粒度分别为5-3mm、3-1mm和1-0mm的颗粒料以及180目和325目的粉料;
e.困料
分别取280kg粒度为5-3mm、260kg粒度为3-1mm、110kg粒度为1-0mm的铬刚玉颗粒料,270kg粒度为180目和30kg粒度为325目的铬刚玉粉料混合;取50kg电熔锆刚玉3-1mm,再加入40kg磷酸(质量浓度65%),搅拌均匀,放置48h;
f.二次混练
取15kg磷酸二氢铝,进行混练,混练时间20分钟;
g.成型与烧成
将经混练的混合预混料使用螺旋电动压砖机,在630Mpa压力下压制成型,经1500℃高温烧成,保温22h,得到铬刚玉砖。
实施例2
原料选择:铬渣中Al2O3质量百分比含量为78%~86%、Cr2O3质量百分比含量为5%~13%、Al2O3和Cr2O3总量的质量百分比含量≥92%;所述烧结刚玉中Al2O3质量百分比含量≥99.0%;所述铬精矿中Al2O3质量百分比含量为15%~26%、Cr2O3质量百分比含量为43%~56%;所述电熔锆莫来石中Al2O3质量百分比含量43%~48%,SiO2质量百分比含量16%~20%,ZrO2质量百分比含量≥30.0%。
具体制备步骤如下:
a.原材料及加工
将铬渣进行破碎至粒度≤5mm;将烧结刚玉进行破碎至粒度≤5mm;将铬精矿粉磨至粒度为40目;将电熔锆莫来石破碎至≤3mm;
b.混合均匀
将破碎至粒度≤5mm的铬渣15吨、粒度≤5mm烧结刚玉2.5吨、粒度为40目铬精矿2.5吨混合均匀,得到混合料;
c.高温冶炼
将6300KVA三相电弧炉冷却水打开,先将碳质引弧剂放到炉底,与石墨电极正对摆放,将石墨电极下降使之接触到引弧剂,给电起弧后,将步骤b混合料加入到三相电弧炉中冶炼,埋弧冶炼至熔融状态,温度控制在2100~2300℃,冶炼时间控制到10小时;高温冶炼完成后,铬渣中含的残余金属铬沉降至炉缸底部与石墨电极中的C形成铬的碳化物,中间价态氧化铬转化成三价铬,氧化钠、氧化钾等低熔点杂质挥发掉,进入收尘系统,铬精矿中的氧化铁沉降至炉缸底部进入铬的碳化物;混合料中的Al2O3、Cr2O3经高温熔炼成铬刚玉相在炉缸上部,降温冷却固化;经取样检验,铬刚玉材料中的Al2O3含量达到74.63%,Cr2O3含量达到15.38%。
d.铬刚玉材料的加工
将炉缸上部的铬刚玉料进行砸选,去除渣皮得到纯净且致密的铬刚玉料,经破碎、粉磨、筛分分级得到粒度分别为5-3mm、3-1mm和1-0mm的颗粒料以及180目和325目的粉料;
e.困料
取310kg粒度为5-3mm、100kg粒度为3-1mm、90kg粒度为1-0mm的铬刚玉颗粒料、200kg粒度为180目、100kg为325目的铬刚玉粉料混合;取200kg电熔锆刚玉3-1mm,再加入30kg磷酸(质量浓度65%),搅拌均匀,放置72h;
f.二次混练
取20kg磷酸二氢铝,进行混练,混练时间25分钟;
g.成型与烧成
将经混练的混合预混料使用螺旋电动压砖机,在630Mpa压力下压制成型,经1550℃高温烧成,保温26h,得到铬刚玉砖。
实施例3
原料选择:铬渣中Al2O3质量百分比含量为78%~86%、Cr2O3质量百分比含量为5%~13%、Al2O3和Cr2O3总量的质量百分比含量≥92%;所述烧结刚玉中Al2O3质量百分比含量≥99.0%;所述铬精矿中Al2O3质量百分比含量为15%~26%、Cr2O3质量百分比含量为43%~56%;所述电熔锆莫来石中Al2O3质量百分比含量43%~48%,SiO2质量百分比含量16%~20%,ZrO2质量百分比含量≥30.0%。
具体制备步骤如下:
a.原材料及加工
将铬渣进行破碎至粒度≤5mm;将板状刚玉进行破碎至粒度≤5mm;将铬精矿粉磨至粒度为40目;将电熔锆莫来石破碎至≤3mm;
b.混合均匀
将破碎至粒度≤5mm的铬渣11.1吨、粒度≤5mm烧结刚玉2.2吨、粒度为40目铬精矿6.7吨混合均匀,得到混合料;
c.高温冶炼
将6300KVA三相电弧炉冷却水打开,先将碳质引弧剂放到炉底,与石墨电极正对摆放,将石墨电极下降使之接触到引弧剂,给电起弧后,将步骤b混合料加入到三相电弧炉中冶炼,埋弧冶炼至熔融状态,温度控制在2100~2300℃,冶炼时间控制到12小时;高温冶炼完成后,铬渣中含的残余金属铬沉降至炉缸底部与石墨电极中的C形成铬的碳化物,中间价态氧化铬转化成三价铬,氧化钠、氧化钾等低熔点杂质挥发掉,进入收尘系统,铬精矿中的氧化铁沉降至炉缸底部进入铬的碳化物;混合料中的Al2O3、Cr2O3经高温熔炼成铬刚玉相在炉缸上部,降温冷却固化;经取样检验,铬刚玉材料中的Al2O3含量达到61.42%,Cr2O3含量达到18.13%。
d.铬刚玉材料的加工
将炉缸上部的铬刚玉料进行砸选,去除渣皮得到纯净且致密的铬刚玉料,经破碎、粉磨、筛分分级得到粒度分别为5-3mm、3-1mm和1-0mm的颗粒料以及180目和325目的粉料;
e.困料
取320kg粒度为5-3mm、180kg粒度为3-1mm、100kg粒度为1-0mm的铬刚玉颗粒料、取260kg粒度为180目、40kg粒度为325目的铬刚玉粉混合;取100kg电熔锆刚玉3-1mm,再加入30kg磷酸(质量浓度70%),搅拌均匀,放置48h;
f.二次混练
取18kg磷酸二氢铝,进行混练,混练时间30分钟;
g.成型与烧成
将经混练的混合预混料使用螺旋电动压砖机,在1000Mpa压力下压制成型,经1650℃高温烧成,保温30h,得到铬刚玉砖。
实施例1~实施例3中的板状刚玉与烧结刚玉可以相互替换。
实施例1~实施例3制得的铬刚玉砖化学成分和理化指标如表2所示:
表2
从表2可以看出,本发明的铬刚玉砖热震稳定性较高,做到了在不降低常温耐压强度等指标的前提下,达到了风冷50次以上,在温度变化较大的窑炉里使用,可以大幅提高使用寿命,降低制品因不耐温度急剧变化而产生的热剥落。
在炼铅、锌的烟化炉或侧吹炉使用时,窑炉内有大量的C,会与砖内的氧化铁发生还原反应,形成单质铁和气体,从而破坏砖的结构,造成砖体损坏;本发明所涉及的产品中氧化铁含量低,在窑炉上使用时,可有效抗还原反应的发生,进而延长砖的使用寿命。在炼铅的烟化炉上,一直使用的是镁铬质耐火材料,使用寿命在6-7个月,使用本产品炉期可达1年以上。
以上仅为本发明的具体实施例而已,并不用于限制本发明,对于本领域的技术人员来说,本发明可以有各种更改和变化。凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (9)
1.一种抗还原反应、抗热震的有色金属冶炼烟化炉或侧吹炉用铬刚玉砖的生产方法,其特征是:具体步骤如下:
a.原料称取
按重量份数计称取以下原料:
b.原料加工
将铬渣进行破碎至粒度≤5mm;将板状刚玉或烧结刚玉破碎至粒度为≤5mm;将铬精矿破碎至粒度为40目~200目;将电熔锆莫来石破碎至粒度至3-1mm;
c.高温冶炼
将破碎后的板状刚玉或烧结刚玉、铬渣和铬精矿混合均匀,得到混合料;先将碳质引弧剂放到炉底,与石墨电极正对摆放,将石墨电极下降使之接触到引弧剂,给电起弧后,将混合料加入到三相电弧炉中冶炼,温度控制在2100℃~2300℃,冶炼时间控制到8小时~12小时,冶炼完成后,铬渣中含的金属铬沉降至炉缸底部形成铬的碳化物,铬渣中中间价态氧化铬转化成三价铬,铬渣中氧化钠低熔点杂质挥发掉,铬精矿中的氧化铁沉降至炉缸底部进入铬的碳化物,铬渣、烧结刚玉、铬精矿三者中的Al2O3、Cr2O3经高温熔炼成铬刚玉相在炉缸上部,降温冷却固化,将炉缸上部的铬刚玉料进行砸选,去除渣皮得到铬刚玉料;
d.铬刚玉材料加工
将步骤c获得的铬刚玉料经破碎、粉磨、筛分分级得到粒度分别为5-3mm、3-1mm和1-0mm的颗粒料以及180目和325目的粉料;
e.困料
按重量份数计取80份~95份的经筛分分级为粒度5-3mm、3-1mm、1-0mm、180目和325目的铬刚玉料,加入5份~20份的3-1mm的电熔锆莫来石,得到混合预混料,最后再加入占混合预混料总质量3%~4%的结合剂磷酸,搅拌均匀,放置≥48h;
f.二次混练
加入占混合预混料总质量1%~2%的结合剂磷酸二氢铝,进行混练;
g.成型与制砖
将经混练的混合预混料进行压制成型,经1500℃~1650℃高温烧成,保温22h~30h,得到铬刚玉砖。
2.根据权利要求1所述的抗还原反应、抗热震的有色金属冶炼烟化炉或侧吹炉用铬刚玉砖的生产方法,其特征是:所述铬刚玉砖的Cr2O3质量含量为10%~23%、Al2O3质量含量为57%~80%、ZrO2质量含量为1.5%~6%、SiO2质量含量为1.0%~3.5%,显气孔率为12%~15%,体积密度为3.35g/cm3~3.45g/cm3。
3.根据权利要求1所述的抗还原反应、抗热震的有色金属冶炼烟化炉或侧吹炉用铬刚玉砖的生产方法,其特征是:所述铬渣中Al2O3质量百分比含量为78%~86%、Cr2O3质量百分比含量为5%~13%、Al2O3和Cr2O3总量的质量百分比含量≥92%。
4.根据权利要求1所述的抗还原反应、抗热震的有色金属冶炼烟化炉或侧吹炉用铬刚玉砖的生产方法,其特征是:所述板状刚玉中Al2O3质量百分比含量≥99.0%;所述烧结刚玉中Al2O3质量百分比含量≥99.0%。
5.根据权利要求1所述的抗还原反应、抗热震的有色金属冶炼烟化炉或侧吹炉用铬刚玉砖的生产方法,其特征是:所述铬精矿中Al2O3质量百分比含量为15%~26%、Cr2O3质量百分比含量为43%~56%。
6.根据权利要求1所述的抗还原反应、抗热震的有色金属冶炼烟化炉或侧吹炉用铬刚玉砖的生产方法,其特征是:所述电熔锆莫来石中Al2O3质量百分比含量43%~48%,SiO2质量百分比含量16%~20%,ZrO2质量百分比含量≥30.0%。
7.根据权利要求1所述的抗还原反应、抗热震的有色金属冶炼烟化炉或侧吹炉用铬刚玉砖的生产方法,其特征是:步骤e的混合预混料配料时,按重量份数计,粒度为5mm-3mm的料为28份~32份、粒度为3mm-1mm的料为28份~31份、粒度为1mm-0mm的料为9份~11份、粒度为180目的粉料为20份~27份、粒度为325目的粉料为3份~10份。
8.根据权利要求1所述的抗还原反应、抗热震的有色金属冶炼烟化炉或侧吹炉用铬刚玉砖的生产方法,其特征是:压制成型时,压制压力为630Mpa~1000Mpa。
9.根据权利要求1所述的抗还原反应、抗热震的有色金属冶炼烟化炉或侧吹炉用铬刚玉砖的生产方法,其特征是:所述磷酸的质量浓度为65%~70%。
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CN117362015A (zh) * | 2023-10-27 | 2024-01-09 | 河南省瑞泰科实业集团有限公司 | 高纯刚玉砖及其制备方法 |
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