CN104673961B - A kind of vanadium extraction by converter blowing chromium slag state regulator and preparation method thereof - Google Patents
A kind of vanadium extraction by converter blowing chromium slag state regulator and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of vanadium extraction by converter blowing chromium slag state regulator and preparation method thereof, belong to field of iron and steel smelting.Regulator of the present invention is SiO20～40wt%, MnO 5～20wt%, Na2O 0～10wt%, CaO 0～8wt%, S < 0.02wt%, H2O < 2wt%, surplus is iron oxides.The vanadium extraction by converter blowing chromium slag state regulator that the present invention provides, can substantially adjust vanadium chromium slag slag state, make vanadium chromium slag melting point reduce, can reduce the utilization of band iron, beneficially resource in vanadium chromium slag, reduce the production cost of vanadium extraction chromium process compared with vanadium extraction by converter blowing.
Description
Technical field
The present invention relates to a kind of vanadium extraction by converter blowing chromium slag state regulator and preparation method thereof, belong to field of iron and steel smelting.
Background technology
China is vanadium titano-magnetite big country, and the red lattice vanadium titano-magnetite of Panzhihua Region is the chromium ore resource that China is maximum, reserves 36
Hundred million tons, it is up to 18,000,000 tons containing Cr2O3, is the nearly twice of other areas, whole nation proved reserves.Chromium type high red lattice vanadium titanium
Magnetic iron ore be not only climb big mining area, Xisi, be also the vanadic titanomagnetite deposit of domestic current maximum.Storage of mineral deposits is in Hai Xi early
The huge stratiform that phase is formed is divided in different Granitic Complex like stratiform neutral and alkali mafic Ultrabasic, and magmatic differentiation is good, belongs to late period
Magmatic crystallization differentiation mineral deposit.Ore body forms big-and-middle-sized mining area, relatively independent 8, and withered mining area, its Road rock mass thickness is big, all kinds of
Ledge is complete, and ore body scale is big, and research degree is the highest, and this district is the most alleged " Hongge Deposit district ", is divided into again " mining area, south " and " north
Mining area ".Different from the resource such as the mining heritages of periphery, ore deposit, Baima, Hongge Deposit in addition to rich in metals such as ferrum, vanadium, titaniums, companion also altogether
The metals such as raw chromium, nickel, cobalt, are China's super-huge multielement mineral intergrowths few in number, have the highest comprehensive utilization value.
As a example by the chromium element of association, red Ge Nan mining area Cr2O3Grade reaches 0.34%, and chromium resource reserves are the most considerable.China is the world
One big rustless steel manufacturing country, domestic chrome ore can not meet far away consumption demand, the most all need to be from the high-grade chromite of external import
And ferrochrome.The chromium of China is metallurgical and chromic salts industry has the highest dependency degree to external chromite.Therefore, for China this
For the country of one chromium resource shortage of sample, it is achieved in high-chromic vanadium-titanium ferroferrite, the scale recovery of chromium resource has particularly significant
Economic worth and strategic importance.
At present, the production method producing vanadium slag both at home and abroad is more, mainly has New Zealand's ladle to blow vanadium technique, South Africa shaking ladle vanadium extraction
Technique, Russian and Chinese vanadium extraction by converter blowing technique etc., other process for extracting vanadium also includes v-bearing steel slag vanadium extraction, process for extracting vanadium from stone coal
Deng.The production process system of vanadium extraction by converter blowing is updating of addition coolant+process temperature+duration of blast both at home and abroad.Molten iron
Vanadium extraction is a selective oxidation technology.Converter supply vanadium extraction is an exothermic process, the elemental oxygen such as [Si], [Mn], [V], [C]
Changing makes molten bath be rapidly heated, and [Si], [Mn] oxidation generation are before [V] aoxidizes, and vanadium extraction can not suppress it to react, and [C],
[V] conversion temperature, about at about 1385 DEG C, therefore to obtain high oxidation rate and [V] recovery rate of [V], it is necessary to adds vanadium extraction cooling
Agent, controls bath temperature and is allowed to approach [C], [V] conversion temperature, reaches vanadium extraction and protects the purpose of carbon, [V] is down to less than 0.05%.
The terminal half steel temperature of vanadium extraction is unsuitable too high, and vanadium extracting process early stage is oxidized to main with vanadium, and the later stage is reduced to main with vanadium, but blows vanadium mistake
Journey is that vanadium is reduced to master.Molten iron temperature is made to drop to suitable scope, converter smelting so use addition coolant when cooling
In by duration of blast and the control of process temperature, the vanadium in half steel is aoxidized, improves recovery rate.
Flos Bombacis Malabarici high lattice vanadium titano-magnetite mineral species is many, and ore structures is complicated, select the ferrum in smelting separation Ore, vanadium, titanium,
The alloying technology difficulty such as chromium, nickel, cobalt are big, are worldwide technological puzzle to be captured.Under normal circumstances, in schreyerite thing
Vanadium is with V3+Form be solid-solution in magnetic iron ore lattice, formed vanadium iron spinelle；Titanium is mainly with oxide TiO2Presented in
In ulvite and ilmenite.Cr3+With Fe3+Ionic radius approximates, and ferric ion in trivalent chromium displacement titanomagnetite, in interior
Matter with as.Chromium is as vanadium, and together with ferrum symbiosis, mineral are FeO (V, Cr)2O3Spinelle.In ore dressing process chromium with
Vanadium more than 80% is enriched in iron ore concentrate.Preferable raw material basis has been established for jointly being extracted vanadium chromium by metallurgical method.Many sections
Grind institutes and colleges and universities to Hongge Deposit from selecting and purchasing, smelt, extract and follow-up vanadium chromium separates and all done substantial amounts of work, establish
Certain theory and practice basis.Capture multiple technical barrier at present, but also have many key technology bottlenecks away from industrialization,
Technology is the most immature.
Dong Pengli is in China rare earth journal, the 2012nd, 30 (S1): 49-54. phase, entitled " chromium, vanadium and oxidation thereof in steelmaking process
The thermodynamic behavior of thing is to thermodynamic behavior in slag of chromium, vanadium and oxide thereof " article in carried out theory analysis, send out
The thermodynamic behavior of existing chromium and vanadium and oxide thereof depends on the partial pressure of oxygen in process of the test, temperature, basicity and slag phase composition.With
Basicity, partial pressure of oxygen increases and temperature reduces, Cr2+Content reduces；Along with the increase of basicity of slag, chromium oxide dissolving in slag
Degree reduces, oxide activity reduces.
Zhang Jianting at Sichuan non-ferrous metal, the 2005th, (1): 1-5. phase, " tax of Hongge iron ore chromium is deposited, is distributed and recycled "
One Liao Yuan Ministry of Geology and Mineral Resources disclosed herein the used ore dressing of mineral products comprehensive utilizating research → rotary kiln prereduction electric furnace ironmaking → experimental converter
Blow chromium type high vanadium slag → from chromium type high vanadium slag extract V2O5And Cr2O3, then obtained two through traditional Roasting And Leaching sedimentation method
Planting product, vanadic anhydride grade and chromic oxide grade are respectively greater than 90% and 98%, from comprehensively receiving of raw ore to product
Rate: ferrum 65%, vanadium 40%～52%, chromium 40%～55%.
Zhang Jianting, old green mineral products protection with utilize, the 2008th, (5): 38-41. phase, " climb western vanadium titano-magnetite essential element compose
Deposit state and recycling " the most with soda and compound oxidizing roasting elder generation of Natrii Sulfas in Iron Ore Powder of a Liao Panyan institute disclosed herein
Vanadium, chromium precipitation are extracted in concentrate shaft furnace gas reduction magnetic separation separation after extracting vanadium chromium, leaching, simple precipitation method from solution,
And have studied various impurity to vanadium chromium precipitation and the affecting laws of product quality, finally given grade and be both greater than the V of 98%2O5
And Cr2O3Product.
In existing blast furnace ironmaking-pneumatic steelmaking process for extracting vanadium, the titanium in vanadium titano-magnetite mainly enters blast furnace with perovskite form
Slag phase, vanadium, chromated oxide are reduced entrance ferrum phase, and the oxidized point forming vanadium iron, ferrochrome respectively during vanadium extraction by converter blowing
Spinel structure enters slag and forms vanadium slag mutually, remains in the vanadium chromium in half steel and can enter height by partial oxidation in further steelmaking process
In the steelmaking slag of basicity.Owing to current molten iron chromium content is low, production technology, just for the recovery of Vanadium in Vanadium Residue, adopts the technology that
High temperature sodium roasting-water logging process for extracting vanadium.Due to the similarity of vanadium chromium physical chemistry behavior in metallurgical process, with red lattice
Ore deposit be raw material vanadium chromium hot melt vanadium extracting process in the oxidation of substantial amounts of chromium certainly will be made to enter in slag, form the vanadium chromium slag of high chrome contents.
Publication No. CN1789435, invention entitled " vanadium extraction from hot metal control calcium coolant and vanadium extraction from hot metal control calcium technique " discloses
A kind of vanadium extraction from hot metal control calcium coolant and vanadium extraction from hot metal control calcium technique, the chemical composition (Wt%) of its vanadium-raising cooling agent is: ferrum oxide
Skin 56-60%, fine iron breeze 30-40%, bonding agent 5-10%, this coolant can increase extraction ratio and the v slag grade of vanadium, surely
Determine vanadium slag calcium oxide content.
Publication No. CN101338351, invention entitled " a kind of vanadium-raising cooling agent and preparation method thereof and using method " is open
A kind of vanadium-raising cooling agent and preparation method thereof and using method, this coolant with iron scale or vanadium extraction mud, containing vanadium iron concentrate,
Bonding agent is raw material production, containing the iron oxides of 80%-95%, the V of SiO2,0.1-0.6% of 3-6%2O5, 1-3%MgCl2。
From the point of view of existing document, smelt about vanadium chromium hot melt and only have a small amount of commerical test report, owing to there being the participation of chromium, contain
Vanadium chromium hot melt oxidation characteristic in converter can be varied from accordingly, and chromated oxide existence in slag can affect the physics of vanadium chromium slag
Chemical property, can cause thermodynamic condition and the change of distribution in slag and in half steel of vanadium chromium that vanadium chromium aoxidizes.In vanadium chromium slag due to
There is Cr2O3Existence, cause vanadium chromium slag viscosity big, substantial amounts of iron shot, abrasive grit are swept along in slag, not only cause vanadium extraction chromium mistake
Journey steel technology, is also unfavorable for the preparation of follow-up vanadium chromium product.
Summary of the invention
The invention provides a kind of vanadium extraction by converter blowing chromium slag state regulator, in order to solve the vanadium of chromium type high containing vanadium and chromium molten iron, chromium extracted
Journey produce vanadium chromium slag slag state thickness, slag ferrum regardless of problem.
A kind of vanadium extraction by converter blowing chromium slag state regulator, this regulator is SiO20～40wt%, MnO 5～20wt%, Na2O 0～
10wt%, CaO 0～8wt%, S < 0.02wt%, H2O < 2wt%, remaining is iron oxides；
Further, the raw material composition of a kind of vanadium extraction by converter blowing chromium slag state regulator described above is SiO by weight percentage2
0～40%, MnO 5～20%, Na2O 0～10%, CaO 0～8%, S < 0.02%, H2O < 2%, surplus is iron oxides,
And SiO the most by weight percentage2+Na2O+CaO=4%～58%.
The composition of vanadium chromium slag, state can change because the composition of containing vanadium and chromium molten iron is different, therefore when the vanadium mobility of chromium slag own are not
Time very poor, can only add MnO and iron oxides；When mobility is very poor, it is necessary to add SiO2、Na2O and CaO,
These three composition can play the effect adjusting vanadium chromium scoriform state.
Wherein, in order to cost-effective, improve the comprehensive utilization ratio of resource, SiO in described regulator2Quartz sand, Silicon stone can be used
Ore deposits etc. are containing SiO2Abundant raw material replaces, and SiO in this raw material2> 80wt%；MnO uses high-grade manganese ore, containing manganese powder dirt etc.
Raw material replaces；Na2O replaces with soda；CaO replaces with active lime；Iron oxides is with the mineral generation such as Iron Ore Powder, iron oxide red
Replace.
A kind of vanadium extraction by converter blowing chromium slag state regulator, the granularity of the most various raw materials should be less than 2.5mm.
Present invention also offers the preparation method of a kind of vanadium extraction by converter blowing chromium slag state regulator.
The preparation method of a kind of vanadium extraction by converter blowing chromium slag state regulator, first calculates the regulator needed and becomes according to hot metal composition during production
Point, calculate the consumption of various raw material further according to the content meter of composition each in regulator composition and raw material, after mix homogeneously, load packaging
In Dai, (10～50kg/ bag) or interpolation bonding agent carry out briquetting.
The preparation method of above-mentioned vanadium extraction by converter blowing chromium slag state regulator, the bonding agent mass percent of described interpolation is 3～8%.
Further, the preparation method of above-mentioned vanadium extraction by converter blowing chromium slag state regulator, the bonding agent mass percent wherein added is excellent
Elect 5% as.
A kind of preparation method of vanadium extraction by converter blowing chromium slag state regulator, described bonding agent is conventional balling-up bonding agent, as waterglass,
In silicon Alumina, cement, bentonite, starch at least one.
Vanadium extraction by converter blowing chromium slag state regulator and preparation method thereof that the present invention provides, can substantially adjust vanadium chromium slag slag state, make vanadium chromium
Slag melting point reduces, shim amount reduces, and can reduce the utilization of band iron, beneficially resource in vanadium chromium slag compared with vanadium extraction by converter blowing,
Reduce the production cost of vanadium extraction chromium process.Meanwhile, in the present invention, the composition of vanadium extraction by converter blowing chromium slag state regulator covers a lot
Composition required for vanadium chromium scoriform state, different vanadium chromium scoriform states uses different compositions, can play good adaptability and science
Property, and do not affect using effect.
Detailed description of the invention
A kind of vanadium extraction by converter blowing chromium slag state regulator, this regulator is SiO20～40wt%, MnO 5～20wt%, Na2O 0～
10wt%, CaO 0～8wt%, S < 0.02wt%, H2O < 2wt%, remaining is iron oxides；
Further, the raw material composition of a kind of vanadium extraction by converter blowing chromium slag state regulator described above is SiO by weight percentage2
0～40%, MnO 5～20%, Na2O 0～10%, CaO 0～8%, S < 0.02%, H2O < 2%, surplus is iron oxides,
And SiO the most by weight percentage2+Na2O+CaO=4%～58%.
The composition of vanadium chromium slag, state can change because the composition of containing vanadium and chromium molten iron is different, are not therefore very when the mobility of vanadium chromium own
During difference, can only add MnO and iron oxides；When mobility is very poor, it is necessary to add SiO2、Na2O and CaO, this
Three kinds of compositions can play the effect adjusting vanadium chromium scoriform state.
Wherein, in order to cost-effective, improve the comprehensive utilization ratio of resource, SiO in described regulator2Quartz sand, Silicon stone can be used
Ore deposits etc. are containing SiO2Abundant raw material replaces, and SiO in this raw material2> 80wt%；MnO uses high-grade manganese ore, containing manganese powder dirt etc.
Raw material replaces；Na2O replaces with soda；CaO replaces with active lime；Iron oxides is with the mineral generation such as Iron Ore Powder, iron oxide red
Replace.
A kind of vanadium extraction by converter blowing chromium slag state regulator, the granularity of the most various raw materials should be less than 2.5mm.
The preparation method of a kind of vanadium extraction by converter blowing chromium slag state regulator, first calculates the regulator needed and becomes according to hot metal composition during production
Point, calculate the consumption of various raw material further according to the content meter of composition each in regulator composition and raw material, after mix homogeneously, load packaging
In Dai, (10～50kg/ bag) or interpolation bonding agent carry out briquetting.
The preparation method of above-mentioned vanadium extraction by converter blowing chromium slag state regulator, the bonding agent mass percent of described interpolation is 3～8%.
Further, the preparation method of above-mentioned vanadium extraction by converter blowing chromium slag state regulator, the bonding agent mass percent wherein added is excellent
Elect 5% as.
The preparation method of a kind of vanadium extraction by converter blowing chromium slag state regulator, described bonding agent is conventional balling-up bonding agent, such as waterglass, silicon
In Alumina, cement, bentonite, starch at least one.
Below in conjunction with embodiment, the detailed description of the invention of the present invention is further described, the most therefore limits the present invention to institute
Among the scope of embodiments stated.
Embodiment 1
Using quartz sand, manganese ore, active lime, soda, Iron Ore Powder is raw material, by each raw material mix homogeneously by a certain percentage,
Slag state regulator composition range is: SiO240wt%, MnO 20wt%, Na2O 10wt%, CaO 8wt%, S < 0.02wt%,
H2O < 2wt%, surplus is iron oxides.
After using this slag adjusting agent to adjust vanadium chromium slag and spatter slag, continue vanadium extraction chromium 6 stove, furnace lining the most still ratio before spattering slag thick 2～4mm.
In vanadium extraction chromium splashing slag in converter, after using this slag state regulator, can effectively reduce vanadium chromium slag melting point, improve vanadium chromium slag
Adhesiveness, strengthen spatter slag and dross effect.
Embodiment 2
Using silica mine, manganese ore, active lime, Iron Ore Powder is raw material, by each raw material mix homogeneously by a certain percentage, slag state
Regulator composition range is: SiO230wt%, MnO 15wt%, CaO 8wt%, S < 0.02wt%, H2O < 2wt%, surplus
For iron oxides.
After using this slag adjusting agent to adjust vanadium chromium slag and spatter slag, continue vanadium extraction chromium 5 stove, furnace lining the most still ratio before spattering slag thick 1～3mm.
In vanadium extraction chromium splashing slag in converter, after using this slag state regulator, can effectively reduce vanadium chromium slag melting point, improve vanadium chromium slag
Adhesiveness, strengthen spatter slag and dross effect.
Embodiment 3
Using quartz sand, manganese ore, soda, iron oxide red is raw material, by each raw material mix homogeneously by a certain percentage, slag state regulator
Composition range is: SiO2< < 2wt%, surplus is ferrum for 0.02wt%, H2O for 35wt%, MnO 15wt%, Na2O 5wt%, S
Oxide.
After using this slag adjusting agent to adjust vanadium chromium slag and spatter slag, continue vanadium extraction chromium 3 stove, furnace lining the most still ratio before spattering slag thick 3～5mm.
In vanadium extraction chromium splashing slag in converter, after using this slag state regulator, can effectively reduce vanadium chromium slag melting point, improve vanadium chromium slag
Adhesiveness, strengthen spatter slag and dross effect.
Embodiment 4
Using active lime, manganese ore, soda, iron oxide red is raw material, and by each raw material mix homogeneously by a certain percentage, slag state adjusts
Agent composition range is: MnO 15wt%, Na2O 1wt%, CaO 3wt%, S < 0.02wt%, H2O < 2wt%, surplus is ferrum
Oxide.
After using this slag adjusting agent to adjust vanadium chromium slag and spatter slag, continue vanadium extraction chromium 3 stove, furnace lining the most still ratio before spattering slag thick 3～5mm.
In vanadium extraction chromium splashing slag in converter, after using this slag state regulator, can effectively reduce vanadium chromium slag melting point, improve vanadium chromium slag
Adhesiveness, strengthen spatter slag and dross effect.
Embodiment 5
Using silica mine, active lime, manganese ore, soda, iron oxide red is raw material, by each raw material mix homogeneously by a certain percentage,
Slag state regulator composition range is: SiO220wt%, MnO 10wt%, Na2O 5wt%, CaO 6wt%, S < 0.02wt%,
H2O < 2wt%, surplus is iron oxides.
After using this slag adjusting agent to adjust vanadium chromium slag and spatter slag, continue vanadium extraction chromium 5 stove, furnace lining the most still ratio before spattering slag thick 4～6mm.
In vanadium extraction chromium splashing slag in converter, after using this slag state regulator, can effectively reduce vanadium chromium slag melting point, improve vanadium chromium slag
Adhesiveness, strengthen spatter slag and dross effect.
Embodiment 6
Using manganese ore, iron oxide red is raw material, and by each raw material mix homogeneously by a certain percentage, slag state regulator composition range is: MnO
5wt%, S < 0.02wt%, H2O < 2wt%, surplus is iron oxides.
After using this slag adjusting agent to adjust vanadium chromium slag and spatter slag, continue vanadium extraction chromium 3 stove, furnace lining the most still ratio before spattering slag thick 1～3mm.
In vanadium extraction chromium splashing slag in converter, after using this slag state regulator, can effectively reduce vanadium chromium slag melting point, improve vanadium chromium slag
Adhesiveness, strengthen spatter slag and dross effect.
Embodiment 7
Using manganese ore, iron oxide red is raw material, and by each raw material mix homogeneously by a certain percentage, slag state regulator composition range is: MnO
20wt%, S < 0.02wt%, H2O < 2wt%, surplus is iron oxides.
After using this slag adjusting agent to adjust vanadium chromium slag and spatter slag, continue vanadium extraction chromium 3 stove, furnace lining the most still ratio before spattering slag thick 2～4mm.
In vanadium extraction chromium splashing slag in converter, after using this slag state regulator, can effectively reduce vanadium chromium slag melting point, improve vanadium chromium slag
Adhesiveness, strengthen spatter slag and dross effect.
Claims (7)
1. a vanadium extraction by converter blowing chromium slag state regulator, it is characterised in that: the raw material of described regulator forms by weight percentage
For SiO20～40%, MnO 5～20%, Na2O 0～10%, CaO 0～8%, S < 0.02%, H2O < 2%, surplus is ferrum
Oxide, the most by weight percentage SiO2+Na2O+CaO=4%～58%, and SiO2、Na2O and CaO three's content is equal
More than 0.
A kind of vanadium extraction by converter blowing chromium slag state regulator the most according to claim 1, it is characterised in that: in described regulator
SiO2With containing SiO2Abundant quartz sand or silica mine replace, and SiO in this raw material2> 80wt%；MnO uses high-grade manganese ore
Or replace containing manganese powder dirt；Na2O replaces with soda；CaO replaces with active lime；Iron oxides replaces with Iron Ore Powder or iron oxide red.
A kind of vanadium extraction by converter blowing chromium slag state regulator the most according to claim 1 and 2, it is characterised in that: described regulator
In the granularity of various raw materials should be less than 2.5mm.
4. the preparation method of a kind of vanadium extraction by converter blowing chromium slag state regulator described in any one of claims 1 to 3, it is characterised in that:
First calculate, according to hot metal composition, the regulator composition needed, further according to the content meter of composition each in regulator composition and raw material during production
Calculate the consumption of various raw material, load in 10～50kg packaging bags after mix homogeneously or interpolation bonding agent carries out briquetting.
The preparation method of a kind of vanadium extraction by converter blowing chromium slag state regulator the most according to claim 4, it is characterised in that: described
The bonding agent percentage by weight added is 3～8%.
The preparation method of a kind of vanadium extraction by converter blowing chromium slag state regulator the most according to claim 5, it is characterised in that: described
The bonding agent percentage by weight added is 5%.
The preparation method of a kind of vanadium extraction by converter blowing chromium slag state regulator the most according to claim 4, it is characterised in that: described
Bonding agent is at least one in waterglass, silicon Alumina, cement, bentonite, starch.
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| CN101928806B (en) * | 2009-06-26 | 2013-02-13 | 攀钢集团攀枝花钢铁研究院有限公司 | Composite slagging agent for semi-steel making and preparation method thereof and semi-steel making method |
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