CN101906498A - Method for comprehensively smelting sefstromite - Google Patents
Method for comprehensively smelting sefstromite Download PDFInfo
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- CN101906498A CN101906498A CN 201010261943 CN201010261943A CN101906498A CN 101906498 A CN101906498 A CN 101906498A CN 201010261943 CN201010261943 CN 201010261943 CN 201010261943 A CN201010261943 A CN 201010261943A CN 101906498 A CN101906498 A CN 101906498A
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Abstract
The invention provides a method for comprehensively smelting sefstromite. The method fundamentally solves the problem that the vanadium content in molten iron is difficult to increase so as not to finally extract vanadium, a valuable resource, because the conventional blast furnace smelting cannot utilize one hundred percent sefstromite by directly reducing the one hundred percent sefstromite into vanadium-titanium sponge iron by a tunnel kiln direct reduction method. The method comprises the following steps of: when the vanadium-titanium sponge iron is smelted in an electric furnace, first reducing V2O5 in slag and putting the V2O5 into steel by controlling a reducing atmosphere and then scratching away oxides of difficultly reduced elements such as Si, Al, Ti, Ca, Mg and the like along with the slag to obtain high titanium slag; and oxidizing the vanadium in the molten steel into the slag by oxidizing and blowing to improve the V2O5 content in the slag so as to provide guarantee for subsequent vanadium extraction from the slag and extremely improve the recovery rate and the recovery economic value of the vanadium. The method can also produce high-quality molten steel for developing steel grade with high added value, so the valuable resource, namely the sefstromite can be fully, effectively and rationally utilized.
Description
Technical field
The present invention relates to a kind of smelting process of sefstromite, especially a kind of method of comprehensively smelting sefstromite belongs to the smelting iron and steel technical field.
Technical background
The direct reduction iron making technology is meant that iron ore is being lower than under the temperature of fusion, is reduced into the production process of sponge iron, and it is the developing direction of following ironmaking technology, also is one of significant technology innovation project that national industrial policies are encouraged and emphasis is supported.According to the classification of employed reducing agent, direct reduction processes of Iron ores can be divided into: with gas as the gas base method of reducing agent with the coal-based method two big classes of coal as reducing agent.Surpass 80% direct-reduced iron at present in the world, all produce as the gas base method of reductive agent in order to gas, the output of coal base reduction iron is less than 20%.The gas base directly reducing technology comparative maturity, use the countries and regions that are adapted at rich producing natural gas.The coal-based direct reduction technological development relatively lags behind, and is adapted at lacking Sweet natural gas, and use the abundant countries and regions of coal reserves.China's natural gas source is relatively deficienter, therefore is not suitable for promoting the use of in China with the gas base directly reducing technology of Sweet natural gas as reductive agent, and should be in conjunction with the resources characteristic of China, development and use have the coal-based direct reduction iron technology of self-character.
V, Ti iron ore are a kind of based on Fe, and association simultaneously has the oxidized ore of multiple rare high value metals such as Ti, V, is that national defence and high-tech industry develop necessary strategic materials.Carrying out the comprehensive utilization of V, Ti iron ore deposit, is exactly wherein in the Fe element, to realize the reasonable utilization of the useful component of its association as far as possible at effective extraction and application.Years of researches and production practice both at home and abroad prove that effective separation of Fe, Ti is the bottleneck technology of V, Ti iron ore deposit comprehensive utilization most critical, and realize the effective recycling of V, Ti, are again the key links that can whole comprehensive utilization process obtain benefit.The country that at present V, Ti iron ore deposit is carried out comprehensive development and utilization mainly contains South Africa, Russia, New Zealand and China etc., and what wherein South Africa and New Zealand adopted is rotary kiln one eaf process flow process, mainly reclaims Fe and V, and electroslag contains the TiO about 30%
2, as paving the way or other raw material; Russia and China adopt blast furnace one converter process flow process, only reclaim Fe and V, and Ti does not temporarily recycle.
The method of at present vanadium extraction generally is divided into two big class, i.e. pyrogenic process and wet methods.Pyrogenic process is adopted in vanadium extraction mostly from contain the vanadium iron ore.It is to be smelt vanadium-bearing hot metal with the magnetic iron ore that contains the vanadium titanium through blast furnace for many years that steel is climbed by China, molten iron enters in the slag vanadium through the oxygen top-blown converter blowing, after pouring out vanadium containing slag, use again what is called " half steel " to make steel, this blast furnace smelting method only can use 57% vanadium titano-magnetite at present, can not accomplish that 100% uses, so the content of vanadium in the molten iron just is restricted also.When the molten iron that obtains was in this way simultaneously made steel, the Si in the molten iron, Mn, P and a small amount of titanium can at first generate various oxides with the reaction of additive generation oxygen and enter in the slag, when vanadium oxidized and generate V
2O
5When entering slag, inevitable be diluted by the oxide of above-mentioned various elements, cause V in the vanadium slag of vanadium extraction by converter blowing
2O
5Content can not be very high, thereby affect the rate of recovery and the economic benefit of vanadium.
Summary of the invention
For existing blast furnace-converter technological process exist because can not 100% using v-bearing titanomagnetite smelting, finally cause V in the From Converter Vanadium-bearing Slag
2O
5Content is not high, affects the problems such as the rate of recovery of vanadium and economic benefit, the invention provides a kind of energy 100% and uses vanadium titano-magnetite, and improve the integrated smelting method of the rate of recovery of vanadium.
The present invention realizes by following technical proposal: a kind of method of comprehensively smelting sefstromite is characterized in that through the following step:
A, 100% sefstromite adopted join the tunnel kiln direct reduced technology of carbon in the routine and be reduced into vanadium titanium sponge iron;
B, the vanadium titanium sponge iron of A step is added in the conventional electric furnace, press the SiO in the vanadium titanium sponge iron
2The mass content meter, add slag former to CaO/SiO
2=0.8～1.3 mass ratio, heating is routinely melted vanadium titanium sponge iron and separation is slagged tap and iron, to allow vanadium enter in the slag;
C, when bath temperature 〉=1450 ℃, press 1～1.5% amount of vanadium titanium sponge iron quality, reductive agent is added in the electric furnace, make and form reducing atmosphere in the stove, be reduced to FeO in the slag≤0.5% o'clock, vanadium in the slag restored enter in the molten steel, and the oxide compound that is difficult for reductive Si, Al, Ti, Ca, Mg element is still in slag, slag tap, get titanium slag;
D, when bath temperature 〉=1500 ℃, molten steel of melting bath is stirred in routinely oxygen blast in the electric furnace, and the control bath temperature is 1500～1560 ℃, the oxygen blast melting during V≤0.05%, stops oxygen blast to the steel, makes that vanadium is oxidized to V in the steel
2O
5Enter in the slag, slag tap vanadium-rich slag;
E, in electric furnace, add routinely slag former to basicity of slag CaO/SiO
2Be 1.8 o'clock, continue heating, heating by O2 blowing to 1630～1660 ℃, after finishing slag making, taking off P, tapping stays 15～30% molten steel of total steel quality, in order to the normal smelting of next stove in stove.
The direct-reduction process of described A step is conventional tunnel kiln direct reduced method, specifically: with 100% sefstromite, amount is with after carbon dust mixes routinely, be tiled on the chassis, send in the tunnel cave, heating up routinely is heated to direct-reduction and goes out vanadium titanium sponge iron, wherein, and the preferred coke blacking of described carbon dust or coal dust.
Described reductive agent is the coke or the spent cathodes of S≤0.4% mass ratio.
The preferred conventional calcium lime powder of the slag former of described B step.
The continuous charging melting is adopted in the fusing of the vanadium titanium sponge iron of described B step, perhaps divide the melting of 2-4 reinforced substep, wherein the melting of gradation Multistep feeding is: 1/2～1/3 the furnace charge that adds earlier total furnace charge amount in the electric furnace, routinely energising heating, the oxygen blast vanadium titanium sponge iron melting rate of fluxing to the stove reaches 80% when above, 1/2～1/3 the furnace charge that adds again total furnace charge amount in the electric furnace, continue heating, oxygen blast is fluxed, and vanadium titanium sponge iron melting rate reaches more than 80% to the stove, at last remaining furnace charge is added in the stove, continue heating, oxygen blast is fluxed, and vanadium titanium sponge iron all melts to the stove.
The control bath temperature of described D step is 1500～1560 ℃: the steel scrap that adds cooling usefulness in electric furnace is finished regulation and control.
After the vanadium-rich slag of the titanium slag of described C step, D step reclaimed respectively, promptly technical point was got wherein titanium and vanadium indescribably routinely.
Key problem in technology of the present invention is:
A, in electric furnace smelting, low for overcoming the tunnel kiln direct reduced iron carbon containing, the fusing hard problem, adopt in the DRI and join carbon technology, improve the reduction efficiency of v element in the fusion process, effectively reduce the DRI fusing point and improve the oxygen blast efficient of fluxing, accelerated burn-off rate.
B, since vanadium titanium sponge iron be solid state reduction, produce increased number of stomata after the reduction oxygen loss, density is lower, directly uses furnace volume and density all to be unfavorable for normally carrying out of smelting process, continuous charging continuous melting mode be must adopt, the fusing of DRI, the reduction of v element accelerated.
C, in fusion process, allocate an amount of reducing agent into, strengthen furnace reduction atmosphere, make V in the slag
2O
5Be reduced into vanadium and enter in the molten steel, titanium is then stayed in the slag and is clawed with the titanium oxide form, improves the rate of recovery of titanium and reclaims economic worth.
Oxygen blast in D, the molten steel after removing titanium slag makes the vanadium in the molten steel be oxidized to oxide V
2O
5Enter in the slag, thereby obtain to contain the higher vanadium-rich slag of vanadium, improve the rate of recovery of vanadium and reclaim economic worth, not only realized the separation of vanadium, titanium, realized separating of vanadium and other metal, nonmetal oxide.
The present invention compared with prior art has following advantages and effect: adopt such scheme, namely by tunnel kiln direct reduced method 100% sefstromite direct-reduction is become vanadium titanium sponge iron, fundamentally solve existing blast furnace process and used sefstromite because of impossible 100%, and be difficult to improve the molten iron vanadium content, finally can't extract the problem of precious resources-vanadium; When electric furnace smelting vanadium titanium sponge iron, earlier by the control of reducing atmosphere, make the V in the slag
2O
5Reduction enters in the steel, and the oxide that is difficult for the elements such as Si, Al, Ti, Ca, Mg of reduction then claws with slag, to obtain high titanium slag, effectively avoids that these become sub-oxides to dilution, the contamination of vanadium in the slag simultaneously; By the oxidation blowing, the vanadium oxidation in the molten steel is entered in the slag again, thereby improve the V in the slag
2O
5Content for the slag vanadium extraction of postorder provides safeguard, has greatly improved the rate of recovery of vanadium and has reclaimed economic worth.After separating simultaneously high titanium, vanadium-rich slag, can produce the high-quality molten steel again, use for exploitation high added value steel grade, create good economic benefit, and make this useful resources of sefstromite obtain fully, utilize effectively and reasonably.The present invention overcomes effectively that direct-reduced iron TFe is low, the high infusibilityization of bringing of foreign matter content, big, the high deficiency of power consumption of the quantity of slag, realizes the short course steelmaking technology of 100% direct-reduced iron electric furnace, helps the popularization of direct reduction iron making technology.Not only be conducive to realize effective utilization of sefstromite, also can be used for smelting simultaneously other iron-bearing material, and can to not possessing the short flow process non-blast furnace ironmaking of the area output technology of implementing conventional steel flowing molten iron journey condition, drive the development of this regional economy.
Embodiment
Below in conjunction with embodiment the present invention is described further.
Embodiment 1
The method of comprehensively smelting sefstromite provided by the invention, process the following step:
A, take TFe content as 67.14%, SiO
2Content is 2.29%, V
2O
5Content is 0.32%, TiO
2Content is that 1.62% sefstromite concentrate is raw material, and to allocate mass ratio into be 33% coal dust, and mass ratio is 13% calcium lime powder, be positioned on the chassis after the mixing tinning, send in the tunnel cave, be heated to routinely 1100～1150 ℃ of direct-reductions and go out vanadium titanium sponge iron, the vanadium titanium sponge iron mass component that restores is: TFe:73.44%, SiO
2: 6.43%, C:4.37%, V
2O
5: 0.27%, TiO
2: 4.59% degree of metalization is 93.04%;
B, utilize the vanadium titanium sponge iron of 10 tons of A steps of 3 tons of electric furnace smeltings, by dividing four reinforced substep melting modes to smelt, press simultaneously the SiO in the vanadium titanium sponge iron
2The mass content meter, adding slag former calcium lime powder to basicity of slag is CaO/SiO
2=0.8, wherein, the furnace charge that adds first is 1/4 (2.5 tons) of total furnace charge amount, routinely energising heating, the oxygen blast vanadium titanium sponge iron melting rate of fluxing to the stove reaches 80% when above, secondary charging, the furnace charge that adds is 1/4 (2.5 tons) of total furnace charge amount, routinely energising heating, the oxygen blast vanadium titanium sponge iron melting rate of fluxing to the stove reaches 80% when above, three times reinforced, the furnace charge that adds is 1/4 (2.5 tons) of total furnace charge amount, routinely energising heating, the oxygen blast vanadium titanium sponge iron melting rate of fluxing to the stove reaches 80% when above, the furnace charge that will remain 1/4 (2.5 tons) adds in the stove, continue heating, oxygen blast is fluxed, and vanadium titanium sponge iron all melts to the stove, slags tap and iron thereby separate, to allow vanadium enter in the slag;
C, when bath temperature 〉=1450 ℃, press 1.5% amount of vanadium titanium sponge iron quality, with reductive agent---the coke powder 150kg of S≤0.4% mass ratio adds in the electric furnace, make and form reducing atmosphere in the stove, be reduced to FeO in the slag≤0.5% o'clock, vanadium in the slag is restored enter in the molten steel, and the oxide compound that is difficult for reductive Si, Al, Ti, Ca, Mg element is still in slag, slag tap to such an extent that grade is 5.84% titanium slag;
D, when bath temperature 〉=1500 ℃, routinely oxygen blast in the electric furnace is stirred molten steel of melting bath, and is added the steel scrap of cooling usefulness, take the control bath temperature as 1540 ℃, the oxygen blast melting during V≤0.05%, stops oxygen blast to the slag, makes that vanadium is oxidized to V in the steel
2O
5Enter in the slag, slag tap to such an extent that grade is 7.37% vanadium slag;
E, in electric furnace, add routinely slag former lime to basicity of slag CaO/SiO
2Be 1.8 o'clock, continue heating, heating by O2 blowing to 1630 ℃, after finishing slag making, taking off P, get qualified Q235 crude molten steel, tap behind the reduction refining routinely, in stove, stay 1.5 tons of molten steel, in order to the normal smelting of next stove;
F, respectively reclaim the vanadium-rich slag of titanium slag, D step of C step after, promptly technical point is got wherein titanium and vanadium indescribably routinely.
Embodiment 2
The method of comprehensively smelting sefstromite provided by the invention, process the following step:
A, take TFe content as 60.84%, SiO
2Content is 2.96%, V
2O
5Content is 0.85%, TiO
2Content is that 5.38% sefstromite concentrate is raw material, and to allocate mass ratio into be 35% coke blacking, and mass ratio is 14% calcium lime powder, be positioned on the chassis after the mixing tinning, send in the tunnel cave, be heated to routinely 1100～1150 ℃ of direct-reductions and go out vanadium titanium sponge iron, the vanadium titanium sponge iron mass component that restores is: TFe:76.88%, SiO
2: 5.26%, C:0.53%, V
2O
5: 0.93%, TiO
2: 6.75%, degree of metalization is 91.43%;
B, utilize the vanadium titanium sponge iron of 10 tons of A steps of 3 tons of electric furnace smeltings, by dividing three reinforced substep melting modes to smelt, press simultaneously the SiO in the vanadium titanium sponge iron
2The mass content meter, add slag former lime to CaO/SiO
2=1.3 mass ratio, wherein, the furnace charge that adds first is 1/3 of total furnace charge amount, routinely energising heating, the oxygen blast vanadium titanium sponge iron melting rate of fluxing to the stove reaches 80% when above, secondary charging, the furnace charge that adds is 1/3 of total furnace charge amount, routinely energising heating, the oxygen blast vanadium titanium sponge iron melting rate of fluxing to the stove reaches 80% when above, remaining furnace charge is added in the stove, continue heating, oxygen blast and flux that vanadium titanium sponge iron all melts to the stove, the fusing of vanadium titanium sponge iron and separation are slagged tap and iron, to allow vanadium enter in the slag;
C, when bath temperature 〉=1450 ℃, press 1% amount of vanadium titanium sponge iron quality, with reductive agent---the coke powder 100kg of S≤0.4% mass ratio adds in the electric furnace, make and form reducing atmosphere in the stove, be reduced to FeO in the slag≤0.5% o'clock, vanadium in the slag is restored enter in the molten steel, and the oxide compound that is difficult for reductive Si, Al, Ti, Ca, Mg element is still in slag, slag tap to such an extent that grade is 22.69% titanium slag;
D, when bath temperature 〉=1500 ℃, routinely oxygen blast in the electric furnace is stirred molten steel of melting bath, and is added the steel scrap of cooling usefulness, take the control bath temperature as 1550 ℃, the oxygen blast melting during V≤0.05%, stops oxygen blast to the slag, makes that vanadium is oxidized to V in the steel
2O
5Enter in the slag, slag tap to such an extent that grade is 10.21% vanadium slag;
E, in electric furnace, add routinely slag former lime to basicity of slag CaO/SiO
2Be 1.8 o'clock, continue heating, heating by O2 blowing to 1660 ℃, after finishing slag making, taking off P, get qualified Q235 crude molten steel, tap behind the reduction refining routinely, in stove, stay 3 tons of molten steel, in order to the normal smelting of next stove;
F, respectively reclaim the vanadium-rich slag of titanium slag, D step of C step after, promptly technical point is got wherein titanium and vanadium indescribably routinely.
Claims (4)
1. the method for a comprehensively smelting sefstromite is characterized in that through the following step:
A, with 100% sefstromite routinely direct-reduction process be reduced into vanadium titanium sponge iron;
B, the vanadium titanium sponge iron of A step is added in the conventional electric furnace, press the SiO in the vanadium titanium sponge iron
2The mass content meter, add slag former to CaO/SiO
2=0.8～1.3 mass ratio, heating is routinely melted vanadium titanium sponge iron and separation is slagged tap and iron, to allow vanadium enter in the slag;
C, when bath temperature 〉=1450 ℃, press 1～1.5% amount of vanadium titanium sponge iron quality, reductive agent is added in the electric furnace, make and form reducing atmosphere in the stove, be reduced to FeO in the slag≤0.5% o'clock, vanadium in the slag restored enter in the molten steel, and the oxide compound that is difficult for reductive Si, Al, Ti, Ca, Mg element is still in slag, slag tap, get titanium slag;
D, when bath temperature 〉=1500 ℃, molten steel of melting bath is stirred in routinely oxygen blast in the electric furnace, and the control bath temperature is 1500～1560 ℃, the oxygen blast melting during V≤0.05%, stops oxygen blast to the steel, makes that vanadium is oxidized to V in the steel
2O
5Enter in the slag, slag tap, get vanadium-rich slag;
E, in electric furnace, add routinely slag former to basicity of slag CaO/SiO
2Be 1.8 o'clock, continue heating, heating by O2 blowing to 1630～1660 ℃, after finishing slag making, taking off P, tapping stays 15～30% molten steel of total steel quality, in order to the normal smelting of next stove in stove.
2. the method for comprehensively smelting sefstromite as claimed in claim 1 is characterized in that the coke or the spent cathodes of the preferred S of described reductive agent≤0.4% mass ratio.
3. the method for comprehensively smelting sefstromite as claimed in claim 1 is characterized in that the preferred unslaked lime of slag former of described B step.
4. the method for comprehensively smelting sefstromite as claimed in claim 1, the continuous charging melting is adopted in the fusing that it is characterized in that the vanadium titanium sponge iron of described B step, perhaps divide the melting of 2-4 reinforced substep, wherein the melting of the reinforced substep of gradation is: 1/2～1/4 the furnace charge that adds earlier total furnace charge amount in the electric furnace, routinely energising heating, the oxygen blast vanadium titanium sponge iron melting rate of fluxing to the stove reaches 80% when above, 1/2～1/4 the furnace charge that adds again total furnace charge amount in the electric furnace, continue heating, oxygen blast is fluxed, and vanadium titanium sponge iron melting rate reaches more than 80% to the stove, at last remaining furnace charge is added in the stove, continue heating, oxygen blast is fluxed, and vanadium titanium sponge iron all melts to the stove.
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| CN108642226A (en) * | 2018-05-28 | 2018-10-12 | 中冶南方工程技术有限公司 | Electric furnace duplex smelts sponge iron process for extracting vanadium |
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