Article(id=1187341679557226813, tenantId=1146029695717560320, journalId=1185652524569653253, issueId=1187341678487679284, articleNumber=1009-5438(2022)02-0008-04, orderNo=null, doi=null, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1644422400000, receivedDateStr=2022-02-10, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1761013916148, onlineDateStr=2025-10-21, pubDate=1650816000000, pubDateStr=2022-04-25, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1761013916148, onlineIssueDateStr=2025-10-21, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1761013916148, creator=13701087609, updateTime=1761013916148, updator=13701087609, issue=Issue{id=1187341678487679284, tenantId=1146029695717560320, journalId=1185652524569653253, year='2022', volume='48', issue='2', pageStart='1', pageEnd='98', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1761013915892, creator=13701087609, updateTime=1761015806887, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1187349609945907689, tenantId=1146029695717560320, journalId=1185652524569653253, issueId=1187341678487679284, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1187349609945907690, tenantId=1146029695717560320, journalId=1185652524569653253, issueId=1187341678487679284, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=8, endPage=11, ext={EN=ArticleExt(id=1187341679720804677, articleId=1187341679557226813, tenantId=1146029695717560320, journalId=1185652524569653253, language=EN, title=Study on Demanganization Process in Ladle Furnace (LF), columnId=1187340472918880861, journalTitle=Science & Technology of Baotou Steel, columnName=Production Practice and Management, runingTitle=null, highlight=null, articleAbstract=

The manganese content of molten iron in the production line of steelmaking in Rare Earth Steel Plate Co. is higher so that the highly purified armco iron could not be smelted by converter process. In the paper, it is introduced the demanganization process with double slag in LF is developed through simulating the demanganization condition of converter with LF, starting with such three aspects as basicity of slag, demanganization temperature and oxidability of slag as well as taking full advantage of existing equipment conditions of production line. The slag with high oxidation after tapping of molten steel from converter is utilized in LF, the ingredient of LF clinker is reasonably adjusted to produce efficient slag of demanganization and promote the steel slag reaction through argon stirring so as to create good thermodynamic and dynamical conditions for demanganization. According to the requirements of manganese content of products, double slag and single slag processes are applied in operations to realize the stable batch production of armco iron with the manganese content less than 0.03% and 0.02%.

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稀土钢板材公司炼钢产线铁水锰含量较高,无法通过转炉工序冶炼高纯度工业纯铁。文章通过LF精炼炉模拟转炉脱锰条件,从炉渣碱度、脱锰温度和渣氧化性三个方面入手,充分利用产线现有设备条件,开发出LF精炼炉双渣脱锰工艺。LF精炼炉通过利用转炉出钢后高氧化性炉渣,合理调整LF炉渣配料,造高效脱锰渣,通过氩气搅拌促进钢渣反应,为脱锰创造良好的热力学与动力学条件。根据产品锰含量要求采用双渣及单渣法进行操作,实现锰含量小于0.03%和0.02%工业纯铁的稳定批量生产。

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徐少华(1986-),男,内蒙古包头市人,工程师, 现从事炼钢精炼生产技术工作。

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徐少华(1986-),男,内蒙古包头市人,工程师, 现从事炼钢精炼生产技术工作。

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徐少华(1986-),男,内蒙古包头市人,工程师, 现从事炼钢精炼生产技术工作。

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Si Mn P S
0.32~0.63 0.35~0.45 0.12~0.13 0.001
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入炉铁水成分(质量分数)%

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Si Mn P S
0.32~0.63 0.35~0.45 0.12~0.13 0.001
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熔炼号 碱度 第一次渣量
/kg
FeO含量
/%
转炉终点锰
含量/%
第一次脱后锰
含量/%
第一次脱锰率
/%
22201678 4.22 2 868 15.62 0.064 0.026 59.37
22201680 3.91 2 601 15.82 0.055 0.025 54.54
22201681 4.36 2 590 17.92 0.036 0.021 41.67
22201682 4.05 2 521 17.55 0.041 0.023 43.90
22201683 4.19 2 799 15.75 0.043 0.023 46.51
), ArticleFig(id=1187341824193606319, tenantId=1146029695717560320, journalId=1185652524569653253, articleId=1187341679557226813, language=CN, label=表2, caption=

LF炉第一次造渣脱锰结果

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熔炼号 碱度 第一次渣量
/kg
FeO含量
/%
转炉终点锰
含量/%
第一次脱后锰
含量/%
第一次脱锰率
/%
22201678 4.22 2 868 15.62 0.064 0.026 59.37
22201680 3.91 2 601 15.82 0.055 0.025 54.54
22201681 4.36 2 590 17.92 0.036 0.021 41.67
22201682 4.05 2 521 17.55 0.041 0.023 43.90
22201683 4.19 2 799 15.75 0.043 0.023 46.51
), ArticleFig(id=1187341824298463921, tenantId=1146029695717560320, journalId=1185652524569653253, articleId=1187341679557226813, language=EN, label=null, caption=null, figureFileSmall=null, figureFileBig=null, tableContent=
熔炼号 碱度 第二次渣量
/kg
FeO含量
/%
第一次脱后锰
含量/%
第二次脱后锰
含量/%
第二次造渣
脱锰率/%
综合脱锰率
/%
22201678 4.89 1 569 15.62 0.026 0.016 38.46 75.00
22201680 5.12 1 380 15.82 0.025 0.018 28.00 67.27
22201681 4.76 1 633 17.92 0.021 0.014 33.33 61.11
22201682 4.91 1 585 17.55 0.023 0.015 34.78 63.41
22201683 5.23 1 496 15.75 0.023 0.016 30.43 62.79
), ArticleFig(id=1187341824357184180, tenantId=1146029695717560320, journalId=1185652524569653253, articleId=1187341679557226813, language=CN, label=表3, caption=

LF炉双渣脱锰结果

, figureFileSmall=null, figureFileBig=null, tableContent=
熔炼号 碱度 第二次渣量
/kg
FeO含量
/%
第一次脱后锰
含量/%
第二次脱后锰
含量/%
第二次造渣
脱锰率/%
综合脱锰率
/%
22201678 4.89 1 569 15.62 0.026 0.016 38.46 75.00
22201680 5.12 1 380 15.82 0.025 0.018 28.00 67.27
22201681 4.76 1 633 17.92 0.021 0.014 33.33 61.11
22201682 4.91 1 585 17.55 0.023 0.015 34.78 63.41
22201683 5.23 1 496 15.75 0.023 0.016 30.43 62.79
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LF精炼炉脱锰工艺的研究
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徐少华 , 李志成 , 赵鸣 , 韩浩田 , 王与帅 , 张明强
包钢科技 | 生产实践与管理 2022,48(2): 8-11
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包钢科技 | 生产实践与管理 2022, 48(2): 8-11
LF精炼炉脱锰工艺的研究
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徐少华, 李志成, 赵鸣, 韩浩田, 王与帅, 张明强
作者信息
  • 内蒙古包钢稀土钢板材有限责任公司, 内蒙古 包头 014010
  • 徐少华(1986-),男,内蒙古包头市人,工程师, 现从事炼钢精炼生产技术工作。

Study on Demanganization Process in Ladle Furnace (LF)
Shao-hua Xu, Zhi-cheng Li, Ming Zhao, Hao-tian Han, Yu-shuai Wang, Ming-qiang Zhang
Affiliations
  • Inner Mongolia Baotou Steel Rare Earth Steel Plate Co., Ltd., Baotou 014010, Inner Mongolia Autonomous Region, China
出版时间: 2022-04-25
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稀土钢板材公司炼钢产线铁水锰含量较高,无法通过转炉工序冶炼高纯度工业纯铁。文章通过LF精炼炉模拟转炉脱锰条件,从炉渣碱度、脱锰温度和渣氧化性三个方面入手,充分利用产线现有设备条件,开发出LF精炼炉双渣脱锰工艺。LF精炼炉通过利用转炉出钢后高氧化性炉渣,合理调整LF炉渣配料,造高效脱锰渣,通过氩气搅拌促进钢渣反应,为脱锰创造良好的热力学与动力学条件。根据产品锰含量要求采用双渣及单渣法进行操作,实现锰含量小于0.03%和0.02%工业纯铁的稳定批量生产。

工业纯铁  /  LF精炼炉  /  脱锰

The manganese content of molten iron in the production line of steelmaking in Rare Earth Steel Plate Co. is higher so that the highly purified armco iron could not be smelted by converter process. In the paper, it is introduced the demanganization process with double slag in LF is developed through simulating the demanganization condition of converter with LF, starting with such three aspects as basicity of slag, demanganization temperature and oxidability of slag as well as taking full advantage of existing equipment conditions of production line. The slag with high oxidation after tapping of molten steel from converter is utilized in LF, the ingredient of LF clinker is reasonably adjusted to produce efficient slag of demanganization and promote the steel slag reaction through argon stirring so as to create good thermodynamic and dynamical conditions for demanganization. According to the requirements of manganese content of products, double slag and single slag processes are applied in operations to realize the stable batch production of armco iron with the manganese content less than 0.03% and 0.02%.

armco iron  /  LF  /  demanganization
徐少华, 李志成, 赵鸣, 韩浩田, 王与帅, 张明强. LF精炼炉脱锰工艺的研究. 包钢科技, 2022 , 48 (2) : 8 -11 .
Shao-hua Xu, Zhi-cheng Li, Ming Zhao, Hao-tian Han, Yu-shuai Wang, Ming-qiang Zhang. Study on Demanganization Process in Ladle Furnace (LF)[J]. Science & Technology of Baotou Steel, 2022 , 48 (2) : 8 -11 .
为满足当今市场需求,高附加值特种钢材的钢种对钢水中锰含量的要求很低,而转炉本身的脱锰能力有限,稀土钢板材公司由于矿石原料条件限制,入炉铁水的锰含量在0.50%左右,用此铁水冶炼超低锰钢种$\left(\omega \right[\mathrm{M}\mathrm{n}]\le 0.02\mathrm{\%})$时转炉终点达到最低的锰含量为0.07%左右,无法达到此类钢种的要求,直接制约着稀土钢板材公司钢种转型升级的进程。在上述背景下,利用高锰铁水冶炼超低锰钢种这一技术难题也就变得日益突出起来,直接制约着以高纯工业纯铁为代表的超低锰钢的开发及生产。
钢渣界面反应可表示为:
[Mn]+(FeO)=(MnO)+[Fe]
$\mathrm{\Delta }{G}^{\theta }=-123307+56.48T$
$\mathrm{l}\mathrm{o}\mathrm{g}{K}^{\theta }=\frac{6441}{T}-2.95$
式中: $\mathrm{\Delta }{G}^{\theta }$标准状态时反应的吉布斯自由能, J/mol; T为热力学温度, K
由式(1)可以得到渣与钢间锰的反应平衡常数${K}^{\theta }$为:
${K}^{\theta }=\frac{{a}_{\left(\mathrm{M}\mathrm{n}\mathrm{O}\right)}{a}_{\left[\mathrm{F}\mathrm{e}\right]}}{{a}_{\left[\mathrm{M}\mathrm{n}\right]}{a}_{\left(\mathrm{F}\mathrm{e}\mathrm{O}\right)}}$
式中: ${a}_{\left(\mathrm{M}\mathrm{n}\mathrm{O}\right)}、{a}_{\left(\mathrm{F}\mathrm{e}\mathrm{O}\right)}$分别为炉渣中MnO和FeO的活度; ${a}_{\left[\mathrm{M}\mathrm{n}\right]}、{a}_{\left[\mathrm{F}\mathrm{e}\right]}$分别为钢水中锰和铁的活度。
当反应达到平衡时,由于钢水中Fe的含量较高,可以认为${a}_{\left[\mathrm{F}\mathrm{e}\right]}=1$,将(4)式经过数学变换可得:
${L}_{\left[\mathrm{M}\mathrm{n}\right]}={K}^{\theta }\times {a}_{\left(\mathrm{F}\mathrm{e}\mathrm{O}\right)}$
式中: ${L}_{\left[\mathrm{M}\mathrm{n}\right]}$为锰在渣与钢间的分配系数。
由式(5)可知,锰元素的渣钢分配比${L}_{\left[\mathrm{M}\mathrm{n}\right]}$随着温度T的升高而降低,随着氧化铁活度的升高而升高,因此从热力学角度分析低温、高氧化铁含量、大渣量均有利于提高精炼渣脱锰能力。
目前国内许多钢企生产工业纯铁,由于原料、设备等方面不同,各厂制定的工艺路线不一。稀土钢板材公司冶炼工业纯铁的主要设备有铁水预处理装置、260 t顶底复吹转炉、LF精炼炉、RH真空精炼炉和双流板坯连铸机。
转炉冶炼环节主要原料使用高炉铁水和自产废钢,铁水预处理不具备脱锰功能,入炉铁水中锰含量在0.35%~0.45%之间,温度1 300 ℃左右,铁水预处理后铁水主要成分见表1
锰与氧的亲和力不如硅与氧的亲和力大,冶炼中被氧化成只溶于炉渣的弱碱性氧化物氧化锰。转炉吹炼中铁水锰有80%左右是在开吹后几分钟内被氧化。钢中锰的氧化程度取决于其氧化产物氧化锰在熔渣中的存在状态。由于炉渣中存在着大量的强碱性氧化物氧化钙,显弱碱性的氧化锰大部分以自由的氧化锰存在,因而冶炼中锰氧化远没有硅彻底,而且转炉吹炼后期熔池温度升高后会发生锰的还原反应。熔渣碱度越高,渣中氧化铁含量越低,以及熔池温度越高,还原出的锰越多,吹炼结束时钢液中的锰含量越高。碱度、温度和炉渣氧化性共同影响了转炉脱锰效率[1]
图1显示转炉终点锰与转炉初始锰的线性关系,在入炉铁水锰含量高达0.35%以上的情况下,转炉终点锰不能稳定控制在高端工业纯铁锰含量不大于0.02%目标,需要开发新的脱锰工艺路线进一步脱锰[2]
由式(5)可知,炉渣中氧化铁含量越高,炉渣对钢液中的锰氧化能力越强。这是因为随着氧化铁含量的增加,渣的氧化性增强,氧化铁的活度增加,为炉渣提供了更多的氧离子,使钢液中的锰被氧化,从而进入渣中。另外一方面,氧化铁含量增加提高了反应物的浓度,促进了锰氧化反应进行[3]图2为炉渣氧化铁含量与锰的分配系数的关系。
炉渣碱度与锰的分配系数之间的关系如图3所示。在碱度低于2.5时,炉渣与钢水间锰的分配系数随着碱度的增加不断降低,这是由于氧化锰是一个弱碱性氧化物,随着渣中氧化钙含量的增加,氧化锰的活度增加,促进了氧化锰的还原,使渣中氧化锰含量降低,钢液中锰含量增加,进而锰的分配系数降低[4]。在碱度高于2.5时,渣中氧化锰浓度随氧化钙含量的增加被稀释,提高了锰的分配系数。考虑到氧化钙含量过高会提高炉渣完全融化温度,所以将碱度控制在5.0左右可以获得较高的锰分配系数和较好的流动性。
根据炉渣碱度具体制定脱锰渣料加入分为两个步骤。
(1)LF在初期加热过程中进行第一次造渣,迅速提高碱度至大于3.5,同时加热至脱锰所需温度。达到目标温度后进行搅拌脱锰,搅拌至钢渣锰平衡后进行倒渣,将富含氧化锰的一次渣料去除。
(2)倒渣后进行第二次造渣,炉渣碱度提高至5.0以上,再次加热至脱锰的目标温度后,大氩气搅拌进行二次脱锰。
LF精炼过程前期,未经加热的钢水温度约为1 530~1 550 ℃,与转炉相似的温度环境为LF精炼炉脱锰创造了良好的热力学条件。LF处理开始后进行吹氩操作,加大氩气流量以增加钢水与炉渣的接触面积,促进锰元素在钢—渣界面进行氧化反应。
第一次造渣加热温度不超过1 580 ℃,以保证渣料快速熔化,使碱度提高至4.5~5.0左右。大氩气搅拌充足时间后进行取样,完成第一次脱锰。
伴随上文所述第二次造渣过程,温度逐步由1 550 ℃加热至1 620 ℃为RH工序提供必要的处理温度。
根据上文所述脱锰条件,创造LF精炼炉高氧化性、高碱度炉渣,伴以较低的钢水温度及钢渣良好的流动性,进行第一次造渣。冶炼过程中,精炼渣碱度控制在3.5~4.5之间,氧化铁含量控制在15%以上,钢水温度范围在1 560~1 580 ℃之间。LF炉第一次造渣脱锰结果见表2
第一次造渣脱锰率最高至59.37%。使用LF炉一次造渣脱锰工艺技术,具备了应用高锰铁水批量生产Mn含量不大于0.03%的超低锰钢的能力。
根据上文所述双渣冶炼方案将一次造渣脱锰结束后进行倒渣操作,倒渣后第二次进行造渣,仍然保持氧化铁含量在15%以上,精炼渣碱度控制在4.5~5.5的高碱度环境,提高钢水温度至1 600~1 620 ℃之间。二次造渣进一步降低钢水中残余的锰,较高的碱度可以保持因后期温度升高及炉渣改质氧化性降低钢中的锰含量不再次上升。第二次造渣脱锰结果见表3
通过第二次造渣脱锰率平均为33%。使用LF炉两次造渣脱锰工艺技术综合脱锰率平均为65.92%,可稳定实现高锰铁水批量生产Mn含量不大于0.02%的超低锰工业纯铁的生产能力。
(1)通过LF精炼炉双渣冶炼,证实保持炉渣FeO含量达到15%的LF炉精炼渣具有良好的脱锰效果,满足生产超低锰钢需要。
(2)采用分批两次造渣,第一次造渣将碱度提高至3.5以上,倒渣后第二次造渣,将炉渣碱度保持在4.5~5.5,可以显著提高炉渣脱锰率,达到快速脱锰效果。同时第二批渣料保持了脱锰后炉渣高碱度水平,使锰在钢—渣间的分配系数保持稳定,达到防止回锰的目的。
(3)初期较低的反应温度为脱锰创造良好的热力学条件,伴随两次加热等手段快速化渣,使炉渣具备快速脱锰的动力学条件,加速脱锰效果,满足工业纯铁连续生产的需求。
(4)经过实践,冶炼低锰钢种$\left(\omega \right[\mathrm{M}\mathrm{n}]\le 0.03\mathrm{\%})$采用一次造渣即可达到目标,冶炼超低锰钢种$\left(\omega \right[\mathrm{M}\mathrm{n}]\le 0.02\mathrm{\%})$采取双渣冶炼方式可以实现批量工业化生产。
参考文献 引证文献
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杨俊峰, 江腾飞, 郝丽霞. 迁钢工业纯铁SYTB生产过程脱磷、脱锰实践[J]. 炼钢, 2019, 35(3):13-16.
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2022年第48卷第2期
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  • 接收时间:2022-02-10
  • 首发时间:2025-10-21
  • 出版时间:2022-04-25
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  • 收稿日期:2022-02-10
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    内蒙古包钢稀土钢板材有限责任公司, 内蒙古 包头 014010
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2种不同金属材料的力学参数

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Genus
种数
Number of
species
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鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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