CN1396961A - 用于液体炉渣脱铬和/或脱镍的方法 - Google Patents

用于液体炉渣脱铬和/或脱镍的方法 Download PDF

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CN1396961A
CN1396961A CN01804059A CN01804059A CN1396961A CN 1396961 A CN1396961 A CN 1396961A CN 01804059 A CN01804059 A CN 01804059A CN 01804059 A CN01804059 A CN 01804059A CN 1396961 A CN1396961 A CN 1396961A
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slag
oxide content
carbon
weight
reduction
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CN1195881C (zh
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A·埃德林格
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Holcim Technology Ltd
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HELSINMU AG
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B5/00General methods of reducing to metals
    • C22B5/02Dry methods smelting of sulfides or formation of mattes
    • C22B5/04Dry methods smelting of sulfides or formation of mattes by aluminium, other metals or silicon
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21BMANUFACTURE OF IRON OR STEEL
    • C21B3/00General features in the manufacture of pig-iron
    • C21B3/04Recovery of by-products, e.g. slag
    • C21B3/06Treatment of liquid slag
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21CPROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C5/00Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
    • C21C5/52Manufacture of steel in electric furnaces
    • C21C5/54Processes yielding slags of special composition
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/04Working-up slag
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21BMANUFACTURE OF IRON OR STEEL
    • C21B2400/00Treatment of slags originating from iron or steel processes
    • C21B2400/02Physical or chemical treatment of slags
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Environmental & Geological Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Processing Of Solid Wastes (AREA)
  • Carbon Steel Or Casting Steel Manufacturing (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Treatment Of Steel In Its Molten State (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)
  • Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)
  • Removal Of Specific Substances (AREA)

Abstract

本发明涉及一种从液体炉渣或炉渣混合物中除去铬和/或镍的方法,其中把液体炉渣加到金属浴上,特别是铁浴上,并通过用碳或碳载体接触进行还原。为了使炉渣的Cr和Ni氧化物含量降低到0.8-0.2重量%,向金属浴中引入碳。在达到预定的炉渣Cr氧化物含量时,加入具有更大还原电势的还原剂如Al、Ca、Si、Fe-Si或Ca-Fe,使Cr和Ni氧化物含量降低到0.15重量%以下,优选的是0.08重量%以下。

Description

用于液体炉渣脱铬和/或脱镍的方法
本发明涉及一种使液体炉渣或炉渣混合物和粉尘脱铬和/或脱镍的方法,其中,把液体炉渣装在金属浴上,特别是铁浴上并通过供给碳或碳载体进行还原。
由生产不锈钢或铁铬合金产生的液体钢厂炉渣,取决于其来源,特别是取决于在钢的生产过程中使用的废铁掺和物的比例和组成,首先含有较高含量的铬氧化物。同时还发现锰的氧化物含量较高。在某些钢渣中,甚至观察到相当高的镍含量和相当高的钒含量。在钢渣的钒含量较高的情况下,在EP 770 149中已经提出,在使用碳载体进行的第一次还原过程之后,使用具有更高还原电势的还原剂在单独的连续安装的还原转炉中回收钒。为此,首先把所有的铬和锰碳热还原,对此在注入碳载体如甲烷的金属浴上方,经较长时间处理炉渣。由于所提出的处理时间较长,为了保持必须的温度,所引入的碳中相当大一部分被消耗。
单独的并且通常也单独加热的还原反应器用于分离钒的应用只有在存在高含量的钒使所回收的钒产生经济效益时才自然是经济有效的。首先,如果应尽可能高程度地进行钢渣脱铬,这将涉及较长的处理时间,因此在已知的加工方式中热损失较高。
本发明的目的是改进初始提到的这类方法,其改进程度使得即使不能保证通过回收贵金属原料获得经济效益,在总处理时间同时缩短的情况下可靠的脱铬也是可行的。为了达到这一目的,根据本发明的方法基本包括向金属浴中送入碳直至熔渣中的Cr和/或Ni的氧化物含量降低到0.8重量%-0.2重量%,并且在达到预定的钢渣中Cr氧化物含量范围时,为了使Cr和/或Ni的氧化物含量降低到0.15重量%以下,优选的0.08重量%以下,加入具有更高还原电势的还原剂如Al、Ca、Si、Fe-Si或Ca-Si。因此,只使用单一的转炉进行根据本发明的方法,其中,通过在某一时刻中止使用碳载体如烃进行的碳热还原,此时在炉渣仍然具有较高的并且是通常不能接受的铬或镍氧化物含量,因此这样的炉渣不能直接用作水泥研磨添加剂,到此时的处理时间明显缩短,并且在达到这样预定的较高铬和/或镍氧化物含量时,通过在相同的转炉中直接加入具有更高还原电势的还原剂,可以在较短时间内完成该方法,并且使铬和/或镍氧化物含量可靠地降低到预定极限值以下。通过这样的分步还原,当然还可以降低其它不锈钢相关成分的含量,例如使炉渣中的钼或钒降低到非临界值。
在这方面,在本发明方法的范围内,有利的是进行该方法使得加入Fe-Si的量为3-15公斤/吨炉渣,优选的是6-10公斤/吨炉渣。如果炉渣中含有可被这样的还原剂还原的其它物质,例如钒氧化物、锰氧化物、镍氧化物或钼氧化物,这些物质当然在该步骤中同时被还原到浴中。
由于碳热还原反应形成的还原炉渣与随后引入的还原剂缓慢反应,对此,如果,例如相应于该方法优选的进一步改进,在加入具有更高还原电势的还原剂以后用惰性气体吹扫该浴,该反应的反应速度并且特别是还原动力学被明显改善。由于注入的惰性气体(例如其可以是氮或氩)的搅拌作用,该反应被明显加速,使得非常短的处理时间即可获得期望的铬氧化物含量。
大体上,特别有利的是第一碳热还原进行15-30分钟,第二还原进行3-10分钟。
在下文中,将通过示例性实施方案更详细解释本发明。
示例性实施方案
在转炉中,把3吨具有以下所示的组成分析的炉渣在液态下装在10吨生铁上:
    钢渣
    重量%
    CaO     47.8
    SiO2     26.3
    Al2O3     5.9
    MgO     8.9
    TiO2     1.3
    FeO     1.7
    MnO     1.4
    Cr2O3     6.7
然后通过同时装入碳和氧使金属氧化物含量降低到以下含量:
碳热还原后的金属氧化物含量
    重量%
    FeO     1.1
    MnO     0.8
    Cr2O3     0.3
此后,加入30公斤硅铁合金并用55Nm3氮气吹扫该浴5分钟。在铁浴中溶解的硅的还原作用产生以下最终炉渣组成:
强还原后的炉渣
    重量%
    CaO     41.6
    SiO2     35.1
    Al2O3     12.8
    MgO     7.5
    TiO2     1.1
    FeO     0.8
    MnO     0.4
    Cr2O3     0.07
可以在一个转炉内进行全部的两阶段还原过程,对此发现从6.7重量%的铬氧化物含量开始,在处理20分钟后在碳热还原结束时铬氧化物含量为0.3重量%。在随后经5分钟的硅热还原中,铬氧化物含量可以从0.3重量%降低到0.07重量%。由于较短的处理时间,可以明显降低热损失,并且更高程度地利用碳载体原料进行还原。

Claims (4)

1.一种使液体炉渣或炉渣混合物脱铬和/或脱镍的方法,其中,把液体炉渣装在金属浴,特别是铁浴上,并通过送入碳或碳载体进行还原,其特征在于向金属浴中送入碳直至炉渣的Cr和/或Ni氧化物含量降低到0.8-0.2重量%,并且在获得预定的熔渣Cr氧化物含量范围时,为了使Cr和/或Ni氧化物含量降低到0.15重量%以下,优选的是0.08重量%以下,加入具有更高还原电势的还原剂如Al、Ca、Si、Fe-Si或Ca-Si。
2.根据权利要求1的方法,其特征在于Fe-Si加入量为3-15公斤/吨炉渣,优选的是6-10公斤/吨炉渣。
3.根据权利要求1或2的方法,其特征在于在加入具有更高还原电势的还原剂以后用惰性气体吹扫该浴。
4.根据权利要求1、2或3的方法,其特征在于经15-30分钟进行第一碳热还原,经3-10分钟进行第二还原。
CNB018040594A 2000-01-28 2001-01-18 用于液体炉渣脱铬和/或脱镍的方法 Expired - Fee Related CN1195881C (zh)

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
CN100587086C (zh) * 2007-09-06 2010-02-03 昆明理工大学 利用可燃物对有色金属铜渣/镍渣进行改性和制备优质燃料的方法
CN110029220A (zh) * 2019-04-25 2019-07-19 北京科技大学 一种两步法还原氧化铬制备金属铬粉的方法

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FR2864074B1 (fr) * 2003-12-18 2006-05-19 Lafarge Sa Composition minerale hydraulique et son procede de fabrication, produits cimentaires et liants hydrauliques contenant une telle composition
WO2005113840A1 (de) * 2004-05-18 2005-12-01 Holcim Ltd. Verfahren zur reduktion von cr aus cr-haltigen metallurgischen schlacken
WO2007035778A2 (en) 2005-09-19 2007-03-29 Histogenics Corporation Cell-support matrix and a method for preparation thereof
JP5191861B2 (ja) * 2008-10-28 2013-05-08 Jfeミネラル株式会社 セメント原料用スラグの製造方法
US10077420B2 (en) 2014-12-02 2018-09-18 Histogenics Corporation Cell and tissue culture container
FI20195830A1 (en) * 2019-09-30 2021-03-31 Outokumpu Oy REDUCTION OVEN PARTITION SOLUTION

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100587086C (zh) * 2007-09-06 2010-02-03 昆明理工大学 利用可燃物对有色金属铜渣/镍渣进行改性和制备优质燃料的方法
CN110029220A (zh) * 2019-04-25 2019-07-19 北京科技大学 一种两步法还原氧化铬制备金属铬粉的方法

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KR20020089331A (ko) 2002-11-29
JP3869270B2 (ja) 2007-01-17
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ATE248236T1 (de) 2003-09-15
CA2398352A1 (en) 2001-08-02
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US20030075019A1 (en) 2003-04-24
CN1195881C (zh) 2005-04-06

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