CN107904395A - A kind of arsenic removing method of iron ore - Google Patents
A kind of arsenic removing method of iron ore Download PDFInfo
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- CN107904395A CN107904395A CN201711069962.2A CN201711069962A CN107904395A CN 107904395 A CN107904395 A CN 107904395A CN 201711069962 A CN201711069962 A CN 201711069962A CN 107904395 A CN107904395 A CN 107904395A
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- arsenic
- iron ore
- removing method
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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
- C22B1/02—Roasting processes
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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
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/2406—Binding; Briquetting ; Granulating pelletizing
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- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Geochemistry & Mineralogy (AREA)
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- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The present invention disclose a kind of arsenic removing method of iron ore, and this method mainly includes in proportion mixed pelletizing and drying miberal powder, coal dust and additive, the step of pelletizing after drying is first carried out to progress reduction roasting after oxidizing roasting.By aoxidizing with reducing the arsenic in the baking modes being combined removing iron ore, to achieve the purpose that to reduce arsenic content in steel.The arsenic-removing rate of this method is up to more than 90%, can handle that arsenic content is high on a large scale and unserviceable ore.
Description
Technical field
The present invention relates to field of iron and steel smelting, and in particular, to a kind of arsenic removing method of iron ore.
Background technology
Though arsenic is trace element, generally objectionable impurities in steel, its harmfulness is similar to phosphorus.Arsenic is as phosphorus, easily
Segregation is produced in the interface of steel, causes " Temper brittleness " phenomenon.Arsenic too high levels can cause steel heat machined surface to be cracked in steel, increase
Add the brittleness of steel, reduce impact value and plasticity of steel etc., influence the performance of steel, reduce the quality of steel.And located in advance by molten iron
Reason and steel-making are all difficult to remove arsenic.Dearsenification generally is carried out by adding calcic slag system, calcium-silicon, rare earth alloy, though this method
Certain dearsenification effect can be obtained, but molten steel carburetting can be caused, increase a series of problems, such as silicon, increase production cost.At present, steel
In terms of field arsenic removing method and task are concentrated mainly on the processing to iron ore.But existing ore arsenic removing method is dirty there are environment
Dye, it is impossible to the problem of depth dearsenification.
The content of the invention
The present invention reduces arsenic in steel by aoxidizing with reducing the arsenic in the baking modes being combined removing iron ore to reach
Content, and then reduce follow-up dearsenification cost, reduce the purpose that arsenic influences steel performance.
According to an aspect of the present invention, there is provided a kind of arsenic removing method of iron ore, this method comprise the following steps：
1) arsenic minerals powder, coal dust and additive will be contained and mixed pelletizing and dried in proportion；
2) pelletizing after drying is subjected to oxidizing roasting under weak oxide atmosphere, obtains acid pellet, while generation includes
As2O3The flue gas of gas and vulcanization arsenic gas；
3) acid pellet obtained in step 2) is subjected to reduction roasting in reducing atmosphere, obtains the metal after dearsenification
Pellet, while generation includes As2O3The flue gas of gas and arsenic steam.
According to one embodiment of present invention, this method further comprises the steps：
The flue gas produced in step 2) and step 3) is subjected to dedirt and second-time burning processing successively so that arsenic and vulcanization
Arsenic is oxidized to As2O3。
According to one embodiment of present invention, it is first to further comprise that the flue gas after second-time burning is handled carries out for this method
The heat recycled, is used for that preheating and baking to be fuel used and combustion air by waste heat recovery processing.
According to one embodiment of present invention, this method further comprise by the flue gas Jing Guo first waste heat recovery processing into
Row secondary waste heat recycles so that the As in flue gas2O3It is condensed into solid and is recycled, the heat recycled is used to do
Dry pelletizing.
According to one embodiment of present invention, the powder containing symplesite of raw material including 80~110 parts by weight in step 1), 5~
The additive of the coal dust of 15 parts by weight and 1~5 parts by weight.
According to one embodiment of present invention, the temperature of oxidizing roasting is 800~1000 DEG C, roasting time for 5~
10min。
According to one embodiment of present invention, CO in the weak oxide atmosphere of oxidizing roasting2/ CO volume ratios for 0.80~
1.70：1.
According to one embodiment of present invention, reduction roasting temperature is 1000~1300 DEG C, the reduction roasting time for 20~
30min。
According to one embodiment of present invention, CO/CO in the reducing atmosphere of reduction roasting2Volume ratio for 1.30~
2.25：1.
According to one embodiment of present invention, pellet size is 8~16mm.
By using the above method of the present invention, following multiple beneficial effect can be obtained：
(1) this method arsenic-removing rate is up to more than 90%, can handle that arsenic content is high on a large scale and unserviceable ore；
(2) ore after dearsenification is used for smelting iron and steel, can reduce influence of the arsenic to steel performance；
(3) dearsenification product As2O3It can be recycled through flue dust recovery device, so as to avoid polluting environment；
(4) product of whole process can recycle, and produced almost without waste, meet the requirement of circular economy.
Brief description of the drawings
Fig. 1 shows the structure diagram of system used in the arsenic removing method of the iron ore of the present invention.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to specific embodiment and attached
Figure, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only explaining this hair
It is bright, it is not intended to limit the present invention.
The present invention provides a kind of iron ore arsenic removing method for aoxidizing and being combined with reduction, is illustrated with reference to Fig. 1.
With reference to figure 1, symplesite powder, coal dust, additive will be contained first by following parts by weight dispensing：Powder containing symplesite 80~
110 parts, 5~15 parts of coal dust, 1~5 part of additive.By pelletizing (8~16mm of spherolite degree) after the mixing of matched somebody with somebody raw material and dry, wherein
Additive can be dolomite, bentonite etc..
Green-ball after drying is distributed into roaster, is heated to 800~1000 DEG C, by adjusting air-fuel ratio, control roasting
Furnace atmosphere is weak oxide atmosphere, wherein CO2/ CO volume ratios are 0.80~1.70：1, keep 5~10min, this rank in the temperature
Section can effectively remove arsenic existing in the form of arsenic iron, and wherein arsenic is mainly with As2O3Gas, arsenones form enter flue gas.
Reaction of the arsenic iron in weak oxide type atmosphere：2FeAsS+5O2=Fe2O3+As2O3+2SO2
Reaction of the iron ore under weak oxide type atmosphere：4FeO+O2=2Fe2O3
Roaster is heated to 1000~1300 DEG C afterwards, adjusts its air-fuel ratio, it is reducing atmosphere to control furnace atmosphere,
Wherein CO/CO2Volume ratio is 1.30~2.25：1,20~30min is kept in the temperature, this stage can be effectively removed with arsenic acid
Arsenic existing for salt form, arsenic is mainly with As2O3The form of gas and arsenic steam enters flue gas.
Reaction of the arsenate under reducing atmosphere：6FeAsO4+ 7CO=2Fe3O4+7CO2+3As2O3
Reaction of the iron ore under reducing atmosphere：Fe2O3+ 3CO=2Fe+3CO2
Due to As2O3Gasify under 800~1000 DEG C of temperature conditionss, therefore the As that oxidation obtains2O3Obtained with reduction
As2O3Enter in the high-temperature flue gas of roaster, secondary combustion system is entered to high-temperature flue gas, and the metallization after dearsenification
Pelletizing (DRI) can be used as steelmaking feed.
Smoke settlement device (such as expansion chamber) is set in roasting outlet of still, high-temperature flue gas is drawn by air-introduced machine, in cigarette
Dedirt is settled through gravity settling section in gas sedimentation device, large dust particle settles down under the effect of gravity, the high temperature after dedirt
Flue gas is directed to secondary combustion chamber.Large dust particle is mainly not sufficiently reactive pelletizing, and it is further sharp that it can return to proportioning room
With.
Flue gas after expansion chamber is handled leads to secondary combustion chamber by wind turbine, by the metallic arsenic and arsenones in high-temperature flue gas
Re-oxidation, is changed into As2O3.The flue-gas temperature that secondary combustion chamber comes out is at 1050~1200 DEG C, As2O3Still in a gaseous form
It is present in flue gas.
The high-temperature flue gas come out from secondary combustion chamber is directed to heat reclamation device through wind turbine, is exchanged heat with mid temperature heat exchanger, is handed over
The heat changed is used to preheat the fuel and combustion air into roaster.After mid temperature heat exchanger exchanges heat, flue-gas temperature is reduced to 500
~600 DEG C, As2O3Still it is present in a gaseous form in flue gas.
Above-mentioned flue gas after the cryogenic heat exchanger heat exchange in heat reclamation device finally with being cooled to 180~200 DEG C, As2O3It is cold
Solid is congealed into, then flue gas enters cleaner collection arsenic oxide arsenoxide dust, and the flue-gas temperature of cleaner discharge is on 100 DEG C of left sides
The right side, the drying that can be further used for after pelletizing.
Illustrate the arsenic removing method of the iron ore of the present invention with reference to specific embodiment.
Embodiment 1
Pelletizing after 100 parts by weight powder containing arsenic minerals, 5 parts by weight coal dusts, 3 parts by weight dolomites are mixed, pellet size are
8mm.Green-ball after drying is distributed into roaster, is heated to 800 DEG C, by adjusting air-fuel ratio, it is weak oxygen to control furnace atmosphere
Change atmosphere, wherein CO2/ CO volume ratios are 1.67：1,5min is kept in the temperature, this stage can be effectively removed with sulphur arsenic iron
The arsenic of form.Roaster is heated to 1200 DEG C afterwards, then adjusts air-fuel ratio, it is reducing atmosphere to control furnace atmosphere, its
Middle CO/CO2Volume ratio is 1.9：1,30min is kept in the temperature, this stage can be effectively removed with existing for arsenate form
Arsenic, you can obtain the metallized pellet after dearsenification.Reaction gained flue gas in roaster is directed into secondary combustion after dedirt is handled
Burn in room, arsenones and arsenic steam in flue gas are changed into As after second-time burning2O3.Secondary combustion chamber discharge contains As2O3Cigarette
Gas contains As after heat reclamation device cools down, using cyclone dust removal recycling2O3Dust.
By above-mentioned oxidation after reducing the baking modes dearsenification being combined processing, more than 90% arsenic is taken off in iron ore
Remove.
Embodiment 2
Pelletizing after 100 parts by weight powder containing arsenic minerals, 10 parts by weight coal dusts, 3 parts by weight dolomites are mixed, pellet size are
12mm.Green-ball after drying is distributed into roaster, is heated to 900 DEG C, by adjusting air-fuel ratio, it is weak oxygen to control furnace atmosphere
Change atmosphere, wherein CO2/ CO volume ratios are 1.2：1,10min is kept in the temperature, this stage can be effectively removed with sulphur arsenic iron
The arsenic of form.Roaster is heated to 1200 DEG C afterwards, then adjusts air-fuel ratio, it is reducing atmosphere to control furnace atmosphere, its
Middle CO/CO2Volume ratio is 1.9：1,25min is kept in the temperature, this stage can be effectively removed with existing for arsenate form
Arsenic, you can obtain the metallized pellet after dearsenification.Reaction gained flue gas in roaster is directed into secondary combustion after dedirt is handled
Burn in room, arsenones and arsenic steam in flue gas are changed into As after second-time burning2O3.Secondary combustion chamber discharge contains As2O3Cigarette
Gas contains As after heat reclamation device cools down, using cyclone dust removal recycling2O3Dust.
By above-mentioned oxidation after reducing the baking modes dearsenification being combined processing, more than 92% arsenic is taken off in iron ore
Remove.
Embodiment 3
Pelletizing after 100 parts by weight powder containing arsenic minerals, 15 parts by weight coal dusts, 3 parts by weight dolomites are mixed, pellet size are
16mm.Green-ball after drying is distributed into roaster, is heated to 1000 DEG C, by adjusting air-fuel ratio, it is weak to control furnace atmosphere
Oxidizing atmosphere, wherein CO2/ CO volume ratios are 0.85：1,10min is kept in the temperature, this stage can be effectively removed with sulphur arsenic
Change the arsenic of iron form.Roaster is heated to 1300 DEG C afterwards, then adjusts air-fuel ratio, it is reproducibility gas to control furnace atmosphere
Atmosphere, wherein CO/CO2Volume ratio is 2.25：1,20min is kept in the temperature, this stage can be effectively removed with arsenate form
Existing arsenic, you can obtain the metallized pellet after dearsenification.Reaction gained flue gas in roaster is directed after dedirt is handled
In secondary combustion chamber, arsenones and arsenic steam in flue gas are changed into As after second-time burning2O3.Secondary combustion chamber discharge contains
As2O3Flue gas after heat reclamation device cools down, using cyclone dust removal recycling contain As2O3Dust.
By above-mentioned oxidation after reducing the baking modes dearsenification being combined processing, more than 95% arsenic is taken off in iron ore
Remove.
Embodiment 4
Pelletizing after 80 parts by weight powder containing arsenic minerals, 5 parts by weight coal dusts, 1 parts by weight of bentonite are mixed, pellet size are
10mm.Green-ball after drying is distributed into roaster, is heated to 850 DEG C, by adjusting air-fuel ratio, it is weak oxygen to control furnace atmosphere
Change atmosphere, wherein CO2/ CO volume ratios are 0.8：1,6min is kept in the temperature, this stage can be effectively removed with sulphur arsenic iron
The arsenic of form.Roaster is heated to 1000 DEG C afterwards, then adjusts air-fuel ratio, it is reducing atmosphere to control furnace atmosphere, its
Middle CO/CO2Volume ratio is 1.3：1,28min is kept in the temperature, this stage can be effectively removed with existing for arsenate form
Arsenic, you can obtain the metallized pellet after dearsenification.Reaction gained flue gas in roaster is directed into secondary combustion after dedirt is handled
Burn in room, arsenones and arsenic steam in flue gas are changed into As after second-time burning2O3.Secondary combustion chamber discharge contains As2O3Cigarette
Gas contains As after heat reclamation device cools down, using cyclone dust removal recycling2O3Dust.
By above-mentioned oxidation after reducing the baking modes dearsenification being combined processing, more than 91% arsenic is taken off in iron ore
Remove.
Embodiment 5
Pelletizing after 110 parts by weight powder containing arsenic minerals, 15 parts by weight coal dusts, 5 parts by weight of bentonite are mixed, pellet size are
12mm.Green-ball after drying is distributed into roaster, is heated to 950 DEG C, by adjusting air-fuel ratio, it is weak oxygen to control furnace atmosphere
Change atmosphere, wherein CO2/ CO volume ratios are 1.7：1,7min is kept in the temperature, this stage can be effectively removed with sulphur arsenic iron
The arsenic of form.Roaster is heated to 1250 DEG C afterwards, then adjusts air-fuel ratio, it is reducing atmosphere to control furnace atmosphere, its
Middle CO/CO2Volume ratio is 1.8：1,22min is kept in the temperature, this stage can be effectively removed with existing for arsenate form
Arsenic, you can obtain the metallized pellet after dearsenification.Reaction gained flue gas in roaster is directed into secondary combustion after dedirt is handled
Burn in room, arsenones and arsenic steam in flue gas are changed into As after second-time burning2O3.Secondary combustion chamber discharge contains As2O3Cigarette
Gas contains As after heat reclamation device cools down, using cyclone dust removal recycling2O3Dust.
By above-mentioned oxidation after reducing the baking modes dearsenification being combined processing, more than 94% arsenic is taken off in iron ore
Remove.
Embodiment described above only expresses embodiments of the present invention, its description is more specific and detailed, but can not
Therefore it is interpreted as the limitation to the scope of the claims of the present invention.It should be pointed out that for those of ordinary skill in the art,
Without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the protection model of the present invention
Enclose.
Claims (10)
1. a kind of arsenic removing method of iron ore, it is characterised in that comprise the following steps：
1) arsenic minerals powder, coal dust and additive will be contained and mixed pelletizing and dried in proportion；
2) pelletizing after drying is subjected to oxidizing roasting under weak oxide atmosphere, obtains acid pellet, while generation includes As2O3
The flue gas of gas and vulcanization arsenic gas；
3) acid pellet obtained in step 2) is subjected to reduction roasting in reducing atmosphere, obtains the metallization ball after dearsenification
Group, while generation includes As2O3The flue gas of gas and arsenic steam.
2. the arsenic removing method of iron ore according to claim 1, it is characterised in that walked below the method is further included
Suddenly：
The flue gas produced in step 2) and step 3) is subjected to dedirt and second-time burning processing successively so that arsenic and arsenones oxygen
Turn to As2O3。
3. the arsenic removing method of iron ore according to claim 2, it is characterised in that further comprise handling second-time burning
Rear flue gas carries out first waste heat recovery processing, and the heat recycled is used for preheating and baking is fuel used and combustion air.
4. the arsenic removing method of iron ore according to claim 3, it is characterised in that further comprise that first waste heat will be passed through
The flue gas of recycling carries out secondary waste heat recycling so that the As in flue gas2O3It is condensed into solid and is recycled, by institute
The heat of recycling is used to dry pelletizing.
5. the arsenic removing method of iron ore according to claim 1, it is characterised in that raw material includes 80~110 in step 1)
The additive of the powder containing symplesite of parts by weight, the coal dust of 5~15 parts by weight and 1~5 parts by weight.
6. the arsenic removing method of iron ore according to claim 1, it is characterised in that the temperature of oxidizing roasting for 800~
1000 DEG C, roasting time is 5~10min.
7. the arsenic removing method of iron ore according to claim 1, it is characterised in that in the weak oxide atmosphere of oxidizing roasting
CO2/ CO volume ratios are 0.80~1.70：1.
8. the arsenic removing method of iron ore according to claim 1, it is characterised in that reduction roasting temperature is 1000~1300
DEG C, the reduction roasting time is 20~30min.
9. the arsenic removing method of iron ore according to claim 1, it is characterised in that in the reducing atmosphere of reduction roasting
CO/CO2Volume ratio is 1.30~2.25：1.
10. the arsenic removing method of iron ore according to claim 1, it is characterised in that pellet size is 8~16mm.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711069962.2A CN107904395A (en) | 2017-11-03 | 2017-11-03 | A kind of arsenic removing method of iron ore |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711069962.2A CN107904395A (en) | 2017-11-03 | 2017-11-03 | A kind of arsenic removing method of iron ore |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111440954A (en) * | 2020-05-13 | 2020-07-24 | 河南昌益有色金属有限公司 | Method and device for recovering arsenic from high-arsenic smoke dust |
| CN115011803A (en) * | 2021-12-23 | 2022-09-06 | 昆明理工大学 | Reduction conversion roasting dearsenification method for high-arsenic germanium-containing neutralization slag |
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| CN101717855A (en) * | 2009-12-22 | 2010-06-02 | 广州有色金属研究院 | Method for removing copper and arsenic of iron ore |
| CN103614554A (en) * | 2013-11-12 | 2014-03-05 | 钢铁研究总院 | Method of arsenic removal in direct reduction process |
| CN105907945A (en) * | 2016-04-28 | 2016-08-31 | 中南大学 | Method for reduction, self vulcanization and dearsenification of refractory high-arsenic high-sulphur gold ore |
| CN106222398A (en) * | 2016-08-25 | 2016-12-14 | 北京矿冶研究总院 | Method for roasting arsenic-containing material to deeply remove arsenic |
| CN106435166A (en) * | 2016-10-28 | 2017-02-22 | 江苏省冶金设计院有限公司 | Method and system for comprehensively utilizing arsenic-bearing iron ore and carbide slag |
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2017
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101717855A (en) * | 2009-12-22 | 2010-06-02 | 广州有色金属研究院 | Method for removing copper and arsenic of iron ore |
| CN103614554A (en) * | 2013-11-12 | 2014-03-05 | 钢铁研究总院 | Method of arsenic removal in direct reduction process |
| CN105907945A (en) * | 2016-04-28 | 2016-08-31 | 中南大学 | Method for reduction, self vulcanization and dearsenification of refractory high-arsenic high-sulphur gold ore |
| CN106222398A (en) * | 2016-08-25 | 2016-12-14 | 北京矿冶研究总院 | Method for roasting arsenic-containing material to deeply remove arsenic |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111440954A (en) * | 2020-05-13 | 2020-07-24 | 河南昌益有色金属有限公司 | Method and device for recovering arsenic from high-arsenic smoke dust |
| CN115011803A (en) * | 2021-12-23 | 2022-09-06 | 昆明理工大学 | Reduction conversion roasting dearsenification method for high-arsenic germanium-containing neutralization slag |
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