CN110055452A - A kind of low titanium ferrophosphorus, preparation method and application - Google Patents
A kind of low titanium ferrophosphorus, preparation method and application Download PDFInfo
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- CN110055452A CN110055452A CN201910389957.2A CN201910389957A CN110055452A CN 110055452 A CN110055452 A CN 110055452A CN 201910389957 A CN201910389957 A CN 201910389957A CN 110055452 A CN110055452 A CN 110055452A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/04—Making ferrous alloys by melting
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C35/00—Master alloys for iron or steel
- C22C35/005—Master alloys for iron or steel based on iron, e.g. ferro-alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/28—Ferrous alloys, e.g. steel alloys containing chromium with titanium or zirconium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/34—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of silicon
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/38—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of manganese
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur
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Abstract
The invention discloses a kind of low titanium ferrophosphorus, preparation method and application comprising following steps: high titanium ferrophosphorus and absorption slag are added to the container melting down melting down object；Nitrogen is blown into melting down object from container bottom under the conditions of 1500~1650K or ammonia blows；After finishing blowing, tapping of skimming under molten condition obtains low titanium ferrophosphorus, the ingredient of high titanium ferrophosphorus includes: P:22~28% by weight, Si≤3%, C≤1%, S≤0.05%, Mn≤2%, Cr≤1%, Ti:0.1~4%, surplus is Fe, the low titanium ferrophosphorus ingredient of preparation includes: P:23~25% by weight, Si:1.7~2.8%, C:0.8~0.9%, S:0.05~0.08%, Mn:0.8~1.7%, Cr:0.6~0.8%, Ti < 0.05%, surplus is Fe, the process flow that the present invention prepares low titanium ferrophosphorus is short, technological operation is simple, environmental pollution is small, the Ti content for the low titanium ferrophosphorus being prepared is lower than 0.05%.
Description
Technical field
The invention belongs to pure ferroalloy smelting production technical field more particularly to a kind of low titanium ferrophosphorus, preparation method and
Using.
Background technique
High-quality silicon steel with excellent electromagnetic property needs to reduce the Ti content in product as far as possible, because of the titanium in steel
It will form with constituent elements such as carbon, oxygen, nitrogen and generate the tiny titanium oxide for being difficult discharge, titanium nitride or carbonization titanium inclusion, thus
The cleanliness of molten steel is reduced, inhibits crystal grain in annealing process to grow up, and then reduce the electromagnetic performance of silicon steel finished product.
Since P elements can improve the casting properties etc. of silicon steel, higher phosphorus is usually contained in silicon steel.Silicon steel production is normal
Use ferrophosphorus as the additive of P elements.Currently, the requirement with high-quality silicon steel to Ti content further increases, it is desirable that titanium contains
Amount is less than 10ppm, and titaniferous amount is difficult to meet its requirement in 0.1~4% common ferrophosphorus.Although leading to during process for making
The measures such as the oxygen content of control refining process and the adding manner of optimization ferrophosphorus are crossed, are brought to reduce the addition of high titanium ferrophosphorus
Adverse effect, but since the Ti content in common ferrophosphorus is excessively high, ingredient fluctuation is big, is difficult to the Ti content in high-quality silicon steel
Stability contorting is carried out, for this purpose, being badly in need of solving the production of high-quality silicon steel low titanium ferrophosphorus.
Summary of the invention
Technical problem to be solved by the present invention lies in: the Ti content in common ferrophosphorus is excessively high, is not able to satisfy high quality silicon
The production requirement of steel provides a kind of low titanium ferrophosphorus, preparation method and application.
The present invention is to solve above-mentioned technical problem, the preparation side of low titanium ferrophosphorus of the invention by the following technical programs
Method includes the following steps:
(1) melting down: high titanium ferrophosphorus is added to the container melting down, temperature 1500 according to weight ratio with absorption slag for 8~15:1
Under~1650K, heat preservation 3~6 minutes up to melting down object；
(2) it blows: being blown into nitrogen to melting down object from container bottom under the conditions of 1500~1650K or ammonia blows；
(3) tapping: after finishing blowing, tapping of skimming in the molten state obtains low titanium ferrophosphorus.
In the step (1), the ingredient of high titanium ferrophosphorus includes: by weight
P:22~28%；
Si≤3%；
C≤1%；
S≤0.05%；
Mn≤2%；
Cr≤1%；
Ti:0.1~4%；
Surplus is Fe.
In the step (1), the ingredient for adsorbing slag includes: by weight
MnO:10~14%；
SiO2: 25~28%；
CaO:28~32%；
Al2O3: 10~14%；
CaF2: 8~10%；
Surplus is FeO.
In the step (1), melting down container is intermediate frequency furnace.
In the step (2), nitrogen or ammonia are blown into melting down object in two stages.
In the step (2), the first stage is blown into nitrogen or ammonia amount is 300~800 liters/100 kilograms high titanium ferrophosphorus, institute
Stating and being blown into flow is 100~200 liters/min.
In the step (2), second stage is blown into nitrogen or ammonia amount is 50~100 liters/100 kilograms high titanium ferrophosphorus, institute
Stating and being blown into flow is 30~50 liters/min.
In the step (3), the low titanium ferrophosphorus ingredient of preparation includes: by weight
P:23~25%；
Si:1.7~2.8%；
C:0.8~0.9%；
S:0.05~0.08%；
Mn:0.8~1.7%；
Cr:0.6~0.8%；
Ti < 0.05%；
Surplus is Fe.
A kind of low titanium ferrophosphorus that the preparation method by low titanium ferrophosphorus is prepared.
A kind of application of low titanium ferrophosphorus on preparation high-quality silicon steel.
Titanium in high titanium ferrophosphorus there are two types of existence form, deposited with Impure forms such as titanium nitride, titanium carbide and titanium oxide by one kind
One kind is dissolved in high titanium ferrophosphorus with simple substance form, and the present invention prepares low titanium ferrophosphorus by high titanium ferrophosphorus, in preparation process, is inhaled
Attached slag is melted during melting down, is blown into nitrogen or ammonia to melting down object in two stages in converting process, the first stage to
Nitrogen or ammonia are blown into melting down object two aspect effects, on the one hand will be high using Gas Stirring, bubble absorption and Float upward function
The impurity such as existing titanium nitride, titanium carbide and titanium oxide blow afloat and are melted absorption slag and adsorbed in titanium ferrophosphorus, to remove height
On the other hand existing titaniferous impurity in titanium ferrophosphorus is reacted with the titanium being dissolved in high titanium ferrophosphorus using nitrogen or ammonia and generates nitrogen
Change titanium, newly-generated titanium nitride, adsorb in the Gas Stirring of nitrogen or ammonia that second stage is blown into melting down object, bubble and
It is blown afloat under Float upward function, and is melted absorption slag absorption, to remove the titanium of solubilised state in high titanium ferrophosphorus, be finally prepared
The density of low titanium ferrophosphorus, the melting absorption slag of adsorbing contaminant is small, floats on melting down container upper layer, the density of low titanium ferrophosphorus is big, sinks to
Lower layer, low titanium ferrophosphorus is poured out in inclination in the molten state after skimming can be realized the separation of melting absorption slag and low titanium ferrophosphorus.
The present invention has the advantage that compared with prior art
1, it is removed as de-titanium agent using Gas Stirring, bubble absorption and Float upward function using cheap nitrogen or ammonia
Existing titaniferous impurity in ferrophosphorus, while being reacted using nitrogen or ammonia with the titanium of dissolution and generating titanium nitride and gone with bubble floating
It removes, thoroughly reduces the Ti content in high titanium ferrophosphorus.
2, other than adsorbing titaniferous impurity, blow stirring and absorption slag are to chromium, silicon in high titanium ferrophosphorus etc. with field trash
There are also removal effects for constituent element existing for form.
3, the present invention is short by the de- titanium preparation low titanium ferrophosphorus process flow of high titanium ferrophosphorus, and technological operation is simple, environmental pollution
It is small.
Detailed description of the invention
Fig. 1 is the SEM figure and EDS energy spectrum analysis figure of titaniferous phase in high titanium ferrophosphorus；
Fig. 2 is the SEM figure and EDS energy spectrum analysis figure of metallic substrates in low titanium ferrophosphorus；
Fig. 3 is the SEM figure and EDS energy spectrum analysis figure of non-metallic inclusion phase in low titanium ferrophosphorus.
Specific embodiment
It elaborates below to the embodiment of the present invention, the present embodiment carries out under the premise of the technical scheme of the present invention
Implement, the detailed implementation method and specific operation process are given, but protection scope of the present invention is not limited to following implementation
Example.
Embodiment 1
500 kilograms high titanium ferrophosphorus and 33 kilograms of absorption slags are added to melting down in intermediate frequency furnace, used high titanium phosphorus
Ferrous components include: P:25%, Si:3%, C:1%, S:0.05%, Mn:1%, Cr:0.8%, Ti:2.2%, surplus by weight
For Fe, the absorption slag ingredient includes: MnO:14%, SiO by weight2: 27%, CaO:32%, Al2O3: 12%, CaF2:
9%, FeO:6%.
Temperature is 1500K after melting down, starts nitrogen blowing after melting down and blows, and it is 300 that the first stage of blowing, which is blown into tolerance,
/ 100 kilograms of ferrophosphorus are risen, at 100 liters/min, gassing time is 15 minutes for flow control；Second stage be blown into tolerance be 50 liters/
100 kilograms of ferrophosphorus, at 30 liters/min, gassing time is 9 minutes for flow control.
After finishing blowing, simultaneously tapping of skimming in the molten state obtains 480 kilograms of low titanium ferrophosphorus.
It is the SEM figure and EDS energy spectrum analysis figure of titaniferous phase in high titanium ferrophosphorus, as can be seen that titanium from energy spectrum diagram such as Fig. 1
Spectral line it is obvious, show that Ti content is higher in the high titanium ferrophosphorus of raw material, if Fig. 2,3 are the Metal Substrate of the low titanium ferrophosphorus prepared respectively
Bottom, the SEM figure of non-metallic inclusion phase and EDS energy spectrum analysis figure, find, either metallic substrates are also non-gold from energy spectrum diagram
Belong in the power spectrum of field trash phase the not no spectral line of titanium, illustrates that Ti content is extremely low in the low titanium ferrophosphorus of preparation.
It is analyzed according to chemical method, tests the low titanium ferrophosphorus ingredient of preparation, include: by weight
P:25%, Si:2.8%, C:0.8%, S:0.05%, Mn:0.8%, Cr:0.8%, Ti:0.04%, Fe:
69.71%.
Embodiment 2
500 kilograms high titanium ferrophosphorus and 45 kilograms of absorption slags are added to melting down in intermediate frequency furnace, used high titanium phosphorus
Ferrous components include: P:23%, Si:2%, C:0.8%, S:0.05%, Mn:2%, Cr:0.9%, Ti:1.4% by weight, remaining
Amount is Fe, and the absorption slag ingredient includes: MnO:12%, SiO by weight2: 28%, CaO:32%, Al2O3: 10%, CaF2:
10%, FeO:8%.
Temperature is 1590K after melting down, starts to blow ammonia after melting down and blow, and it is 500 that the first stage of blowing, which is blown into tolerance,
Rise/100 kilograms of ferrophosphorus, at 150 liters/min, gassing time is 17 minutes for flow control, second stage be blown into tolerance be 70 liters/
100 kilograms of ferrophosphorus, at 45 liters/min, gassing time is 8 minutes for flow control.
After finishing blowing, simultaneously tapping of skimming in the molten state, the density of slag is small, floats on above, and the density of iron is big, sinks to
In the following, inclination pours out molten iron after skimming in the molten state, it is public to can be obtained low titanium ferrophosphorus 470 of the Ti content lower than 0.05%
Jin.
It is analyzed according to chemical method, tests the low titanium ferrophosphorus ingredient of preparation, include: by weight
P:23%, Si:1.7%, C:0.8%, S:0.05%, Mn:1.7%, Cr:0.8%, Ti:0.03%, Fe:
71.92%.
Embodiment 3
500 kilograms high titanium ferrophosphorus and 62.5 kilograms of absorption slags are added to melting down in intermediate frequency furnace, used high titanium
Ferrophosphorus ingredient includes: P:23%, Si:2%, C:0.8%, S:0.05%, Mn:2%, Cr:0.9%, Ti:1.4% by weight,
Surplus is Fe, and the absorption slag ingredient includes: MnO:12%, SiO by weight2: 26%, CaO:31%, Al2O3: 12%,
CaF2: 9%, FeO:10%.
Temperature is 1650K after melting down, starts to blow ammonia after melting down and blow, and it is 800 that the first stage of blowing, which is blown into tolerance,
/ 100 kilograms high titanium ferrophosphorus is risen, at 200 liters/min, gassing time is 20 minutes for flow control.Second stage is blown into tolerance
100 liters/100 kilograms high titanium ferrophosphorus, at 50 liters/min, gassing time is 10 minutes for flow control.
After finishing blowing, skims in the molten state and tapping obtains the low titanium ferrophosphorus 470 that Ti content is lower than 0.05%
Kilogram.
It is analyzed according to chemical method, tests the low titanium ferrophosphorus ingredient of preparation, include: by weight
P:22%, Si:1.7%, C:0.8%, S:0.05%, Mn:1.7%, Cr:0.8%, Ti:0.03%, Fe:
72.92%.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. a kind of preparation method of low titanium ferrophosphorus, which comprises the steps of:
(1) melting down: by high titanium ferrophosphorus with absorption slag according to weight ratio be 8~15:1 be added to the container it is melting down, temperature 1500~
Under 1650K, heat preservation 3~6 minutes up to melting down object；
(2) it blows: being blown into nitrogen to melting down object from container bottom under the conditions of 1500~1650K or ammonia blows；
(3) tapping: after finishing blowing, tapping of skimming in the molten state obtains low titanium ferrophosphorus.
2. a kind of preparation method of low titanium ferrophosphorus according to claim 1, which is characterized in that in the step (1), Gao Tai
The ingredient of ferrophosphorus includes: by weight
P:22~28%；
Si≤3%；
C≤1%；
S≤0.05%；
Mn≤2%；
Cr≤1%；
Ti:0.1~4%；
Surplus is Fe.
3. a kind of preparation method of low titanium ferrophosphorus according to claim 1, which is characterized in that in the step (1), absorption
The ingredient of slag includes: by weight
MnO:10~14%；
SiO2: 25~28%；
CaO:28~32%；
Al2O3: 10~14%；
CaF2: 8~10%；
Surplus is FeO.
4. a kind of preparation method of low titanium ferrophosphorus according to claim 1, which is characterized in that melting down in the step (1)
Container is intermediate frequency furnace.
5. a kind of preparation method of low titanium ferrophosphorus according to claim 1, which is characterized in that in the step (2), be divided to two
A stage is blown into nitrogen or ammonia to melting down object.
6. a kind of preparation method of low titanium ferrophosphorus according to claim 1, which is characterized in that in the step (2), first
Stage is blown into nitrogen or ammonia amount is 300~800 liters/100 kilograms high titanium ferrophosphorus, and the flow that is blown into is 100~200 liters/min
Clock.
7. a kind of preparation method of low titanium ferrophosphorus according to claim 1, which is characterized in that in the step (2), second
Stage is blown into nitrogen or ammonia amount is 50~100 liters/100 kilograms high titanium ferrophosphorus, and the flow that is blown into is 30~50 liters/min.
8. a kind of preparation method of low titanium ferrophosphorus according to claim 1, which is characterized in that in the step (3), preparation
Low titanium ferrophosphorus ingredient include: by weight
P:23~25%；
Si:1.7~2.8%；
C:0.8~0.9%；
S:0.05~0.08%；
Mn:0.8~1.7%；
Cr:0.6~0.8%；
Ti < 0.05%；
Surplus is Fe.
9. a kind of low titanium ferrophosphorus that the preparation method by low titanium ferrophosphorus according to any one of claims 1 to 8 is prepared.
10. a kind of application of low titanium ferrophosphorus as claimed in claim 9 on preparation high-quality silicon steel.
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| CN111187971A (en) * | 2020-02-25 | 2020-05-22 | 新冶高科技集团有限公司 | Low-titanium-phosphorus-iron alloy and preparation method thereof |
| CN111304408A (en) * | 2020-03-25 | 2020-06-19 | 中国科学院过程工程研究所 | Method for refining ferrophosphorus |
| CN111334703A (en) * | 2020-03-12 | 2020-06-26 | 湖南创大钒钨有限公司 | Production method of low-titanium-phosphorus iron alloy |
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| CN111304408A (en) * | 2020-03-25 | 2020-06-19 | 中国科学院过程工程研究所 | Method for refining ferrophosphorus |
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