WO2008009178A1 - Dephosphorization method in the process of smelting ni-cr pig iron from a nickel oxide ore - Google Patents

Dephosphorization method in the process of smelting ni-cr pig iron from a nickel oxide ore Download PDF

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Publication number
WO2008009178A1
WO2008009178A1 PCT/CN2006/002032 CN2006002032W WO2008009178A1 WO 2008009178 A1 WO2008009178 A1 WO 2008009178A1 CN 2006002032 W CN2006002032 W CN 2006002032W WO 2008009178 A1 WO2008009178 A1 WO 2008009178A1
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nickel
ore
limestone
pig iron
phosphorus
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PCT/CN2006/002032
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French (fr)
Chinese (zh)
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Guanghuo Liu
Shenjie Liu
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Guanghuo Liu
Shenjie Liu
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Priority to EP06775350A priority Critical patent/EP2039788A4/en
Publication of WO2008009178A1 publication Critical patent/WO2008009178A1/en

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/14—Agglomerating; Briquetting; Binding; Granulating
    • C22B1/16—Sintering; Agglomerating
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B13/00—Making spongy iron or liquid steel, by direct processes
    • C21B13/006—Starting from ores containing non ferrous metallic oxides
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B13/00—Making spongy iron or liquid steel, by direct processes
    • C21B13/008—Use of special additives or fluxing agents
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B13/00—Making spongy iron or liquid steel, by direct processes
    • C21B13/14—Multi-stage processes processes carried out in different vessels or furnaces
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/005—Preliminary treatment of ores, e.g. by roasting or by the Krupp-Renn process
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/02—Obtaining nickel or cobalt by dry processes
    • C22B23/023—Obtaining nickel or cobalt by dry processes with formation of ferro-nickel or ferro-cobalt
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • C22B5/10—Dry methods smelting of sulfides or formation of mattes by solid carbonaceous reducing agents

Definitions

  • the invention belongs to the field of metallurgy, and in particular relates to a phosphorus reduction method for smelting nickel-chromium pig iron in nickel oxide ore.
  • the demand for phosphorus content in the blast furnace smelting process is not high.
  • the phosphorus content of the pig iron in the steelmaking is 0.15, and the phosphorus content of the cast iron is 0.06 as the quality product, and the phosphorus content of the stainless steel product is compared. ⁇
  • the amount of phosphorus is required to be less than 0. 035.
  • CN03808054. 0 discloses a device for oxygen top blowing to dephosphorization for dephosphorization, but requires a specific device and also increases the cost of smelting.
  • CN200410021379 discloses a stainless steel reducing dephosphorization agent for a vacuum induction furnace, which is mainly composed of Ca and Mg, and is also added to molten steel after the end of refining, and a dephosphorization step is added.
  • the object of the present invention is to solve the deficiencies of the prior art and to provide a phosphorus reduction method for smelting a nickel-chromium pig iron process in a nickel oxide ore.
  • the object of the present invention is achieved by the following technical scheme: a phosphorus reduction method for smelting a nickel-chromium pig iron process by a nickel oxide ore, wherein the raw ore is added with limestone or silica to adjust the binary alkalinity to 0. 4-0. 7, further adding limestone and coke breeze for sintering, obtaining a sinter having a binary basicity value of 0.5-0.8, and further smelting the sinter to obtain nickel-chromium pig iron.
  • the amount of limestone added to the original ore is 12% (% by weight, the same below). When calcined, the amount of limestone added is 10-12%, and the amount of coke is 9-17%.
  • the CaO content in the limestone is not less than 80%.
  • the phosphorus content of the coke in the raw material is not more than 0. 016%, the phosphorus content in the limestone is not more than 0. 008%, the phosphorus content in the ore is not more than 0. 012%.
  • the furnace sintering material contains Fe 6-46%, P 0. 019%, Si0 2 18-41%, MgO 16-21%, CaO 16-24%, Ni 1-3%, Cr 1-3%. .
  • the method provided by the invention actually allocates the type and proportion of the injected flux in the smelting process, achieves the appropriate binary alkalinity, directly dephosphorizes and reduces phosphorus in the smelting process, does not need to add special equipment, and does not need to be made.
  • Special dephosphorization agent can be applied to the smelting of various furnace types such as blast furnace and electric furnace. The dephosphorization can be achieved at a low cost and without pollution to below 0. 035.
  • Embodiment 1 is a diagrammatic representation of Embodiment 1:
  • the ore is mixed with 80% limestone containing CaO, wherein the amount of limestone is 12% by weight; after drying, 14-16% of coke (78-80% of carbon) is added, and the content of Ca084% is added.
  • Limestone 10-12%, sintered, the resulting sinter composition is Fe 25. 38%, phosphorus 0. 019%, Si0 21. 5%, CaO 20. 29%, MgO 15. 17%, F 1-3%, Cr 0. 7-1. 5%, Ni 1. 2- 1. 8%;
  • the sinter is put into the furnace for smelting.
  • the sintering reduces the alkalinity to between 0.5 and 0.8.
  • the balance of silicon, magnesium and fluorine causes the phosphorus to enter the slag liquid in a large amount.
  • the smelting of the nickel-chromium pig iron composition is as follows: phosphorus 0. 035% or less, sulfur 0. 08 or less, iron 69% - 92%, nickel 3-16%, chromium 2-7%, manganese 0. 5%, silicon 1 0-2. 4%, carbon 1-4%.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Geology (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

A dephosphorization method in the process of smelting Ni-Cr pig iron from a nickel oxide ore compi basicity oft lica, then adding limestorses the following steps: adjusting the heraw ore to 0.4-0.7 by adding limestone or si ne and coke powder, sintering to obtain sintered ore with abasicity of 0.5-0.7, and smelting the sintered ore to obtain Ni-Cr pig iron, in which the amount of the coke powderin the sintering process is 9-17% based on total weight, P content ofthe coke is not greater than 0.016%, P content of the limestone is not greater than 0.008%, P content of the raw ore is not greater than 0.012%.The P content could be reduced to lessthan 0.035% in one pass and in low cost without contamination by using the method.

Description

氧化镍矿冶炼镍铬生铁工艺的降磷方法  Phosphorus reduction method for smelting nickel-chromium pig iron in nickel oxide ore
技术领域： Technical field:
本发明属冶金领域，特别涉及一种氧化镍矿冶炼镍铬生铁工艺的 降磷方法。  The invention belongs to the field of metallurgy, and in particular relates to a phosphorus reduction method for smelting nickel-chromium pig iron in nickel oxide ore.
背景技术：  Background technique:
目前高炉冶炼工艺中， 对于含磷量的要求不高， 炼钢生铁含磷量 在 0. 15为优质品， 铸造生铁含磷量 0. 06为优质品， 而对于不锈钢产品 含磷量要求比较高，其中 304系列不锈钢要求含磯量在 0. 035以下， 200 系列不锈钢要求含磷量在 0. 05以下。为了达到这一要求， 对于大型高 炉需要使用脱磷专用的三脱机， 但其造价高， 又不能保留原矿中的金 属铬， 造成原料浪费， 同时对于中小型高炉， 不合适投入大量资金进 行脱磷。 已有的脱磷方法还有一些， 如 CN85101003A公开了一种喷射 冶金的方法， 用碱金属或碱土金属或其合金粉末喷入钢包内， 可将钢 水中磷含量降至 0. 005以下，但这种方法成本太高，不宜大生产使用。 CN03808054. 0公开了一种氧气顶吹予脱磷的装置用来予脱磷，但需要 特定的装置，也增加了冶炼成本。 CN200410021379公开了一种用于真 空感应炉的不锈钢还原脱磷剂， 主要由 Ca、 Mg组成， 也是在精炼结束 后加入钢水中， 增加了一个脱磷工序。  At present, the demand for phosphorus content in the blast furnace smelting process is not high. The phosphorus content of the pig iron in the steelmaking is 0.15, and the phosphorus content of the cast iron is 0.06 as the quality product, and the phosphorus content of the stainless steel product is compared.至以下。 In the case of the 304 series of stainless steels, the amount of phosphorus is required to be less than 0. 035. In order to meet this requirement, for the large blast furnace, it is necessary to use the three off-line special for dephosphorization, but its high cost, and can not retain the metal chromium in the ore, which causes waste of raw materials. At the same time, it is not suitable for small and medium-sized blast furnaces. phosphorus. 005以下, but the phosphorus content of the molten steel is reduced to less than 0.005, but the method of spraying the metallurgy, the alkali metal or alkaline earth metal or its alloy powder is sprayed into the ladle. This method is too costly and should not be used in large production. CN03808054. 0 discloses a device for oxygen top blowing to dephosphorization for dephosphorization, but requires a specific device and also increases the cost of smelting. CN200410021379 discloses a stainless steel reducing dephosphorization agent for a vacuum induction furnace, which is mainly composed of Ca and Mg, and is also added to molten steel after the end of refining, and a dephosphorization step is added.
发明内容：  Summary of the invention:
本发明的目的是解决现有技术的不足，提供一种氧化镍矿冶炼镍 铬生铁工艺的降磷方法。  The object of the present invention is to solve the deficiencies of the prior art and to provide a phosphorus reduction method for smelting a nickel-chromium pig iron process in a nickel oxide ore.
本发明的目的是通过下述技术方案实现的：氧化镍矿冶炼镍铬生 铁工艺的降磷方法， 其中原矿加入石灰石或硅石将二元碱度调节至 0. 4-0. 7, 再加入石灰石和焦末进行烧结， 得到二元碱度值为 0. 5-0. 8 的烧结矿， 将烧结矿进一步冶炼得到镍铬生铁。 The object of the present invention is achieved by the following technical scheme: a phosphorus reduction method for smelting a nickel-chromium pig iron process by a nickel oxide ore, wherein the raw ore is added with limestone or silica to adjust the binary alkalinity to 0. 4-0. 7, further adding limestone and coke breeze for sintering, obtaining a sinter having a binary basicity value of 0.5-0.8, and further smelting the sinter to obtain nickel-chromium pig iron.
原矿中调二元碱度加入石灰石量为 12% (重量百分比， 下同） 烧 结时加入石灰石量为 10-12%、 焦末量 9- 17%。  The amount of limestone added to the original ore is 12% (% by weight, the same below). When calcined, the amount of limestone added is 10-12%, and the amount of coke is 9-17%.
所述石灰石中 CaO含量不小于 80%。  The CaO content in the limestone is not less than 80%.
所述石灰石用生石灰代替。  The limestone is replaced with quicklime.
其中原料中焦炭的磷含量不大于 0. 016%,石灰石中磷含量不大于 0. 008%, 原矿中磷含量不大于 0. 012%。  012%。 The phosphorus content of the coke in the raw material is not more than 0. 016%, the phosphorus content in the limestone is not more than 0. 008%, the phosphorus content in the ore is not more than 0. 012%.
所述入炉烧结料中含有 Fe 6-46%, P 0. 019%、 Si02 18-41%、 MgO 16- 21%、 CaO 16-24%、 Ni 1-3%、 Cr 1-3%。 The furnace sintering material contains Fe 6-46%, P 0. 019%, Si0 2 18-41%, MgO 16-21%, CaO 16-24%, Ni 1-3%, Cr 1-3%. .
本发明提供的方法，实际上是在冶炼过程中调配所投入熔剂的种 类和配比， 达到适宜的二元碱度， 在冶炼过程中直接脱磷降磷， 无需 添置专用设备， 也无需制成专用脱磷剂， 可适用于高炉、 电炉等多种 炉型的冶炼。 可以低成本无污染地实现一次脱磷达到 0. 035以下。  The method provided by the invention actually allocates the type and proportion of the injected flux in the smelting process, achieves the appropriate binary alkalinity, directly dephosphorizes and reduces phosphorus in the smelting process, does not need to add special equipment, and does not need to be made. Special dephosphorization agent, can be applied to the smelting of various furnace types such as blast furnace and electric furnace. The dephosphorization can be achieved at a low cost and without pollution to below 0. 035.
具体实施方式：  detailed description:
下面结合本发明的实施例作具体说明，下列实施例并不限制本发 明的保护范围，所有基于本发明的思想做的修改和调整都属于本发明 保护的范围。  The following embodiments are described in detail with reference to the embodiments of the present invention. The following examples are not intended to limit the scope of the invention, and all modifications and adaptations based on the inventive concept are within the scope of the invention.
实施例一：  Embodiment 1:
原矿成分：  Original ore composition:
含结晶水 35%, Fe 30%, 磷 0. 010%, SiO, 38. 62%, CaO 6. 42%， AI2O3 1. 80%, MgO 18. 44%, nO 0. 52%, Ni 1. 2-1. 8%， Cr 1-1. 5%。  Containing 35% of crystal water, Fe 30%, phosphorus 0. 010%, SiO, 38.62%, CaO 6. 42%, AI2O3 1. 80%, MgO 18. 44%, nO 0. 52%, Ni 1. 2-1. 8%, Cr 1-1. 5%.
将原矿与含 CaO 80% 的石灰石混合搅拌， 其中石灰石用量以重量 百分比计为 12%; 晒干后加入 14- 16%的焦末 (其中含碳 78- 80%) ， 配 入含 Ca084%的石灰石 10- 12%， 进行烧结， 所得烧结矿成分为， Fe 25. 38%, 磷 0. 019%, Si0 21. 5%， CaO 20. 29%, MgO 15. 17%, F 1-3%, Cr 0. 7-1. 5%， Ni 1. 2-1. 8%; The ore is mixed with 80% limestone containing CaO, wherein the amount of limestone is 12% by weight; after drying, 14-16% of coke (78-80% of carbon) is added, and the content of Ca084% is added. Limestone 10-12%, sintered, the resulting sinter composition is Fe 25. 38%, phosphorus 0. 019%, Si0 21. 5%, CaO 20. 29%, MgO 15. 17%, F 1-3%, Cr 0. 7-1. 5%, Ni 1. 2- 1. 8%;
将烧结矿入炉冶炼， 经烧结时， 烧结降低了碱度为 0. 5 0. 8之 间，由硅、镁、 氟的平衡作用， 使磷大量进入炉渣液体中，出渣时， 随 炉渣排出，得到的镍铬生铁成分如下： 磷 0. 035%以下，硫 0. 08以下， 铁 69%- 92%,镍 3-16%,铬 2-7%，锰 0. 5%,硅 1. 0-2. 4%,碳 1一4%。  The sinter is put into the furnace for smelting. When sintered, the sintering reduces the alkalinity to between 0.5 and 0.8. The balance of silicon, magnesium and fluorine causes the phosphorus to enter the slag liquid in a large amount. 5%的硅1。 The smelting of the nickel-chromium pig iron composition is as follows: phosphorus 0. 035% or less, sulfur 0. 08 or less, iron 69% - 92%, nickel 3-16%, chromium 2-7%, manganese 0. 5%, silicon 1 0-2. 4%, carbon 1-4%.

Claims

权利 要求书 Claim
1、 氧化镍矿冶炼镍铬生铁工艺的降磷方法， 其特征在于： 原矿 加入石灰石或硅石将二元碱度调节至 0. 4-0. 7， 再加入石灰石和焦末 进行烧结， 得到二元碱度值为 0. 5-0. 8的烧结矿， 将烧结矿进一步冶 炼得到镍铬生铁。  1. The method of reducing phosphorus in a nickel-chromium pig iron process for smelting a nickel-nickel ore is characterized in that: the raw ore is added with limestone or silica to adjust the binary alkalinity to 0.4 to 0.4, and then the limestone and the coke are added for sintering to obtain two The sinter ore having a basicity of 0. 5-0. 8 is further smelted to obtain nickel-chromium pig iron.
2、 根据权利要求 1所述的氧化镍矿冶炼镍铬生铁工艺的降磷方 法， 其特征在于： 以重量百分比计， 原矿中调二元碱度加入石灰石量 为 12%, 烧结时加入石灰石量为 10— 12%、 焦末量 9一 17%。  2. The method of reducing phosphorus in a nickel-chromium pig iron smelting process according to claim 1, characterized in that: in terms of weight percentage, the amount of limestone added to the binary alkalinity of the ore is 12%, and the amount of limestone is added during sintering. It is 10-12%, and the amount of coke is 9-17%.
3、 根据权利要求 1或 2所述的氧化镍矿冶炼镍铬生铁工艺的降磷 方法，其特征在于：以重量百分比计所述石灰石中 CaO含量不小于 80%。  A method of reducing phosphorus in a nickel-chromium pig iron smelting process according to claim 1 or 2, wherein the limestone has a CaO content of not less than 80% by weight.
4、 根据权利要求 1或 2所述的氧化镍矿冶炼镍铬生铁工艺的降磷 方法， 其特征在于： 所述石灰石用生石灰代替。  A method of reducing phosphorus in a nickel-chromium pig iron smelting process according to claim 1 or 2, wherein the limestone is replaced with quicklime.
5、 根据权利要求 1或 2所述的氧化镍矿冶炼镍铬生铁工艺的降磷 方法， 其特征在于： 以重量百分比计原料中焦炭的磷含量不大于 0. 016%，石灰石中磷含量不大于 0. 008%,原矿中磷含量不大于 0. 012%。  The phosphorus content of the coke in the raw material is not more than 0.016%, the phosphorus content in the limestone is not 012%。 The greater than 0. 008%, the phosphorus content of the original ore is not greater than 0. 012%.
6、 根据权利要求 1或 2所述的氧化镍矿冶炼镍铬生铁工艺的降磷 方法， 其特征在于： 以重量百分比计所述入炉烧结料中含有 Mg 12—30%、 Si 15-40%、 Ca 12-30%、 F 0. 3- 4%。  The method for reducing phosphorus in a nickel-nickel pig iron smelting process according to claim 1 or 2, characterized in that: the sintering material contained in the furnace contains Mg 12-30%, Si 15-40 %, Ca 12-30%, F 0. 3- 4%.
7、 根据权利要求 6所述的氧化镍矿冶炼镍络生铁工艺的降磷方法， 其特征在于：所述入炉烧结料中含有 Fe 6-46%, P 0. 019%,Si0 8-41% MgO 16—21%、 CaO 16—24%、 Ni 1-3%, Cr 1一3%。  7. The method of reducing phosphorus in a nickel-nickel ore-smelting process of nickel oxide ore according to claim 6, wherein the furnace frit contains Fe 6-46%, P 0.019%, Si0 8-41 % MgO 16-21%, CaO 16-24%, Ni 1-3%, Cr 1 - 3%.
PCT/CN2006/002032 2006-07-12 2006-08-11 Dephosphorization method in the process of smelting ni-cr pig iron from a nickel oxide ore WO2008009178A1 (en)

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CN100532579C (en) * 2007-04-30 2009-08-26 郑州永通特钢有限公司 Method for smelting base material of low phosphorous stainless steel by using low-grade limonite containing nickel-chromium
CN102312033A (en) * 2011-07-28 2012-01-11 山西太钢不锈钢股份有限公司 Dephosphorization method of high-phosphorous chromium-nickel pig iron
CN104152676B (en) * 2014-07-25 2016-04-06 中南大学 A kind of Iron Ore Matching in Sintering method of red soil nickel ore
CN104561736A (en) * 2014-12-29 2015-04-29 芜湖国鼎机械制造有限公司 High-strength gray cast iron, casting and preparation method of high-strength gray cast iron
CN104946832B (en) * 2015-06-29 2017-07-28 中冶京诚工程技术有限公司 A kind of method that utilization lateritic nickel ore produces nickel-containing molten iron
CN109251779B (en) * 2018-09-30 2021-09-17 柳州钢铁股份有限公司 NOx emission reduction method based on modified fuel iron ore sintering process

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