CN110438279A - A kind of slag type system of electric furnace smelting vanadium titano-magnetite - Google Patents
A kind of slag type system of electric furnace smelting vanadium titano-magnetite Download PDFInfo
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- CN110438279A CN110438279A CN201910860368.8A CN201910860368A CN110438279A CN 110438279 A CN110438279 A CN 110438279A CN 201910860368 A CN201910860368 A CN 201910860368A CN 110438279 A CN110438279 A CN 110438279A
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- vanadium
- slag
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- magnetite
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/0006—Making spongy iron or liquid steel, by direct processes obtaining iron or steel in a molten state
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/006—Starting from ores containing non ferrous metallic oxides
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/008—Use of special additives or fluxing agents
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/12—Making spongy iron or liquid steel, by direct processes in electric furnaces
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1218—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by dry processes
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Abstract
The invention discloses a kind of slag type systems of electric furnace smelting vanadium titano-magnetite, belong to schreyerite field of comprehensive utilization, and raw material uses low silicon v-ti magnetite concentrate, and v-ti magnetite concentrate prereduction product is sent into electric furnace and is smelted, according to CaO:SiO in electric furnace smelting2(mass ratio)=0.6~1.0, MgO:TiO2(molar ratio)=(1.1~0.8): 1 addition calcic, the regulation clinker of flux containing magnesium form, and main titaniferous object is mutually magnesium titanate phase in clinker.Slag type system proposed by the present invention can realize in electric furnace smelting vanadium into molten iron, effective control of titanium slag input, vanadium extraction by converter blowing recycling vanadium can be used in resulting vanadium-bearing hot metal, Ti-containing slag meet sulfate process titanium dioxide ingredient requirement, it can be achieved that in vanadium titano-magnetite iron, vanadium, titanium comprehensive utilization；Smelting process vanadium titanium moves towards easy to control, and smelting operation difficulty is low.
Description
Technical field
The invention belongs to schreyerite field of comprehensive utilization, and in particular to a kind of slag type system of electric furnace smelting vanadium titano-magnetite
Degree.
Background technique
The vanadium titano-magnetite resource reserve in China is huge, but overall development producing level is also very low, with Panxi Diqu vanadium titanium
It is being in leading production technology with steel, the recovery utilization rate of titanium and vanadium is not high at present, the wasting of resources for resource of magnetite
Seriously, therefore, the level of comprehensive utilization for improving China's v-ti magnetite ore resources has weight to China's steel and the development of vanadium titanium industry
The meaning wanted.
At present for v-ti magnetite concentrate processing method in, non-blast furnace process can be achieved V-Ti-magnetite smelt, iron, vanadium,
Titanium recovery rate is high, and in blast furnace process, coke, which had not only been used as reducing agent but also fuel is used as to provide, smelts required temperature, causes in blast furnace
Reduction potential is stronger.When smelting vanadium titano-magnetite, coke region is constantly in carbon surplus state, easily causes titanium oxide mistake in slag
Reduction generates the high-melting-point substances such as titanium carbonitride, and clinker is made to become sticky, poor fluidity, and slag difficulty goes out, and band iron is more in slag, and iron loss is high.
In order to inhibit the reduction of this region titanium oxide, blast furnace process uses the TiO reduced in slag with addition of common mine2Content, and then drop
Low TiO2Activity, inhibit titanium oxide to cross reduction to reach, reduce titanium carbonitride and generate, guarantee slag iron separation and smelting direct motion
Purpose, but reduce TiO in blast furnace slag with addition of common iron ore2Content, TiO in the blast furnace Ti-containing slag of production2Content is low
(TiO2Mass fraction in 20%-25% or so) can not economic recovery utilize, be only capable of recycling iron and vanadium.Compared with blast furnace process,
Prereduction-electric furnace process the recycling of ferrovanadium titanium, production scale, in terms of have greater advantage.
Prereduction-electric furnace process detailed process are as follows: v-ti magnetite concentrate is first subjected to prereduction, prereduction product is in electric furnace
It is smelted, the separation of iron, vanadium, titanium can be completed in electric furnace.From smelting process, when prereduction-electric furnace process is smelted, heating
Process is to be converted to provide by electric energy, and the coke of supplying only makees reducing agent, and reduction potential is controllable, and this reduces the controls of smelting process
Difficulty, this is that it can realize the main reason for V-Ti-magnetite is smelted, while clinker titanium grade is high, creates for the recycling of titanium
Advantage.
Electric furnace smelting vanadium titano-magnetite process can be divided into electric furnace and melt split flow and electric furnace deeply also according to the trend of vanadium in smelting
Former process two major classes.It is that the v-ti magnetite concentrate of prereduction is melted to separation in electric furnace that electric furnace, which melts split flow, vanadium and titanium enrichment
In slag phase, vanadium titanium is extracted from slag phase.Electric furnace reduction process deeply is to carry out the v-ti magnetite concentrate product of prereduction in electric furnace
Deep reduction, makes vanadium enter molten iron, titanium is enriched in slag phase.Melting main problem existing for split flow for electric furnace is required raw material
Degree of metalization is relatively high, and subsequent vanadium extraction, titanium are difficult, and vanadium and titanium slag treatment long flow path, and production energy consumption is high.Deeply also for electric furnace
For former process, its advantage is that be conducive to recycle vanadium, while deep reduction post-processing process short, the production energy consumption that compared with electric furnace melts split flow
Low, environmental pollution is relatively small, and external South Africa and New Zealand all use electric furnace depth reducing and smelting vanadium titano-magnetite.On the other hand, it adopts
It is much larger than the vanadium slag amount that electric furnace depth reduction process obtains with the molten vanadium and titanium slag amount got of electric furnace, to the treating capacity of vanadium slag
Can be more, since environmental pollution is serious for vanadium extracting process, and the electric furnace reduction subsequent vanadium extraction technology maturation of process deeply, and vanadium extracting process
Material handling capacity is relatively low, and ambient pollution burden is relatively small, is conducive to the control of environmental pollution, but electric furnace reduction process iron deeply
Vanadium titanium strike angle is more difficult, such as can solve vanadium titanium and moves towards problem, electric furnace reduction process deeply as electric furnace smelting process more
It is ideal.
Restore existing slag iron separation difficulty deeply for electric furnace, vanadium titanium moves towards the problems such as difficult to control, external South Africa and Xin Xi
Quartz and dolomite is added in Lan Deng enterprise in smelting process, is restored using the crossing for technology controlling and process titanium oxide of excessive slag making,
It is gone on smoothly though can make to smelt, slag iron separation is good, can only recycle iron and vanadium, gained Ti-containing slag TiO2Grade only has 30-
35% or so, and main titaniferous object is mutually the Perovskite Phase of acid hydrolysis difference, titanium resource therein is unable to get effective recycling.
It Sichuan Long Mang group and climbs steel vanadium titano-magnetite is smelted using rotary hearth furnace direct-reduction-electric furnace reduction process deeply, in smelting process
In for guarantee Ti-containing slag TiO2Grade, using not slagging process, though TiO can be obtained2The Ti-containing slag of grade 50% or so, but
It is unfavorable for vanadium titanium strike angle, that there are slag iron separation effects is poor, smelting process is difficult to control, furnace inner lining corrodes the problems such as serious,
It is out of service at present.In summary, it there is no a suitable slag type system that can both realize vanadium titano-magnetite electric furnace smelting at present
Refining process vanadium titanium strike angle, and it is able to achieve titanium resource recycling, this severely limits China's prereduction-electric furnace process to comprehensively utilize vanadium
The industrial applications of titanomagnetite.
Summary of the invention
For there are titanium, barium oxide reduction to move towards slag iron hardly possible difficult to control during v-bearing titanomagnetite smelting in the prior art
Separation, the problems such as lining wear is serious, titanium resource difficult recycling, the object of the present invention is to provide a kind of achievable vanadium titano-magnetite electricity
Furnace smelting process vanadium titanium strike angle and the slag type system of titanium recycling, reduce smelting operation difficulty, are that prereduction-electric furnace process is comprehensive
It closes and provides technical support using the industrial application of vanadium titano-magnetite.
The present invention is the following technical schemes are provided: a kind of slag type system of electric furnace smelting vanadium titano-magnetite, comprising:
Electric furnace is added to by setting ratio by vanadium titano-magnetite prereduction product, containing calcium flux, flux containing magnesium and reducing agent
The deep reduction of middle progress, smelting temperature are 1550~1650 DEG C, after slag iron separation, obtain vanadium-bearing hot metal and Ti-containing slag, titaniferous furnace
The main titaniferous object of slag is mutually magnesium titanate phase (MgTiO3), gained vanadium-bearing hot metal is used for vanadium extraction by converter blowing, and Ti-containing slag can be used
Sulfuric acid process mentions titanium；
In smelting, calcium content forms CaO:SiO according to clinker2(mass ratio)=0.6~1.0, which is added, contains calcium flux；Magnesium contains
Amount forms MgO:TiO according to clinker2(molar ratio)=(1.1~0.8): 1 is added flux containing magnesium.
Further, the SiO in the vanadium titano-magnetite prereduction product2Content is lower than 4%.
Further, be added containing calcium flux include but is not limited to lime, lime stone, dolomite, quick lime, calcium oxide,
Calcium carbonate.
Further, the flux containing magnesium being added includes but is not limited to dolomite, magnesite, magnesia, magnesium carbonate.
The present invention uses magnesium titanate (MgTiO3) it is used as the main object phase of slag making, reduction generates the titanium carbide for making clinker retrogradation
Temperature it is high, be conducive to the reduction for inhibiting titanium, reduce smelting operation difficulty；Magnesium titanate acidolysis performance is good, using it as titanium slag
Main object be mutually conducive to subsequent sulphuric acid method recovery Pd.Smelt vanadium titano-magnetite when titanium oxide cross reduction generate titanium carbide or
Titanium carbonitride easily causes cinder viscosity to increase, and difficult even smelt of slag iron separation can not direct motion.In order to inhibit going back for titanium oxide
Original increases the reduction difficulty of titanium oxide in slag, and the titaniferous object in slag mutually should be mainly based on the titanium oxide of hardly possible reduction.In
Under standard state, CaTiO3、MgTiO3、MgTi2O5The temperature for reverting to titanium carbide is respectively 1863K, 1659K and 1629K.Calcium
Although titanium ore is more difficult to restore, but Perovskite Phase acid hydrolysis is poor, if using perovskite as slag making object phase if subsequent titanium resource be difficult to use
Mature sulfuric acid process is recycled, and then acid hydrolysis is good for the phase of object containing magnesium magnesium titanate, and reduction temperature is also higher, can be used as slag making master
Object phase is wanted, the purpose for inhibiting titanium reduction while guaranteeing titanium resource recoverable is advantageously implemented.Due to low price barium oxide category
In basic anhydride, properly increasing basicity of slag may advantageously facilitate vanadium reduction into molten iron, realize the control of vanadium titanium trend.
The present invention has the advantages that
, it can be achieved that V-Ti-magnetite is smelted, the vanadium-bearing hot metal of production can be recycled slag type system proposed by the present invention by converter
Iron and vanadium, for the titanium slag of production with magnesium titanate for main titaniferous object phase, acid hydrolysis is good, can be used as the raw material of sulfate process titanium dioxide, real
The comprehensive utilization of vanadium titano-magnetite is showed；It also can guarantee gained after appropriate slag making as raw material using low silicon v-ti magnetite concentrate
Titanium slag TiO with higher2Grade, to meet the requirement that subsequent sulphuric acid method prepares titanium dioxide；It is used as and is made using magnesium titanate
Slag object is mutually conducive to the reduction for inhibiting the reduction of titanium oxide and promoting barium oxide, reduces smelting operation difficulty, realizes
Vanadium is into molten iron, effective control of titanium slag input in electric furnace smelting；During electric furnace smelting vanadium titano-magnetite, the low furnace of content of magnesium
Slag easily corrodes furnace lining containing magnesium, and using magnesium titanate as slag making object phase, the content of magnesium of clinker is high, can reduce clinker to electric furnace liner
Erosion, prolong the service life, reduce production cost.
Specific embodiment
A specific embodiment of the invention, but a specific embodiment of the invention are further illustrated below by embodiment
It is not limited to following embodiment.
The vanadium titano-magnetite pre-reduced pellet that the present embodiment uses mainly forms as follows: TFe=71.37%, MFe=
64.56%, TiO2=15.53%, SiO2=3.71%.
Embodiment 1
It is proportionally added into electric furnace, presses by v-ti magnetite concentrate pre-reduced pellet, containing calcium flux, flux containing magnesium and reducing agent
According to MgO:TiO2Magnesia flux is added in molar ratio 0.8:1, according to the prewired basicity 0.8 of v-ti magnetite concentrate prereduction product form
(mass ratio CaO:SiO2), 1550 DEG C of smelting temperature, duration of heat 60min, mixed carbon comtent 2% and contains isolated vanadium-bearing hot metal
Titanium clinker, gained vanadium-bearing hot metal are used for vanadium extraction by converter blowing, can obtain containing TiO2=48.15% Ti-containing slag, the master of Ti-containing slag
Wanting object is mutually magnesium titanate, and sulfuric acid process preparing titanium dioxide can be used in Ti-containing slag.
Embodiment 2
It is proportionally added into electric furnace, presses by v-ti magnetite concentrate prereduction product, containing calcium flux, flux containing magnesium and reducing agent
According to MgO:TiO2Magnesia flux is added in molar ratio 1:1, according to the prewired basicity 0.7 of v-ti magnetite concentrate prereduction product form
(mass ratio CaO:SiO2), 1600 DEG C of smelting temperature, duration of heat 40min, mixed carbon comtent 2% and contains isolated vanadium-bearing hot metal
Titanium clinker, gained vanadium-bearing hot metal are used for vanadium extraction by converter blowing, can obtain containing TiO2=46.45% Ti-containing slag, the master of Ti-containing slag
Wanting object is mutually magnesium titanate, and sulfuric acid process preparing titanium dioxide can be used in Ti-containing slag.
Embodiment 3
It is proportionally added into electric furnace, presses by v-ti magnetite concentrate prereduction product, containing calcium flux, flux containing magnesium and reducing agent
According to MgO:TiO2Magnesia flux is added in molar ratio 1.1:1, according to the prewired basicity 0.6 of v-ti magnetite concentrate prereduction product form
(mass ratio CaO:SiO2), 1650 DEG C of smelting temperature, duration of heat 20min, mixed carbon comtent 2% and contains isolated vanadium-bearing hot metal
Titanium clinker, gained vanadium-bearing hot metal are used for vanadium extraction by converter blowing, can obtain containing TiO2=45.90% Ti-containing slag, the master of Ti-containing slag
Wanting object is mutually magnesium titanate, and sulfuric acid process preparing titanium dioxide can be used in Ti-containing slag.
The above is only a preferred embodiment of the present invention, protection scope of the present invention is not limited merely to above-mentioned implementation
Example.To those of ordinary skill in the art, obtained improvement and change in the case where not departing from the technology of the present invention concept thereof
It changes and also should be regarded as protection scope of the present invention.
Claims (4)
1. a kind of slag type system of electric furnace smelting vanadium titano-magnetite, characterized by comprising:
By vanadium titano-magnetite prereduction product, containing calcium flux, flux containing magnesium and reducing agent by setting ratio be added in electric furnace into
The deep reduction of row, smelting temperature are 1550~1650 DEG C, after slag iron separation, obtain vanadium-bearing hot metal and Ti-containing slag, Ti-containing slag
Main titaniferous object is mutually magnesium titanate phase, and gained vanadium-bearing hot metal is used for vanadium extraction by converter blowing, and Ti-containing slag can be used sulfuric acid process and mention titanium；
In smelting, calcium content forms CaO and SiO according to clinker2Mass ratio be 0.6~1.0 be added contain calcium flux；Content of magnesium is pressed
MgO and TiO is formed according to clinker2Molar ratio be (1.1~0.8): 1 be added flux containing magnesium.
2. a kind of slag type system of electric furnace smelting vanadium titano-magnetite according to claim 1, which is characterized in that the vanadium titanium
SiO in magnetic iron ore prereduction product2Content is lower than 4%.
3. a kind of slag type system of electric furnace smelting vanadium titano-magnetite according to claim 1, which is characterized in that be added
It include but is not limited to lime, lime stone, dolomite, quick lime, calcium oxide, calcium carbonate containing calcium flux.
4. a kind of slag type system of electric furnace smelting vanadium titano-magnetite according to claim 1, which is characterized in that be added
Flux containing magnesium includes but is not limited to dolomite, magnesite, magnesia, magnesium carbonate.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113846236A (en) * | 2021-09-18 | 2021-12-28 | 中南大学 | Method for removing vanadium, manganese and chromium impurities in acid-soluble titanium slag |
| CN114774612A (en) * | 2022-04-15 | 2022-07-22 | 黑龙江建龙钢铁有限公司 | Method for vanadium-titanium ore gas-based shaft furnace reduction-electric furnace melting reduction |
| CN115522074A (en) * | 2022-09-19 | 2022-12-27 | 攀钢集团攀枝花钢铁研究院有限公司 | Slagging method for electric furnace smelting of vanadium-titanium magnetite |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115522074A (en) * | 2022-09-19 | 2022-12-27 | 攀钢集团攀枝花钢铁研究院有限公司 | Slagging method for electric furnace smelting of vanadium-titanium magnetite |
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