JP5364091B2 - Method for producing a chromium metal block from chromite or concentrate - Google Patents

Method for producing a chromium metal block from chromite or concentrate Download PDF

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JP5364091B2
JP5364091B2 JP2010508969A JP2010508969A JP5364091B2 JP 5364091 B2 JP5364091 B2 JP 5364091B2 JP 2010508969 A JP2010508969 A JP 2010508969A JP 2010508969 A JP2010508969 A JP 2010508969A JP 5364091 B2 JP5364091 B2 JP 5364091B2
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chromium
chromite
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カプール、ガジャナン、ユー．
タサバドカール、ヴィラス、ディー．
ラオ、サリパッリ、エム．
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タータ スチール リミテッド
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    • 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
    • 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
    • C22B1/02—Roasting processes
    • C22B1/10—Roasting processes in fluidised form
    • 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
    • C22B1/24—Binding; Briquetting ; Granulating
    • C22B1/2406—Binding; Briquetting ; Granulating pelletizing
    • 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
    • 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
    • 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
    • C22B7/00—Working 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
    • C22B7/04—Working-up slag
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Description

本発明は、クロム塊を製造するための方法の開発に係り、具体的には、低温予備酸化されたクロマイト鉱／精鉱によって金属化率５０〜７０％のクロム塊を製造する方法の開発に関するものである。   The present invention relates to the development of a method for producing a chromium block, and more particularly to the development of a method for producing a chromium block having a metallization rate of 50 to 70% by low-temperature pre-oxidized chromite or concentrate. Is.

あらゆる合金製造総合組織体において、高炭素フェロクロムは、溶解・還元工程によって生産されるのが普通である。これは、高度にエネルギー集約的であり、還元剤として輸入された低灰分コークスを必要とする。低灰分コークスも電気も、共に高価な資源である。故に、フェロクロム形態である金属化率５０〜７０％のクロマイト鉱を得るために、予備酸化されたクロム鉱石を、還元剤として石炭を用いて還元する新規工程が開発されている。   In all alloy manufacturing integrated structures, high carbon ferrochrome is usually produced by a dissolution / reduction process. This is highly energy intensive and requires low ash coke imported as a reducing agent. Both low ash coke and electricity are expensive resources. Therefore, in order to obtain a chromite ore having a metallization rate of 50 to 70% in the form of ferrochrome, a new process for reducing preoxidized chromium ore using coal as a reducing agent has been developed.

かくして、本発明の目的は、従来技術の欠点を解消すべく、予備酸化されたクロマイト鉱／精鉱を低温還元することによりクロム塊を製造する方法を提案することである。   Thus, the object of the present invention is to propose a method for producing a chromium block by low-temperature reduction of preoxidized chromite / concentrate in order to overcome the drawbacks of the prior art.

本発明の別の目的は、エネルギーを節約すべく、予備酸化されたクロマイト鉱／精鉱を低温還元してクロム塊を製造する方法を提案することである。   Another object of the present invention is to propose a method for producing a chromium mass by low-temperature reduction of pre-oxidized chromite / concentrate to save energy.

本発明の更に別の目的は、フェロクロム製造コストを２０％低減化すべく、予備酸化されたクロマイト鉱／精鉱を低温還元してクロム塊を製造する方法を提案することである。   Still another object of the present invention is to propose a method for producing a chromium block by low-temperature reduction of pre-oxidized chromite / concentrate to reduce ferrochrome production costs by 20%.

本発明の更に別の目的は、コークス消費を低減化すべく、予備酸化されたクロマイト鉱／精鉱を低温還元してクロム塊を製造する方法を提案することである。   Yet another object of the present invention is to propose a method for producing chromium agglomerates by low-temperature reduction of preoxidized chromite / concentrate to reduce coke consumption.

本発明の更に別の目的は、更なる鉄鋼溶解の過程中において、より良い反応表面を有する、予備酸化されたクロマイト鉱／精鉱を低温還元してクロム塊を製造する方法を提案することである。   Yet another object of the present invention is to propose a method for producing a chromium block by low-temperature reduction of a pre-oxidized chromite / concentrate having a better reaction surface in the course of further steel melting. is there.

本発明の更に別の目的は、予備酸化されたクロマイト鉱／精鉱を低温還元してクロム塊を製造する方法であって、ステンレス鋼製造に直接使用するために転用可能な方法を提案することである。   Yet another object of the present invention is to propose a method for producing a chromium block by low-temperature reduction of preoxidized chromite / concentrate, which can be diverted for direct use in stainless steel production. It is.

Ｃｒ：Ｆｅ比＝１．０〜３．３のクロマイト鉱／精鉱を低温（９００℃）で酸化した。酸化された試料は、ＦｅＯ相からＦｅ２Ｏ３への完全な酸化を示す。酸化されたクロマイト鉱／精鉱の還元は、石炭ガス還元剤を用いて行われた。使用したフラックスは、シリカ源（石英）および石灰から成る。還元試験は、制御された雰囲気の高温炉を使用して行った。そこで共に使用した原料は、組成が下記表で与えられる。 A chromite / concentrate with a Cr: Fe ratio of 1.0 to 3.3 was oxidized at a low temperature (900 ° C.). The oxidized sample shows complete oxidation from the FeO phase to Fe 2 O 3 . The reduction of the oxidized chromite / concentrate was performed using a coal gas reducing agent. The flux used consists of a silica source (quartz) and lime. The reduction test was performed using a controlled atmosphere high temperature furnace. The raw materials used together therewith are given in the table below.

還元に関する試験研究は、１４００〜１５５０℃の低温で行われた。石炭還元剤は、鉱石中の酸化鉄（Ｆｅ２Ｏ３）および酸化クロム（Ｃｒ２Ｏ３）の還元のために、化学量論的な炭素必要量の３０〜５０％過剰量で使用される。設計された特別なスラグに基づき、フラックス添加は、酸化アルミニウムおよび酸化マグネシウムをスラグに溶解させるために必要な０から１０％過剰量の範囲で石英添加として行われた。石灰添加は、クロマイト鉱／精鉱の３〜１０％の範囲で行われた。還元は、１４００〜１５５０℃の温度範囲で１．５〜３．０時間行われた。クロマイト鉱塊生成物を図１に示す。 Test studies on reduction were performed at a low temperature of 1400-1550 ° C. Coal reducing agents are used in a 30-50% excess of the stoichiometric carbon requirement for the reduction of iron oxide (Fe 2 O 3 ) and chromium oxide (Cr 2 O 3 ) in the ore. . Based on the special slag designed, the flux addition was done as a quartz addition in the 0-10% excess range required to dissolve aluminum oxide and magnesium oxide in the slag. Lime addition was performed in the range of 3-10% of chromite / concentrate. The reduction was performed at a temperature range of 1400 to 1550 ° C. for 1.5 to 3.0 hours. The chromite ore product is shown in FIG.

相組成と合わせて、生成物試料のマイクロ組織を図２に示す。金属が、クロムが多い相および他の成分が多い相の２つの相を示すことが分かる。塊状生成物中のクロムの存在は、クロムカーバイド（Ｃｒ７Ｃ３）および鉄クロムカーバイドの形態である。 Together with the phase composition, the microstructure of the product sample is shown in FIG. It can be seen that the metal exhibits two phases, a phase rich in chromium and a phase rich in other components. The presence of chromium in the bulk product is in the form of chromium carbide (Cr 7 C 3 ) and iron chromium carbide.

生成した金属クロム塊およびスラグ生成物の成分を表２に示す。金属塊の直径は０．５〜２５ｃｍである。金属およびスラグの相分離は明らかであり、水中で急冷した後に物理的分離方法により分離できる。   Table 2 shows the components of the formed metallic chromium block and slag product. The diameter of the metal mass is 0.5 to 25 cm. The phase separation of metal and slag is obvious and can be separated by physical separation methods after quenching in water.

反応機構
ＦｅＯ、クロマイト鉱／精鉱の酸化は、スピネル構造を広げ、これは、空隙の形成によりクロマイト・スピネルの反応性を向上させる。 Reaction Mechanism The oxidation of FeO, chromite / concentrate expands the spinel structure, which improves the reactivity of chromite spinel by the formation of voids.

クロマイト鉱の酸化は、また還元時間の低減化を促進する。フラックスとしての石灰が存在しないクロマイト鉱／精鉱の還元機構は、一般に、以下の順に進行する。酸化クロムは、１２００〜１６００℃で炭素と反応して、Ｃｒ３Ｃ２、Ｃｒ７Ｃ３から成るカーバイドのいずれかを形成する。
３Ｃｒ２Ｏ３＋１３Ｃ→２Ｃｒ３Ｃ２＋９ＣＯ（１１５０〜１２００℃）
２７Ｃｒ３Ｃ＋５ＣｒＯ→１３ＣｒＣ＋１５ＣＯ（１２００〜１６００℃） The oxidation of chromite ore also helps reduce the reduction time. The reduction mechanism of chromite / concentrate without lime as a flux generally proceeds in the following order. Chromium oxide reacts with carbon at 1200 to 1600 ° C. to form one of carbides composed of Cr 3 C 2 and Cr 7 C 3 .
3Cr 2 O 3 + 13C → 2Cr 3 C 2 + 9CO (1150 to 1200 ° C.)
27Cr 3 C + 5CrO → 13CrC + 15CO (1200 to 1600 ° C.)

更に高い温度では、Ｃｒ７Ｃ３がＣｒ２３Ｃ６と反応して、最終的に１８２０℃超で金属Ｃｒが優位である生成物となる。しかしながら、前記成分でフラックスとして石灰を用いることにより、スラグ生成反応は、低温で酸化クロムの還元が行われる際に重要な役割を果たす。フラックス成分としての石灰が存在すると、スラグ生成反応は低温で起こり、これによりスラグ中の溶解による還元が促進される。 At higher temperatures, Cr 7 C 3 reacts with Cr 23 C 6 , eventually resulting in a product with a predominance of metallic Cr above 1820 ° C. However, by using lime as a flux in the above components, the slag generation reaction plays an important role when chromium oxide is reduced at low temperatures. When lime as a flux component is present, the slag generation reaction occurs at a low temperature, thereby promoting reduction by dissolution in the slag.

酸化されたクロマイト鉱／精鉱の他の還元により生成するクロム塊の写真。A picture of the chromium mass produced by other reductions of oxidized chromite / concentrate. 金属クロム塊の微小構造を示す図。The figure which shows the microstructure of a metal chromium block. クロム塊製造工程図。Chrome block manufacturing process diagram.

図３に、クロム塊を商業生産するための工程図を示す。クロマイト鉱／精鉱（１）の酸化は、流動床（２）回転炉（２）で行われ、加熱された空気（３）吹きつけ手段もそこに設けられる。酸化された鉱石／精鉱は貯蔵所（４）に供給され、還元剤用貯蔵所（５）およびフラックス用貯蔵所（６）が酸化装置の近くに設けられる。   FIG. 3 shows a process diagram for commercial production of a chromium block. Oxidation of the chromite / concentrate (1) takes place in the fluidized bed (2) rotary furnace (2), where heated air (3) blowing means are also provided. Oxidized ore / concentrate is supplied to a reservoir (4), and a reducing agent reservoir (5) and a flux reservoir (6) are provided near the oxidizer.

次に、酸化された鉱石は、ミキサー（７）で混合され、混合後、還元剤である石炭およびフラックス（シリカ、石灰）と共に供給されてペレット化される。ペレットは、還元のために回転炉床炉（９）に供給される。回転炉床炉（９）から得られた金属およびスラグ生成物は、金属クロム塊（１２）とスラグ（１３）を分離するために物理的分離装置（１１）に供給される。   Next, the oxidized ore is mixed by a mixer (7), and after mixing, is supplied together with coal as a reducing agent and flux (silica, lime) and pelletized. The pellets are fed to a rotary hearth furnace (9) for reduction. The metal and slag product obtained from the rotary hearth furnace (9) is fed to a physical separator (11) to separate the metallic chromium block (12) and slag (13).

１ クロマイト鉱／クロマイト精鉱（図３）
２ 流動床／複式炉床炉（図３）
３ 酸素供給（加熱された空気）（図３）
４ 還元剤である石炭の貯蔵所（図３）
５ フラックス用石灰および石英の貯蔵所（図３）
６ ミキサー（図３）
７ ペレット製造装置（図３）
８ 還元装置である回転炉床炉（図３）
９ 加熱された還元ガス（図３）
１０ クロム塊およびスラグ（図３）
１１ 分離装置（図３）
１２ クロム塊（図３）
１３ スラグ（図３） 1 Chromite / chromite concentrate (Fig. 3)
2 Fluidized bed / double hearth furnace (Figure 3)
3 Oxygen supply (heated air) (Figure 3)
4 Reservoir coal storage (Fig. 3)
5 Flux lime and quartz storage (Figure 3)
6 Mixer (Figure 3)
7 Pellet production equipment (Figure 3)
8 Rotary hearth furnace as a reduction device (Figure 3)
9 Heated reducing gas (Figure 3)
10 Chromium blocks and slag (Figure 3)
11 Separation device (Fig. 3)
12 Chrome block (Fig. 3)
13 Slag (Figure 3)

Claims (6)

クロム塊を製造する方法であって、該方法が、
クロマイト鉱又はクロマイト精鉱を９００℃の低温で予備酸化する段階と、
予備酸化されたクロマイト鉱又はクロマイト精鉱を、還元剤石炭、並びにフラックスである石灰およびシリカと混合して混合物とする段階と、
前記混合物をペレットに固め、次に、該ペレットを温度１４００〜１５５０℃で還元する段階と、
還元されたクロム塊とスラグの混合体を冷却し、前記クロム塊と前記スラグとを分離する段階とを含み、
前記クロム塊の化学組成が、質量％で、
Ｃｒ： ５０〜６４％、
Ｃ： ３．０〜６．０％、
Ｓｉ： ０．７〜１．０％、
Ｓ： ０．０１〜０．０３％、
Ｐ： ０．００３〜０．０４％、
残部が鉄
であり、
前記クロム塊の直径が０．５〜２．５ｃｍである、クロム塊の製造方法。 A method for producing a chromium mass comprising:
Pre-oxidizing chromite or chromite concentrate at a low temperature of 900 ° C . ;
Mixing the pre-oxidized chromite or chromite concentrate with the reducing agent coal and the fluxes lime and silica into a mixture;
Solidifying the mixture into pellets and then reducing the pellets at a temperature of 1400-1550 ° C .;
Cooling the reduced chromium mass and slag mixture, and separating the chromium mass and the slag.
The chemical composition of the previous chrysanthemums ROM mass, in mass%,
Cr: 50 to 64 %,
C: 3.0-6.0%,
Si: 0.7 to 1.0%,
S: 0.01-0.03%,
P: 0.003~0.04%,
The balance is iron <br/>
A method for producing a chromium block , wherein the diameter of the chromium block is 0.5 to 2.5 cm. 前記クロマイト鉱又はクロマイト精鉱のＣｒ：Ｆｅ比が１．０〜３．３であり、
前記予備酸化する段階を、酸素を含む大気中で行う、請求項１に記載されたクロム塊の製造方法。 The Cr: Fe ratio of the chromite or chromite concentrate is 1.0 to 3.3,
The method for producing a chromium block according to claim 1, wherein the preliminary oxidation is performed in an atmosphere containing oxygen . 前記混合して混合物とする段階をミキサー内で行う、請求項１に記載されたクロム塊の製造方法。 The method for producing a chromium block according to claim 1 , wherein the step of mixing to form a mixture is performed in a mixer . 前記混合物をペレットに固めることをペレット製造装置で行う、請求項１に記載されたクロム塊を製造する方法。 The method for producing a chromium block according to claim 1, wherein the mixture is hardened into pellets by a pellet production apparatus . 前記還元する段階を回転炉床炉内で行う、請求項１に記載されたクロム塊を製造する方法。The method for producing a chromium block according to claim 1, wherein the reducing step is performed in a rotary hearth furnace. 前記分離する段階を物理的分離装置により行う、請求項１に記載されたクロム塊を製造する方法。The method for producing a chromium block according to claim 1, wherein the separating is performed by a physical separation device.
JP2010508969A 2007-05-24 2008-02-12 Method for producing a chromium metal block from chromite or concentrate Expired - Fee Related JP5364091B2 (en)

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IN802/KOL/2007 2007-05-24
IN802KO2007 2007-05-24
PCT/IN2008/000087 WO2008142704A1 (en) 2007-05-24 2008-02-12 Process for the production of chromium metal nuggets from chromite ores/concentrates.

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