KR20100021620A - Process for the production of chromium metal nuggets from chromite ores/concentrates - Google Patents

Process for the production of chromium metal nuggets from chromite ores/concentrates Download PDF

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KR20100021620A
KR20100021620A KR1020097026723A KR20097026723A KR20100021620A KR 20100021620 A KR20100021620 A KR 20100021620A KR 1020097026723 A KR1020097026723 A KR 1020097026723A KR 20097026723 A KR20097026723 A KR 20097026723A KR 20100021620 A KR20100021620 A KR 20100021620A
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chromium
nugget
concentrate
ore
chromite ore
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KR101498995B1 (en
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가자난 유. 카푸르
빌라스 디. 타사바드카르
사리팔리 엠. 라오
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타타 스틸 리미티드
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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

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Abstract

A process for the production of chromium nuggets from chromite ore/concentrate comprises:-oxidizing chromite ore/chromium concentrate (1) comprising a Cr : Fe-ratio ranging from 1.0 to 3.3 in a furnace (2) at a temperature of 900 °C,-mixing (7) the oxidized ore (4) with reductant coal (5) and fluxes (lime, silica) (6),-pelletizing (8) the mixture,-reducing the pellets in a rotary furnace (9) at a temperature between 1.400 and 1.600 °C,-separating the thus produced chromium nuggets (12) from slag (13) in a separation unit (11).

Description

크롬철광 광석／정광으로부터 크롬 금속 너깃을 제조하는 방법{PROCESS FOR THE PRODUCTION OF CHROMIUM METAL NUGGETS FROM CHROMITE ORES／CONCENTRATES}PROCESS FOR THE PRODUCTION OF CHROMIUM METAL NUGGETS FROM CHROMITE ORES / CONCENTRATES

본 발명은 크롬 너깃(chromium nuggets) 제조방법 개발에 관한 것이다. 더 상세하게는, 본 발명은 50 내지 70%로 금속화된, 저온의 예비 산화된 크롬철광 광석/정광으로부터 크롬 너깃을 제조하는 방법을 개발하는 것에 관한 것이다.The present invention relates to the development of a method for producing chromium nuggets. More particularly, the present invention relates to the development of a process for producing chromium nugget from low temperature pre-oxidized chromite ore / concentrate, metalized to 50-70%.

일관 생산의 금속 합금(integrated metal alloy) 제조 구조에 있어서, 고탄소(high carbon) 페로크롬(Ferro chromium)은 대개 용융-환원 방법(smelting-reduction route)에 의해 생성된다. 용융-환원 방법은 많은 에너지를 소비하며(highly energy intensive), 또한 환원제로 재함량이 낮은 코크스(imported low-ash coke)를 필요로 한다. 재함량이 낮은 코크스 및 전기(electricity)는 모두 값비싼 원자재이다. 따라서, 환원제로 석탄을 사용하여 예비-산화된 크롬 광석을 환원시킴으로써 50 내지 70%로 금속화된 크롬철광 광석을 페로크롬 형태로 제조하는 새로운 공정방법의 개발이 절실히 요구된다. In an integrated metal alloy fabrication structure, high carbon Ferro chromium is usually produced by a melt-reduction route. Melt-reduction methods are highly energy intensive and also require imported low-ash coke as reducing agent. Low ash content coke and electricity are both expensive raw materials. Therefore, there is an urgent need for the development of a new process method for producing a ferrochrome metalized chromite ore by 50 to 70% by reducing the pre-oxidized chromium ore using coal as the reducing agent.

따라서, 본 발명은 종래기술의 문제점을 해결할 수 있는 예비-산화된 크롬철광 광석/정광의 저온 환원에 의한 크롬 너깃 제조방법을 제공하고자 한다. Accordingly, the present invention is to provide a method for producing chromium nugget by low temperature reduction of pre-oxidized chromite ore / concentrate which can solve the problems of the prior art.

또한, 본 발명은 에너지를 절약할 수 있는 예비-산화된 크롬철광 광석/정광의 저온 환원에 의한 크롬 너깃 제조방법을 제공하고자 한다. In addition, the present invention is to provide a method for producing chromium nugget by low temperature reduction of pre-oxidized chromite ore / concentrate that can save energy.

또한, 본 발명은 페로크롬 제조비용을 20% 정도 절감할 수 있는 예비-산화된 크롬철광 광석/정광의 저온 환원에 의한 크롬 너깃 제조방법을 제공하고자 한다. In addition, the present invention is to provide a method for producing chromium nugget by low-temperature reduction of pre-oxidized chromite ore / concentrate which can reduce the ferrochrome production cost by about 20%.

또한, 본 발명은 코크스(coke) 소비를 감소시킬 수 있는 예비-산화된 크롬철광 광석/정광의 저온 환원에 의한 크롬 너깃 제조방법을 제공하고자 한다. The present invention also seeks to provide a method for producing chromium nugget by low temperature reduction of pre-oxidized chromite ore / concentrate which can reduce coke consumption.

또한, 본 발명은 강철이 용융되는 동안 표면반응이 개선된 예비-산화된 크롬철광 광석/정광의 저온 환원에 의한 크롬 너깃 제조방법을 제공하고자 한다. In addition, the present invention is to provide a method for producing chromium nugget by low temperature reduction of pre-oxidized chromite ore / concentrate with improved surface reaction during the melting of steel.

더욱이 본 발명은 스테인레스 강철 제품 제조에 즉시 이용 가능한 예비-산화된 크롬철광 광석/정광의 저온 환원에 의한 크롬 너깃 제조방법을 제공하고자 한다. Furthermore, the present invention seeks to provide a method for producing chromium nugget by low temperature reduction of pre-oxidized chromite ore / concentrate ready for use in the production of stainless steel products.

도 1은 산화된 크롬철광 광석/정광의 환원 후 생성된 크롬 너깃을 사진촬영한 도면이다. 1 is a photograph of a chromium nugget generated after reduction of oxidized chromite ore / concentrate.

도 2는 크롬 금속 너깃의 미세 구조(micro-structure)를 나타낸 도면이다. 2 shows a micro-structure of chromium metal nugget.

도 3은 크롬 너깃 생성을 위한 공정흐름도이다.3 is a process flow diagram for the production of chromium nugget.

Cr : Fe의 비가 1.0 내지 3.3 범위인 크롬철광 광석/정광을 저온(900℃)에서 산화시킨다. 산화된 시료(samples)는 일산화철(FeO)에서 삼산화이철(Fe2O3)로 완전 히 산화됨을 나타낸다. 산화된 크롬철광 광석/정광을 환원제로서 석탄을 사용하여 환원시킨다. 용제(flux)로는 실리카 원료(silica source) 및 석회(lime)가 사용된다. 환원실험은 분위기 제어(controlled atmosphere) 고온 용광로(furnace)에서 수행된다. 사용된 원료물질 및 그 조성은 다음 표와 같다.Chromite ore / concentrate having a Cr: Fe ratio in the range of 1.0 to 3.3 is oxidized at low temperature (900 ° C.). Oxidized samples indicate complete oxidation of iron monoxide (FeO) to ferric trioxide (Fe 2 O 3 ). Oxidized chromite ore / concentrate is reduced using coal as reducing agent. As a flux, a silica source and a lime are used. Reduction experiments are carried out in a controlled atmosphere high temperature furnace. The raw materials used and their composition are shown in the following table.

표 1. 원료물질 및 조성(wt%)Table 1. Raw materials and composition (wt%)

Cr/Fe의 비율Cr / Fe ratio Cr2O3 Cr 2 O 3 Fe(t)Fe (t) SiO2 SiO 2 Al2O3 Al 2 O 3 MgOMgO CaOCaO VMVM AshAsh 크롬철광 광석/정광Chromite Ore / Concentrate 1.0-3.31.0-3.3 30-5630-56 11-2011-20 1.0-9.01.0-9.0 9-169-16 6-136-13 0.01-0.040.01-0.04 -- -- 석탄Coal -- -- -- -- -- -- -- 10-10- 10-10- 석영quartz -- -- -- -- 85-9885-98 -- -- -- -- 석회lime -- -- -- -- -- -- 60-7060-70 -- --

환원에 대한 실험연구는 1400 내지 1550℃ 정도의 저온에서 수행된다. 석탄은 광석 내의 삼산화이철(Fe2O3) 및 산화크롬(Cr2O3)의 환원에 필요한 탄소 화학량론의 30-50%를 초과하여 과잉 사용된다. 특별한 슬래그 설계에 근거하여, 용제로서 석영이 산화알루미늄 및 산화마그네슘을 슬래그로 분리하는데 필요한 양의 0 내지 10% 초과 범위로 첨가된다. 석회는 크롬철광 광석/정광의 3 내지 10% 범위로 첨가된다. 환원과정은 1400 내지 1550℃의 온도범위에서 1.5 내지 3.0 시간동안 수행된다. 도 1은 생성된 크롬철광(chromite) 너깃을 도시한 것이다. Experimental studies on the reduction is carried out at low temperatures of about 1400 to 1550 ℃. Coal is used in excess of 30-50% of the carbon stoichiometry required for the reduction of ferric trioxide (Fe 2 O 3 ) and chromium oxide (Cr 2 O 3 ) in the ore. Based on the special slag design, quartz as the solvent is added in the range of 0 to 10% more than the amount necessary to separate aluminum oxide and magnesium oxide into slag. Lime is added in the range of 3 to 10% of chromite ore / concentrate. The reduction process is carried out for 1.5 to 3.0 hours in the temperature range of 1400 to 1550 ℃. 1 shows the resulting chromite nugget.

상 조성(phase composition)에 따른 생성물의 미세 구조 시료(sample)는 도 2에 도시된 바와 같다. 금속에서 2개의 상(phase)을 나타내며, 하나는 크롬이 우세한 상이고 다른 하나는 다른 원소가 우세한 상을 나타낸다. 크롬은 너깃 생성물 내에서 탄화크롬(chromium carbides) 및 철탄화크롬(iron chromium carbides)의 형태 로 존재한다. A microstructured sample of the product according to the phase composition is shown in FIG. 2. Two phases in the metal, one with chromium and one with the other. Chromium is present in the form of chromium carbides and iron chromium carbides in the nugget product.

생성된 크롬 금속, 너깃 및 슬래그 생성물의 화학적 조성은 표 2와 같다. 금속 너깃의 직경은 0.5 내지 25cm 범위이다. 물에 담금질(quenching) 후 물리적 분리(physical separation) 방법에 의해 금속과 슬래그로 상분리 가능함은 명백하다. The chemical compositions of the resulting chromium metal, nugget and slag products are shown in Table 2. The diameter of the metal nugget is in the range from 0.5 to 25 cm. It is apparent that after quenching in water, it is possible to phase separate into metal and slag by a physical separation method.

표 2. 크롬 금속 너깃 및 슬래그의 화학적 조성Table 2. Chemical Composition of Chrome Metal Nuggets and Slags

금속metal CrCr CC SiSi SS PP 50-64%50-64% 3.0-603.0-60 0.7-1.0%0.7-1.0% 0.01-0.03%0.01-0.03% 0.003-0.04%0.003-0.04% 슬래그Slag Al2O3 Al 2 O 3 MgOMgO SiO2 SiO 2 Cr2O3 Cr 2 O 3 CaOCaO 18-40%18-40% 15-24%15-24% 10-34%10-34% 14-3014-30 1-7.5%1-7.5%

반응 메커니즘(reaction mechanisms):Reaction mechanisms:

크롬철광(FeO) 광석/정광의 산화는 공극(vacancies) 형성으로 인해 크롬 스피넬의 반응성을 증가시키는 스피넬 구조(spinel structure)가 가능하도록 한다. Oxidation of chromite ore or concentrates enables spinel structures that increase the reactivity of chrome spinels due to the formation of vacancies.

크롬철광 광석의 산화는 또한 환원 시간 감소에 기여한다. 용제로서 석회를 사용하지 않는 크롬철광 광석/정광의 환원 메커니즘은 일반적으로 다음 과정과 같이 진행된다. 산화 크롬(chromium oxide)은 1200 내지 1600℃의 온도에서 탄소와 반응하여 Cr3Cr2, Cr7C3 중 하나를 생성한다. Oxidation of chromite ores also contributes to reduction of reduction time. The reduction mechanism of chromite ore / concentrate, which does not use lime as a solvent, generally proceeds as follows. Chromium oxide reacts with carbon at a temperature of 1200 to 1600 ° C. to produce one of Cr 3 Cr 2 and Cr 7 C 3 .

3Cr2O3, + 13C → 2Cr3C2 + 9CO(1150-1200℃) 3Cr 2 O 3 , + 13C → 2Cr 3 C 2 + 9CO (1150-1200 ℃)

27CR3C + 5CrO → 13CrC + 15CO(1200-1600℃) 27CR3C + 5CrO → 13CrC + 15CO (1200-1600 ℃)

Cr7C3은 상당히(still) 높은 온도에서 Cr23C6 과 반응하여 1820℃ 이상의 온도 에서 최종적으로 양질의 크롬 금속을 생성한다. 그러나, 전술한 조성에서 용제로서 석회를 사용함으로 인해 슬래그 형성반응은 저온에서 산화크롬을 환원시키는 데 중요한 역할을 한다. 용제로서 석회가 첨가되는 경우, 슬래그 형성 작용은 저온에서 일어나며, 슬래그 내에서 용해되어 환원을 촉진한다.Cr 7 C 3 reacts with Cr 23 C 6 at a still high temperature to finally produce good chromium metal at temperatures above 1820 ° C. However, the slag formation reaction plays an important role in reducing chromium oxide at low temperatures due to the use of lime as a solvent in the above compositions. When lime is added as a solvent, slag formation takes place at low temperatures, and dissolves in the slag to promote reduction.

도 3은 크롬 너깃을 생성하기 위한 공정흐름도이다. 크롬 광석/정광(1)의 산화는 유동식(fluidized bed)(2) 회전식 용광로(rotary furnace)(2) 내에서 이루어지며, 용광로에는 열기(hot air)(3)가 주입된다. 산화된 광석/정광은 저장소(4)에 공급되며, 산화장치(oxidation unit) 근처에는 환원제 저장소(5) 및 용제 저장소(6)가 제공된다. 3 is a process flow diagram for producing chromium nugget. Oxidation of the chromium ore / concentrate 1 takes place in a fluidized bed 2 rotary furnace 2, in which hot air 3 is injected. Oxidized ore / concentrate is supplied to the reservoir 4, near the oxidation unit is provided with a reducing agent reservoir 5 and a solvent reservoir 6.

다음으로, 산화된 광석은 혼합기(mixer)(7)에서 석탄 환원제 및 용제(실리카, 석회)와 혼합된 후 펠러타이저(pelletizer)(8)로 운반된다. 알갱이들은 회전식 용광로(9)로 공급되며, 용광로 내에서 환원반응이 일어난다. 회전식 용광로(9)에서 생성된 금속 및 슬래그 생성물은 물리적 분리장치(physical separation unit)(11)에 공급되어 크롬 금속 너깃(12) 및 슬래그(13)로 분리된다. The oxidized ore is then mixed with a coal reducing agent and a solvent (silica, lime) in a mixer 7 and then conveyed to a pelletizer 8. The granules are fed to a rotary furnace 9 and a reduction reaction takes place in the furnace. The metal and slag products produced in the rotary furnace 9 are fed to a physical separation unit 11 and separated into chromium metal nugget 12 and slag 13.

주요 특징(주요 구성요소)(key features)Key features

참조부호Reference 주요 특징(주요 구성요소)Key Features (Major Components) 도면drawing 1One 크롬철광 광석/크롬철광 정광Chromite Ore / Chrome Ore Concentrate 도3Figure 3 22 유동식(fluidized bed)/다층식(multiple hearth) 용광로Fluidized bed / multiple hearth furnaces 도3Figure 3 33 열기(hot air)로서 산소공급Oxygen supply as hot air 도3Figure 3 44 환원제인 석탄이 저장되는 저장소Reservoir where coal is stored 도3Figure 3 55 용제인 석회 및 석영이 저장되는 저장소Reservoir in which solvent lime and quartz are stored 도3Figure 3 66 혼합장치Mixing device 도3Figure 3 77 펠러타이저Feller 도3Figure 3 88 환원장치로서 회전식 용광로Rotary Furnace as Reduction Device 도3Figure 3 99 고온 환원 가스High temperature reducing gas 도3Figure 3 1010 크롬 너깃 및 슬래그Chrome nugget and slag 도3Figure 3 1111 분리장치Separator 도3Figure 3 1212 크롬 너깃Chrome nugget 도3Figure 3 1313 슬래그Slag 도3Figure 3

Claims (5)

크롬철광 광석/정광(chromite ore/concentrate)의 저온 예비 산화에 의한 크롬 너깃 제조방법에 있어서, In the method for producing chromium nugget by low temperature preliminary oxidation of chromite ore / concentrate, 크롬(Cr) 50 내지 60 %, Chromium (Cr) 50-60%, 탄소(C) 3.0 내지 6.0 %, Carbon (C) 3.0-6.0%, 규소(Si) 0.7 내지 1.0%, Silicon (Si) 0.7-1.0%, 황(S) 0.01 내지 0.03%, Sulfur (S) 0.01-0.03%, 인(P) 0.003 내지 0.04%의 화학적 조성을 갖는 크롬 금속 너깃으로서, 상기 금속 너깃의 직경은 0.5 내지 2.5cm 범위인 크롬 너깃 제조방법. Phosphorus (P) A chromium metal nugget having a chemical composition of 0.003 to 0.04%, wherein the diameter of the metal nugget is in the range of 0.5 to 2.5 cm. 크롬철광 광석/크롬 정광(Cr:Fe의 혼합비가 1.0 내지 3.3 범위임)을 900℃의 저온 용광로에서 산화시키는 과정과;Oxidizing chromite ore / chromium concentrate (mixing ratio of Cr: Fe in the range of 1.0 to 3.3) in a low temperature furnace at 900 ° C .; 산화된 광석을 혼합기(7)에서 석탄 환원제 및 용제(석회, 실리카)와 혼합하는 과정과;Mixing the oxidized ore with a coal reducing agent and a solvent (lime, silica) in a mixer 7; 상기 혼합물을 펠러타이저(pelletizer)(8)에서 알갱이화하는 과정과;Granulating the mixture in a pelletizer 8; 상기 알갱이를 1400 내지 1600℃ 온도의 회전식 용광로에서 환원시키는 과정; 및Reducing the granules in a rotary furnace at a temperature of 1400 to 1600 ° C .; And 분리장치(11)에서 슬래그로부터 크롬 너깃을 분리하는 과정을 포함하는 크롬 너깃 제조방법. Chromium nugget manufacturing method comprising the step of separating the chromium nugget from the slag in the separator (11). 제2항에 있어서, 크롬철광 광석의 금속화는 50 내지 70%인 크롬 너깃 제조방법. The method of claim 2, wherein the metallization of chromite ore is from 50 to 70%. 첨부 도면들을 참조하여 설명 및 개시한 저온 예비 산화된 크롬철광 광석/정광에 의한 크롬 너깃 제조방법.Method for producing chromium nugget by low temperature pre-oxidized chromite ore / concentrate described and disclosed with reference to the accompanying drawings. 첨부 도면들을 참조하여 설명 및 개시한 바와 같은 전술한 방법에 의해 제조된 크롬 너깃.Chromium nugget produced by the above-described method as described and disclosed with reference to the accompanying drawings.
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