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WO2013187348A1 - Procédé de fabrication de chrome métallique - Google Patents

Procédé de fabrication de chrome métallique Download PDF

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Publication number
WO2013187348A1
WO2013187348A1 PCT/JP2013/065927 JP2013065927W WO2013187348A1 WO 2013187348 A1 WO2013187348 A1 WO 2013187348A1 JP 2013065927 W JP2013065927 W JP 2013065927W WO 2013187348 A1 WO2013187348 A1 WO 2013187348A1
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WO
WIPO (PCT)
Prior art keywords
metal
chromium
aluminum
primary
content
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2013/065927
Other languages
English (en)
Japanese (ja)
Inventor
博一 杉森
博樹 浅田
晋弘 藤田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JFE Material Co Ltd
Original Assignee
JFE Material Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by JFE Material Co Ltd filed Critical JFE Material Co Ltd
Priority to JP2014521314A priority Critical patent/JP6230531B2/ja
Publication of WO2013187348A1 publication Critical patent/WO2013187348A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • C22B5/04—Dry methods smelting of sulfides or formation of mattes by aluminium, other metals or silicon
    • 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
    • C22B34/00—Obtaining refractory metals
    • C22B34/30—Obtaining chromium, molybdenum or tungsten
    • C22B34/32—Obtaining chromium
    • 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
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/10—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals with refining or fluxing agents; Use of materials therefor, e.g. slagging or scorifying agents
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/06—Alloys based on chromium

Definitions

  • the present invention relates to a method for producing metallic chromium used for corrosion-resistant / heat-resistant materials (superalloy), electronic materials, etc. (for example, magnetic materials, semiconductor materials).
  • Patent Document 1 As a typical method for producing metal chromium, the applicant has proposed a method for producing metal chromium in which chromium oxide is reduced by silicon (see Patent Document 1).
  • silicon reduction method first, chromium oxide, metallic silicon, and lime are charged into an electric furnace as raw materials. Metallic silicon is used as a reducing agent. Next, the electric furnace is energized to melt these raw materials. The dissolved metal silicon and chromium oxide react, and chromium oxide is reduced by silicon. Silicon oxide (SiO 2 ) generated by the reduction reaction reacts with lime (CaO) to form slag.
  • the iron content attributable to the metal silicon can be reduced.
  • the silicon reduction method it is necessary to increase the basicity (CaO / SiO 2 ) in order to advance the reduction reaction, and for that purpose, a large amount of lime is used. Since this large amount of lime also contains iron, there is a problem that there is a limit in reducing the iron content of metallic chromium.
  • acicular aluminum (Al) as a reducing agent is mixed with chromium oxide (Cr 2 O 3 ), and the mixture is charged into a reaction furnace.
  • magnesium powder is placed on the mixture and ignited. Heat is propagated through the mixture to initiate the reaction between chromium oxide and aluminum.
  • Aluminum generates high temperatures while reducing chromium oxide. This high heat causes metal chromium metal to settle to the bottom of the reactor. Slag with a lighter specific gravity than metal is separated from the metal.
  • the reduction reaction of the aluminum thermite method continues for 10 to 15 minutes. After the molten metal and slag are solidified, the molten metal and slag are taken out from the reaction furnace, and the metal is pulverized to obtain metal chromium.
  • this invention aims at providing the manufacturing method of the metal chromium which can also raise the yield of chromium collection
  • one embodiment of the present invention includes a step of charging chromium oxide, aluminum, and lime as raw materials into an electric furnace, and the electric furnace is energized to dissolve the raw materials, Reducing with aluminum to produce a primary metal containing chromium and primary slag; extracting the primary slag from the electric furnace; adding basic flux to the primary metal of the electric furnace; A method of producing metallic chromium, comprising: energizing the electric furnace to dissolve the basic flux and oxidizing and removing aluminum remaining in the primary metal to generate a secondary metal.
  • the heat for melting the raw material is guaranteed by the electric furnace, so that the reduction reaction of chromium oxide can be maintained for a long time, and the reduction reaction can proceed with a high yield.
  • the iron and P contents contained in the reducing agent can be reduced.
  • aluminum when aluminum is used as the reducing agent, aluminum remains in the primary metal, but the primary metal aluminum can be removed by oxidizing and refining the primary metal. Therefore, the iron content and aluminum content of the metal chromium recovered as a product can be reduced.
  • FIG. 1 shows a flowchart of a method for producing metallic chromium of the present embodiment.
  • chromium oxide Cr 2 O 3
  • Al aluminum
  • CaO lime
  • an arc melting furnace is used in which arc discharge is caused by using a graphite electrode and the raw material is melted by using a large amount of heat generated at that time.
  • the power source for generating the arc may be direct current or alternating current.
  • An arc melting furnace that can be tilted to discharge the generated molten metal and discharge the slag is used.
  • Chromium oxide is a product obtained by chemically treating chromium ore and / or chromium ore. Lime is used as a flux that promotes the melting of chromium ore. If there is no flux on the metal, a stable arc cannot be generated in the arc melting furnace. The amount of lime is less than the amount of lime used in the silicon reduction process. This is because, in the silicon reduction method, the reduction efficiency of chromium oxide increases as the basicity (CaO / SiO 2 ) increases, so that the amount of lime used increases. This is because the chromium metal production method of the present embodiment reduces chromium oxide with aluminum, and the reduction efficiency of chromium oxide is independent of basicity.
  • Aluminum is used as a reducing agent. Only aluminum is used as the reducing agent, and silicon is not used. As the aluminum, bulk metallic aluminum such as 40 g, 10 g, 1 g, or the like is used. Since the heat for melting the aluminum is guaranteed by the electric furnace, there is no need to use acicular aluminum as used in the aluminum thermite method. Since aluminum has a low specific gravity, it floats when dissolved, and the reduction reaction may not proceed. For this reason, when charging a raw material in an arc melting furnace, chromium oxide, aluminum, and lime are mixed.
  • the arc melting furnace is energized to perform a reduction process (S1).
  • S1 a reduction process
  • the raw material is melted, the molten aluminum and chromium oxide react as shown in the following reaction formula, and reduction with aluminum proceeds while producing Al 2 O 3 .
  • the primary metal containing chromium is generated arc melting furnace, the primary slag and the Al 2 O 3 was produced by the reduction reaction of CaO reacts is formed.
  • the chromium content of the primary metal is 95% or more.
  • the aluminum content, silicon content, and iron content are not reduced to the target levels (for example, the aluminum content is 0.02% by mass or less and the silicon content is 0.05% by mass or less). For this reason, a refining process is required. The refining process will be described later.
  • the chromium content of the primary slag is 1% or less.
  • the aluminum content in the primary metal is set to about 0.2 to 3 mass%.
  • the main component of primary slag is calcium aluminate containing CaO and Al 2 O 3 as main components. This calcium aluminate is used as a desulfurizing agent for steel making.
  • FIG. 2 shows the relationship between the aluminum content in the primary metal and the Cr content in the primary slag.
  • the aluminum content in the primary metal is 0.2% by mass or more
  • the Cr content in the primary slag is reduced to 1.0% by mass. For this reason, the yield of chromium can be set to a high value of 90% or more.
  • the basic flux is lime (CaO) or magnesia (MgO). In this embodiment, lime (CaO) is used.
  • Secondary metal is obtained by this oxidative refining (S4).
  • the aluminum content in the secondary metal is 0.02 mass% or less, the silicon content is 0.05 mass% or less, the sulfur content is 0.001 mass% or less, the iron content is 0.20 mass% or less, phosphorus Content is 0.003 mass% or less.
  • the aluminum content in the primary metal is reduced from about 0.2 to 3% by mass to 0.02% by mass or less.
  • silicon since silicon is not used as the reducing agent, the silicon content in the primary metal is about 0.3% by mass.
  • the silicon content in the primary metal is reduced to 0.05 mass% or less.
  • the sulfur content becomes extremely low at 0.001% by mass or less by high temperature refining and high basicity operation. Chrome yield is over 94%.
  • the cooled secondary metal ingot is taken out of the mold and crushed into briquettes (S5, S6).
  • the metallic chromium thus obtained is of high purity but has a slightly high oxygen content and nitrogen content. Therefore, these gas components are removed by vacuum heat treatment in a vacuum processing facility (S7).
  • metallic chromium having a chromium content of 99.0% or more is produced (S8).
  • the content of impurity elements (aluminum, iron, silicon, sulfur, phosphorus, oxygen, nitrogen) in metallic chromium is extremely low.
  • Iron and phosphorus contained in metallic chromium are derived from the introduction of raw materials.
  • aluminum the reducing agent, the amount of iron derived from the reducing agent can be reduced as compared with the case of using metal silicon as the reducing agent.
  • restoration process of chromium oxide can also be decreased, content of iron and phosphorus derived from lime can be reduced.
  • the raw material was charged into a 500 kVA arc melting furnace with 45 kg of chromium oxide, 9 kg of quicklime, and 17.4 kg of aluminum. Then, the graphite electrode was energized to dissolve the raw material, and the reduction reaction of chromium oxide was advanced to obtain 29.5 kg of primary metal and 26.0 kg of primary slag.
  • composition of the primary metal was as shown in Table 1 below.
  • the composition of the primary slag is as shown in Table 2 below.
  • primary slag was used as a desulfurization agent for steelmaking.
  • 9 kg of quicklime was added to 29.5 kg of the primary metal, and the arc melting furnace was re-energized.
  • Quick lime was dissolved to form secondary slag, and the metal smelt was oxidized and refined by the secondary slag.
  • the composition of the secondary metal is as shown in Table 3 below.
  • the arc melting furnace was tilted to discharge the secondary metal and secondary slag into the mold. After cooling, the secondary slag adhering to the surface of the secondary metal was removed by shot blasting.
  • the ingot of metal chromium was crushed to 40 mm or less by a crusher and charged into a vacuum heating furnace. Then, it cooled to normal temperature in the vacuum heating furnace, and the ingot of metal chromium was taken out from the vacuum heating furnace. Carbon, oxygen, and nitrogen were removed by vacuum heat treatment. The metal chromium finally obtained was high-purity metal chromium with few impurities.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Manufacture And Refinement Of Metals (AREA)
PCT/JP2013/065927 2012-06-15 2013-06-10 Procédé de fabrication de chrome métallique Ceased WO2013187348A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2014521314A JP6230531B2 (ja) 2012-06-15 2013-06-10 金属クロムの製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2012-135698 2012-06-15
JP2012135698 2012-06-15

Publications (1)

Publication Number Publication Date
WO2013187348A1 true WO2013187348A1 (fr) 2013-12-19

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JP (1) JP6230531B2 (fr)
WO (1) WO2013187348A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015174046A (ja) * 2014-03-17 2015-10-05 Ｊｆｅマテリアル株式会社 粉末冶金用クロムの製造方法
WO2017175605A1 (fr) * 2016-04-04 2017-10-12 Ｊｆｅマテリアル株式会社 Procédé de production de métal contenant du tungstène et métal contenant du tungstène
JP2019023347A (ja) * 2018-09-14 2019-02-14 Ｊｆｅマテリアル株式会社 粉末冶金用クロムの製造方法
WO2018068066A3 (fr) * 2016-09-21 2019-05-31 Beylefeld Jacques Procédé de production d'un ferrochrome à faible teneur en carbone par réduction métallurgique et affinage à l'oxygène
CN116732367A (zh) * 2023-05-22 2023-09-12 四川华铸新材料有限公司 一种利用废铬系晶体材料冶炼二元合金的制备方法
CN119750622A (zh) * 2024-12-10 2025-04-04 锦州宏大金属新材料科技有限公司 一种用生产铬生成的废渣制备氧化铝空心球保温材料方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113913629B (zh) * 2020-07-09 2023-03-03 王景军 一种用于金属铬冶炼的净化渣及金属铬的冶炼方法
CN114921648B (zh) * 2022-06-17 2023-06-23 山西太钢万邦炉料有限公司 一种矿热炉生产高硅炉料铬铁的方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS52123313A (en) * 1976-04-09 1977-10-17 Japan Metals & Chem Co Ltd Production of low p low c high cr ferro alloy
JPS6280236A (ja) * 1985-10-01 1987-04-13 Nisshin Steel Co Ltd クロム鉱石を用いた含クロム溶銑の製造方法
JP2001316712A (ja) * 2000-05-02 2001-11-16 Nippon Steel Corp 含クロム滓からのクロム回収方法
JP2001323329A (ja) * 2000-03-07 2001-11-22 Nkk Corp クロム含有金属及びその製造方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6247436A (ja) * 1985-08-26 1987-03-02 Toyo Soda Mfg Co Ltd 高純度金属クロムの製造法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS52123313A (en) * 1976-04-09 1977-10-17 Japan Metals & Chem Co Ltd Production of low p low c high cr ferro alloy
JPS6280236A (ja) * 1985-10-01 1987-04-13 Nisshin Steel Co Ltd クロム鉱石を用いた含クロム溶銑の製造方法
JP2001323329A (ja) * 2000-03-07 2001-11-22 Nkk Corp クロム含有金属及びその製造方法
JP2001316712A (ja) * 2000-05-02 2001-11-16 Nippon Steel Corp 含クロム滓からのクロム回収方法

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015174046A (ja) * 2014-03-17 2015-10-05 Ｊｆｅマテリアル株式会社 粉末冶金用クロムの製造方法
WO2017175605A1 (fr) * 2016-04-04 2017-10-12 Ｊｆｅマテリアル株式会社 Procédé de production de métal contenant du tungstène et métal contenant du tungstène
WO2018068066A3 (fr) * 2016-09-21 2019-05-31 Beylefeld Jacques Procédé de production d'un ferrochrome à faible teneur en carbone par réduction métallurgique et affinage à l'oxygène
JP2019023347A (ja) * 2018-09-14 2019-02-14 Ｊｆｅマテリアル株式会社 粉末冶金用クロムの製造方法
CN116732367A (zh) * 2023-05-22 2023-09-12 四川华铸新材料有限公司 一种利用废铬系晶体材料冶炼二元合金的制备方法
CN116732367B (zh) * 2023-05-22 2025-10-14 四川华铸新材料有限公司 一种利用废铬系晶体材料冶炼二元合金的制备方法
CN119750622A (zh) * 2024-12-10 2025-04-04 锦州宏大金属新材料科技有限公司 一种用生产铬生成的废渣制备氧化铝空心球保温材料方法

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