CN105779820B - The production method of low impurity content ferrotianium - Google Patents
The production method of low impurity content ferrotianium Download PDFInfo
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- CN105779820B CN105779820B CN201610182034.6A CN201610182034A CN105779820B CN 105779820 B CN105779820 B CN 105779820B CN 201610182034 A CN201610182034 A CN 201610182034A CN 105779820 B CN105779820 B CN 105779820B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C14/00—Alloys based on titanium
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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
- C22C1/02—Making non-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
- 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
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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
- C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium
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Abstract
The present invention relates to the production method of low impurity content ferrotianium, belong to ferroalloy smelting technical field.Present invention solves the technical problem that being to provide the production method of low impurity content ferrotianium; it is source of iron that the method uses common molten iron; molten iron is smelted; impurity element total content in molten iron is controlled within 0.5%, while molten iron is warmed up into more than 1700 DEG C, is hung under the conditions of vacuum or inert gas shielding; and will be melting down under the conditions of vacuum or inert gas shielding in advance and be warmed up to more than 1690 DEG C of titanium liquid and be poured into ladle; liquidated mixing, argon bottom-blowing, and cooling of then casting is obtained final product.The inventive method can not only produce the ferrotianium series of products of different Ti content requirements, and production method is simple and easy to apply, Composition Control high precision, impurity and harmful element content is low, ferrotianium quality of finished is high, efficiently solves traditional problem that ferrotianium controlling of production process difficulty is big, impurity content is high.
Description
Technical field
The present invention relates to the production method of low impurity content ferrotianium, belong to ferroalloy smelting technical field.
Background technology
Titanium can increase the wearability and tensile strength of steel, can be used as deoxidier, degasifier.The deoxidizing capacity of titanium is significantly
Higher than silicon, manganese, and ingotism can be reduced, improve ingot quality, improve recovery rate.And the proportion of Titanium is low, only 4.5
Grams per milliliter, fusing point is again high, is 1690 DEG C, and oxidizable, is oxidized on molten steel face and burnt a lot, and loss is too big, and not easily-controllable
Content processed, and elemental metals reparation technology is complicated, production cost is high, expensive etc., therefore be not suitable for simple metal and
During nonmetallic free state is directly added into molten steel in steel-making.These elements and iron have been made for this metallargist studies
Alloy, is just called " ferroalloy ", and the alloy melting point and steel of titanium elements and iron are approached, and proportion and steel are similar and not oxidizable, its
, again than producing the simple metal and nonmetallic simple, production cost is than pure elemental metals and nonmetallic low many, valency for production technology
Lattice are low, are particularly suitable for making steel and produce in various hitech materials and using.Therefore ferroalloy turns into steel-making and new material industry
In important materials.Current ferroalloy kind has tens of kinds of binary and polynary ferroalloy, and wherein ferrotianium belongs to consumption most
One of big binary iron alloys.Ferro-titanium is production circular chain steel, anchor steel, makes hull steel, stainless steel, welding rod and electricity
The important source material of son, war products etc..
At present, it is titanium material that the production of domestic ferrotianium mainly uses ilmenite concentrate, titanium slag etc., and producing ferrotianium by reducing process closes
Gold.
Patent 201010514572.3 is disclosed " a kind of method of preparing high-titanium iron by step-by-step metal thermal reduction ", including a step
Aluminothermic reduction melting, two steps reinforcing two steps of reduction refining, in mass ratio, feed proportioning is：Rutile or high titanium slag:Aluminium
Powder:Iron ore concentrate:Slag former:KClO3=1.0:0.37~0.50:0.05~0.10:0.15~0.25:0.20~0.25, smelt
1900 DEG C~2200 DEG C of temperature；Two steps strengthen 10~30min of reduction refining time, and after refining terminates, cooling, ingot, removal of impurities are obtained
To high ferrotitanium alloy；Complex reducing agent is calcium-magnesium alloy.Patent CN200710049216.7 discloses " a kind of to be smelted with titanium material
The method for producing serial ferro-titanium ", processing step is as follows：At Panxi Diqu titanium material, calcareous metallurgic auxiliary materials and calcium-sodium system
In reason agent feeding revolving burner, through rapidly pre-warming after, then be sufficiently mixed in the feeding blender of storehouse uniform through connecting, then from batch bin
Metallic aluminium, iron system raw material, assistant reducing agent and potassium chlorate are sequentially added, the raw material and auxiliary material in blender are well mixed
Afterwards, fallen into warmed-up smelting furnace through docking storehouse, add igniting agent, 2~3min reactions to add retarder, cooling 20 after terminating
~40h, is finally separating slag and ferro-titanium, and ferro-titanium product is put in storage after inspection, packaging.Patent CN200810230203.4
" method and device that high quality high ferrotitanium alloy is prepared based on aluminothermic reduction " is disclosed, method is comprised the following steps：(1) by aluminium
Thermal reduction agent is preheating to liquid；By titaniferous materials, iron compound and slag former by being continuously added to metal bath after ball milling, roasting
In carry out high melt；(2) injection particle reduction agent is smelted；(3) through supercooling, ingot is played, goes the removal of impurity, obtain high-quality
Ferrotianium high.Patent CN201110113452.7 discloses " a kind of bismuth ferro-titanium and application thereof ", and the bismuth ferro-titanium is with it
The weight percentage of component and each component is：Bismuth 15-68wt%, titanium 15-68wt%, inevitable impurity≤0.8wt%,
Iron：5~70%.Its preparation method is the first melting pig iron and useless by proportion ingredient by bismuth metal, titanium sponge, the pig iron and steel scrap
Steel, then titanium sponge is added and is stirred, so that titanium is fully dissolved into iron liquid, in the process, continuous with titanium adds
Enter, heat temperature raising is carried out to aluminium alloy, until titanium sponge is completely dissolved and bismuth metal is pressed into gold with bell jar again after uniformly mixing
In category liquid and be stirred so that bismuth is fully dissolved into ferrotianium liquid, after bismuth metal be completely dissolved it is uniform after aluminium alloy
It is poured into ingot mould and quickly cools down, that is, is made bismuth ferro-titanium ingot.Patent CN201310507878.X disclose " with titanium slag with
Ilmenite concentrate is the method that titanium, iron material produce high ferrotitanium alloy ", with titanium slag and ilmenite concentrate as titanium, iron material, including following step
Suddenly：Raw material is pressed into 1 part of quality proportioning titanium slag, 0.35~0.51 part of ilmenite concentrate, 0.83 part of aluminium powder, 0.36 part of potassium chlorate, fluorite
0.14~0.16 part, after 0.11~0.15 part of lime mixes, using upper point pyrometallurgical smelting, obtain high ferrotitanium alloy.Patent
CN201310449481.X discloses " method and niobium ferro-titanium that sharp reduction with carbon prepares niobium ferro-titanium ", the method bag
Include：(1) carbon high-temp reduction, by titanium high richness niobium slag, carbon and the first solvent in 1550-1700 DEG C of fusing, is then incubated reducing and smelting,
Obtain carbide；And (2) secondary smelting.Patent CN201310413509.4 discloses a kind of " side for preparing ferro-titanium
Method ", by ilmenite concentrate in electric furnace smelting titanium slag；After titanium slag smelting terminates, at least one alkali metal carbonic acid of addition in electric furnace
Salt, is passed through air or oxygen and stirs, so that the titanium oxide in titanium slag is converted into titanate；With graphite as anode and with electric furnace
The molten iron of bottom is electrolysed for negative electrode, generates Titanium, and Titanium enters formation liquid phase ferro-titanium in the iron for melting；
The molten iron and the liquid phase ferro-titanium are discharged under inert gas shielding and is cooled down, obtain ferro-titanium.Patent
CN201310507100.9 discloses a kind of " magnalium method produces high ferrotitanium alloy ", and raw material is pressed into 1 part of quality proportioning ilmenite concentrate, titanium
2.3 parts of slag, 1.73~1.93 parts of aluminium powder, magnesium powder be 0.17~0.23 part, 0.27~0.37 part of fluorite, 0.33~0.4 part of lime,
After 0.83 part of potassium chlorate is mixed, using upper point pyrometallurgical smelting, high ferrotitanium alloy is obtained.Patent CN201310449614.3 is disclosed
" preparation method and niobium ferro-titanium of niobium ferro-titanium ", the preparation method of niobium ferro-titanium includes following operation：(1) high temperature
Carbonization, by rich niobium slag, carbon and the first flux in 1500-1700 DEG C of fusing, is then incubated reducing and smelting, obtains niobium titanium carbide；
And (2) reoxidize, first iron scale is added in the carbide that operation (1) is obtained, is smelted in 1550-1700 DEG C of reaction, then
The second flux is added at 1550-1700 DEG C of keeping temperature, follow-up continuation of insurance temperature is melted and is smelted for a period of time, obtain the conjunction of niobium ferrotianium
Gold.
From the point of view of invention disclosed patent, the production of ferrotianium is mainly using titaniferous things such as ilmenite concentrate, titanium slag, rutile
Matter is titanium source, and aluminium, magnesium, carbon etc. are reducing agent, while using lime, fluorite etc. as slag former, part invention also uses chloric acid
Potassium is igniting agent, although these methods can successfully produce the ferro-titanium of different Ti contents, method has reaction
Acutely, the shortcomings of reaction time is short, the production cycle is long, alloying component fluctuation is big, impurity content is high, extreme influence titanium alloy steel grade
Composition precision controlling.Such as：The different Ti content alloy existences that above method is produced differ, the ferrotianium of low titanium content
The easy efflorescence of alloy, the ferro-titanium hardness disaster of high titanium content is crushed, and this is resulted in carries out alloying using low titanium content alloy
When addition control difficulty it is big.The ferrotianium that existing method is produced fluctuates larger on composition, and the impurity element for containing simultaneously contains
Amount is high, therefore requirement of the GB to ferrotianium composition is more wide in range (chemical composition of ferrotianium is shown in Table 1 in GB), and silicon, manganese, aluminium etc. contain
Amount can 1% and more than, phosphorus, sulfur content are higher, and the ferrotianium of the trade mark high also has oxygen, nitrogen content (such as
The nitrogen content of FeTi70 is up to 0.80%, oxygen content more than 5.00%), these molten steel all during extreme influence Ti Alloying
The control of the precise control and harmful element of composition.
The chemical composition of ferro-titanium in the GB of table 1
The content of the invention
Present invention solves the technical problem that the production method of low impurity content ferrotianium is to provide, using the method for the present invention not
Can only produce the ferrotianium series of products of different Ti content requirements, and impurity and harmful element content is low, ferrotianium in product
Quality of finished is high.
The production method of low impurity content ferrotianium of the present invention, comprises the following steps：
A, the melting down of titanium source is carried out in vacuum or atmosphere of inert gases, it is melting down after be warmed up to more than 1690 DEG C, obtain titanium
Liquid；Ti content >=99.5% of the titanium source；
B, to use common molten iron be source of iron, molten iron is smelted, by C, Si, Mn, P, S, Al, V and Ti unit in molten iron
The total content of element is controlled within 0.5%, while molten iron temperature is raised into more than 1700 DEG C；
C, will heat up after molten iron be hung in vacuum or atmosphere of inert gases, ferrotianium board needed for a steps gained titanium liquid is pressed
Number desired weight is poured into ladle, and molten iron and titanium liquid carried out into the mixing that liquidates, argon bottom-blowing, for argon intensity for 0.25~
1.0m3/ (mint), argon blowing time is 2~15min；Obtain ferro-titanium liquid；
D, ferro-titanium liquid is cast under vacuum or in atmosphere of inert gases, treated that alloy cools to 100 DEG C
And its it is following after, ferro-titanium is carried out into crushing packing, obtain ferro-titanium.
Preferably, the titanium source is to wait at least in outer titanium sponge, titanium bits, titanium alloy bits, titanium wood shavings, titanium alloy wood shavings
Kind.
Further, a steps are warmed up to 1690~1700 DEG C, and molten iron is warmed up to 1700~1720 DEG C by b step.
Preferably, in a steps, the melting down of titanium source is carried out using crucible furnace or resistance furnace；In b step, using can be to iron
The equipment that water carries out decarburization, dephosphorization and desulfurization is smelted to molten iron.
Wherein, in the equipment that decarburization, dephosphorization and desulfurization can be carried out to molten iron preferably converter, electric furnace, LF stoves
It is at least one.
Preferably, in step c, other alloying components are entered in ferro-titanium, is used to obtain containing other alloying components
Ferro-titanium, described other alloying components are at least one in chromium, niobium, nickel.
Wherein, inert gas is preferably helium, neon, argon gas, Krypton, xenon or radon gas.
Preferably, the impurity content of the low impurity content ferrotianium<0.3%.
Ferrotianium production method of the invention can not only produce the ferrotianium series of products of different Ti content requirements, Er Qiesheng
Product method is simple and easy to apply, Composition Control high precision, impurity and harmful element content is low, ferrotianium quality of finished is high, efficiently solves
The problem such as traditional ferrotianium controlling of production process difficulty is big, impurity content is high, the ferrotianium for being produced can be high-end Ti-containing steel
Production provides high-quality ferro-titanium.
Specific embodiment
The production method of low impurity content ferrotianium of the present invention, comprises the following steps：
A, the melting down of titanium source is carried out in vacuum or atmosphere of inert gases, it is melting down after be warmed up to more than 1650 DEG C, obtain titanium
Liquid；Ti content >=99.5% of the titanium source；
B, to use common molten iron be source of iron, and decarburization, dephosphorization, desulfurization can be carried out to molten iron using converter, electric furnace, LF stoves etc.
Equipment molten iron is smelted, by the control of the total content of C, Si, Mn, P, S, Al, V and Ti element in molten iron 0.5% with
It is interior, while molten iron temperature is raised into more than 1700 DEG C；
C, will heat up after molten iron be hung in vacuum or atmosphere of inert gases, ferrotianium board needed for a steps gained titanium liquid is pressed
Number desired weight is poured into ladle, and molten iron and titanium liquid carried out into the mixing that liquidates, argon bottom-blowing, for argon intensity for 0.25~
1.0m3/ (mint), argon blowing time is 2~15min；Obtain ferro-titanium liquid；
After the completion of d, homogenization, ferro-titanium liquid is cast under vacuum or in atmosphere of inert gases, wait to close
Gold cool to 100 DEG C and its it is following after, ferro-titanium is carried out into crushing packing, obtain ferro-titanium.
The production method of low impurity content ferrotianium of the present invention, by the control to titanium source, molten iron impurity, and was mixing
Argon bottom-blowing in journey, can not only play the purpose of homogenization of composition, moreover it is possible to the miscellaneous purpose of control be reached, in reduction ferro-titanium
Impurity content.Preferably, it is 0.25~1.0m for argon intensity3/ (mint), argon blowing time is 2~15min.
Wherein, the titanium source is the high titanium content material that Ti content is 99.5%, preferably described titanium source for wait outer titanium sponge,
At least one in titanium bits, titanium alloy bits, titanium wood shavings, titanium alloy wood shavings.
Further, it is preferred that a steps are warmed up to 1690~1700 DEG C, and molten iron is warmed up to 1700~1720 DEG C by b step.
Further, in a steps, it is preferred to use crucible furnace or resistance furnace carry out the melting down of titanium source.
In b step, preferably using converter, electric furnace, LF stoves etc. can carry out the equipment pair of decarburization, dephosphorization, desulfurization to molten iron
Molten iron is smelted, and its smelting process is state of the art, be will not be described here.
When adding other alloying component (such as chromium, niobium, nickel) in ferro-titanium if necessary, can be added in step c
Corresponding metal or ferroalloy.I.e. in step c, other alloying components are added in ferro-titanium, be used to obtain containing corresponding conjunction
The ferro-titanium of gold.
Further, inert gas of the invention does not include nitrogen, is preferably helium, neon, argon gas, Krypton, xenon
Or radon gas.
By the production method of low impurity content ferrotianium of the present invention, impurity content in the ferro-titanium for obtaining<0.3%.
Content in the present invention is mass percent.
Specific embodiment of the invention is further described with reference to embodiment, is not therefore limited the present invention
System is among described scope of embodiments.
Embodiment 1
Using crucible furnace, the outer titanium sponge (Ti content 99.8%) such as general is melting down in a vacuum, and is warmed up to 1700 DEG C；Using
Converter and LF stoves process to 0.4% [C] of molten iron+[Si]+[Mn]+[P]+[S]+[Al]+[V]+[Ti], and are warmed up to 1710
℃；Source of iron and titanium source weight ratio are 7:3, high temperature liquid iron is hung under vacuum condition, and will be led under the conditions of vacuum protection in advance
Cross crucible furnace melting down and be warmed up to 1700 DEG C of titanium liquid and be poured into ladle, two kinds of molten metals are entered into the mixing that liquidates, and in bag
Bottom using be blown argon gas by the way of carry out homogenization of composition and control it is miscellaneous, for argon intensity be 0.25m3/ (mint), argon blowing time is
15min；Ferro-titanium liquid is carried out into board-like casting under vacuum after the completion of homogenization, treat alloy cool to 100 DEG C and its
After below, ferro-titanium is carried out into crushing packing.In gained ferro-titanium Ti contents be 29.89%, remaining than iron element contain
Amount total amount<0.3%.
Embodiment 2
It is in Ar gas shielded atmosphere that titanium wood shavings (Ti content 99.5%) are melting down using resistance furnace, and it is warmed up to 1690 DEG C；
Using electric furnace by [C] of molten iron+[Si]+[Mn]+[P]+[S]+[Al]+[V]+[Ti] treatment to 0.3%, and it is warmed up to 1700
℃；Source of iron and titanium source weight ratio are 3:7, high temperature liquid iron is hung under argon gas protective condition, and will be in advance in argon gas protective condition
It is melting down by resistance furnace down and be warmed up to 1650 DEG C of titanium liquid and be poured into ladle, two kinds of molten metals are entered into the mixing that liquidates, and
Bag bottom using injection argon gas by the way of carry out homogenization of composition and control it is miscellaneous, for argon intensity be 0.5, argon blowing time is 10min；
Ferro-titanium liquid is carried out into board-like casting under vacuum after the completion of homogenizing, after alloy cool to 100 DEG C and its it is following after, will
Ferro-titanium carries out crushing packing.Ti contents are 79.81% in gained ferro-titanium, remaining constituent content total amount than iron<
0.3%.
Embodiment 3
It is in a vacuum that titanium bits (Ti content 99.9%) is melting down using resistance furnace, and it is warmed up to 1698 DEG C；Using electric furnace+LF
Stove processes to 0.4% [C] of molten iron+[Si]+[Mn]+[P]+[S]+[Al]+[V]+[Ti], and is warmed up to 1720 DEG C；Source of iron
It is 5 with titanium source weight ratio:5, high temperature liquid iron is hung under argon gas protective condition, and will be in advance under argon gas protective condition by electricity
Resistance stove is melting down and is warmed up to 1680 DEG C of titanium liquid and is poured into ladle, two kinds of molten metals is entered into the mixing that liquidates, and adopt bottom is wrapped
With injection argon gas mode carry out homogenization of composition and control it is miscellaneous, for argon intensity be 1.0m3/ (mint), argon blowing time is 2min；
Ferro-titanium liquid is carried out into board-like casting under vacuum after the completion of homogenization, after alloy cool to 100 DEG C and its it is following after,
Ferro-titanium is carried out into crushing packing.Ti contents are 59.83% in gained ferro-titanium, remaining constituent content total amount than iron<
0.3%.
Claims (7)
1. the production method of low impurity content ferrotianium, it is characterised in that comprise the following steps：
A, the melting down of titanium source is carried out in vacuum or atmosphere of inert gases, it is melting down after be warmed up to more than 1690 DEG C, obtain titanium liquid；Institute
State Ti content >=99.5% of titanium source；
B, to use common molten iron be source of iron, molten iron is smelted, by C, Si, Mn, P, S, Al, V and Ti element in molten iron
Total content is controlled within 0.5%, while molten iron temperature is raised into more than 1700 DEG C；
C, will heat up after molten iron be hung in vacuum or atmosphere of inert gases, the ferrotianium trade mark needed for a steps gained titanium liquid is pressed will
The weight asked is poured into ladle, and molten iron and titanium liquid carried out into the mixing that liquidates, argon bottom-blowing, for argon intensity be 0.25~
1.0m3/ (mint), argon blowing time is 2~15min；Obtain ferro-titanium liquid；
D, ferro-titanium liquid is cast under vacuum or in atmosphere of inert gases, treat alloy cool to 100 DEG C and its
After below, ferro-titanium is carried out into crushing packing, obtain ferro-titanium；
The impurity content of the low impurity content ferrotianium<0.3%.
2. the production method of low impurity content ferrotianium according to claim 1, it is characterised in that：The titanium source for etc. off-lying sea
At least one in continuous titanium, titanium bits, titanium alloy bits, titanium wood shavings, titanium alloy wood shavings.
3. the production method of low impurity content ferrotianium according to claim 1, it is characterised in that：A steps are warmed up to 1690
~1700 DEG C, molten iron is warmed up to 1700~1720 DEG C by b step.
4. the production method of low impurity content ferrotianium according to claim 1, it is characterised in that：In a steps, using crucible
Stove or resistance furnace carry out the melting down of titanium source；In b step, using the equipment of decarburization, dephosphorization and desulfurization can be carried out to molten iron to iron
Water is smelted.
5. the production method of low impurity content ferrotianium according to claim 4, it is characterised in that：It is described molten iron to be entered
The equipment of row decarburization, dephosphorization and desulfurization is at least one in converter, electric furnace, LF stoves.
6. the production method of low impurity content ferrotianium according to claim 1, it is characterised in that：In step c, closed in ferrotianium
Other alloying components are added in gold, are used to obtain the ferro-titanium containing other alloying components, described other alloying components be chromium,
At least one in niobium, nickel.
7. the production method of low impurity content ferrotianium according to claim 1, it is characterised in that：Inert gas be helium,
Neon, argon gas, Krypton, xenon or radon gas.
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| CN105779820A (en) | 2016-07-20 |
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