Background technology: ferrotianium is the titaniferous that obtains through reduction or remelting at 20%~75% iron and titanium master alloy, wherein titaniferous 60%~75% be high ferrotianium.The titaniferous amount, and is widely used and pays close attention to because it has excellent use propertieies such as corrosion-resistant, high temperature resistant, wear-resisting, that proportion is suitable at 65%~75% high ferrotianium.High ferrotianium is the important raw and processed materials that smelting special steel, structure iron close special alloy, it is irreplaceable important raw and processed materials in Aeronautics and Astronautics, the weapon industry, and be widely used in military-civil industry such as oil, chemical industry, machinery, naval vessel, ocean, electric power, medical device, in social development, have more and more important position.For example, high ferrotianium is because its eutectic composition fusing point low (1085 ℃ are hanged down 342 ℃ than low ferrotianium), the proportion (5.4g/cm that suits
3), and the titaniferous height (in the molten iron add-on only be low ferrotianium 40%), foreign matter content is few, but save energy is used in steel-making, molten steel composition is even, reduced in segregation, the quality height of steel.
Tradition ferro-titanium preparation method adopts thermit reduction (promptly, perrin process) produces, this technology is that concentrated ilmenite powder and aluminium powder, ferrosilicon powder are mixed according to a certain percentage, then with the initiation reaction of magnesium powder and rely on id reaction heat to carry out redox and obtain the ferrotianium product.This technology is very successful for the low ferrotianium product of producing titaniferous 25%~45%.Exist the oxygen level height for preparation fine high ferrotianium, problem such as Al, Si etc. are wayward.
At present, the preparation method's major metal hot reducing method (being mainly thermit reduction) and the remelting process of high ferrotianium.Wherein, metallothermics is to be main raw material with the rutile, and metallic aluminium is main reductive agent, also adds CaO, CaF in the batching
2Deng being slag former, KClO
3Be heat-generating agent, batch mixing adopts local igniting to cause thermal reduction reaction, and the heat oneself of utilization reaction self keeps and carries out, and casting, slagging-off obtain the high ferrotitanium alloy ingot casting.These method raw material sources are wide, low price, and energy consumption is low, and production cost is low.This prepared gets high ferrotianium and gets main chemical compositions and be Ti65%~75%, Al≤5.0%, Si≤4.0%, C≤0.3%, 06%~12% for (quality %), because too high oxygen level, therefore do not satisfy customer need, the use of high ferrotianium is restricted.Remelting process is to be main raw material with useless titanium material, adds iron during batching, remelting in middle frequency furnace or medium-frequency induction furnace, and casting, the high ferrotitanium alloy ingot casting is prepared in slagging-off.Remelting process prepares high ferrotianium can control oxygen level in the alloy effectively, but its raw material sources are limited, and production cost is high, is difficult to meet the need of market.And the high ferrotianium of China's high-quality all is that cost is high from external import at present, has seriously restricted China's development of high-tech.
Summary of the invention: the invention provides a kind of method for preparing high-quality high ferrotianium based on thermite reduction-vacuum induction melting, its purpose is to solve the metal current hot reducing method because too high oxygen level, do not satisfy customer need, make the problem that use is restricted and aspects such as the remelting process raw material sources are few, production cost height exist of high ferrotianium.
The present invention is achieved through the following technical solutions:
A kind ofly prepare the method for high-quality high ferrotianium based on thermite reduction-vacuum induction melting, it is characterized in that: this method mainly comprises thermite reduction smelting, secondary blowing and vacuum induction melting stage two steps; Thermite reduction smelting stage batching wherein is as follows: rutile (or titanium slag): reductive agent: iron ore concentrate: slag former: KClO
3=1.0: 0.43~0.55: 0.01~0.08: 0.15~0.25: 0.20~0.25 mass percent batching, in vertical smelting furnace, smelting temperature is in 2200 ℃~2400 ℃ scopes; In the smelting process by the winding-up mouth metal magnesium powder of in high-temperature fusant, jetting, tap to tap time 10~30mins; The ferrotianium high-temperature fusant that obtains through the thermite reduction smelting stage, to directly be added to without the refrigerative high-temperature fusant then and carry out vacuum induction melting in the vacuum induction furnace, the batching in vacuum induction melting stage is as follows: the high ferrotianium high-temperature fusant that thermite reduction is smelted: reductive agent: slag former: Fe=1.0: 0.04~0.07: 0.15~0.25: 0.05~0.10 mass percent batching, in vacuum induction furnace, carry out vacuum melting, the temperature of vacuum melting is in 1350 ℃~1550 ℃ scopes, vacuum tightness is carried out under the vacuum condition of 4000~6000Pa, smelting time 10~40mins, after melting finishes, the superalloy melt is cooled off, play ingot, removal of impurities obtains high ferrotitanium alloy.
The stage is smelted in thermite reduction and the reductive agent of vacuum induction melting in the stage is complex reducing agent, and complex reducing agent consists of Al-5%~30%Mg alloy, Al-5%~15%Ca alloy.
The stage is smelted in thermite reduction and the slag former of vacuum induction melting in the stage is that matrix is CaO, with CaF
2, Li
2O, Na
2O, B
2O
3, BaO binary or the composite slag of polybasic formed, CaF
2Dosage is 10%~30% mass percent of CaO, Li
2O, Na
2O, B
2O
3, among the BaO one or more, addition is 10%~30% mass percent of CaO.
Can also add the metal Na of 3~8% mass percents, the alloy that Li forms in the complex reducing agent; And alloy block, alloy granule that complex reducing agent adopts non-powdered mixture to form.
This preparation technology at first will smelt the stage through thermite reduction, in smelting process, to spray magnesium and carry out drastic reduction, magnesium powder winding-up amount is 0.003~0.008% mass percent of rutile dosage, and it is high ferrotianium product below 5% that this stage can directly obtain oxygen level.
The high ferrotianium raw material in vacuum induction melting stage be form in the thermite reduction stage without refrigerative ferrotianium high-temperature fusant, need to have replenished iron powder or powdered iron ore in the vacuum melting process, magnitude of recruitment is high ferrotianium high-temperature fusant: Fe=1.0: 0.05~0.10 mass percent.
Rutile (or titanium slag) is TiO
2>88%, Si<5%, Al<5.5%, granularity is less than 40 purpose raw materials; Iron ore concentrate or powdered iron ore are ∑ Fe>65%, FeO<10.0%, SiO
2<8.0%, granularity is less than the raw material of 1mm; KClO
3Content greater than 99.0%, granularity is a heat-generating agent less than 1mm; The purity of complex reducing agent is greater than 98.0%, and granularity is a raw material less than 4mm; Slag former is CaO and CaF
2, Li
2O, Na
2O, B
2O
3, BaO binary or the polynary slag system formed, be industrial goods, purity is greater than 90.0%, granularity is less than the raw material of 1mm.
To remove organic impurity and moisture to 550 ℃~750 ℃ roastings of rutile (or titanium slag) before the batch mixing; Iron ore concentrate, slag former carry out ball milling, calcination process, guarantee its drying; Reductive agent, KClO
3Between 150 ℃~180 ℃, carry out drying treatment.
Use the conduit of liner magnesia material to be connected at the leakage fluid dram of vertical smelting furnace bottom with the vacuum charging storehouse of intermediate frequency vacuum induction furnace; In vacuum induction furnace, be lined with the magnesia layer with the plumbago crucible inwall.
The high ferrotitanium alloy chemical ingredients that makes is: Ti65%~75%, oxygen level is stable to be controlled at below 1%~2.0% Al≤2.0%, Si≤2.0%, C≤0.3%, P≤0.05%, S≤0.04%.
The inventive method is compared with the technology of the high ferrotianiums of preparation such as traditional thermite reduction, vacuum melting has great advance and advantage.At first, this inventive method is to be raw material with rutile (or titanium slag), iron ore concentrate, aluminium powder, it is wide to have raw material sources, advantages such as production cost is low, this point adds the iron remelting or vacuum melting technique is compared the progress with essence with traditional, traditional melting technology all is to be raw material with useless titanium material, and production cost is high, and the production cost of the inventive method is less than 1/2 of traditional remelting process; Secondly, this inventive method is in thermite reduction stage in smelting process or when smelt finishing, secondary winding-up MAGNESIUM METAL is carried out drastic reduction, compare with traditional thermite reduction technology and also to have obvious improvement, this stage also can directly obtain high ferrotitanium alloy, and its oxygen level is below 5.0%, and for some oxygen level being required is not extra high ferro-titanium, this preparation technology is very successful, and the high ferrotitanium alloy oxygen level of traditional thermit reduction preparation is all 10%~12%; Three, the raw material in vacuum melting stage is the high-temperature fusant in thermite reduction stage, compare with traditional vacuum melting, this technology energy consumption very low, only need boosting just passable; Four, the inventive method is in thermite reduction stage and vacuum melting stage, what reductive agent all adopted is complex reducing agent, also adopt winding-up magnesium to carry out drastic reduction in the thermite reduction stage, therefore oxygen level is effectively controlled, in the high ferrotitanium alloy of vacuum melting gained, oxygen level is lower than 1%~2%.In thermite reduction stage and vacuum melting stage, the slag system that is adopted all is composite slag, therefore oxide compound etc. is mingled with and defective such as pore is all thoroughly eliminated in the high ferrotitanium alloy, has guaranteed that also oxygen level is effectively controlled, and its Al, Si content are all below 2.0%; At last, the inventive method will be a raw material with rutile (or titanium slag), iron ore concentrate, aluminium powder, thermite reduction and vacuum melting two technologies are combined formed the short flow process novel process for preparing high ferrotianium based on thermite reduction-vacuum melting, have that flow process is short, production cost is low, energy consumption is low, the quality product advantages of higher, prepared high ferrotitanium alloy, oxygen level is lower than 1%~2%, Al, Si content are lower than 2.0%, and the product microtexture is even, fine and close.
Embodiment:
The present invention proposes a kind of novel process for preparing high ferrotianium, prepares the novel method of the high ferrotianium of hypoxemia based on thermite reduction-vacuum induction melting that is:.High ferrotianium titanium content Ti65%~75% of this method preparation, oxygen level is stable to be controlled at below 1%~2.0%, and Al≤2.0%, Si≤2.0%, C≤0.3%, P≤0.05%, S≤0.04% can be met consumers' demand well.
The inventive method is the same with production of high titanium iron by use of aluminothermy, the thermite reduction stage with rutile (or titanium slag) (TiO
2>88%, Si<5%, Al<5.5%, granularity is less than 40 orders), iron ore concentrate (∑ Fe>65%, FeO<10.0%, SiO
2<8.0%, granularity is less than 1mm) be raw material, KClO
3(content is greater than 99.0%, and granularity is less than 1mm) is heat-generating agent, and reductive agent is Al-5%~30%Mg, Al-5~15%Ca, also can add the metal Na below 5%, the complex reducing agent that Li forms, and wherein reductive agent purity is greater than 98.0%, and granularity is less than 4mm.And slag former is CaO and CaF
2, Li
2O, Na
2O, B
2O
3, BaO binary or the polynary slag system formed, be industrial goods, purity is greater than 90.0%, granularity is less than 1mm.
Thermite reduction smelting stage batching is as follows: rutile (or titanium slag): Al: iron ore concentrate: CaO: KClO
3=1.0: 0.43~0.55: 0.01~0.08: 0.15~0.25: 0.20~0.25 mass percent batching.Reductive agent Al is substituted by complex reducing agent in the actual batching, and complex reducing agent consists of Al-5%~30%Mg alloy, Al-5%~15%Ca alloy, wherein can also add the metal Na about 5%, the alloy that Li forms; CaO is substituted by composite slag in the actual batching, and it is CaO that composite slag is formed matrix, CaF
2Dosage is 10%~30% of CaO, Li
2O, Na
2O, B
2O
3, BaO total addition level be 10%~30% of CaO.
The batching in vacuum melting stage is as follows: the high ferrotianium that thermite reduction is smelted (O5.0% is following): Al: CaO: Fe=1.0: 0.04~0.07: 0.15~0.25: 0.05~0.10.Reductive agent Al is substituted by complex reducing agent in the actual batching, and complex reducing agent consists of Al-5%~30%Mg alloy, Al-5%~15%Ca alloy, wherein can also add the metal Na about 5%, the alloy that Li forms; CaO is substituted by composite slag in the actual batching, and it is CaO that composite slag is formed matrix, CaF
2Dosage is 10%~30% of CaO, Li
2O, Na
2O, B
2O
3, BaO total addition level be 10%~30% of CaO.
The inventive method prepares high ferrotitanium alloy and mainly comprises thermite reduction smelting, two stages of vacuum melting.
Fs, thermite reduction smelt stage
Concrete operations are: will remove organic impurity and moisture to 550 ℃~750 ℃ left and right sides roastings of rutile before the batch mixing; Iron ore concentrate, CaO carry out ball milling, calcination process, guarantee its drying; Al, KClO
3Between 150 ℃~180 ℃, carry out drying treatment.Press rutile: Al: iron ore concentrate: CaO: KClO
3(mass percent)=1.0: 0.43~0.55: 0.01~0.08: 0.15~0.25: 0.20~0.25 mass percent batching, batch mixing, (priming mixture is KClO to add priming mixture
3With the mixture of Mg, Mg/KClO
3Mol ratio is 3: 1), adopt bottom igniting, smelting, slagging.Reductive agent Al is substituted by complex reducing agent in the actual batching, and complex reducing agent consists of Al-5%~30%Mg alloy, Al-5%~15%Ca alloy, wherein can also add the metal Na about 5%, the alloy that Li forms; CaO is substituted by composite slag in the actual batching, and it is CaO that composite slag is formed matrix, CaF
2Dosage is 10%~30% of CaO, Li
2O, Na
2O, B
2O
3, BaO total addition level be 10%~30% of CaO.
Used smelting equipment is a shaft furnace, has winding-up mouth, leakage fluid dram and slag-drip opening, and wherein the winding-up mouth is in smelting process, and the MAGNESIUM METAL of jetting in high-temperature fusant is carried out drastic reduction to melt, fully reduces oxygen level in the high ferrotitanium alloy.This stage is effectively controlled the content of O, Si, Al etc. in order fully to remove being mingled with of alloy melt, and slag former is selected the compound slag of joining for use, promptly adds CaF at CaO
2, Li
2O, Na
2O, B
2O
3, among the BaO two or more, form composite slag, CaF
2Addition is 10%~30% of a CaO dosage, Li
2O, Na
2O, B
2O
3, the BaO addition is 10%~30% of CaO dosage, before batching, at first composite slag melting is handled by the certain ingredients composition requirement.
Subordinate phase, vacuum melting stage
Fs thermite reduction is smelted the ferro-titanium high-temperature fusant that obtains without cooling, directly join and carry out vacuum melting in the vacuum induction furnace.Concrete operations are: the leakage fluid dram of shaft furnace smelting furnace bottom is connected with the vacuum charging storehouse of intermediate frequency vacuum induction furnace with the conduit of liner magnesia material.After the aluminothermy melting finishes, open leakage fluid dram without cooling and directly the ferrotianium high-temperature fusant is joined in the crucible of vacuum induction furnace and carry out vacuum melting.In order further to remove oxygen and the Al in the high ferrotitanium alloy
2O
3Deng oxide inclusion, obtain hypoxemia high-performance ferro-titanium, in the vacuum melting process, need further to add the complex reducing agent of Al-Mg or Al-Ca alloy, in order to improve reducing degree, carry out degree of depth deoxidation, can also add minor N a, Li, Ba reductive agent at complex reducing agent.In order further to remove Al in the high ferrotitanium alloy
2O
3Deng being mingled with, to be still with CaO be matrix to slag former in the vacuum melting process, adds CaF
2, Li
2O, Na
2O, B
2O
3, the composite slag formed of BaO, before composite slag uses still the needs slag handle.The vacuum melting temperature is 1350 ℃~1550 ℃, and smelting time is 10mins~30mins.Vacuum casting, the cooling slagging-off obtains hypoxemia high ferrotitanium alloy ingot casting.In order to remedy iron loss in the melting, this stage need be allocated an amount of iron powder into, and also the available iron concentrate substitutes.
Because the thermite reduction stage carries out under open environment,, in smelting process, need cover one deck covering slag and protect at the high-temperature fusant liquid level in order to prevent oxygenation in smelting process.Because thermite reduction stage smelting temperature is between 2200 ℃~2400 ℃, vacuum melting is carried out under 1350 ℃~1550 ℃ vacuum conditions, and the component of complex reducing agent all has very strong volatility, vapour pressure is very high, therefore reduce when adding than theoretical value excessive 3%~6%, simultaneously reductive agent adopts each component component alloy piece, alloy granule, and without the powdered mixture of each component.Because the CaF in the composite slag
2, Li
2Components such as O have very strong volatility, and in order to guarantee to join the reliability of slag ingredient, before smelting and melting, at first carry out the melting slag and handle, be composite slag melting desired composition promptly.
The used crucible of traditional vacuum melting all is magnesia crucibles, and it is little to exist the crucible load, and heat-up rate is slow, and perhaps smelting temperature is not enough, causes the melting failure, and the energy consumption height.The inventive method adopts plumbago crucible in the vacuum melting process, and its load is big, and heat-up rate is fast.In order to prevent carburetting, be lined with the magnesia layer at the plumbago crucible inwall, so just can guarantee carrying out smoothly of fusion process, and energy loss is little.
The pre-treatment of embodiment 1 raw material is carried out according to summary of the invention is desired.According to rutile: Al-10%Mg: iron ore concentrate: CaO-30%CaF
2-10%Li
2O: KClO
3(mass percent)=1.0: 0.45: 0.03: 0.15: 0.20 mass percent batching, batch mixing, mixed material is added in the vertical smelting furnace, add KClO
3With the mixture of Mg powder be priming mixture, adopt bottom igniting initiation reaction, smelting, by the winding-up mouth metal magnesium powder of jetting in high-temperature fusant, magnesium powder winding-up amount is 0.005% of a rutile dosage, after reaction finishes 20mins in the smelting process, open the slag-drip opening slagging, cool off and remove furnace shell after 15 hours, cool off 2h again, play ingot, be cooled to normal temperature, obtain high ferrotitanium alloy.Its chemical ingredients % is: Ti, 73.4; Al, 2.1; Si, 2.2; C, 0.4; P, 0.05; S, 0.04; O, 4.8; Mn, 1.0.
Embodiment 2 raw materials pretreatment are carried out according to summary of the invention is desired.According to titanium slag: Al-5%Mg: iron ore concentrate: CaO-20%CaF
2-10%Na
2O: KClO
3(mass percent)=1.0: 0.48: 0.05: 0.18: 0.20 mass percent batching, batch mixing, mixed material is added in the vertical smelting furnace, add KClO
3With the mixture of Mg powder be priming mixture, adopt bottom igniting initiation reaction, smelting, by the winding-up mouth metal magnesium powder of jetting in high-temperature fusant, magnesium powder winding-up amount is 0.005% of a rutile dosage in the smelting process.
Open the leakage fluid dram of smelting furnace bottom, to directly be added in the special crucible of Reaktionsofen of vacuum pumping without the vacuum charging storehouse of refrigerative ferrotianium superalloy melt by induction furnace, the composite slag that to smelt then and complex reducing agent also are added in the special crucible of induction furnace by the vacuum feeding device of induction furnace, and composite slag is formed: CaO-20%CaF
2-10%Na
2O, reductive agent is formed: Al-5%Mg-2%Li, superalloy melt: complex reducing agent: composite slag: the Fe ratio of components is 1.0: 0.05: 0.20: 0.05.1350 ℃ of smelting temperatures, smelting time 30min, vacuum tightness is 5000Pa.Melting is cast to the superalloy melt in the copper crystallizer that has recirculated water cooling after finishing, and cooling plays ingot, removal of impurities, obtains high ferrotitanium alloy.Its chemical ingredients % is: Ti, 71.5; Al, 1.8; Si, 2.0; C, 0.3; P, 0.04; S, 0.04; O, 1.8; Mn, 0.8.
Embodiment 3 raw materials pretreatment are carried out according to summary of the invention is desired.According to rutile: Al-20%Mg-5%Li: iron ore concentrate: CaO-20%CaF
2-10%Na
2O: KClO
3(mass percent)=1.0: 0.50: 0.06: 0.20: 0.22 mass percent batching, batch mixing, mixed material is added in the vertical smelting furnace, add KClO
3With the mixture of Mg powder be priming mixture, adopt bottom igniting initiation reaction, smelting, by the winding-up mouth metal magnesium powder of jetting in high-temperature fusant, magnesium powder winding-up amount is 0.005% of a rutile dosage in the smelting process.
Open the leakage fluid dram of smelting furnace bottom, to directly be added in the special crucible of Reaktionsofen of vacuum pumping without the vacuum charging storehouse of refrigerative ferrotianium superalloy melt by induction furnace, the composite slag that to smelt then and complex reducing agent also are added in the special crucible of induction furnace by the vacuum feeding device of induction furnace, and composite slag is formed: CaO-30%CaF
2, reductive agent is formed: Al-20%Mg, superalloy melt: complex reducing agent: composite slag: the Fe ratio of components is 1.0: 0.06: 0.22: 0.08.1450 ℃ of smelting temperatures, smelting time 10min, vacuum tightness is 5000Pa.Melting is cast to the superalloy melt in the copper crystallizer that has recirculated water cooling after finishing, and cooling plays ingot, removal of impurities, obtains high ferrotitanium alloy.Its chemical ingredients % is: Ti, 70.7; Al, 1.5; Si, 1.8; C, 0.3; P, 0.03; S, 0.03; O, 1.2; Mn, 0.7.
Embodiment 4 raw materials pretreatment are carried out according to summary of the invention is desired.According to rutile: Al-30%Mg: iron ore concentrate: CaO-20%CaF
2-5%Na
2O-5%B
2O
3: KClO
3(mass percent)=1.0: 0.55: 0.08: 0.25: 0.25 mass percent batching, batch mixing, mixed material is added in the vertical smelting furnace, add KClO
3With the mixture of Mg powder be priming mixture, adopt bottom igniting initiation reaction, smelting, by the winding-up mouth metal magnesium powder of jetting in high-temperature fusant, magnesium powder winding-up amount is 0.005% of a rutile dosage in the smelting process.
Open the leakage fluid dram of smelting furnace bottom, to directly be added in the special crucible of Reaktionsofen of vacuum pumping without the vacuum charging storehouse of refrigerative ferrotianium superalloy melt by induction furnace, the composite slag that to smelt then and complex reducing agent also are added in the special crucible of induction furnace by the vacuum feeding device of induction furnace, and composite slag is formed: CaO-20%CaF
2-10%Na
2O, reductive agent is formed: Al-30%Mg, superalloy melt: complex reducing agent: composite slag: the Fe ratio of components is 1.0: 0.07: 0.25: 0.10.1550 ℃ of smelting temperatures, smelting time 15min, vacuum tightness is 5000Pa.Melting is cast to the superalloy melt in the copper crystallizer that has recirculated water cooling after finishing, and cooling plays ingot, removal of impurities, obtains high ferrotitanium alloy.Its chemical ingredients % is: Ti, 64.7; Al, 1.5; Si, 1.9; C, 0.3; P, 0.25; S, 0.03; O, 0.97; Mn, 0.9.