CN104673964B - The method for modifying of converter height silicon vanadium chromium slag - Google Patents
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Abstract
The present invention relates to the method for modifying of converter height silicon vanadium chromium slag, belong to field of iron and steel smelting.Present invention solves the technical problem that the method for modifying being to provide converter height silicon vanadium chromium slag.The method comprises the steps: a, extracts before vanadium chromium according to the consumption of the cubage slag adjusting agent of vanadium chromium element in containing vanadium and chromium molten iron in converter, and in molten iron, the percentage by weight sum of vanadium and chromium is more than or equal to 1%, and the consumption of slag adjusting agent is 3.5～6.5kg/tFe；In molten iron, the percentage by weight sum of vanadium and chromium is more than 0.5% and less than 1%, and the consumption of slag adjusting agent is 2.5～5.5kg/tFe；B, converter process containing vanadium and chromium molten iron start after 3～5min, by the calculated consumption of a step add slag adjusting agent；After c, converter process terminate, obtain vanadium chromium slag and half steel.The method for modifying of the present invention, can not only reduce the consumption of slag adjusting agent, additionally it is possible to the utilization and the vanadium extraction chromium production cost that reduce band iron, beneficially resource in vanadium chromium slag reduce.
Description
Technical field
The present invention relates to the method for modifying of converter height silicon vanadium chromium slag, 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, containing Cr2O3Up to 18,000,000 tons, be the nearly twice of other areas, whole nation proved reserves.Chromium type high red lattice vanadium titanium magnetic
Iron mine be not only climb big mining area, Xisi, be also the vanadic titanomagnetite deposit of domestic current maximum.Storage of mineral deposits is in early Hercynian period
The huge stratiform formed is divided in different Granitic Complex like stratiform neutral and alkali mafic Ultrabasic, and magmatic differentiation is good, belongs to rock in late period
Slurry crystallization-differentiation 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 containing ore deposit
Layer 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 " Bei Kuang
District ".Different from resources such as the mining heritages of periphery, ore deposits, Baima, Hongge Deposit in addition to rich in metals such as ferrum, vanadium, titaniums, association the most altogether
The metals such as chromium, nickel, cobalt, are China's super-huge multielement mineral intergrowths few in number, have the highest comprehensive utilization value.With
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 first in the world
Big rustless steel manufacturing country, domestic chrome ore can not meet far away consumption demand, the most all need to 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 so
For the country of one chromium resource shortage, it is achieved in high-chromic vanadium-titanium ferroferrite, the scale recovery of chromium resource has highly important
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] yield of [V], it is necessary to add vanadium-raising cooling agent,
Control bath temperature to be allowed to approach [C], [V] conversion temperature, reach vanadium extraction and protect the purpose of carbon, [V] is down to less than 0.05%.Carry
The terminal half steel temperature of vanadium 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 blowing vanadium process is vanadium
It is reduced to main.Make molten iron temperature drop to suitable scope so use addition coolant when cooling, converter smelting passes through
Duration of blast and the control of process temperature, aoxidize the vanadium in half steel, 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 titanium
In ferrum spar and ilmenite.Cr3+With Fe3+Ionic radius approximates, and ferric ion in trivalent chromium displacement titanomagnetite, in endoplasm
With as.Chromium is as vanadium, and together with ferrum symbiosis, mineral are FeO (V, Cr)2O3Spinelle.Chromium and vanadium 80% in ore dressing process
More than it is enriched in iron ore concentrate.Preferable raw material basis has been established for jointly being extracted vanadium chromium by metallurgical method.Many scientific research institutions
And colleges and universities to Hongge Deposit from selecting and purchasing, smelt, extract and follow-up vanadium chromium separate all done substantial amounts of work, established certain
Theory and practice basis.Capture multiple technical barrier at present, but also have many key technology bottlenecks, technique skill away from industrialization
Art is the most immature.
" thermodynamic behavior of chromium, vanadium and oxide thereof in steelmaking process " one that Dong Pengli delivers on " China rare earth journal "
Wen Zhong, has carried out theory analysis to chromium, vanadium and oxide thereof the thermodynamic behavior in slag, finds chromium and vanadium and oxide thereof
Thermodynamic behavior depend on the partial pressure of oxygen in process of the test, temperature, basicity and slag phase composition.Along with basicity, partial pressure of oxygen increase
And temperature reduces, Cr2+Content reduces；Along with the increase of basicity of slag, chromium oxide dissolubility in slag reduces, oxide activity
Reduce.
" tax of Hongge iron ore chromium is deposited, is distributed and recycled " that Zhang Jianting etc. deliver on " Sichuan non-ferrous metal ", comprehensive utilization
With institute use ore dressing → 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 kinds of products, vanadic anhydride grade and three oxidations two through traditional Roasting And Leaching sedimentation method
Chromium grade is respectively greater than 90% and 98%, from the comprehensive recovery rate of raw ore to product: ferrum 65%, vanadium 40%～52%, chromium 40%～
55%.
Concentrate shaft furnace after vanadium chromium, leaching is first extracted in the compound oxidizing roasting the most with soda and Natrii Sulfas in Iron Ore Powder of Pan Yan institute
Gas reduction magnetic separation separation, simple precipitation method extract vanadium, chromium precipitation from solution, and have studied various impurity to vanadium chromium precipitation
And the affecting laws of product quality, finally give grade and be both greater than the V of 98%2O5And Cr2O3Product.(Zhang Jianting, Chen Bi. climb
Western vanadium titano-magnetite essential element occurrence status and recycling [J]. mineral products protection and utilization, 2008, (5): 38-41.)
2012 Nian Pan steel groups take Hongge Deposit → rotary hearth furnace prereduction → electric furnace melt point → technological process of induction furnace blowing is to red lattice
Ore deposit is extracted chromium type high vanadium slag and has been carried out experimental study, has obtained containing V2O3About 8%, Cr2O3The chromium type high vanadium slag of about 8% and containing TiO2
The Ti-enriched slag that grade is higher, this technique based on third generation ironmaking technology, present preferably extract simultaneously and separate vanadium, titanium,
Chromium, the prospect of ferrum.
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.
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, also results in thermodynamic condition and the change of distribution in slag and in half steel of vanadium chromium of the oxidation of vanadium chromium.In vanadium chromium slag by
In there being 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
Process steel technology, is also unfavorable for the preparation of follow-up vanadium chromium product.
CN1789435 discloses a kind of vanadium extraction from hot metal control calcium coolant and vanadium extraction from hot metal control calcium technique, the chemistry of its vanadium-raising cooling agent
Composition (Wt%) is: iron scale 56-60%, fine iron breeze 30-40%, bonding agent 5-10%, and this coolant can increase carrying of vanadium
Take rate and v slag grade, stablize vanadium slag calcium oxide content.CN101338351 discloses 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 as raw material production, containing 80%-95%
Iron oxides, the SiO of 3-6%2, the V of 0.1-0.6%2O5, 1-3%MgCl2.When it uses, consumption is 22～30kg/tFe,
And start 0～3min in oxygen blast and all add.
In terms of above-mentioned prior art, it is the control to vanadium slag, and with slag adjusting agent, vanadium chromium slag slag state is controlled yet there are no report,
Still belong to precedent.
Summary of the invention
Present invention solves the technical problem that the method for modifying being to provide converter height silicon vanadium chromium slag.
The method for modifying of converter height silicon vanadium chromium slag of the present invention, comprises the steps:
A, extract before vanadium chromium according to the consumption of the cubage slag adjusting agent of vanadium chromium element in containing vanadium and chromium molten iron in converter, if in molten iron
The percentage by weight sum of vanadium and chromium be more than or equal to 1% (i.e. [V]+[Cr] >=1%), then the consumption of slag adjusting agent be 3.5～
6.5kg/tFe；If the percentage by weight sum of vanadium and chromium is more than 0.5% and less than 1% (i.e. 0.5% < [V]+[Cr] < 1%) in molten iron,
Then the consumption of slag adjusting agent is 2.5～5.5kg/tFe；
B, converter process containing vanadium and chromium molten iron start after 3～5min, by the calculated consumption of a step add slag adjusting agent；
After c, converter process terminate, obtain vanadium chromium slag and half steel.
Wherein, the method for converter process containing vanadium and chromium molten iron is preferably oxygen top-blown converter or top and bottom combined blown converter.
Further, preferred slag adjusting agent is made up of the component of following percetage by weight: Al2O315%～45%, MgO 0～45%,
TiO20～5%, CaO 0～3%, S < 0.02%, H2O < 2%, remaining is FeO.The composition of slag adjusting agent can be according to vanadium chromium slag
Composition is adjusted.Preferably, described slag adjusting agent is made up of the component of following percetage by weight: Al2O345%,
MgO 45%, TiO25%, CaO 3%, S < 0.02%, H2O < 2%, remaining is FeO；Or described slag adjusting agent is by following heavy
The component composition of amount percent: Al2O315%, MgO 25%, TiO23%, S < 0.02%, H2O < 2%, remaining is FeO；
Or described slag adjusting agent is made up of the component of following percetage by weight: Al2O338%, S < 0.02%, H2O < 2%, remaining is FeO；
Or described slag adjusting agent is made up of the component of following percetage by weight: Al2O325%, TiO25%, CaO 3%, S < 0.02%,
H2O < 2%, remaining is FeO.
Further, in described containing vanadium and chromium molten iron, the percentage by weight of silicon > 0.40%.
The method for modifying of converter height silicon vanadium chromium slag of the present invention, can not only reduce the consumption of slag adjusting agent, additionally it is possible to reduces in vanadium chromium slag and carries
The utilization of iron, beneficially resource and the reduction of vanadium extraction chromium production cost.
Detailed description of the invention
The method for modifying of converter height silicon vanadium chromium slag of the present invention, comprises the steps:
A, extract before vanadium chromium according to the consumption of the cubage slag adjusting agent of vanadium chromium element in containing vanadium and chromium molten iron in converter, if in molten iron
[V]+[Cr] > 1%, then the consumption of slag adjusting agent should be 3.5～6.5kg/tFe；If 0.5% < [V]+[Cr] < 1%, then residue adjustment in molten iron
The consumption of agent is 2.5～5.5kg/tFe；
B, converter process containing vanadium and chromium molten iron start after 3～5min, by the calculated consumption of a step add slag adjusting agent；
After c, converter process terminate, obtain vanadium chromium slag and half steel.
Wherein, converter commonly used in the art processes the method for containing vanadium and chromium molten iron and is all applicable to the present invention, in order to reduce the life of vanadium extraction chromium
Producing cost, converter processes the method for containing vanadium and chromium molten iron and is preferably oxygen top-blown converter or top and bottom combined blown converter.
Slag adjusting agent commonly used in the art is all applicable to the present invention, and in order to improve slag making efficiency, preferred slag adjusting agent is by following weight hundred
The component composition of mark: Al2O315%～45%, MgO 0～45%, TiO20～5%, CaO 0～3%, S < 0.02%,
H2O < 2%, remaining is FeO.Preferably, described slag adjusting agent is made up of the component of following percetage by weight: Al2O345%,
MgO 45%, TiO25%, CaO 3%, S < 0.02%, H2O < 2%, remaining is FeO；Or described slag adjusting agent is by following heavy
The component composition of amount percent: Al2O315%, MgO 25%, TiO23%, S < 0.02%, H2O < 2%, remaining is FeO；
Or described slag adjusting agent is made up of the component of following percetage by weight: Al2O338%, S < 0.02%, H2O < 2%, remaining is FeO；
Or described slag adjusting agent is made up of the component of following percetage by weight: Al2O325%, TiO25%, CaO 3%, S < 0.02%,
H2O < 2%, remaining is FeO.
Further, in described containing vanadium and chromium molten iron, the percentage by weight of silicon > 0.40%.
Concrete, the present invention is applicable to containing vanadium and chromium molten iron and carries out vanadium chromium slag producing process, and concrete operating procedure is as follows:
(1) oxidation carrying out vanadium chromium in molten iron in converter separates, and converter can use oxygen top-blown converter, top when extracting vanadium chromium
Bottom blown converter and other correlation techniques, according to the basic consumption of the cubage slag adjusting agent of vanadium chromium element in molten iron before vanadium extraction chromium,
If [V]+[Cr] > 1% in molten iron, then the consumption of slag adjusting agent should be between 3.5～6.5kg/tFe；If in molten iron
0.5% < [V]+[Cr] < 1%, then the consumption of slag adjusting agent should be between 2.5～5.5kg/tFe；
(2) after oxygen blast or additive method process after vanadium chromium hot melt starts 3～5min, in slag adjusting agent is added stove or in hot-metal bottle,
Composition and vanadium chromium slag in slag adjusting agent is made to react formation high-melting-point substances, to reach the purpose of the vanadium rapid efflorescence of chromium slag；
(3) component requirements of slag adjusting agent is as follows: Al2O315%～45%, MgO 0～45%, TiO20～5%, CaO 0～3%,
S < 0.02%, H2O < 2%, remaining is FeO.Be applicable to the molten iron silicon content used by vanadium extraction by converter blowing chromium slag > 0.40% time.
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
(1) oxidation carrying out vanadium chromium in molten iron in converter separates, and converter uses oxygen top-blown converter, in vanadium extraction when extracting vanadium chromium
Measuring content [V]+[Cr]=1.8% of vanadium chromium element in molten iron before chromium, molten iron silicon content is 0.53%；
(2) 3min after oxygen blast starts, adds slag adjusting agent in stove, makes composition and vanadium chromium slag in slag adjusting agent react formation high-melting-point
Material, to reach the purpose of the vanadium rapid efflorescence of chromium slag, wherein, the consumption of slag adjusting agent is 6.5kg/tFe；Slag adjusting agent is by following weight
The component composition of percent: Al2O345%, MgO 45%, TiO25%, CaO 3%, S < 0.02%, H2O < 2%, remaining
For FeO.
In the vanadium chromium slag obtained after converter, the percetage by weight of ferrum is 8%, with general vanadium extraction by converter blowing chromium after iron content 12% in vanadium chromium slag
Comparing, the inventive method can reduce utilization and the reduction of vanadium extraction chromium production cost of band iron, beneficially resource in vanadium chromium slag.
Embodiment 2
(1) oxidation carrying out vanadium chromium in molten iron in converter separates, and converter uses oxygen top-blown converter, in vanadium extraction when extracting vanadium chromium
Measuring content [V]+[Cr]=1.3% of vanadium chromium element in molten iron before chromium, molten iron silicon content is 0.43%；
(2) 5min after oxygen blast starts, adds slag adjusting agent in stove, makes composition and vanadium chromium slag in slag adjusting agent react formation high-melting-point
Material, to reach the purpose of the vanadium rapid efflorescence of chromium slag, wherein, the consumption of slag adjusting agent is 3.5kg/tFe；Slag adjusting agent is by following weight
The component composition of percent: Al2O315%, MgO 25%, TiO23%, S < 0.02%, H2O < 2%, remaining is FeO.
In the vanadium chromium slag obtained after converter, the percetage by weight of ferrum is 7%, with general vanadium extraction by converter blowing chromium after iron content 12% in vanadium chromium slag
Comparing, the inventive method can reduce utilization and the reduction of vanadium extraction chromium production cost of band iron, beneficially resource in vanadium chromium slag.
Embodiment 3
(1) oxidation carrying out vanadium chromium in molten iron in converter separates, and converter uses oxygen top-blown converter, in vanadium extraction when extracting vanadium chromium
Measuring content [V]+[Cr]=0.8% of vanadium chromium element in molten iron before chromium, molten iron silicon content is 0.43%；
(2) 4min after oxygen blast starts, adds slag adjusting agent in stove, makes composition and vanadium chromium slag in slag adjusting agent react formation high-melting-point
Material, to reach the purpose of the vanadium rapid efflorescence of chromium slag, wherein, the consumption of slag adjusting agent is 2.5kg/tFe；Slag adjusting agent is by following weight
The component composition of percent: Al2O338%, S < 0.02%, H2O < 2%, remaining is FeO.
In the vanadium chromium slag obtained after converter, the percetage by weight of ferrum is 7.5%, with general vanadium extraction by converter blowing chromium after iron content in vanadium chromium slag
12% compares, and the inventive method can reduce utilization and the reduction of vanadium extraction chromium production cost of band iron, beneficially resource in vanadium chromium slag.
Embodiment 4
(1) oxidation carrying out vanadium chromium in molten iron in converter separates, and converter uses oxygen top-blown converter, in vanadium extraction when extracting vanadium chromium
Measuring content [V]+[Cr]=0.6% of vanadium chromium element in molten iron before chromium, molten iron silicon content is 0.41%；
(2) 5min after oxygen blast starts, adds slag adjusting agent in stove, makes composition and vanadium chromium slag in slag adjusting agent react formation high-melting-point
Material, to reach the purpose of the vanadium rapid efflorescence of chromium slag, wherein, the consumption of slag adjusting agent is 3.5kg/tFe；Slag adjusting agent is by following weight
The component composition of percent: Al2O325%, TiO25%, CaO 3%, S < 0.02%, H2O < 2%, remaining is FeO.
In the vanadium chromium slag obtained after converter, the percetage by weight of ferrum is 6%, with general vanadium extraction by converter blowing chromium after iron content 12% in vanadium chromium slag
Comparing, the inventive method can reduce utilization and the reduction of vanadium extraction chromium production cost of band iron, beneficially resource in vanadium chromium slag.
Claims (4)
1. the method for modifying of converter height silicon vanadium chromium slag, it is characterised in that comprise the steps:
A, extract before vanadium chromium according to the consumption of the cubage slag adjusting agent of vanadium chromium element in containing vanadium and chromium molten iron in converter, if in molten iron
The percentage by weight sum of vanadium and chromium is more than or equal to 1%, then the consumption of slag adjusting agent is 3.5～6.5kg/tFe；If vanadium in molten iron
More than 0.5% and be less than 1% with the percentage by weight sum of chromium, then the consumption of slag adjusting agent is 2.5～5.5kg/tFe；
B, converter process containing vanadium and chromium molten iron start after 3～5min, by the calculated consumption of a step add slag adjusting agent；
After c, converter process terminate, obtain vanadium chromium slag and half steel；
Described slag adjusting agent is made up of the component of following percetage by weight: Al2O315%～45%, MgO 0～45%, TiO20～5%,
CaO 0～3%, S < 0.02%, H2O < 2%, remaining is FeO.
The method for modifying of converter height silicon vanadium chromium slag the most according to claim 1, it is characterised in that: converter processes containing vanadium and chromium ferrum
The method of water is oxygen top-blown converter or top and bottom combined blown converter.
The method for modifying of converter height silicon vanadium chromium slag the most according to claim 1, it is characterised in that:
Described slag adjusting agent is made up of the component of following percetage by weight: Al2O345%, MgO 45%, TiO25%, CaO 3%,
S < 0.02%, H2O < 2%, remaining is FeO；
Or described slag adjusting agent is made up of the component of following percetage by weight: Al2O315%, MgO 25%, TiO23%,
S < 0.02%, H2O < 2%, remaining is FeO；
Or described slag adjusting agent is made up of the component of following percetage by weight: Al2O338%, S < 0.02%, H2O < 2%, remaining
For FeO；
Or described slag adjusting agent is made up of the component of following percetage by weight: Al2O325%, TiO25%, CaO 3%, S < 0.02%,
H2O < 2%, remaining is FeO.
4. according to the method for modifying of the converter height silicon vanadium chromium slag described in any one of claims 1 to 3, it is characterised in that: described contain
In vanadium chromium hot melt, the percentage by weight ＞ 0.40% of silicon.
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