CN101765670B - 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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CN101765670B
CN101765670B CN2008800171953A CN200880017195A CN101765670B CN 101765670 B CN101765670 B CN 101765670B CN 2008800171953 A CN2008800171953 A CN 2008800171953A CN 200880017195 A CN200880017195 A CN 200880017195A CN 101765670 B CN101765670 B CN 101765670B
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chromium metal
metal block
chromite ore
chromium
production
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CN101765670A (en
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G·U·卡普尔
V·D·塔塔瓦德卡
S·M·拉奥
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Tata Steel Ltd
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Tata Steel Ltd
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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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Geochemistry & Mineralogy (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Manufacture And Refinement Of Metals (AREA)

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 DEG 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 DEG C, separating the thus produced chromium nuggets (12) from slag (13) in a separation unit (11).

Description

Method by chromite ore or ferrochrome concentrate production chromium metal block
Invention field
The present invention relates to develop a kind of method of producing the chromium metal block.More specifically, the present invention relates to develop the chromite ore of low-temperature reduction preoxidation or the method that the ferrochrome concentrate is produced the metallized chromium metal block of 50-70%.
Background of invention
At any comprehensive metal alloy maker, high carbon ferro-chrome is produced by melting-reducing process route usually.This technology belongs to the high energy gamma source intensity, and the high carbon coke of a kind of import of needs is as reductive agent.High carbon coke and electric power all are expensive resources.Therefore, developed a kind of new operational path, namely by using coal as chromite ore or the ferrochrome concentrate of reductive agent reduction preoxidation, produced that 50-70% is metallized, the product of siderochrome or chromium metal block form.
Goal of the invention
Therefore, an object of the present invention is to propose the method that the low-temperature reduction of a kind of chromite ore by preoxidation or ferrochrome concentrate is produced the chromium metal block, this method has been eliminated the shortcoming of prior art.
Another object of the present invention is the method that proposes the low-temperature reduction production chromium metal block of a kind of chromite ore by preoxidation or ferrochrome concentrate, and this method can be saved the energy.
Another purpose of the present invention is the method that proposes the low-temperature reduction production chromium metal block of a kind of chromite ore by preoxidation or ferrochrome concentrate, and this method can make the ferrochrome production cost reduce by 20%.
A further object of the present invention is the method that proposes the low-temperature reduction production chromium metal block of a kind of chromite ore by preoxidation or ferrochrome concentrate, and this method can reduce coke consumption.
It is the method that proposes the low-temperature reduction production chromium metal block of a kind of chromite ore by preoxidation or ferrochrome concentrate that the present invention has a purpose again, and described chromium metal block is carrying out having better reaction surface when next step steel-making is handled.
A further object of the invention is the method that proposes the low-temperature reduction production chromium metal block of a kind of chromite ore by preoxidation or ferrochrome concentrate, and described chromium metal block is suitable for being directly used in stainless production.
Summary of the invention
We are the chromite ore/concentrate of oxidized Cr: Fe ratio in from 1.0 to 3.3 scopes under low temperature (900 ℃).Sample after the oxidation shows that FeO is completely oxidized to Fe mutually 2O 3Use coal as reductive agent, implemented the reduction of already oxidised chromite ore or ferrochrome concentrate.The flux that uses is made up of silica source (quartz) and lime.Adopt the High Temperature Furnaces Heating Apparatus of controlled atmosphere, implemented the reduction experiment.The raw material and the composition thereof that use have been provided in the following table.
Table 1 raw material and composition thereof (wt%)
Figure GSB00000546107300021
Under 1400-1550 ℃ low temperature, carried out the experimental study about reduction.Use exceeds the ferric oxide (Fe in the reduction ore 2O 3) and chromic oxide (Cr 2O 3) required stoichiometry carbon requires the coal reductant of 30-50%.Based on designed specific slag, implement the interpolation of flux as follows, namely quartzy being added on exceeds aluminum oxide and magnesium oxide is dissolved in the scope of required 0-10% in the slag.In the scope of the 3-10% that is added on chromite ore or ferrochrome concentrate of lime.In 1400-1550 ℃ temperature range, reduced 1.5-3.0 hour.Ferrochrome nugget product is shown in Fig. 1.
The sample microstructure of described product is shown in Fig. 2 together with phase composite.As can be seen, metal presents two-phase, chromium enrichment mutually with other enrichment mutually.Chromium in the described ferrochrome nugget product is with chromium carbide (C 7C 3) and the form of siderochrome carbide exist.
Provided in the table 2 and produced the chromium metal block that obtains and the chemical constitution of slag product.The diameter of metal block is in the scope of 0.5-25cm.Metal and slag are separated obviously, and it can separate by physical separation method after quenching-in water.
The chemical constitution of table 2 chromium metal block and slag
Metal
Cr C Si S P
50-64％ 3.0-60 0.7-1.0％ 0.01-0.03％ 0.003-0.04％
Slag
Al 2O 3 MgO SiO 2 Cr 2O 3 CaO
18-40％ 15-24％ 10-34％ 14-30 1-7.5％
Reaction mechanism:
Spinel structure has been opened in the oxidation of FeO in chromite ore or the ferrochrome concentrate, and this formation owing to the room has improved the reactivity of chromite spinel.
The oxidation of chromite ore also helps to shorten the recovery time.Under the situation that does not have lime as flux, the reduction mechanism of chromite ore or ferrochrome concentrate is carried out usually as follows.In 1200 to 1600 ℃ of following chromated oxides and carbon reaction, form Cr 3Cr 2, Cr 7C 3In a kind of.
3Cr 2O 3+13C→2Cr 3C 2+9CO(1150-1200℃)
27CR3C+5CrO→13CrC+15CO(1200-1600℃)
Cr under higher temperature 7C 3With Cr 23C 6Reaction finally is being higher than under the temperature of 1820C, and the Cr metal is the most dominant product.Yet owing to use lime as molten component, slag forms reaction and plays a significant role for the reduction of carrying out chromic oxide under lower temperature.In the presence of as the lime of molten component, slag forms to be reflected under the lower temperature and takes place, and this has promoted reduction by being melted in slag.
Accompanying drawing describes in detail
Fig. 1 has shown the photographic view of the chromium metal block of producing by the chromite ore of reduction-oxidation or ferrochrome concentrate.
Fig. 2 has shown the microstructure of chromium metal block.
Fig. 3 has shown the process flow sheet of producing the chromium metal block.
The detailed description of invention preferred implementation
Fig. 3 has shown the process flow sheet of commercial production chromium metal block.The oxidation of chromite ore or ferrochrome concentrate (1) is carried out in fluidized-bed (2) rotary kiln (2), and the there also provides warm air (3) blowing device.Ore/concentrate after the oxidation is sent into storage silo (4), a reduction storehouse (5) and a flux storehouse (6) are provided near oxidation unit.
Then, the ore after the oxidation is mixed in mixing tank (7), and after mixing with coal reductant and flux (silica, lime), it is sent into pelletizer (8).Pelletizing sent in the rotary hearth furnace (9) reduce.To send into the slag product from the metal that rotary hearth furnace (9) obtains and carry out the physical sepn unit (11) separating of chromium metal block (12) and slag (13).
Key feature
Label Key feature Figure
1 Chromite ore/ferrochrome concentrate 3
2 Fluidized-bed/multiple hearth furnace 3
3 Oxygen supply as warm air 3
4 The storage silo of reductive agent coal 3
5 Flux lime and quartzy storage silo 3
6 Mixer unit 3
7 Pelletizer 3
8 Rotary hearth furnace as reduction unit 3
9 Thermal reduction gas 3
10 Chromium metal block and slag 3
11 Separating unit 3
12 The chromium metal block 3
13 Slag 3

Claims (1)

1. produce the method for chromium metal block, comprising:
Under 900 ℃ low temperature in stove oxidation Cr: Fe than chromite ore or ferrochrome concentrate in from 1.0 to 3.3 scope;
-chromite ore or ferrochrome concentrate with oxidation in mixing tank (7) mixes with silica with reductive agent coal and flux lime;
-in pelletizer (8), mixture is made ball;
-under 1400-1550 ℃ the temperature in rotary hearth furnace (9) reducting pellet and
-in separating unit (11), the chromium metal block is separated with slag,
Wherein the chromium metal block that is obtained by aforesaid method has following chemical constitution, and % represents with weight:
Cr 50-64％
C 3.0-6.0％
Si 0.7-1.0％
S 0.01-0.03％
P 0.003-0.04％。
CN2008800171953A 2007-05-24 2008-02-12 Process for the production of chromium metal nuggets from chromite ores/concentrates Expired - Fee Related CN101765670B (en)

Applications Claiming Priority (3)

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IN802/KOL/07 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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KR101469679B1 (en) * 2009-03-02 2014-12-05 신화메탈 주식회사 Low carbon-ferrochromium manufacturing method by using continuous thermit reaction
RU2551729C2 (en) * 2009-09-14 2015-05-27 Чонгкинг Рюифан Реньювэбл Ресорсес Девелопмент Ко., Лтд. Method of chromium slag neutralisation using annealing method and blast-furnace process
WO2013011521A1 (en) * 2011-07-18 2013-01-24 Tata Steel Limited A method for direct reduction of oxidized chromite ore fines composite agglomerates in a tunnel kiln using carbonaceous reductant for production of reduced chromite product/ agglomerates applicable in ferrochrome or charge chrome production.
CN102432068B (en) * 2011-09-28 2013-10-16 北京科技大学 Process for producing sodium chromate
CN102994850A (en) * 2012-10-29 2013-03-27 海门市金易焊接材料有限公司 Low-carbon chromium metal
WO2015015250A1 (en) * 2013-08-01 2015-02-05 North-West University Process for enhanced pre-reduction of chromite
WO2016115593A1 (en) * 2015-01-20 2016-07-28 Pelleton Ip Holdings Limited Method for producing a chromite agglomerate
EP3601625B1 (en) * 2017-03-21 2021-05-19 Brother Group (Hong Kong) Limited Process for preparing iron- and chrome-containing particles
US10982300B2 (en) 2017-05-02 2021-04-20 Her Majesty The Queen In Right Of Canada As Represented By The Minister Of Natural Resources Carbothermic direct reduction of chromite using a catalyst for the production of ferrochrome alloy
CN107699685A (en) * 2017-08-09 2018-02-16 江苏省冶金设计院有限公司 A kind of production method of silicochromium
US10508319B1 (en) 2019-06-27 2019-12-17 MM Metals USA, LLC Method and system for producing low carbon ferrochrome from chromite ore and low carbon ferrochrome produced thereby
CN112251600A (en) * 2019-07-22 2021-01-22 孙凌玉 Preparation method and application of chromium metallization ball
CN110306058B (en) * 2019-07-23 2021-03-12 中南大学 Process for efficiently treating zinc-iron-containing metallurgical dust and sludge by rotary hearth furnace
CN112226615B (en) * 2020-10-15 2021-11-12 中南大学 Comprehensive utilization method of stainless steel solid waste
GB202108524D0 (en) 2021-06-15 2021-07-28 Eestech Inc Improved smelting system
CN118389823A (en) * 2024-06-28 2024-07-26 内蒙古新太元新材料有限公司 Chromite prereduced pellet and preparation method thereof

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KR101498995B1 (en) 2015-03-06
WO2008142704A1 (en) 2008-11-27
ZA200908067B (en) 2010-07-28
JP5364091B2 (en) 2013-12-11
KR20100021620A (en) 2010-02-25
JP2010528184A (en) 2010-08-19
EP2152925A1 (en) 2010-02-17
CN101765670A (en) 2010-06-30
TR200908848T1 (en) 2012-02-21

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