CN1795276A - 从电弧炉的含金属氧化物的渣中回收金属元素特别是金属铬的方法 - Google Patents
从电弧炉的含金属氧化物的渣中回收金属元素特别是金属铬的方法 Download PDFInfo
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Abstract
本发明涉及一种用于从电弧炉的含氧化物特别是含氧化铬的渣中回收金属元素特别是金属铬的方法。其中在熔融后该渣不经在单独的步骤中还原,而按下列步骤进行:将加料加入电弧炉中后熔融该加料以形成金属熔体和渣。出炉该熔体并保留该未经还原的渣于炉容器中。加入另一批料以及适于渣的还原剂。在该加料的熔融过程中还原该渣。接着出炉该熔体和渣。该方法也可用于罐式冶金或转炉冶金中。
Description
本发明涉及一种用于从电弧炉、转炉以及罐式冶金(Pfannenmetallurgie)的含氧化物特别是含氧化铬的渣中回收金属元素特别是金属铬的方法。
在电弧炉中熔融金属废屑时发生氧化过程,该熔体中的金属元素反应生成氧化物。在不锈钢如含铬钢和含铬镍钢的情况下,主要是经氧化的昂贵的铬。同时该氧化物又经还原。在高铬含量钢的情况下,基本的机理主要是氧化铬经碳还原。这时铬的初级氧化同时由在熔体中溶解的碳以平行进行的还原所补偿。该反应在鼓泡表面和在金属/渣的相界面发生。该反应产物即金属铬返回熔体中。所形成的一氧化碳经扩散进在表面的气泡中后进入炉氛中。
进行如下反应:
在下列的热力学平衡条件下进行所述反应:
其中
其中P是参数。
由于碳还原铬的不完全性,部分量的氧化铬以各种尖晶石形形进入渣中。在渣中的氧化铬含量依过程运行的类型不同而变化,并在5%以上。该方法的经济性基于氧化铬的还原和金属铬的回收。
为此通常在熔融处理的末端用呈FeSi形式的高亲合性硅单独还原渣。
由WO 00/79014 A1中已知一种技术方案,以使从转炉工艺或真空冶炼工艺的含氧化铬的渣中回收金属铬的方法更为经济。其提出放弃通常的渣还原的处理步骤。例如将在转炉中或罐中在吹氧过程后存在的渣未经还原地从金属熔体中去除,并加入到串接的电弧炉中。通过加到电弧炉中的废钢屑中的碳辅料和硅,需要时通过其余粉尘在熔融过程中直接将渣中的氧化铬还原成金属铬。
由WO 02/33130 A1已知,在进行熔炼过程和吹气过程的冶金容器中,特别是在Conarc工艺中,通过使第一次吹气过程后所形成的渣不经还原地保留在容器中来实现金属铬的回收。将该渣与下一次的加料在同一容器中加热、还原和接着出炉。然后再进行下一吹气过程,其中将所形成的渣再次保留在容器中。
由该现有技术出发,本发明的目的在于提供一种从电孤炉的熔融过程所形成的渣中循环氧化物特别是氧化铬的经济的方法。
该目的通过具有权利要求1和6的特征的方法解决的。该方法的优选方案在从属权利要求中提出。
本发明的基本设想是放弃至今常用的在熔融后的第一熔体中的渣还原。渣还原处理步骤在第二加料或其它加料的第二熔融期间再进行。
一一详述下列方法步骤:将废钢屑加入电弧炉中,并将其熔融形成金属熔体和渣。中止通常进行的渣还原步骤。将该熔体出炉,并将含高含量氧化铬的和由锰-铁氧化物饱和的渣未经还原地保留在炉容器中。
将下一次的加料加到该渣上。该加料包括废钢屑以及适于该渣的还原剂,特别是碳和/或硅。建议以富碳和富硅的合金材料的形式加入碳和/或硅。碳和硅例如是呈加料铬、铬铁合金或镍铁合金形式。其承担主要的还原作用。在某些情况下可附加碳辅料和/或硅辅料如FeSi或铝。还原剂也可包含在加入的其余粉尘中。
借助于还原剂该渣在通电能的熔融过程中直接还原。在电炉中于大气压力下发生氧化铬经碳或硅的直接还原。在熔融过程中进行的金属氧化按此方式通过还原反应(过度)补偿,并回收得到金属铬。接着除去渣。在罐式冶金中发生类似的工艺过程,其中该金属已作为熔体存在。
在电炉中的实施可通过按操作法用剩余的金属炉底物来实施该方法而加以大大改进。通过金属炉底物可大大提高渣的还原质量等级。这时第一熔体不完全出炉,而是在熔融容器中保留金属炉底物的情况下仅部分出炉。其优点在于,渣在炉中浮动地保留在金属炉底物上,由此不会粘固或烧结在炉底上。对这种有利的方案,可将熔体过程组合成形成熔体期、分离熔体期以及暂时在此期间发生的熔融和还原的重复期。与在Conarc过程中的已知方法不同,该Conarc过程由用于制备钢的熔融和氧吹组成,而本发明方法涉及在电弧炉中熔融时的铬回收,该过程较简单和更短。铬含量也是不可相比的,在熔融时渣的铬含量较低,约为14-15%。
特别在含铬不锈钢或含铬镍的不锈钢情况下可应用该所建议的方法。根据总体工艺,即在电弧炉中无单独的渣还原处理的不锈钢工艺可以以成本最佳化和能耗最佳化来设计该过程。该渣是否以固态、液态或以中间状态存在对此方法是不重要的。其仅对在电弧炉中的熔融时间和能耗有影响。
在熔融过程中为还原所需的充分混合优选由惰性气体产生,该惰性气体通过在电孤炉中的炉底喷射器和/或侧喷嘴和/或通过炉顶吹管送入。由此增加渣和金属之间的反应面积。
总的来说,该所建议的方法还具有下列优点:
·按工艺类型将熔体的总处理时间缩短到15分钟,其中弃去了已知的单独的还原步骤
·降低了FeSi耗量
·降低了造渣剂的耗量
·高的金属熔体的提取
·增加了炉的耐火材料使用寿命
·增加冲洗石(Spüelsteine)/冲洗器的使用寿命
·改进电弧炉的能耗
·改进金属的纯净度
该方法的各步骤将在下面按附图详细描述,图中以流程简图形式示出在EAF方法或电弧炉方法中的金属走向。
在第一步骤中,熔融不含炉底物的初始熔体。为此熔融废钢屑加料以形成金属熔体和渣。将熔体出炉,但仅出炉一部分,以使含有在其上的浮动的渣的金属炉底物保留在炉容器中。该渣是未经还原的。
在其后的熔融期和还原期中在该含渣的金属炉底物上加入废钢屑。此外还加入适于渣的还原剂如碳和硅。在熔融过程中渣被还原。这时发生与碳或与硅的还原反应:
由此渣中的氧化铬含量值下降到小于其起始值。
出炉经还原过的渣。在下一步过程中出炉熔体,但仍只是部分出炉以在炉容器底部保留金属炉底物。在该金属炉底物上重新再加料。重新直接还原在熔融时再次形成的渣。对炉运行期中的每一熔体均重复这些步骤。当该炉运行期结束时,不是部分出炉而是熔体和金属炉底物一起全部出炉。
该方法可在电弧炉中其它熔炉以及在罐式冶金或转炉冶金或其它冶金容器中实施。
Claims (7)
1.一种用于从电弧炉的含氧化物特别是含氧化铬的渣中回收金属元素特别是金属铬的方法,其包括下列步骤:
a)将加料加入电弧炉中,
b)熔融该加料以形成金属熔体和渣;
c)出炉该熔体并保留未经还原的渣于炉容器中;
d)加入另一批料,其含废钢屑和适于渣的还原剂如碳和/或硅和/或铝,
e)熔融和在熔融过程中通过该加料中的还原剂直接还原渣,特别是氧化铬;
g)出炉熔体和经还原的渣。
2.权利要求1的方法,其特征在于,在熔融运行开始时熔融初始熔体;在步骤c)中部分出炉该熔体以保留金属炉底物于炉容器中;将另一加料加到所保留的金属炉底物和渣上;经其后的熔融和渣还原后部分出炉金属熔体;对运行中的每一熔体重复该加料、熔融和渣还原步骤或通过卸出熔体和金属炉底物一起全部出炉结束熔融运行。
3.权利要求1或2的方法,其特征在于,还原剂碳和/或硅和/或铝以含高碳含量和硅含量的合金材料形式加入。
4.权利要求1-3之一的方法,其特征在于,加入其余粉尘作为特别是含铬渣的还原剂。
5.权利要求1-4之一的方法,其特征在于,用惰性气体进行充分混合,该惰性气体经电弧炉中的炉底喷射器和/或侧喷嘴和/或经炉顶吹管送入。
6.一种用于从罐式冶金或转炉冶金中的含氧化物特别是含氧化铬的渣中回收金属元素特别是金属铬的方法,其包括下列步骤:
a)将含渣的第一金属熔体加到罐中或转炉中,
b)经熔体处理,特别是用氧处理后,出炉该熔体以保留未经还原的渣于罐中或转炉中,
c)加入另一熔体和适于渣的还原剂如碳和/或硅和/或铝,
d)充分混合熔体和渣,这时通过还原剂直接还原渣,特别是还原氧化铬,
g)出炉该熔体和经还原的渣。
7.权利要求6的方法,其特征在于,在步骤b)中部分出炉熔体以保留金属炉底物于罐中;将另一熔体加到所保留的金属炉底物和渣上;经其后的渣还原后在步骤g)中部分出炉金属熔体;对运行中的每一熔体重复该加料和渣还原步骤或通过卸出熔体和金属炉底物的全部出炉结束运行。
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JP2007502369A (ja) | 2007-02-08 |
CA2525559C (en) | 2011-07-26 |
WO2004104233A1 (de) | 2004-12-02 |
TW200502404A (en) | 2005-01-16 |
JP4912880B2 (ja) | 2012-04-11 |
RU2005140569A (ru) | 2006-05-10 |
ES2277253T3 (es) | 2007-07-01 |
DE502004002628D1 (de) | 2007-02-22 |
EP1627085B1 (de) | 2007-01-10 |
UA82239C2 (uk) | 2008-03-25 |
CN100350057C (zh) | 2007-11-21 |
EP1627085A1 (de) | 2006-02-22 |
CA2525559A1 (en) | 2004-12-02 |
ZA200508277B (en) | 2006-12-27 |
RU2352672C2 (ru) | 2009-04-20 |
US20060196308A1 (en) | 2006-09-07 |
KR20060012288A (ko) | 2006-02-07 |
DE10323507A1 (de) | 2004-12-09 |
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