CN107354338A - The method for preparing manganese-silicon - Google Patents
The method for preparing manganese-silicon Download PDFInfo
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- CN107354338A CN107354338A CN201710624784.9A CN201710624784A CN107354338A CN 107354338 A CN107354338 A CN 107354338A CN 201710624784 A CN201710624784 A CN 201710624784A CN 107354338 A CN107354338 A CN 107354338A
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- manganese
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/10—Alloys containing non-metals
- C22C1/1036—Alloys containing non-metals starting from a melt
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C22/00—Alloys based on manganese
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Abstract
The invention discloses the method for preparing manganese-silicon, including：Manganese ore, ferronickel slag and coke are mixed, to obtain mixed material；The mixed material is supplied and smelted into electric furnace, to obtain manganese-silicon and to produce clinker.This method uses ferronickel slag as the silicon source and fluxing agent for preparing manganese-silicon, on the one hand manganese-silicon can effectively be prepared, and reduce cost of material, iron oxide in another aspect ferronickel slag can be also reduced during electric furnace smelting is recycled utilization, realizes the comprehensive utilization of magnesia, silica and iron oxide in ferronickel slag.
Description
Technical field
The invention belongs to chemical field, in particular to the method for preparing manganese-silicon.
Background technology
At present, the domestic ferronickel slag overwhelming majority is that the lateritic nickel ore of humic soil type extracts under high temperature fused state through reduction
After nickel and part iron, the caused Water Quenching Slag under water quenching quenched condition.Mineral hot furnace is used using laterite nickel ore and producing ferronickel is most
Reduction melting, slag amount have accounted for the 80%-90% of raw material, enormous amount, and lateritic nickel ore is general nickeliferous left in 1.0-2.0%
The right side, exemplified by producing 20% ferronickel, the comprehensive recovery of nickel metal presses 90%, and the yield of slag is at least more than 91%.According to system
Meter, China's whole year ferronickel yield in 2013 is up to 710,000 tons, and the ferronickel slag supervened is more than 45,000,000 tons.2015, ferronickel slag
Total release close to 100,000,000 tons.
At present, China makes a low multiple use to ferronickel slag, and its processing mode is more based on outdoor stockpiling or landfill, and this is not
The waste of resource is only caused, and takes substantial amounts of soil, destroys the ecological environment on periphery.Compared with other metallurgical slags, ferronickel
Slag valuable metal recovery value is low, and bed drain purge is big, progressively turns into a great problem of metallurgical slag processing.Therefore, seek as early as possible
Correctly disposal and comprehensive utilization ferronickel slag tool are of great significance the technological approaches of economical rationality.
The content of the invention
It is contemplated that at least solves one of technical problem in correlation technique to a certain extent.Therefore, the present invention
One purpose is the method that proposition prepares manganese-silicon.This method regard ferronickel slag as the silicon source for preparing manganese-silicon and fluxing
Agent, manganese-silicon on the one hand can effectively be prepared, and reduce cost of material, on the other hand during electric furnace smelting, nickel
Iron oxide in scum can also be reduced into iron, realize the comprehensive utilization of magnesia, silica and iron oxide in ferronickel slag.
The present invention is mainly based upon what following discovery was completed：Manganese-silicon is one of alloy that purposes is most wide, dosage is maximum,
The 90% of world's manganese yield is consumed in steel and iron industry, and producing the raw material of manganese-silicon has manganese ore, Mn-rich slag, silica, dolomite (to have
When substituted with lime stone) and coke, wherein, manganese ore, Mn-rich slag and silica are primary raw material, and coke is reducing agent, and dolomite is
Fluxing agent, in addition, silica can also do fluxing agent use.However, manganese-silicon production method is using a large amount of high in the prior art
Expensive 75% or 90% silica and dolomite, significantly increase the production cost of manganese-silicon.Inventor by feeling free to try,
Ferronickel slag is substituted into silica and dolomite to be used to smelt manganese-silicon, effect is ideal, and while prepare manganese-silicon
Iron oxide in ferronickel slag can also be effectively reclaimed, and then new utilization ways are searched out for substantial amounts of ferronickel slag.
Therefore, according to an aspect of the present invention, the present invention proposes a kind of method for preparing manganese-silicon, including：
Manganese ore, ferronickel slag and coke are mixed, to obtain mixed material；
The mixed material is supplied and smelted into electric furnace, to obtain manganese-silicon and to produce clinker.
The method for preparing manganese-silicon of the above embodiment of the present invention using manganese ore, ferronickel slag and coke as raw material, wherein, nickel
Scum serves not only as fluxing agent use, even more prepares the silicon source of manganese-silicon.Thus, manganese-silicon is prepared by using the present invention
Method, on the one hand can effectively prepare manganese-silicon, and reduce cost of material, on the other hand the ferronickel during electric furnace smelting
Iron oxide in slag can also be reduced into iron, realize the comprehensive utilization of magnesia, silica and iron oxide in ferronickel slag.
In addition, the method according to the above embodiment of the present invention for preparing manganese-silicon can also have technology additional as follows
Feature：
In some embodiments of the invention, the method for preparing manganese-silicon further comprises：The manganese ore is broken in advance
It is 10-80 millimeters to be broken to average grain diameter.Thus, it is possible to significantly improve efficiency.
In some embodiments of the invention, the method for preparing manganese-silicon further comprises：In advance by the ferronickel slag
It is 20-50 millimeters to be crushed to average grain diameter.Thus, it is possible to significantly improve efficiency.
In some embodiments of the invention, the average grain diameter of the coke is 3-25 millimeters.Thus, it is possible to further carry
High efficiency.
In some embodiments of the invention, by the manganese ore, the ferronickel slag and the coke according to (80-90)：
(10-20)：The mass ratio of (15-30) carries out the mixing.Thus, it is possible to manganese-silicon is effectively prepared and makes in ferronickel slag
Iron oxide effectively reduced.
In some embodiments of the invention, SiO in the ferronickel slag2Mass fraction be 40-60%, MgO quality
Fraction is 15-25%, and FeO mass fraction is 5-12%.Thus, not only required silicon can be provided to prepare manganese-silicon,
Ferronickel slag can also be made to play preferably fluxing action in smelting process.
In some embodiments of the invention, Mn mass fraction is 30-60% in the manganese ore, and Fe mass fraction is
2-10%, and Mn and Fe mass ratio is not less than 5 in the manganese ore.Thus, it is possible to further improve the quality of manganese-silicon.
In some embodiments of the invention, Mn mass fraction is 60-64% in the manganese-silicon, and Si quality is divided
Number is 20-28%, and C mass fraction is 1-6%.
In some embodiments of the invention, the temperature of the smelting is 1550-1750 degrees Celsius.Thus, it is possible to significantly
Improve efficiency.
Embodiment
Embodiments of the invention are described below in detail.The embodiments described below is exemplary, it is intended to for explaining this
Invention, and be not considered as limiting the invention.
According to an aspect of the present invention, the present invention proposes a kind of method for preparing manganese-silicon, including：By manganese ore,
Ferronickel slag and coke are mixed, to obtain mixed material；Mixed material is supplied and smelted into electric furnace, to obtain
Manganese-silicon simultaneously produces clinker.
The method for preparing manganese-silicon of the above embodiment of the present invention using manganese ore, ferronickel slag and coke as raw material, wherein, nickel
Scum serves not only as fluxing agent use, even more prepares the silicon source of manganese-silicon.Thus, manganese-silicon is prepared by using the present invention
Method, manganese-silicon on the one hand can effectively be prepared, and reduce cost of material, the iron oxide in another aspect ferronickel slag
It can also be reduced during electric furnace smelting and be utilized so as to be recycled, realize magnesia, silica and oxidation in ferronickel slag
The comprehensive utilization of iron.
The raw material for preparing manganese-silicon of the above embodiment of the present invention is described in detail below.
According to an embodiment of the invention, the raw material for preparing manganese-silicon is manganese ore, ferronickel slag and coke.Wherein, coke is
Reducing agent, ferronickel slag are the silicon source of fluxing agent and manganese-silicon.
In all steel grade production, manganese is indispensable element, and it is used as a kind of additive in steelmaking process, mainly with conjunction
The form of gold element plays an important role to the performance of steel.In addition, it acts not only as the deoxidizing capacity that deoxidier improves silicon,
And main desulfurization element, the hot-short of steel can be prevented, increases the intensity of steel.In steel-making production can be improved using this alloy
Rate, improve steel quality and reduce smelting cost.With modern society's being continuously increased to the demand of steel, silicomangan is got over
More to play its very important effect.
Inventor has found that the smelting process of manganese-silicon is actually the reduction process of various oxides, in pyrolytic semlting
In, manganese in furnace charge, silicon peroxide breaks down or be reduced into as low oxide, during 1373-1473K, high price manganese oxide is gone back
Original is then combined the relatively low manganous silicate of generation fusing point, remaining be reduced directly again by carbon generates into manganese monoxide with silica
Mn3C.With the rise of temperature, silica is reduced to elementary silicon, Si reduction Mn by carbon3C obtains MnSi alloys.In addition, in order to
Clinker is smoothly discharged, improve the rate of recovery of manganese, it is also necessary to the fluxing agent such as dolomite or lime stone is added in furnace charge, is made
Clinker has preferable mobility.The current domestic ferronickel slag overwhelming majority is the lateritic nickel ore of humic soil type in high temperature fused state
It is lower through reduction extraction nickel and part iron after, the caused Water Quenching Slag under water quenching quenched condition, mainly by magnesium, iron, aluminium silicate
Component is formed, and main component is MgO, SiO2And FeO, belong to FeO-MgO-SiO2Ternary slag system, submember are A12O3、
Cr2O3, CaO etc., its main mineral composition is 2FeOSiO2、FeO·SiO2And MgOSiO2.Thus, inventor utilizes nickel
Silica and the high property of content of magnesia, as the silicon source and fluxing agent for smelting manganese-silicon, are being prepared in scum
The iron oxide in ferronickel slag is set also to be recycled utilization while high manganese-silicon.
According to a particular embodiment of the invention, ferronickel slag can be lateritic nickel ore by direct-reduction-mill ore magnetic selection processing
Obtained ferronickel tailings or the ferronickel melting slag for managing to obtain by direct-reduction-molten office for lateritic nickel ore.Thus, it is of the invention
In by being used as from above-mentioned ferronickel slag prepare the raw material of manganese-silicon, solid waste ferronickel slag can be made to obtain effective recycling,
And then solve the problems, such as that ferronickel slag utilization rate is low, bulk deposition.
According to a particular embodiment of the invention, SiO in ferronickel slag2Mass fraction can be 40-60%, MgO quality
Fraction can be 15-25%, and FeO mass fraction can be 5-12%.SiO in ferronickel slag2It is prepare manganese-silicon important
Composition, on the one hand on the other hand it can make smelting process with MgO collectively as fluxing agent as the silicon source of manganese-silicon
Middle slag liquid has preferably mobility, and then promotes the separation of manganese-silicon and clinker.Thus, by using above-mentioned in the present invention
Silica and the higher ferronickel slag of content of magnesia, required silicon can be not only provided for manganese-silicon, can also make ferronickel
Slag plays preferably fluxing action in smelting process, and then ensures the smooth row being smoothed out with reduzate of reduction reaction
Go out.
According to a particular embodiment of the invention, Mn mass fraction can be 30-60% in manganese ore, and Fe mass fraction can
Think 2-10%, and Mn and Fe mass ratio can be not less than 5 in manganese ore.The manganese content of manganese ore is to influence manganese-silicon smelting to refer to
Target principal element, in order to ensure the grade of silicomangan, typically require that manganese content is the higher the better in manganese ore, while iron content is not
Can be too high, Mn and Fe mass ratio are not less than 5.Thus, the present invention can be improved further by the manganese ore from mentioned component
The quality of manganese-silicon.
The method for preparing manganese-silicon of the above embodiment of the present invention is described in detail below.
According to a particular embodiment of the invention, the method for preparing manganese-silicon may further include：Manganese ore is broken in advance
It is 10-80 millimeters to be broken to average grain diameter；It is 20-50 millimeters that ferronickel slag is crushed into average grain diameter in advance.By pre- in the present invention
First manganese ore and ferronickel slag are crushed, not only can further improve the contact area between manganese ore and ferronickel slag and coke,
It can also make that there is between each raw material preferable gas permeability, and then promote being smoothed out for reduction reaction and heat exchange, significantly improve
The efficiency of smelting.
According to a particular embodiment of the invention, the average grain diameter of coke can be 3-25 millimeters.Thus, it is possible to further promote
Enter being smoothed out for reduction reaction and heat exchange, significantly improve the efficiency of smelting.
According to a particular embodiment of the invention, can be by manganese ore, ferronickel slag and coke according to (80-90)：(10-20)：
The mass ratio of (15-30) is mixed.Inventor has found, when when the amount of allocating of ferronickel slag is excessive or very few, can influence manganese
The quality of silicon alloy, especially when ferronickel slag amount of allocating is very few, fluxing effect can be also influenceed, is unfavorable for manganese-silicon and clinker
Separation；When the amount of allocating of coke is very few, the reduction effect of manganese and silicon can be influenceed, reduces the quality of manganese-silicon, and as Jiao
When the amount of allocating of charcoal is excessive, the rate of recovery and grade of manganese can not be further improved, can also cause coke data to waste.The present invention
By the way that manganese ore, ferronickel slag and coke are mixed according to above-mentioned mass ratio, manganese in manganese ore and iron can not only be made abundant
Reduction, moreover it is possible to the iron oxide in ferronickel slag and part of silica is also reduced, it is final to obtain manganese-silicon and produce clinker.
According to a particular embodiment of the invention, the temperature of smelting can be 1550-1750 degrees Celsius.Thus, it is possible to significantly
Improve efficiency.
According to a particular embodiment of the invention, it is raw material by using manganese ore, ferronickel slag and coke in the present invention, and upper
State and smelt manganese-silicon under conditions of embodiment, manganese-silicon can effectively be prepared and produce clinker, and finally give
Mn mass fraction is 60-64% in manganese-silicon, and Si mass fraction is 20-28%, and C mass fraction is 1-6%；Clinker
Middle SiO2Mass fraction be 34-42%, MgO and CaO gross mass and SiO2Mass ratio be 0.60-0.80, now, clinker
With preferable mobility, the separation of manganese-silicon and clinker is advantageously implemented.
In summary, the method for preparing manganese-silicon of the above embodiment of the present invention at least has the advantages that it
One：
(1) solve the problems, such as that ferronickel slag utilization rate is low, bulk deposition, the utilization for metallurgical solid wastes such as ferronickel slags is opened up
Wide thinking.
(2) the characteristics of making full use of magnesia and high silica in ferronickel slag, the silicon smelted as manganese-silicon
Source and fluxing agent, meanwhile, the iron oxide in ferronickel slag is also reduced during electric furnace smelting to be utilized so as to be recycled, and is realized
The comprehensive utilization of magnesia, silica and iron oxide in ferronickel slag.
(3) expensive silica and dolomite are substituted as the raw material of manganese-silicon by the use of ferronickel slag, significantly reduces preparation
The cost of material of manganese-silicon, improves the competitiveness of product in market.
Embodiment 1
By manganese ore that granularity is 10-80mm, (Mn mass fractions are the mass ratio that 57%, Fe mass fractions are 8%, Mn and Fe
For 7.1), granularity be 20-50mm ferronickel slags (SiO2Mass fraction is that 60%, MgO mass fractions are for 23%, FeO mass fractions
12%) coke in mass ratio 80 with granularity for 3-25mm:20:1550 DEG C of progress meltings directly in electric furnace, melt after 15 dispensings
Refining terminates slag sluicing system and obtains manganese-silicon and clinker.Manganese-silicon composition：Mn mass fraction is 63.79%, Si quality
Fraction is that 22.15%, C mass fractions are 3.42%, slag composition：SiO2Mass fraction is 36.60%, MgO and CaO total matter
Amount and SiO2Mass ratio be 0.79, manganese-silicon and clinker good separating effect.
Embodiment 2
By manganese ore that granularity is 10-80mm, (Mn mass fractions are the mass ratio that 40%, Fe mass fractions are 6%, Mn and Fe
For 6.7), granularity be 20-50mm ferronickel slags (SiO2Mass fraction is that 50%, MgO mass fractions are for 18%, FeO mass fractions
10%) coke in mass ratio 90 with granularity for 3-25mm:10:1650 DEG C of progress meltings directly in electric furnace, melt after 20 dispensings
Refining terminates slag sluicing system and obtains manganese-silicon and clinker.Manganese-silicon composition：Mn mass fraction is 61.01%, Si quality
Fraction is 24.94%, C mass fractions 3.94%, slag composition：SiO2Mass fraction is 37.43%, MgO and CaO gross mass
With SiO2Mass ratio be 0.72, manganese-silicon and clinker good separating effect.
Embodiment 3
By manganese ore that granularity is 10-80mm, (Mn mass fractions are the mass ratio that 35%, Fe mass fractions are 3%, Mn and Fe
For 11.7), granularity be 20-50mm ferronickel slags (SiO2Mass fraction is that 40%, MgO mass fractions are 15%, FeO mass fractions
For the coke in mass ratio 88 for being 5%) 3-25mm with granularity:12:1750 DEG C of progress meltings directly in electric furnace, melt after 30 dispensings
Refining terminates slag sluicing system and obtains manganese-silicon and clinker.Manganese-silicon composition：Mn mass fraction is 60.04%, Si quality
Fraction is that 27.98%, C mass fractions are 4.16%, slag composition：SiO2Mass fraction is 40.15%, MgO and CaO total matter
Amount and SiO2Mass ratio be 0.64, manganese-silicon and clinker good separating effect.
Embodiment 4
By manganese ore that granularity is 10-80mm, (Mn mass fractions are the mass ratio that 30%, Fe mass fractions are 2%, Mn and Fe
For 15.0), granularity be 20-50mm ferronickel slags (SiO2Mass fraction is that 45%, MgO mass fractions are 25%, FeO mass fractions
For the coke in mass ratio 85 for being 12%) 3-25mm with granularity:15:1600 DEG C of progress meltings directly in electric furnace after 25 dispensings,
Melting terminates slag sluicing system and obtains manganese-silicon and clinker.Manganese-silicon composition：Mn mass fraction is 60.01%, Si matter
It is that 20.63%, C mass fractions are 1.42% to measure fraction, slag composition：SiO2Mass fraction be 34.60%, MgO and CaO it is total
Quality and SiO2Mass ratio be 0.60, manganese-silicon and clinker good separating effect.
It can be drawn by embodiment 1-4 to draw a conclusion：The method that manganese-silicon is prepared by using the present invention can be effective
It is prepared manganese-silicon, Mn mass fraction is 60-64% in manganese-silicon, and Si mass fraction is 20-28%, C matter
Amount fraction is 1-6%；SiO in clinker2Mass fraction be 34-42%, MgO and CaO gross mass and SiO2Mass ratio be
0.60-0.80, manganese-silicon have preferably separating effect with clinker.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or the spy for combining the embodiment or example description
Point is contained at least one embodiment or example of the present invention.In this manual, to the schematic representation of above-mentioned term not
Identical embodiment or example must be directed to.Moreover, specific features, structure, material or the feature of description can be any
Combined in an appropriate manner in individual or multiple embodiments or example.In addition, in the case of not conflicting, the technology of this area
Different embodiments or example and the feature of different embodiments or example described in this specification can be combined by personnel
And combination.
Although embodiments of the invention have been shown and described above, it is to be understood that above-described embodiment is example
Property, it is impossible to limitation of the present invention is interpreted as, one of ordinary skill in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, changed, replacing and modification.
Claims (9)
- A kind of 1. method for preparing manganese-silicon, it is characterised in that including：Manganese ore, ferronickel slag and coke are mixed, to obtain mixed material；The mixed material is supplied and smelted into electric furnace, to obtain manganese-silicon and to produce clinker.
- 2. the method according to claim 1 for preparing manganese-silicon, it is characterised in that further comprise：It is 10-80 millimeters that the manganese ore is crushed into average grain diameter in advance.
- 3. the method according to claim 1 for preparing manganese-silicon, it is characterised in that further comprise：It is 20-50 millimeters that the ferronickel slag is crushed into average grain diameter in advance.
- 4. the method according to claim 1 for preparing manganese-silicon, it is characterised in that the average grain diameter of the coke is 3- 25 millimeters.
- 5. the method according to claim 1 for preparing manganese-silicon, it is characterised in that by the manganese ore, the ferronickel slag With the coke according to (80-90)：(10-20)：The mass ratio of (15-30) carries out the mixing.
- 6. the method according to claim 1 for preparing manganese-silicon, it is characterised in that SiO in the ferronickel slag2Quality Fraction is 40-60%, and MgO mass fraction is 15-25%, and FeO mass fraction is 5-12%.
- 7. the method according to claim 1 for preparing manganese-silicon, it is characterised in that Mn mass fraction in the manganese ore For 30-60%, Fe mass fraction is 2-10%, and Mn and Fe mass ratio is not less than 5 in the manganese ore.
- 8. the method according to claim 1 for preparing manganese-silicon, it is characterised in that Mn quality in the manganese-silicon Fraction is 60-64%, and Si mass fraction is 20-28%, and C mass fraction is 1-6%.
- 9. the method according to claim 1 for preparing manganese-silicon, it is characterised in that the temperature of the smelting is 1550- 1750 degrees Celsius.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114606404A (en) * | 2022-03-09 | 2022-06-10 | 石横特钢集团有限公司 | Method for producing manganese-silicon alloy by using steel slag to replace light-burned dolomite |
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| KR900006610B1 (en) * | 1986-05-20 | 1990-09-13 | 한국과학기술원 | Process for making high-purity fe-si |
| CN104245974A (en) * | 2012-04-27 | 2014-12-24 | 姜远燮 | Method for preparing ferro-silicon and magnesium using ferro-nickel slag, preparation apparatus used therefor, and smelting reduction furnace |
| KR20150106661A (en) * | 2014-03-12 | 2015-09-22 | 주식회사 포스코 | Manufacturing method of Fe-Si from Fe-Ni slag |
-
2017
- 2017-07-27 CN CN201710624784.9A patent/CN107354338A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR900006610B1 (en) * | 1986-05-20 | 1990-09-13 | 한국과학기술원 | Process for making high-purity fe-si |
| CN104245974A (en) * | 2012-04-27 | 2014-12-24 | 姜远燮 | Method for preparing ferro-silicon and magnesium using ferro-nickel slag, preparation apparatus used therefor, and smelting reduction furnace |
| KR20150106661A (en) * | 2014-03-12 | 2015-09-22 | 주식회사 포스코 | Manufacturing method of Fe-Si from Fe-Ni slag |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114606404A (en) * | 2022-03-09 | 2022-06-10 | 石横特钢集团有限公司 | Method for producing manganese-silicon alloy by using steel slag to replace light-burned dolomite |
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