CN101457270A - Method and device for preparing high quality high ferrotitanium alloy based on aluminothermy reduction - Google Patents
Method and device for preparing high quality high ferrotitanium alloy based on aluminothermy reduction Download PDFInfo
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- CN101457270A CN101457270A CNA2008102302034A CN200810230203A CN101457270A CN 101457270 A CN101457270 A CN 101457270A CN A2008102302034 A CNA2008102302034 A CN A2008102302034A CN 200810230203 A CN200810230203 A CN 200810230203A CN 101457270 A CN101457270 A CN 101457270A
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Abstract
A method for preparing high-quality high ferrotitanium based on aluminothermic reduction and a device thereof belong to the technical field of metallurgy. The method comprises the following steps: (1) preheating an aluminothermic reducing agent into a liquid state; and ball milling and baking a titanium-containing substance, an iron-containing substance and a slagging medium, and then continuously adding an obtained mixture to a molten metal bath to perform high-temperature smelting; (2) blowing a particle reducing agent to perform smelting; and (3) cooling, obtaining ingot, removing impurities and obtaining the high-quality high ferrotitanium. The device comprises a charging device and a smelting device; the charging device comprises a charging hopper and a charging tube; and the smelting device comprises a resistance furnace, a magnesite bottom socket, a heat-resistant steel tube, a refractory material and a magnesite lining. The method has the advantages of short process, low production cost, low energy consumption, high product quality and the like, and the device has the advantages of simple structure, convenient operation and good application prospect.
Description
Technical field
The invention belongs to the alloy preparing technical field, particularly a kind of method and device for preparing high quality high ferrotitanium alloy based on thermite reduction.
Background technology
The reducing power of titanium is better than silicon and magnesium greatly, and is poorer than aluminium and zirconium, but that titanium has is low with respect to zirconium product fusing point, to advantage such as the reductibility of slag is strong.Titanium combines with other element as alloy and is used for steel-making, combine the welding quality and the erosion resistance that can improve steel with carbon in stainless steel and the high temperature steel, and the physical strength of raising steel also can be carried out degasification, desulfurization etc. to steel.Ferrotianium is mainly used in the steel-making as reductive agent and alloying element, and 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 because that it has is corrosion-resistant, high temperature resistant, wear-resisting, proportion is suitable etc. excellent use properties, and be widely used and pay close attention to.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.
Tradition ferro-titanium preparation method adopts the outer thermit reduction production of stove, and 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%.Be main raw material with the rutile when it prepares high ferrotianium, 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.This method exists the oxygen level height for the high ferrotianium of preparation fine, problems such as Al, Si etc. are wayward, do not satisfy customer need, the use of high ferrotianium is restricted, and its main chemical compositions is that (quality %) is Ti 65～75%, Al≤5.0%, Si＜4.0%, C≤0.3%, O 6～12%.And 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.
Thermit reduction obtains very big development in recent years.For example, adopt the outer thermit reduction of stove to make the quality better products, except that oxygen level, all the other compositions all reach the requirement of exported product.South Africa Mintek company adopts direct current to shift the high ferrotianium test of thermite reduction manufactured of plasma heating, reacts under heat insulation air, can reduce the nitrogen content of product, but can not effectively reduce the oxygen level of product.Production of high titanium iron by use of aluminothermy has obtained great development in China, and provinces such as Liaoning, Shandong and Guangxi have all set up the thermite process production line.But the high ferrotianium of the high-quality of China all is that cost is high from external import, has seriously restricted China's development of high-tech.
Summary of the invention
The invention provides that a kind of thermal reduction prepares the method and the device of high quality high ferrotitanium alloy based on liquid aluminium, its purpose is to solve present conventional aluminum hot reducing method too high oxygen level, the problem that the use of high ferrotianium is restricted, and problems such as the remelting process raw material sources are few, production cost height.
Method of the present invention may further comprise the steps:
1, reducing and smelting:
The thermite reduction agent is preheating to 650～850 ℃ is fused into liquid state, bath surface covering protection slag is in case oxidation; After titaniferous materials (rutile or titanium slag), iron compound (iron ore concentrate or powdered iron ore) and slag former mixed, ball milling to granularity less than 80 orders, roasting preheating to 800～1400 ℃ then; Mixture behind the roasting preheating is added continuously by feeding device in the metal pool of liquid aluminium thermal reduction agent formation, smelt 10～30min, obtain high-temperature fusant.
Wherein the ratio of components of titaniferous materials, iron compound, slag former and thermite reduction agent is a titaniferous materials by weight: iron compound: slag former: thermite reduction agent=1: 0.01～0.08: 0.15～0.25: 0.42～0.65.
The composition of titaniferous materials (rutile or titanium slag) is by weight percentage for containing TiO
288%, Si＜5%, Al＜5.5%; The granularity of titaniferous materials raw material is less than 40 orders.
The composition of iron compound (iron ore concentrate or powdered iron ore) is by weight percentage for containing ∑ Fe〉65%, FeO＜10.0%, SiO
2＜8.0%, the granularity of iron compound raw material is less than 1mm.
Slag former is matrix with CaO, by CaO and CaF
2, Li
2O, Na
2O, B
2O
3, the BaO binary or Recompounded multielement slag, the wherein CaF that form
2Weight percent is 10～30%; Li
2O, Na
2O, B
2O
3, one or more the weight percent among the BaO is 0～10%; The granularity of slag former is less than 1mm.
The thermite reduction agent is an Al base alloy, and Al base alloying constituent contains 0～8% Na or Li by weight percentage for to contain 5～50% Mg or Ca, and surplus is Al; Thermite reduction agent granularity is less than 4mm.
Covering slag is continuous casting covering slag or sodium aluminum fluoride.
2, spray refining:
The inner winding-up of high-temperature fusant particle reductive agent to the thermite reduction gained is strengthened reduction, and carrier gas is a rare gas element, and the winding-up amount accounts for 0.005～0.015% of titaniferous materials weight by the particle reductive agent, smelts 5～20min.
Wherein the particle reductive agent is thermite reduction agent or metal M g, CaB
6, (Ca content is 5～30wt%) or CaC to the SiCa alloy
2Deng reductive agent; Granularity is less than 4mm.
3, removal of impurities is handled:
Product after the spray refining plays ingot through overcooling, removes impurity, obtain high-quality high ferrotianium, its composition is by weight percentage for containing Ti65%～75%, O≤2%, Al≤4.0%, Si≤2.0%, C≤0.3%, P≤0.05%, S≤0.04%, surplus are Fe.
The inventive system comprises feeding device and smelting device, feeding device comprises feed hopper and filling tube, and smelting device comprises nest at the bottom of resistance furnace, the magnesia, heat resisting pipe, refractory materials and magnesite lining; Heat resisting pipe inner-wall spraying magnesite lining, and being fixed in the resistance furnace is provided with refractory materials between heat resisting pipe and the resistance furnace inwall, and the resistance furnace inner bottom part is provided with nest at the bottom of the magnesia, and the feed hopper bottom connects filling tube, and the other end of filling tube inserts heat resisting pipe inside.In nest place, heat resisting pipe sidewall or filling tube at the bottom of the magnesia, be provided with the winding-up pipe, winding-up pipe coupling blowing device.
Wherein heat resisting pipe can take out in resistance furnace, when winding-up smelt to finish and after overcooling, directly heat resisting pipe taken out, takes out the cast metals after the spray refining simultaneously.
Device using method of the present invention is:
Preheating thermite reduction agent in smelting device joins in the hot metal molten bath that liquid aluminium thermal reduction agent forms continuously by the mixture of feeding device after with roasting preheating, carries out reducing and smelting; By the winding-up pipe that the connects blowing device particle reductive agent of jet in high-temperature fusant, winding-up is smelted and is finished and after overcooling, directly with the heat resisting pipe taking-up, takes out the cast metals after the spray refining simultaneously.
When wherein adding mixture, filling tube inserts metal bath inside; During winding-up particle reductive agent, the winding-up mouth of winding-up pipe is positioned at high-temperature fusant inside.
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 (or powdered iron ore), 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 smelting process, carry out secondary winding-up reductive agent drastic reduction, compare with traditional thermite reduction technology and also to have obvious improvement, obtain the high ferrotitanium alloy oxygen level below 2.0%, and the high ferrotitanium alloy oxygen level of traditional thermit reduction preparation is all 10%～12%; The 3rd compares with vacuum melting technique, and the required energy consumption of this technology is low, only needs boosting just passable; Four, the reductive agent that is adopted in the inventive method thermite reduction process is a complex reducing agent, and the winding-up reductive agent carries out drastic reduction in the thermite reduction process, so oxygen level is effectively controlled, and the high ferrotitanium alloy oxygen level of gained is lower than 2%.The slag system that is adopted in the thermite reduction process all is composite slag, so 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 Al content is lower than 4.0%, Si content is below 2.0%; Five, owing to adopted boosting, reductive agent at first is preheating to liquid state, and rutile (or titanium slag), iron ore concentrate (or powdered iron ore), slag former etc. have also been carried out thermal pretreatment, and can effectively control the reaction system condition of high temperature, guarantee that metal and the effective of slag separate; Six, inert carrier gas is adopted in spray refining, the agitaion of winding-up carrier gas and high-temperature steam, and the sepn process of reinforced metal and slag has reached being mingled with of abundant removal alloy melt, effectively controls the purposes such as content of O, Si, Al etc.; Seven, compare with traditional thermit reduction, this inventive method does not need priming mixture to light, and has avoided the pollution that priming mixture caused; At last, the inventive method will be a raw material with rutile (or titanium slag), iron ore concentrate (or powdered iron ore), Al alloy powder, and handle at the thermite reduction process drastic reduction of jetting, formation prepares the short flow process novel method of high ferrotianium based on the thermite reduction single stage method, this method has 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 2%, Al content is lower than 4.0%, Si content is lower than 2.0%, and the product microtexture is even, fine and close.
It is of the present invention that thermal reduction prepares the method for high quality high ferrotitanium alloy based on liquid aluminium, titanium content is 65%～75% in the prepared high ferrotianium, oxygen level is stable to be controlled at below 2.0%, contain Al≤4.0%, Si≤2.0%, C≤0.3%, P≤0.05%, S≤0.04%, surplus is Fe, can meet consumers' demand well.Apparatus structure of the present invention is simple, and is easy to operate, has a good application prospect.
Description of drawings
Fig. 1 is for preparing high quality high ferrotitanium alloy device synoptic diagram based on thermite reduction in the embodiment of the invention, among the figure 1, filling tube, and 2, heat resisting pipe, 3, magnesite lining, 4, resistance furnace, 5, nest at the bottom of the magnesia, 6, the sleeve pipe lifting and fixing device, 7, feed hopper.
Embodiment
The slag former that adopts in the embodiment of the invention is by CaO and CaF
2, Li
2O, Na
2O, B
2O
3, the BaO binary or Recompounded multielement slag, the wherein CaF that form
2Weight percent is 10～30%; Li
2O, Na
2O, B
2O
3, one or more the weight percent among the BaO is 0～10%; Granularity is less than 1mm; Above material is industrial goods, and purity is greater than 90.0%.
The particle reductive agent that adopts in the embodiment of the invention is thermite reduction agent (Al base alloy) or metal M g, CaB
6, (Ca content is 5～30wt%) or CaC to the SiCa alloy
2Deng reductive agent, granularity is less than 4mm; Above feed purity is greater than 98%.
The titaniferous materials that adopts in the embodiment of the invention is rutile or titanium slag, and composition is by weight percentage for containing TiO
288%, Si＜5%, Al＜5.5%; Granularity is less than 40 orders.
The iron compound that adopts in the embodiment of the invention is iron ore concentrate or powdered iron ore, and composition is by weight percentage for containing ∑ Fe〉65%, FeO＜10.0%, SiO
2＜8.0%, granularity is less than 1mm.
The rare gas element that adopts when jetting the particle reductive agent in the embodiment of the invention is an argon gas.
The refractory materials that adopts in the embodiment of the invention is a magnesite refractory, and refractoriness is greater than 1800 ℃.
The covering slag that adopts in the embodiment of the invention is industrial continuous casting covering slag or sodium aluminum fluoride.
It below is the preferred embodiment of the present invention.
Prepare the high quality high ferrotitanium alloy device as shown in Figure 1 based on thermite reduction, this device comprises feeding device and smelting device, feeding device comprises feed hopper 7 and filling tube 1, and smelting device comprises nest 5 at the bottom of resistance furnace 4, the magnesia, heat resisting pipe 2 and magnesite lining 3; Feeding device sleeved lifting and fixing device 6, the height of feeding device can be regulated by sleeve pipe lifting and fixing device 6.
Heat resisting pipe 2 inner-wall sprayings have magnesite lining 3, and be fixed in the resistance furnace 4, being provided with refractory materials between heat resisting pipe 2 and resistance furnace 4 inwalls, the bottoms in the resistance furnace 4 are provided with nest 5 at the bottom of the magnesia, feed hopper 7 bottoms connect filling tube 1, and the other end of filling tube 1 inserts heat resisting pipe 2 inside; Be provided with the winding-up pipe in the filling tube, winding-up pipe coupling blowing device.Winding-up mouth during use on filling tube bottom and the winding-up pipe is positioned at the inside of resistance furnace metal pool.
By sleeve pipe lifting device 6 feeding device is risen before feeding in raw material, by sleeve pipe lifting device 6 feeding device is descended when needing to feed in raw material, make filling tube 1 be inserted into metal bath inside.
Adopt said apparatus, the thermite reduction agent is preheating to 650 ℃ is fused into liquid state, form metal pool, the thermite reduction agent is an Al base alloy, contains Mg10wt%; At thermite reduction agent surface coverage one deck covering slag; With rutile, iron ore concentrate and slag former mixing and ball milling to granularity less than 80 orders, be preheating to 800 ℃ then, join the metal bath that liquid aluminium thermal reduction agent forms by feeding device, wherein the slag former composition is by weight percentage for containing Li
2O8% contains CaF
230%, surplus is CaO; Charging capacity is a rutile by weight: iron ore concentrate: slag former: thermite reduction agent=1.0: 0.03: 0.15: 0.42; Smelt 10min after reinforced the finishing.
By the metal magnesium powder of in resistance furnace, jetting in the metal pool of the winding-up pipe in the filling tube, carrier gas is an argon gas, the winding-up amount accounts for the 0.005wt% of rutile total amount by metal magnesium powder, continue to smelt 20min, behind the cooling 15h heat resisting pipe is taken out, take out the cast metals after the spray refining simultaneously, remove the impurity on the cast metals, be cooled to room temperature and obtain high ferrotitanium alloy, its composition is by weight percentage for containing Ti73.5%, Al3.1%, Si2.0%, C0.3%, P0.05%, S0.04%, O2.0%, Mn1.0%, surplus is Fe.
The device that adopts is with embodiment 1.
The thermite reduction agent is preheating to 700 ℃ is fused into liquid state, form metal pool, the thermite reduction agent is an Al base alloy, contains Mg5wt%; At thermite reduction agent surface coverage one deck covering slag; With rutile, iron ore concentrate and slag former mixing and ball milling to granularity less than 80 orders, be preheating to 900 ℃ then, join the metal bath that liquid aluminium thermal reduction agent forms by feeding device, wherein the slag former composition is by weight percentage for containing Na
2O 10%, contains CaF
220%, surplus is CaO; Charging capacity is a rutile by weight: iron ore concentrate: slag former: thermite reduction agent=1.0: 0.05: 0.18: 0.48; Smelt 30min after reinforced the finishing.
By the CaB6 that in resistance furnace, jets in the metal pool of the winding-up pipe in the filling tube
,Carrier gas is an argon gas, and the winding-up amount is pressed CaB
6Account for the 0.006wt% of rutile total amount, continue to smelt 10min, behind the cooling 15h heat resisting pipe is taken out, take out the cast metals after the spray refining simultaneously, remove the impurity on the cast metals, be cooled to room temperature and obtain high ferrotitanium alloy, its composition is by weight percentage for containing Ti71.5%, Al1.8%, Si1.8%, C0.3%, P0.04%, S0.04%, O1.2%, Mn0.8%, surplus is Fe.
The device that adopts is with embodiment 1.
The thermite reduction agent is preheating to 800 ℃ is fused into liquid state, form metal pool, the thermite reduction agent is an Al base alloy, contains Mg20wt%, Li5wt%; At thermite reduction agent surface coverage one deck covering slag; With rutile, iron ore concentrate and slag former mixing and ball milling to granularity less than 80 orders, be preheating to 1200 ℃ then, join the metal bath that liquid aluminium thermal reduction agent forms by feeding device, wherein the slag former composition is by weight percentage for containing Na
2O 10%, contains CaF
220%, surplus is CaO; Charging capacity is a rutile by weight: iron ore concentrate: slag former: thermite reduction agent=1.0: 0.06: 0.20: 0.50; Smelt 20min after reinforced the finishing.
By the CaB that in resistance furnace, jets in the metal pool of the winding-up pipe in the filling tube
6, carrier gas is an argon gas, the winding-up amount is pressed CaB
6Account for the 0.008wt% of rutile total amount, continue to smelt 10min, behind the cooling 15h heat resisting pipe is taken out, take out the cast metals after the spray refining simultaneously, remove the impurity on the cast metals, be cooled to room temperature and obtain high ferrotitanium alloy, its composition is by weight percentage for containing Ti70.3%, Al1.7%, Si1.9%, C0.3%, P0.04%, S0.04%, O1.0%, Mn0.5%, surplus is Fe.
The device that adopts is with embodiment 1.
The thermite reduction agent is preheating to 850 ℃ is fused into liquid state, form metal pool, the thermite reduction agent is an Al base alloy, contains Mg50wt%; At thermite reduction agent surface coverage one deck covering slag; With rutile, iron ore concentrate and slag former mixing and ball milling to granularity less than 80 orders, be preheating to 1400 ℃ then, join the metal bath that liquid aluminium thermal reduction agent forms by feeding device, wherein the slag former composition is by weight percentage for containing Na
2O 5%, contains CaF
230%, surplus is CaO; Charging capacity is a rutile by weight: iron ore concentrate: slag former: thermite reduction agent=1.0: 0.08: 0.25: 0.62; Smelt 20min after reinforced the finishing.
By SiCa (the containing Ca30wt%) alloy of in resistance furnace, jetting in the metal pool of the winding-up pipe in the filling tube, carrier gas is an argon gas, the winding-up amount accounts for the 0.013wt% of rutile total amount by the SiCa alloy, continue to smelt 10min, behind the cooling 15h heat resisting pipe is taken out, take out the cast metals after the spray refining simultaneously, remove the impurity on the cast metals, be cooled to room temperature and obtain high ferrotitanium alloy, its composition is by weight percentage for containing Ti70.7%, Al1.5%, Si1.5%, C0.3%, P0.05%, S0.03%, O1.2%, Mn0.7%, surplus is Fe.
The device that adopts is with embodiment 1.
The thermite reduction agent is preheating to 650 ℃ is fused into liquid state, form metal pool, the thermite reduction agent is an Al base alloy, contains Ca5wt%; At thermite reduction agent surface coverage one deck covering slag; With rutile, iron ore concentrate and slag former mixing and ball milling to granularity less than 80 orders, be preheating to 800 ℃ then, join the metal bath that liquid aluminium thermal reduction agent forms by feeding device, wherein the slag former composition is by weight percentage for containing Li
2O 8%, contains CaF
230%, surplus is CaO; Charging capacity is a rutile by weight: iron ore concentrate: slag former: thermite reduction agent=1.0: 0.03: 0.15: 0.45; Smelt 10min after reinforced the finishing.
By the metal magnesium powder of in resistance furnace, jetting in the metal pool of the winding-up pipe in the filling tube, carrier gas is an argon gas, the winding-up amount accounts for the 0.005wt% of rutile total amount by metal magnesium powder, continue to smelt 20min, behind the cooling 15h heat resisting pipe is taken out, take out the cast metals after the spray refining simultaneously, remove the impurity on the cast metals, be cooled to room temperature and obtain high ferrotitanium alloy, its composition is by weight percentage for containing Ti73.5%, Al3.0%, Si1.3%, C0.4%, P0.05%, S0.04%, O1.9%, Mn0.9%, surplus is Fe.
The device that adopts is with embodiment 1.
The thermite reduction agent is preheating to 700 ℃ is fused into liquid state, form metal pool, the thermite reduction agent is an Al base alloy, contains Ca10wt%; At thermite reduction agent surface coverage one deck covering slag; With rutile, iron ore concentrate and slag former mixing and ball milling to granularity less than 80 orders, be preheating to 900 ℃ then, join the metal bath that liquid aluminium thermal reduction agent forms by feeding device, wherein the slag former composition is by weight percentage for containing Na
2O 10%, contains CaF
220%, surplus is CaO; Charging capacity is a rutile by weight: iron ore concentrate: slag former: thermite reduction agent=1.0: 0.05: 0.18: 0.50; Smelt 30min after reinforced the finishing.
By the CaB that in resistance furnace, jets in the metal pool of the winding-up pipe in the filling tube
6, carrier gas is an argon gas, the winding-up amount is pressed CaB
6Account for the 0.007wt% of rutile total amount, continue to smelt 10min, behind the cooling 15h heat resisting pipe is taken out, take out the cast metals after the spray refining simultaneously, remove the impurity on the cast metals, be cooled to room temperature and obtain high ferrotitanium alloy, its composition is by weight percentage for containing Ti72.2%, Al2.5%, Si1.8%, C0.3%, P0.04%, S0.04%, O0.9%, Mn0.9%, surplus is Fe.
Embodiment 7
The device that adopts is with embodiment 1.
The thermite reduction agent is preheating to 800 ℃ is fused into liquid state, form metal pool, the thermite reduction agent is an Al base alloy, contains Ca20wt%, Li5wt%; At thermite reduction agent surface coverage one deck covering slag; With rutile, iron ore concentrate and slag former mixing and ball milling to granularity less than 80 orders, be preheating to 800 ℃ then, join the metal bath that liquid aluminium thermal reduction agent forms by feeding device, wherein the slag former composition is by weight percentage for containing Na
2O 10%, contains CaF
220%, surplus is CaO; Charging capacity is a rutile by weight: iron ore concentrate: slag former: thermite reduction agent=1.0: 0.06: 0.20: 0.55; Smelt 20min after reinforced the finishing.
By SiCa (the containing Ca30wt%) alloy of in resistance furnace, jetting in the metal pool of the winding-up pipe in the filling tube, carrier gas is an argon gas, the winding-up amount accounts for the 0.010wt% of rutile total amount by the SiCa alloy, continue to smelt 10min, behind the cooling 15h heat resisting pipe is taken out, take out the cast metals after the spray refining simultaneously, remove the impurity on the cast metals, be cooled to room temperature and obtain high ferrotitanium alloy, its composition is by weight percentage for containing Ti71.5%, Al1.8%, Sil.6%, C0.3%, P0.04%, S0.04%, O0.9%, Mn0.5%, surplus is Fe.
Embodiment 8
The device that adopts is with embodiment 1.
The thermite reduction agent is preheating to 850 ℃ is fused into liquid state, form metal pool, the thermite reduction agent is an Al base alloy, contains Ca50wt%; At thermite reduction agent surface coverage one deck covering slag; With rutile, iron ore concentrate and slag former mixing and ball milling to granularity less than 80 orders, be preheating to 1400 ℃ then, join the metal bath that liquid aluminium thermal reduction agent forms by feeding device, wherein the slag former composition is by weight percentage for containing Na
2O 5%, contains CaF
230%, surplus is CaO; Charging capacity is a rutile by weight: iron ore concentrate: slag former: thermite reduction agent=1.0: 0.08: 0.25: 0.65; Smelt 20min after reinforced the finishing.
By the CaB that in resistance furnace, jets in the metal pool of the winding-up pipe in the filling tube
6, carrier gas is an argon gas, the winding-up amount is pressed CaB
6Account for the 0.015wt% of rutile total amount, continue to smelt 10min, behind the cooling 15h heat resisting pipe is taken out, take out the cast metals after the spray refining simultaneously, remove the impurity on the cast metals, be cooled to room temperature and obtain high ferrotitanium alloy, its composition is by weight percentage for containing Ti70.2%, Al1.4%, Si1.5%, C0.3%, P0.05%, S0.03%, O0.6%, Mn0.7%, surplus is Fe.
Embodiment 9
The device that adopts is with embodiment 1.
The thermite reduction agent is preheating to 650 ℃ is fused into liquid state, form metal pool, the thermite reduction agent is an Al base alloy, contains Ca40wt%, Na5wt%; At thermite reduction agent surface coverage one deck covering slag; With titanium slag, powdered iron ore and slag former mixing and ball milling to granularity less than 80 orders, be preheating to 900 ℃ then, join the metal bath that liquid aluminium thermal reduction agent forms by feeding device, wherein the slag former composition is by weight percentage for containing B
2O
35%, contain CaF
225%, surplus is CaO; Charging capacity is a titanium slag by weight: powdered iron ore: slag former: thermite reduction agent=1.0: 0.02: 0.18: 0.65; Smelt 10min after reinforced the finishing.
By the CaC that in resistance furnace, jets in the metal pool of the winding-up pipe in the filling tube
2, carrier gas is an argon gas, the winding-up amount is pressed CaC
2Account for the 0.015wt% of titanium slag total amount, continue to smelt 15min, behind the cooling 15h heat resisting pipe is taken out, take out the cast metals after the spray refining simultaneously, remove the impurity on the cast metals, be cooled to room temperature and obtain high ferrotitanium alloy, its composition is by weight percentage for containing Ti69.5%, Al1.9%, Si1.3%, C0.2%, P0.04%, S0.02%, O1.1%, Mn0.8%, surplus is Fe.
Embodiment 10
The device that adopts is with embodiment 1.
The thermite reduction agent is preheating to 700 ℃ is fused into liquid state, form metal pool, the thermite reduction agent is an Al base alloy, contains Ca30wt%, Na5wt%; At thermite reduction agent surface coverage one deck covering slag; With titanium slag, powdered iron ore and slag former mixing and ball milling to granularity less than 80 orders, be preheating to 1000 ℃ then, join the metal bath that liquid aluminium thermal reduction agent forms by feeding device, wherein the slag former composition for containing BaO5%, contains CaF by weight percentage
220%, surplus is CaO; Charging capacity is a titanium slag by weight: powdered iron ore: slag former: thermite reduction agent=1.0: 0.01: 0.15: 0.50; Smelt 20min after reinforced the finishing.
By the CaC that in resistance furnace, jets in the metal pool of the winding-up pipe in the filling tube
2, carrier gas is an argon gas, the winding-up amount is pressed CaC
2Account for the 0.012wt% of titanium slag total amount, continue to smelt 20min, behind the cooling 15h heat resisting pipe is taken out, take out the cast metals after the spray refining simultaneously, remove the impurity on the cast metals, be cooled to room temperature and obtain high ferrotitanium alloy, its composition is by weight percentage for containing Ti67.6%, Al1.7%, Si1.8%, C0.3%, P0.03%, S0.04%, O0.9%, Mn1.0%, surplus is Fe.
Embodiment 11
The device that adopts is with embodiment 1.
The thermite reduction agent is preheating to 850 ℃ is fused into liquid state, form metal pool, the thermite reduction agent is an Al base alloy, contains Ca25wt%, Na10wt%; At thermite reduction agent surface coverage one deck covering slag; With titanium slag, powdered iron ore and slag former mixing and ball milling to granularity less than 80 orders, be preheating to 1400 ℃ then, join the metal bath that liquid aluminium thermal reduction agent forms by feeding device, wherein the slag former composition is by weight percentage for containing CaF
215%, surplus is CaO; Charging capacity is a titanium slag by weight: powdered iron ore: slag former: thermite reduction agent=1.0: 0.01: 0.25: 0.60; Smelt 30min after reinforced the finishing.
By SiCa (the containing Ca5wt%) alloy of in resistance furnace, jetting in the metal pool of the winding-up pipe in the filling tube, carrier gas is an argon gas, the winding-up amount accounts for the 0.009wt% of titanium slag total amount by the SiCa alloy, continue to smelt 10min, behind the cooling 15h heat resisting pipe is taken out, take out the cast metals after the spray refining simultaneously, remove the impurity on the cast metals, be cooled to room temperature and obtain high ferrotitanium alloy, its composition is by weight percentage for containing Ti68.3%, Al1.7%, Si1.7%, C0.2%, P0.04%, S0.02%, O1.1%, Mn0.7%, surplus is Fe.
Claims (8)
1, a kind ofly prepare the method for high quality high ferrotitanium alloy based on thermite reduction, it is characterized in that carrying out according to the following steps: (1) is preheating to 650～850 ℃ with the thermite reduction agent and is fused into liquid state, and the surface coverage covering slag is in case oxidation; With titaniferous materials, iron compound and slag former ball milling to granularity less than 80 orders, roasting preheating to 800～1400 ℃ then; Material behind the roasting preheating is joined in the liquid aluminium thermal reduction agent continuously, the ratio of components of add-on is a titaniferous materials by weight: iron compound: slag former: thermite reduction agent=1: 0.01～0.08: 0.15～0.25: 0.42～0.65, smelt 10～30min, obtain high-temperature fusant; Wherein titaniferous materials is rutile or titanium slag, and iron compound is iron ore concentrate or powdered iron ore; (2) strengthen reduction to the inner winding-up of high-temperature fusant particle reductive agent, carrier gas is a rare gas element, the winding-up amount account for by the particle reductive agent titaniferous materials weight 0.005～0.015%, smelt 5～20min; (3) product after the spray refining plays ingot through overcooling, removes impurity, obtains high-quality high ferrotianium product.
2, a kind of method for preparing high quality high ferrotitanium alloy based on thermite reduction according to claim 1, it is characterized in that described thermite reduction agent is an Al base alloy, this alloying constituent for containing Mg or Ca5～50%, contains Na or Li0～8% by weight percentage, and surplus is Al.
3, according to claim 1ly a kind ofly prepare the method for high quality high ferrotitanium alloy, it is characterized in that described slag former is is matrix with CaO, with CaF based on thermite reduction
2, Li
2O, Na
2O, B
2O
3, BaO binary or the Recompounded multielement slag formed, by weight percentage for containing CaF
210～30%, Li
2O, Na
2O, B
2O
3, among the BaO one or more are 0～10%; Surplus is CaO.
4, according to claim 1ly a kind ofly prepare the method for high quality high ferrotitanium alloy, it is characterized in that described particle reductive agent is metal M g, CaB based on thermite reduction
6, SiCa alloy, CaC
2Or the thermite reduction agent, wherein Ca content is 5～30% by weight percentage in the SiCa alloy.
5, a kind of method for preparing high quality high ferrotitanium alloy based on thermite reduction according to claim 1, the composition that it is characterized in that described high-quality high ferrotianium is Ti65～75% by weight percentage, O≤2%, Al≤4.0%, Si≤2.0%, C≤0.3%, P≤0.05%, S≤0.04%, surplus are Fe.
6, according to claim 1ly a kind ofly prepare the method for high quality high ferrotitanium alloy based on thermite reduction, the composition that it is characterized in that described rutile or titanium slag is by weight percentage for containing TiO
288%, Si＜5%, Al＜5.5%; The composition of iron ore concentrate or powdered iron ore is by weight percentage for containing ∑ Fe〉65%, FeO＜10.0%, SiO
2＜8.0%.
7, a kind of thermal reduction prepares the device of high quality high ferrotitanium alloy based on liquid aluminium, and it is characterized in that: this device comprises feeding device and smelting device, and feeding device comprises feed hopper and filling tube; Smelting device comprises nest at the bottom of resistance furnace, the magnesia, heat resisting pipe, refractory materials and magnesite lining; Heat resisting pipe inner-wall spraying magnesite lining wherein, and be fixed in the resistance furnace, being provided with refractory materials between heat resisting pipe and the resistance furnace inwall, the resistance furnace inner bottom part is provided with nest at the bottom of the magnesia, the feed hopper bottom connects filling tube, and the other end of filling tube inserts heat resisting pipe inside; In nest place, heat resisting pipe sidewall or filling tube at the bottom of the magnesia, be provided with the winding-up pipe.
8, according to claim 7 a kind of thermal reduction prepares the device of high quality high ferrotitanium alloy based on liquid aluminium, it is characterized in that described heat resisting pipe can take out in resistance furnace.
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Application publication date: 20090617 Assignee: SHANDONG ZIBO FUSHAN ENTERPRISE GROUP CO., LTD. Assignor: Northeastern University Contract record no.: 2017210000007 Denomination of invention: Method and device for preparing high quality high ferrotitanium alloy based on aluminothermy reduction Granted publication date: 20101201 License type: Exclusive License Record date: 20170328 |