CN1888101A - Direct titanium alloy producing process with titanium containing mineral - Google Patents
Direct titanium alloy producing process with titanium containing mineral Download PDFInfo
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- CN1888101A CN1888101A CN 200610089788 CN200610089788A CN1888101A CN 1888101 A CN1888101 A CN 1888101A CN 200610089788 CN200610089788 CN 200610089788 CN 200610089788 A CN200610089788 A CN 200610089788A CN 1888101 A CN1888101 A CN 1888101A
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Abstract
The present invention is direct titanium alloy producing process with titanium containing mineral and belongs to the field of metal titanium smelting technology. The production process includes: arc furnace melting titanium-containing mineral with added reductant to obtain high titanium slag; setting the high titanium slag, rutile or titanium white into plasma high temperature furnace and introducing argon as plasma gas source and electrolytic aluminum to reduce titania to obtain Ti-Al alloy mother liquid, adding slagging agent with the calcium fluoride to adsorb produced alumina to obtain solid crude Ti-Al alloy; making the crude Ti-Al alloy with deoxidant into consumable electrode and electroslag remelting in a vacuum electric furnace to obtain Ti-Al alloy product with oxygen content of 0.05-0.15 wt%. Compared with traditional process, the process of the present invention has short production period, low production cost, less environmental pollution and other advantages.
Description
One, technical field
The invention belongs to the metal titanium field of metallurgy, relate to a kind of method of utilizing titaniferous ore direct Preparation of Titanium and titanium alloy.
Two, technical background
Titanium is a kind of important structural metal that grows up the fifties, titanium alloy because of have the intensity height, characteristics such as density is little, solidity to corrosion good, thermotolerance height, be good 26S Proteasome Structure and Function material, be widely used in fields such as aerospace, medicine equipment, chemical industry equipment, military project and sports equipment.Many in the world countries all recognize the importance of titanium alloy material, in succession it are researched and developed, and have obtained practical application, if can change the production technique of present titanium sponge, expectation 21 century titanium and titanium alloy will be greatly developed.
The production of titanium alloy derives from melting of metal such as titanium sponge and smelts and form, yet, adopt magnesium reduction process (Kroll method) to produce titanium sponge at present.At first handle ilmenite and obtain TiO
2The titanium slag that content is high is sent rich titanium material (titanium slag, rutile) and refinery coke into the fluidization fluidizing furnace then, obtains thick TiCl after the chlorination
4, the back adopts chemical method and rectification method to purify removal impurity must make with extra care TiCl
4, use magnesium reduction process (Kroll method) to obtain titanium sponge again, adopt alloying process to be made into titanium alloy then.Kroll method flow process is: under argon shield, and smart TiCl
4With Mg at the steel container internal reaction of 800～900 ℃ of temperature 3～5 days, most of by product MgCl
2And excessive Mg separates from reactor, but reduzate still contains a small amount of Mg and MgCl
2, need to remove the MgCl of recovery with vacuum distillation method or pickling process
2Electrolytic regeneration Mg and Cl
2, recycle.Although both at home and abroad the Kroll method has been carried out perfect,, do not have the Kroll method technology of radical change 1948 exploitation, have long flow path, operation is many, cost is high, productivity is low, thereby limited the use range of titanium alloy.For seeking the production technique of new low cost titanium, all done number of research projects both at home and abroad, TiCl is arranged
4Fused salt electrolysis process, TiO
2Methods such as direct electrolysis method, flowing-type gas phase continuous processing, liquid high temperature and high pressure method, hydrogen carbon and other reduction method, wherein TiCl
4Fused salt electrolysis process is once near suitability for industrialized production, but still can't replace existing magnesium reduction, and additive method all is in laboratory scale, move towards the industrialization also to face many technical barriers.
Present most widely used titanium alloy is the Ti-6Al-4V alloy, because its thermotolerance, intensity, plasticity, toughness, plasticity, weldability, solidity to corrosion and biocompatibility are all better, and becoming trump alloy in the titanium alloy industry, this alloy usage quantity has accounted for 75%～85% of whole titanium alloys.Other many titanium alloys can be regarded the remodeling of Ti-6Al-4V alloy as.
According to the great strategic value of titanium and the status in the national economy, 1,000,000 tons of the global annual production should exceeds of metal titanium are more reasonable, and just about 100,000 tons of in fact present world annual production, main Japan, USSR (Union of Soviet Socialist Republics), the U.S. and the China of concentrating.Major cause is that process complexity, the technical process of the extraction metal titanium of employing at present is long, productivity is extremely low, causes the processing of titanium and production cost too high, has greatly limited the range of application of metal titanium and alloy thereof.
The present invention is directed to the problems referred to above, work out the simple economic again production titanium of a kind of technology and the novel method of titanium alloy thereof.This method is used for plasma high-temperature metallurgy the production of titanium alloy; under the high temperature argon protection; with metallic aluminium reduction-oxidation titanium; the aluminum oxide that generates is by the Calcium Fluoride (Fluorspan) fractionation by adsorption of slag; and break through the thinking of traditional " first refining pure metal, alloying is carried out in fusing again ", a kind of novel process of directly smelting titanium aluminum alloy (Ti:70%～85%, Al:10%～30%, O:0.5%～3%) without pure titanium (titanium sponge) refinement operation is proposed.The present invention compares with traditional method owing to do not use chlorine and titanium tetrachloride, shortens production technique significantly, reduces production costs, reduces advantages such as environmental pollution and broadened application scope.
Three, summary of the invention
A kind of method of directly producing the metal titanium or titanium alloy from titaniferous ore is a raw material with the titaniferous ore, and the adding reductive agent carries out the arc melting deironing and makes titanium slag (TiO
2: Fe 92%～99%,
2O
3: 0.5%～2.5%), with above-mentioned titanium slag, or rutile (TiO
2: 95%～99%), or titanium white (TiO
2: Al 90%～99.99%,
2O
3: 0.00%～10.00%) in the plasma high-temperature stove, with argon gas as plasma body work source of the gas, add electrolytic aluminum (Al:99.99%) reduction-oxidation titanium, obtain titanium aluminum alloy mother liquor (Ti:70%～85%, Al:10%～30%, O:0.5%～3%), the aluminum oxide that generates is by the Calcium Fluoride (Fluorspan) fractionation by adsorption of slag, add in the slag former in the plasma high-temperature stove and contain Calcium Fluoride (Fluorspan), its addition is 1%～10% of a titanium oxide, the solid titanium aluminium alloy parent that obtains, allocate the reductor of 10%-15% into, be processed into consumable electrode, through esr system, can obtain oxygen level is the titanium aluminum alloy finished product of 0.05%-0.15% in vacuum electric furnace.
Overall craft flow process of the present invention as shown in Figure 1.
The main chemical reactions that takes place in the technological process is:
Reaction (1) is carried out in ore-smelting furnace, reduces titaniferous ore with refinery coke, and ferriferous oxide is reduced to metallic iron, and titanium oxide can be enriched in the slag by carbon reduction, since bigger with the specific gravity difference of iron liquid, thus separate easily, and obtain titanium slag.
Reaction (2) is finished in plasma furnace, and the device synoptic diagram as shown in Figure 2.With titanium oxide, titanium slag (TiO for example
2: Fe 92%～99%,
2O
3: 0.5%～2.5%), or rutile (TiO
2: 95%～99%), or titanium white (TiO
2: Al 90%～99.99%,
2O
3: 0.00%～10.00%), electrolytic aluminum (Al:99.99%) and the slag former thorough mixing that contains CaF, CaO, adopt the transferred-arc plasma heating,, make TiO by mixing in the body of heater that feeding device adds inert atmosphere
2Fully react the Al in the reaction product isolated with Al
2O
3, obtain titanium aluminum alloy.Because reaction (2) is strong exothermic process, has reduced the energy consumption of whole production technology significantly.
The method of employing esr is removed the impurity element in the titanium aluminum alloy, obtains the titanium alloy finished product.Fig. 3 is the esr schematic representation of apparatus.The titanium aluminum alloy that will react (2) generation is as sacrificial electrode, after connecting power supply, in slag bath, form powerful electric current, the heat that produces raises the slag temperature, when the slag temperature surpasses the titanium aluminum alloy fusing point, electrode is melted, the alloy of fusing passes slag bath from electrode surface by gravity with the form of drop, in this course, slag bath absorbs harmful element in the metallic substance and inclusion, titanium aluminum alloy after the purification converges into the molten bath in the slag bath bottom, can form the titanium aluminum alloy finished product after the cooled and solidified.
Another one characteristics of the present invention are: the plasma high-temperature technology is applied to electrolytic aluminum reduction-oxidation titanium prepares titanium and titanium aluminum alloy, avoided in traditional electric furnace smelting process Graphite Electrodes that the pollution of metal melt is guaranteed not form in the reduction reaction process detrimental impurity such as TiC, TiN; Realize metal smelting and alloying in the metallothermic reduction process, shortened process cycle, it is low to have reduced production cost.
Four, description of drawings
Fig. 1 is a titanium alloy production technique overall procedure synoptic diagram.
Fig. 2 is a plasma melting stove synoptic diagram, and by plasma body furnace body 1, plasma torch 2 mixes feeding device 3, water-cooled mould 4, and argon bottom-blowing device 5 and bottom anode 6 are formed.
Fig. 3 is a titanium aluminum alloy esr synoptic diagram, by consumable electrode 7, and covering slag agent 8, esr furnace body 9, fused titanium alloy 10, titanium alloy 11 that solidifies and power supply 12 are formed.
Five, embodiment
1. be the raw material production titanium aluminum alloy with Guangxi ilmenite placer
Guangxi ilmenite placer, its main chemical compositions are TiO
2(50.94%), FeO (28.61%), Fe
2O
3(16.68%), contains a spot of SiO in addition
2, Al
2O
3, P
2O
5, MgO, MnO, CaO etc.In the hot type electric arc furnace of ore deposit, under 1600～1800 ℃ of high temperature, be that reductive agent reduces with the refinery coke at first, reaction product isolated Fe makes titanium slag.With titanium slag, Al powder and CaO thorough mixing, in the transferred-arc plasma process furnace, react, generate Ti and Al
2O
3, separation of C aO-Al
2O
3Slag obtains titanium aluminum alloy.Adopt the method for esr to remove impurity element in the titanium aluminum alloy then, obtain the titanium alloy finished product.
2. adopt rutile ore to produce titanium aluminum alloy
The rutile main chemical compositions is TiO
2So, do not need through the reduction iron removal step.With rutile, electrolytic aluminum and CaF
2, slag agent thorough mixing such as CaO, in the transferred-arc plasma process furnace, react the metal titanium of generation and Al
2O
3, separation of C aO-Al
2O
3Slag obtains titanium aluminum alloy.Adopt the method for esr to remove impurity element in the titanium aluminum alloy then, can obtain oxygen level and be lower than 0.15% titanium aluminum alloy finished product.
Owing to adopt the method for electrolytic aluminum reduction-oxidation titanium, when both react, can produce a large amount of heats, in addition, process optimization does not use expensive titanium tetrachloride as the raw material of producing titanium sponge, therefore, power consumption of the present invention titanium per ton can be in being controlled at 2500～8000kW h scope, and the power consumption of current technology is about titanium 16000kW h per ton.
Claims (5)
1. method of directly producing the metal titanium or titanium alloy from titaniferous ore is characterized in that: be raw material with the titaniferous ore, add reductive agent and carry out the arc melting deironing and make titanium slag (TiO
2: Fe 92%～99%,
2O
3: 0.5%～2.5%), with above-mentioned titanium slag, or rutile (TiO
2: 95%～99%), or titanium white (TiO
2: Al 90%～99.99%,
2O
3: 0.00%～10.00%) in the plasma high-temperature stove, with argon gas as plasma body work source of the gas, add electrolytic aluminum (Al:99.99%) reduction-oxidation titanium, obtain titanium aluminum alloy mother liquor (Ti:70%～85%, Al:10%～30%, O:0.5%～3%), the aluminum oxide that generates is by the Calcium Fluoride (Fluorspan) fractionation by adsorption of slag, add in the slag former in the plasma high-temperature stove and contain Calcium Fluoride (Fluorspan), its addition is 1%～10% of a titanium oxide, the solid titanium aluminium alloy parent that obtains, allocate the reductor of 10%-15% into, be processed into consumable electrode, through esr, can obtain oxygen level is the titanium aluminum alloy finished product of 0.05%-0.15% in vacuum electric furnace.
2. in accordance with the method for claim 1, it is characterized in that: adopt titanium slag, or rutile, or titanium white, in the plasma high-temperature stove, as plasma body work source of the gas, add electrolysis aluminium reducing titanium oxide with argon gas, obtain the titanium aluminum alloy mother liquor, described plasma furnace is by plasma body furnace body (1), and plasma torch (2) mixes feeding device (3), mould (4), argon bottom-blowing device (5) and bottom anode (6) are formed.
3. in accordance with the method for claim 1; it is characterized in that: the titanium aluminum alloy parent adopts the method for esr to carry out refining; described electroslag remelting process device is by consumable electrode (7); covering slag agent (8); esr furnace body (9); fused titanium alloy (10), titanium alloy that solidifies (11) and power supply (12) are formed.
4. in accordance with the method for claim 1, it is characterized in that: plasma body furnace body (1) is blown into Ar gas by argon bottom-blowing device (5), CaO thorough mixing with titanium slag, Al powder and a fluxing effect, add in the body of heater by mixing feeding device (3), between plasma torch (2) and bottom anode (6), form transferred arc and carry out plasma heating, make TiO
2Fully react the Al in the reaction product isolated with Al
2O
3, in mould (4), obtain thick Ti-Al alloy.
5. in accordance with the method for claim 1; it is characterized in that: esr furnace body (9) is full of protection of inert gas; with thick Ti-Al alloy as sacrificial electrode (7); after connecting power supply (12); in slag bath, form powerful electric current; the heat that produces raises covering slag agent (8) temperature; when the slag temperature surpasses the Ti-Al alloy melting point; electrode is melted; the alloy of fusing passes slag from electrode surface by gravity with the form of drop, and in this course, slag absorbs harmful element in the metallic substance and inclusion; fused titanium alloy (10) converges into the molten bath below slag bath, the titanium alloy that solidifies (11) is Ti-Al alloy finished product.
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| CN100523235C (en) * | 2007-11-19 | 2009-08-05 | 攀钢集团攀枝花钢铁研究院 | Method for obtaining metallic titanium by reducing titanium-containing material |
| CN101487067B (en) * | 2009-03-03 | 2011-06-15 | 北京金坤宏宇矿业科技有限公司 | Industrial production method for directly producing iron and vanadium-titanium-aluminum alloy from vanadium-titanium magnet placer |
| CN102834537A (en) * | 2010-01-20 | 2012-12-19 | 威森波-阿维斯玛股份公司 | Secondary titanium alloy and method for manufacturing same |
| CN103173628A (en) * | 2013-04-18 | 2013-06-26 | 北京科技大学 | Process for extracting titanium from titanium-containing blast furnace slag through aluminothermic method |
| CN103484683A (en) * | 2013-10-12 | 2014-01-01 | 钢铁研究总院 | Comprehensive utilization method of molten titanium-bearing blast furnace slag |
| CN104498734A (en) * | 2015-01-09 | 2015-04-08 | 重庆大学 | Titanium recovery treatment method for titanium-bearing blast furnace slag based on vacuum carbothermal reduction |
| CN105603134A (en) * | 2015-12-31 | 2016-05-25 | 尹昭祥 | Production process for smelting high titanium slag and acid-soluble slag through electric-arc furnace |
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| CN101487067B (en) * | 2009-03-03 | 2011-06-15 | 北京金坤宏宇矿业科技有限公司 | Industrial production method for directly producing iron and vanadium-titanium-aluminum alloy from vanadium-titanium magnet placer |
| US9458527B2 (en) | 2010-01-20 | 2016-10-04 | Vsmpo-Avisma Corporation | Secondary titanium alloy and the art of its manufacture |
| CN102834537A (en) * | 2010-01-20 | 2012-12-19 | 威森波-阿维斯玛股份公司 | Secondary titanium alloy and method for manufacturing same |
| CN102834537B (en) * | 2010-01-20 | 2014-11-26 | 威森波-阿维斯玛股份公司 | Secondary titanium alloy and method for manufacturing same |
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| CN103173628B (en) * | 2013-04-18 | 2014-12-24 | 北京科技大学 | Process for extracting titanium from titanium-containing blast furnace slag through aluminothermic method |
| CN103484683A (en) * | 2013-10-12 | 2014-01-01 | 钢铁研究总院 | Comprehensive utilization method of molten titanium-bearing blast furnace slag |
| CN104498734A (en) * | 2015-01-09 | 2015-04-08 | 重庆大学 | Titanium recovery treatment method for titanium-bearing blast furnace slag based on vacuum carbothermal reduction |
| CN105603134A (en) * | 2015-12-31 | 2016-05-25 | 尹昭祥 | Production process for smelting high titanium slag and acid-soluble slag through electric-arc furnace |
| WO2019033784A1 (en) * | 2017-08-18 | 2019-02-21 | 王武生 | Method of producing titanium or titanium alloy directly by using titanium dioxide |
| WO2019192372A1 (en) * | 2018-04-03 | 2019-10-10 | 王武生 | Method for directly producing titanium and titanium alloy by using high titanium slag |
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