CN106319154B - A method of vortex is involved in carbon in lime stone removing cupric molten iron - Google Patents

A method of vortex is involved in carbon in lime stone removing cupric molten iron Download PDF

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CN106319154B
CN106319154B CN201610851744.3A CN201610851744A CN106319154B CN 106319154 B CN106319154 B CN 106319154B CN 201610851744 A CN201610851744 A CN 201610851744A CN 106319154 B CN106319154 B CN 106319154B
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molten iron
cupric
cupric molten
slag
decarburization
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CN106319154A (en
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张廷安
豆志河
张保敬
张子木
刘燕
牛丽萍
王东兴
吕国志
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Northeastern University China
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Priority to PCT/CN2017/082309 priority patent/WO2018058952A1/en
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    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21CPROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/04Removing impurities by adding a treating agent
    • C21C7/068Decarburising

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)

Abstract

A method of vortex is involved in carbon in lime stone removing cupric molten iron, belongs to metallurgical technology field, specific steps are as follows: (1) the cupric molten iron that carbonaceous reducing agent obtains will be added by copper ashes and import in induction furnace, guarantee cupric molten iron temperature >=1450 DEG C;(2) center stirring is carried out to cupric molten iron, forms the vortex that ratio of height to diameter is 0.5~2.5;(3) limestone powder is sprayed into swirl center, continues center stirring, limestone powder carries out eccentric stirring, makes the CO generated after spraying into2It is mixed with whirlpool more abundant;(4) limestone powder is directly involved in fill in molten iron with molten iron and react by whirlpool, cupric molten iron and slag after obtaining decarburization;(5) the cupric molten iron after decarburization and slag layering discharge.This method simple process, small investment, energy conservation and environmental protection is low in cost, and economic value with higher can not only reach decarburization purpose, moreover it is possible to copper therein be protected not to be burnt.

Description

A method of vortex is involved in carbon in lime stone removing cupric molten iron
Technical field:
The invention belongs to metallurgical technology fields, and in particular to a kind of vortex is involved in the side of carbon in lime stone removing cupric molten iron Method.
Background technique:
1 ton of copper of every production can generate 2.2 tons of copper ashes, and with the rapid development of copper making technology, the volume of cargo in storage of copper ashes is also significantly Increase.Contain a large amount of valuable metal element in copper ashes, and the utilization of copper ashes is also focused at present and individually mentions copper and individually mentions In terms of iron, using being also only limitted to copper-iron alloy while copper and iron element.The extraction of copper and iron element mostly uses carbonaceous reducing agent also Oxide and sulfide in native copper slag, to guarantee that reduction effect, carbonaceous reducing agent are mostly excessively added, this copper made Contain a large amount of carbon in ferroalloy, largely reduces the utility value of alloy, cupric molten iron is used to smelt cupric and is resisted Bacterium stainless steel need to carry out decarbonizing process.
The method of industrial decarburization has common oxygen decarburization method and vacuum decarburization method, although the degree of decarburization is different, all Carbon to be passed through in oxygen and alloy, which reacts, reaches decarburization effect, and the method is widely applied during molten iron-steelmaking.It is right In cupric molten iron, being passed through for oxygen can make copper scaling loss.
O2+ [Cu]=Cu2O
So that relatively low copper content further decreases, and the application of cupric molten iron needs to guarantee that certain copper contains Amount, martensite copper-bearing antibacterial stainless steel copper content requirement are 2.5~4.0%, and copper content is too low also to be needed in the follow-up process Copper alloy is added, loses more than gain.
Industrially the addition of solid additive is mostly suspended in bath surface, it is difficult to come into full contact with, add with molten slag bath Add agent utilization rate extremely low, and the lesser additive volatilization of some density is serious, causes environmental pollution very serious.Therefore, it looks for It is very important to the carbon in a kind of new decarburizer removing cupric molten iron, not only the carbon effectively in removing alloy, also It can protect a small amount of valuable element in alloy, in addition to this, need a kind of new addition manner also to improve the utilization of decarburizer Rate.
Application No. is 201210104356.0 patents to propose a kind of novel KR desulfurization stirring means, is related to iron before converter Water external desulfurzation is involved in the desulfurizing agent on molten iron surface in molten iron and mixes desulfurization by the rotational agitation of blender, but not It is related to decarburization field.Application No. is 201510802460.0 patents to propose the method that RH forces oxygen decarburization, in vacuum condition Under carbon content can be dropped to 9ppm, but pertain only to molten steel decarburization, be not directed to cupric molten steel decarburization.Application No. is A kind of method that the patent of 201510471169.X proposes high violent content molten iron of argon oxygen decarburizing furnace smelting high carbon, is also not directed to cupric Molten steel decarburization.Application No. is 201610144809.0 patents to propose that a kind of stirring is involved in the method for coal reduction copper ashes, stirring Vortex is formed, has extraordinary reduction effect, but be not directed to decarburization field.
Summary of the invention:
For the deficiency of existing solid additive adding manner and oxygen decarburization, the invention proposes a kind of vortex to be involved in stone The method that lime stone removes carbon in cupric molten iron.This method generates whirlpool using center stirring rotational agitation molten iron, by the stone of powdery Lime stone is added to swirl center and is involved in molten iron depths by whirlpool at once, is sufficiently mixed and reacts with molten iron, and lime stone is at high temperature Calcium oxide and CO are resolved into rapidly2, CO2It reacts with the carbon in molten iron and generates CO, and CO2As weak oxide gas, not with copper It reacts.Calcium oxide can promote the progress of dephosphorization, desiliconization process, and slag making floats on bath surface and shields.
To achieve the above object, the invention adopts the following technical scheme:
A method of vortex is involved in carbon in lime stone removing cupric molten iron, comprising the following steps:
(1) cupric molten iron is imported into induction furnace, guarantees temperature >=1450 DEG C of cupric molten iron;
(2) cupric molten iron is stirred, forms the vortex that ratio of height to diameter is 0.5~2.5;
(3) limestone powder is injected to swirl center, during penetrating, persistently carries out the stirring of step (2), and keep Continue 20~40min of stirring after limestone powder is blown in whirlpool temperature >=1450 DEG C;Wherein, in mass ratio, lime stone Powder: cupric molten iron=(1~4): 10;
(4) limestone powder is directly involved in molten iron by whirlpool and comes into full contact with and react with molten iron, after obtaining decarburization Cupric molten iron and slag;
(5) the cupric molten iron after decarburization and slag layering discharge.
In the step (1), cupric molten iron is to obtain after carbonaceous reducing agent is added in copper ashes, and cupric molten iron temperature is 1450~1650 DEG C.
In the step (1), carbon containing mass percent is 2.0~6.0% in cupric molten iron.
In the step (1), cupric mass percent is 4.68~5.88% in cupric molten iron.
In the step (1), guarantee that the method for temperature >=1450 DEG C of cupric molten iron is induction furnace conducting self-heating.
In the step (1), induction furnace includes slag-drip opening and row's molten iron mouth, and the lower part of the side of the induction furnace is set The row's of being equipped with molten iron mouth is provided with slag-drip opening on the top of the other side of induction furnace;
The induction furnace is provided with agitating paddle, agitating paddle jacking system, fan housing, flue gas purification system, waste heat recycling system System and scrubbing tower;The agitating paddle is arranged inside induction furnace;The top of induction furnace, the cigarette is arranged in the fan housing The entrance of gas purification system is connected by pipeline with fan housing, and the entrance of the residual neat recovering system passes through pipeline and gas cleaning The outlet of system connects, and the washing tower inlet is connected by the outlet of pipeline and residual neat recovering system, the scrubbing tower It exports in atmosphere;The agitating paddle is connected with agitating paddle jacking system, for replacing agitating paddle;The powder spraying apparatus For being blown limestone powder.
It in the step (2), is stirred centered on agitating mode, adjustment agitating paddle is inserted into cupric molten iron level height At 1/3~1/2, center stirring is carried out, center mixing speed is 50~200r/min.
In the step (3), after limestone powder is blown, the stirring of progress is eccentric stirring, bias stirring speed Degree is 50~200r/min, and the degree of eccentricity is 0.1~0.8, it is therefore an objective to make the CO generated2Dispersion mixes more abundant with whirlpool.
In the step (4), carbon containing mass percent≤0.2% in cupric molten iron after decarburization.
In the step (4), cupric mass percent is Cu:4.67~5.87% in cupric molten iron after decarburization.
In the step (4), the main component of slag is CaO.
In the step (4), while cupric molten iron and slag after obtaining decarburization, gas is generated, gas is mainly Remaining CO2, flue gas purification system is gone to via fan housing, after purified treatment, through residual neat recovering system recovery waste heat, and by washing Tower is washed, with Ca (OH)2Solution is recycled, and CaCO is obtained3Precipitating returns in induction furnace as agstone powder stock, again sharp With.
In the step (5), in induction furnace, upper layer is slag, and lower layer is the cupric molten iron after decarburization, by slag from row Cinder notch discharge, cupric molten iron is discharged from row's molten iron mouth after decarburization.
Decarburization principle:
CaCO3=CaO+CO2(g)
CO2+ [C]=2CO (g)
Beneficial effects of the present invention:
(1) by stirring means, blender center stirring rotational agitation generates whirlpool in molten iron, and swirling flow is by powder spraying apparatus The lime stone for being added to molten iron surface is involved in molten iron depths at once, and lime stone, which decomposes rapidly, generates CO2, in cupric molten iron [C], which reacts, reaches decarburization effect.
(2)CO2For weak oxide gas, copper will not be made to aoxidize while decarburization, not only achieve the effect that decarburization, but also be avoided that The scaling loss of copper.
(3) decarburizer uses relatively inexpensive lime stone, and stirs and be added, and the lime stone of addition can be mixed into rapidly molten iron, It is swift in response thoroughly, duration process is short.
(4) carbon content in molten iron, the CO of generation be can effectively reduce by the way that lime stone is added2Bring oxidizing condition facilitates The removing of phosphorus, silicon in molten iron makes molten iron is carbon containing to drop to 0.2% hereinafter, meeting steely iron water demand, and do not reduce melt Copper content.
(5) this method simple process, induction furnace add stirring system, small investment, energy conservation and environmental protection is low in cost, have compared with High economic value.
Detailed description of the invention:
Fig. 1 is the induction furnace system structure diagram using the method for the present invention, in which: 1- slag-drip opening;2- arranges molten iron mouth;3- Agitating paddle;4- agitating paddle jacking system;5- powder spraying apparatus;6- fan housing;7- flue gas purification system;8- residual neat recovering system;9- is washed Wash tower.
Specific embodiment:
Below with reference to embodiment, the present invention is described in further detail.
Embodiment 1
Cupric molten iron used, specific ingredient are as shown in table 1 in the present embodiment.
Each element component content (mass fraction, %) in 1 cupric molten iron of table
The induction furnace system structure diagram that the present embodiment uses is shown in Fig. 1.
A method of vortex is involved in carbon in lime stone removing cupric molten iron, comprising the following steps:
(1) after taking copper ashes that carbonaceous reducing agent is added, the cupric molten iron restored, temperature is 1450 DEG C, quality 20t, It is added in induction furnace, the temperature of control cupric molten iron is 1450 DEG C, and mass percent containing C is 2.0% in cupric molten iron, contains Cu Mass percent is 4.68%;
(2) adjustment agitating paddle 3 is inserted at the 1/3 of cupric molten iron level height, is carried out center stirring to cupric molten iron, is stirred Mixing speed is 50r/min, forms the vortex that ratio of height to diameter is 0.5;
Agitating paddle 3 is replaced by agitating paddle jacking system 4 according to reaction needs;
(3) 2t limestone powder is injected to swirl center by powder spraying apparatus 5, persistently carries out center stirring, and pass through sense Furnace is answered, keeping whirlpool temperature is 1450 DEG C, and limestone powder is changed to eccentric stirring after being blown, and the degree of eccentricity 0.1, bias is stirred Mixing the time is 20min, makes the CO generated2Dispersion mixes more abundant with whirlpool;
(4) limestone powder is directly involved in molten iron by whirlpool and comes into full contact with and react with molten iron, after obtaining decarburization Cupric molten iron and slag, remaining CO2, flue gas purification system 7 is gone to via fan housing 6, after purified treatment, is recycled through waste heat and is It unites 8 recovery waste heats, and by scrubbing tower 9, with Ca (OH)2Solution is recycled, and CaCO is obtained3Precipitating is former as limestone powder Material returns in induction furnace, re-uses;
(5) in induction furnace, upper layer is slag, and the main component of slag is CaO, and lower layer is the cupric molten iron after decarburization, is taken off Cupric molten iron after carbon is discharged by row's molten iron mouth 2, and slag is discharged by slag-drip opening l, wherein mass containing C in cupric molten iron after decarburization Percentage is 0.08%, and mass percent containing Cu is 4.67% in cupric molten iron after decarburization, and mass fraction containing P is 0.105%, is contained Si mass fraction is 0.215%.
Embodiment 2
Cupric molten iron used, specific ingredient are as shown in table 2 in the present embodiment.
Each element component content (mass fraction, %) in 2 cupric molten iron of table
The induction furnace system structure diagram that the present embodiment uses is shown in Fig. 1.
A method of vortex is involved in carbon in lime stone removing cupric molten iron, comprising the following steps:
(1) after taking copper ashes that carbonaceous reducing agent is added, the cupric molten iron restored, temperature is 1500 DEG C, quality 20t, It is added in induction furnace, the temperature of control cupric molten iron is 1500 DEG C, and mass percent containing C is 3.2% in cupric molten iron, contains Cu Mass percent is 5.06%;
(2) adjustment agitating paddle 3 is inserted at the 1/3 of cupric molten iron level height, is carried out center stirring to cupric molten iron, is stirred Mixing speed is 100r/min, forms the vortex that ratio of height to diameter is 1.5;
Agitating paddle 3 is replaced by agitating paddle jacking system 4 according to reaction needs;
(3) 4t limestone powder is injected to swirl center by powder spraying apparatus 5, persistently carries out center stirring, and pass through sense Furnace is answered, keeping whirlpool temperature is 1500 DEG C, and lime stone is changed to eccentric stirring, the degree of eccentricity 0.3, when bias stirs after being blown Between be 30min, make generate CO2Dispersion mixes more abundant with whirlpool;
(4) limestone powder is directly involved in molten iron by whirlpool and comes into full contact with and react with molten iron, after obtaining decarburization Cupric molten iron and slag, remaining CO2, flue gas purification system 7 is gone to via fan housing 6, after purified treatment, is recycled through waste heat and is It unites 8 recovery waste heats, and by scrubbing tower 9, with Ca (OH)2Solution is recycled, and CaCO is obtained3Precipitating is former as limestone powder Material returns in induction furnace, re-uses;
(5) in induction furnace, upper layer is slag, and the main component of slag is CaO, and lower layer is the cupric molten iron after decarburization, is taken off Cupric molten iron after carbon is discharged by row's molten iron mouth 2, and slag is discharged by slag-drip opening 1, wherein mass containing C in cupric molten iron after decarburization Percentage is 0.13%, and mass percent containing Cu is 5.04% in cupric molten iron after decarburization, and mass fraction containing P is 0.08%, is contained Si mass fraction is 0.135%.
Embodiment 3
Cupric molten iron used, specific ingredient are as shown in table 3 in the present embodiment.
Each element component content (mass fraction, %) in 3 cupric molten iron of table
The induction furnace system structure diagram that the present embodiment uses is shown in Fig. 1.
A method of vortex is involved in carbon in lime stone removing cupric molten iron, comprising the following steps:
(1) after taking copper ashes that carbonaceous reducing agent is added, the cupric molten iron restored, temperature is 1550 DEG C, quality 30t, It is added in induction furnace, the temperature of control cupric molten iron is 1550 DEG C, and mass percent containing C is 4.5% in cupric molten iron, contains Cu Mass percent is 5.24%;
(2) adjustment agitating paddle 3 is inserted at the 1/2 of cupric molten iron level height, is carried out center stirring to cupric molten iron, is stirred Mixing speed is 150r/min, forms the vortex that ratio of height to diameter is 2.0;
Agitating paddle 3 is replaced by agitating paddle jacking system 4 according to reaction needs;
(3) 9t limestone powder is injected to swirl center by powder spraying apparatus 5, persistently carries out center stirring, and pass through sense Furnace is answered, keeping whirlpool temperature is 1550 DEG C, and lime stone is changed to eccentric stirring, the degree of eccentricity 0.6, when bias stirs after being blown Between be 35min, make generate CO2Dispersion mixes more abundant with whirlpool;
(4) limestone powder is directly involved in molten iron by whirlpool and comes into full contact with and react with molten iron, after forming decarburization Cupric molten iron and slag, remaining CO2, flue gas purification system 7 is gone to via fan housing 6, after purified treatment, is recycled through waste heat and is It unites 8 recovery waste heats, and by scrubbing tower 9, with Ca (OH)2Solution is recycled, and CaCO is obtained3Precipitating is former as limestone powder Material returns in induction furnace, re-uses;
(5) in induction furnace, upper layer is slag, and the main component of slag is CaO, and lower layer is the cupric molten iron after decarburization, is taken off Cupric molten iron after carbon is discharged by row's molten iron mouth 2, and slag is discharged by slag-drip opening 1, wherein mass containing C in cupric molten iron after decarburization Percentage is 0.10%, and mass percent containing Cu is 5.23% in cupric molten iron after decarburization, and mass fraction containing P is 0.11%, is contained Si mass fraction is 0.205%.
Embodiment 4
Cupric molten iron used, specific ingredient are as shown in table 4 in the present embodiment.
Each element component content (mass fraction, %) in 4 cupric molten iron of table
The induction furnace system structure diagram that the present embodiment uses is shown in Fig. 1.
A method of vortex is involved in carbon in lime stone removing cupric molten iron, comprising the following steps:
(1) after taking copper ashes that carbonaceous reducing agent is added, the cupric molten iron restored, temperature is 1650 DEG C, quality 20t, It is added in induction furnace, the temperature of control cupric molten iron is 1650 DEG C, and mass percent containing C is 6.0% in cupric molten iron, contains Cu Mass percent is 5.88%;
(2) adjustment agitating paddle 3 is inserted at the 1/2 of cupric molten iron level height, is carried out center stirring to cupric molten iron, is stirred Mixing speed is 200r/min, forms the vortex that ratio of height to diameter is 2.5;
Agitating paddle 3 is replaced by agitating paddle jacking system 4 according to reaction needs;
(3) 8t limestone powder is injected to swirl center by powder spraying apparatus 5, persistently carries out center stirring, and pass through sense Furnace is answered, keeping whirlpool temperature is 1650 DEG C, and lime stone is changed to eccentric stirring, the degree of eccentricity 0.8, when bias stirs after being blown Between be 40min, make generate CO2Dispersion mixes more abundant with whirlpool;
(4) limestone powder is directly involved in molten iron by whirlpool and comes into full contact with and react with molten iron, after forming decarburization Cupric molten iron and slag, remaining CO2, flue gas purification system 7 is gone to via fan housing 6, after purified treatment, is recycled through waste heat and is It unites 8 recovery waste heats, and by scrubbing tower 9, with Ca (OH)2Solution is recycled, and CaCO is obtained3Precipitating is former as limestone powder Material returns in induction furnace, re-uses;
(5) in induction furnace, upper layer is slag, and the main component of slag is CaO, and lower layer is the cupric molten iron after decarburization, is taken off Cupric molten iron after carbon is discharged by row's molten iron mouth 2, and slag is discharged by slag-drip opening 1, wherein mass containing C in cupric molten iron after decarburization Percentage is 0.2%, and mass percent containing Cu is 5.87% in cupric molten iron after decarburization, and mass fraction containing P is 0.092%, is contained Si mass fraction is 0.165%.

Claims (5)

1. a kind of method that vortex is involved in carbon in lime stone removing cupric molten iron, which comprises the following steps:
(1) cupric molten iron is imported into induction furnace, guarantees that the temperature of cupric molten iron is 1450 ~ 1650 DEG C;Wherein, described Cupric molten iron is to obtain after carbonaceous reducing agent is added in copper ashes;
(2) cupric molten iron is stirred, forms the vortex that ratio of height to diameter is 0.5 ~ 2.5;Wherein, during the agitating mode is Heart stirring, adjustment agitating paddle are inserted at the 1/3 ~ 1/2 of cupric molten iron level height, carry out center stirring, center mixing speed For 50 ~ 200r/min;
(3) limestone powder is injected to swirl center, during penetrating, persistently carries out the stirring of step (2), and keep whirlpool Continue 20 ~ 40min of stirring after limestone powder is blown in whirlpool temperature >=1450 DEG C;Wherein, in mass ratio, agstone End: cupric molten iron=(1 ~ 4): 10;After limestone powder is blown, the stirring of progress is eccentric stirring, and eccentric mixing speed is 50 ~ 200r/min, the degree of eccentricity are 0.1 ~ 0.8;
(4) limestone powder is directly involved in molten iron by whirlpool and comes into full contact with and react with molten iron, containing after obtaining decarburization Copper and iron water and slag;
(5) the cupric molten iron after decarburization and slag layering discharge.
2. the method that vortex according to claim 1 is involved in carbon in lime stone removing cupric molten iron, which is characterized in that described The step of (1) in, induction furnace include slag-drip opening and row molten iron mouth, the lower part of the side of the induction furnace is provided with row's molten iron Mouthful, the top of the other side of induction furnace is provided with slag-drip opening;
The induction furnace be provided with agitating paddle, agitating paddle jacking system, fan housing, flue gas purification system, residual neat recovering system and Scrubbing tower;The agitating paddle is arranged inside induction furnace;The top of induction furnace is arranged in the fan housing, and the flue gas is net The entrance of change system is connected by pipeline with fan housing, and the entrance of the residual neat recovering system passes through pipeline and flue gas purification system Outlet connection, the scrubbing tower connected by the outlet of pipeline and residual neat recovering system;The agitating paddle, which is connected with, to be stirred Paddle jacking system is mixed, for replacing agitating paddle;Powder spraying apparatus is for being blown limestone powder.
3. the method that vortex according to claim 1 is involved in carbon in lime stone removing cupric molten iron, which is characterized in that described The step of (4) in, carbon containing mass percent≤0.2% in cupric molten iron after decarburization.
4. the method that vortex according to claim 2 is involved in carbon in lime stone removing cupric molten iron, which is characterized in that described The step of (4) in, while cupric molten iron and slag after obtaining decarburization, obtain remaining CO2, gas cleaning is gone to via fan housing System, after purified treatment, through residual neat recovering system recovery waste heat, and by scrubbing tower, with Ca (OH)2Solution is recycled, and is obtained To CaCO3Precipitating returns in induction furnace as agstone powder stock, re-uses.
5. the method that vortex according to claim 2 is involved in carbon in lime stone removing cupric molten iron, which is characterized in that described The step of (5) in, in induction furnace, upper layer is slag, and lower layer is the cupric molten iron after decarburization, and slag is discharged from slag-drip opening, is taken off Cupric molten iron is discharged from row's molten iron mouth after carbon.
CN201610851744.3A 2016-09-27 2016-09-27 A method of vortex is involved in carbon in lime stone removing cupric molten iron Active CN106319154B (en)

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PCT/CN2017/082309 WO2018058952A1 (en) 2016-09-27 2017-04-28 Method of removing carbon in copper-containing molten iron by using vortex to draw in limestone
AU2017333111A AU2017333111B2 (en) 2016-09-27 2017-04-28 Method of removing carbon in copper-containing molten iron by using vortex to draw in limestone

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JPS56123318A (en) * 1980-02-29 1981-09-28 Kawasaki Steel Corp Refining method of metal refining furnace for producing large amount of co for recovering exhaust gas
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CN104294002B (en) * 2014-10-23 2016-04-13 北京科技大学 A kind of method introducing carbonic acid gas converter single stage method smelting middle-low-carbon ferrochrome
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