CN101724752B - Method for smelting medium ferrovanadium - Google Patents
Method for smelting medium ferrovanadium Download PDFInfo
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- CN101724752B CN101724752B CN2009103124946A CN200910312494A CN101724752B CN 101724752 B CN101724752 B CN 101724752B CN 2009103124946 A CN2009103124946 A CN 2009103124946A CN 200910312494 A CN200910312494 A CN 200910312494A CN 101724752 B CN101724752 B CN 101724752B
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- 238000003723 Smelting Methods 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 54
- PNXOJQQRXBVKEX-UHFFFAOYSA-N iron vanadium Chemical compound [V].[Fe] PNXOJQQRXBVKEX-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910000628 Ferrovanadium Inorganic materials 0.000 title claims abstract description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000000463 material Substances 0.000 claims abstract description 35
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 33
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052742 iron Inorganic materials 0.000 claims abstract description 29
- 239000004411 aluminium Substances 0.000 claims abstract description 23
- 238000007670 refining Methods 0.000 claims abstract description 19
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 18
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 18
- 239000004571 lime Substances 0.000 claims abstract description 18
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000010436 fluorite Substances 0.000 claims abstract description 10
- 229910045601 alloy Inorganic materials 0.000 claims description 28
- 239000000956 alloy Substances 0.000 claims description 28
- 239000004615 ingredient Substances 0.000 claims description 24
- 229910014460 Ca-Fe Inorganic materials 0.000 claims description 16
- 238000005453 pelletization Methods 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 abstract description 22
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 abstract description 22
- 238000006243 chemical reaction Methods 0.000 abstract description 17
- 238000011084 recovery Methods 0.000 abstract description 16
- 239000002893 slag Substances 0.000 abstract description 10
- 241001062472 Stokellia anisodon Species 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000005272 metallurgy Methods 0.000 abstract description 3
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 abstract 6
- 229910021541 Vanadium(III) oxide Inorganic materials 0.000 abstract 2
- 238000006722 reduction reaction Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- -1 aluminium calcium iron Chemical compound 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229910004261 CaF 2 Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000013467 fragmentation Methods 0.000 description 3
- 238000006062 fragmentation reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- 239000003832 thermite Substances 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 241001417490 Sillaginidae Species 0.000 description 1
- XQKJGVVPXOQJDD-UHFFFAOYSA-N [Fe].[C].[V] Chemical compound [Fe].[C].[V] XQKJGVVPXOQJDD-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000003886 thermite process Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention belongs to the metallurgy field and in particular relates to a method for smelting medium ferrovanadium. The invention aims to solve the technical problem of an electro-aluminothermic process with high vanadium recovery from smelting and is specifically characterized by adopting the mixed materials of V2O5 and V2O3 as the raw materials and using the electro-aluminothermic process to smelt the medium ferrovanadium. The method comprises the following steps: A. preparing bottom materials and main materials; B firstly adding the bottom materials for smelting at the initial stage of smelting; C. then adding the main materials after the bottom materials react steadily; and D. refining. The bottom materials include aluminium, V2O5, iron and lime. The main materials include V2O3, aluminium, V2O5, iron, lime and fluorite. The method not only fully utilizes the reaction heat, but also simplifies the technological process, reduces the viscosity of the slag and ensures the ferrovanadium recovery from smelting to be steadily increased by over 96%.
Description
Technical field
The invention belongs to field of metallurgy, be specifically related to middle method for smelting medium ferrovanadium.
Background technology
Vanadium is widely used in industries such as metallurgy, aerospace, chemical industry with the form of vanadium iron, vanadium compound and vanadium metal, and vanadium iron is the important alloy addition of Iron And Steel Industry, can improve intensity, toughness, ductility and the thermotolerance of steel.
At present, the method for vanadium iron mainly contains electro-silicothermic process and thermit reduction in the production both at home and abroad.
The vanadium iron initial reaction stage was reductive agent reduction barium oxide with FeSi75 during electro-silicothermic process was smelted; Is the refining agent refining reduction in refining period with the Alsimin, and smelting cycle is about 4-6h, and the vanadium smelting recovery is more than 96%; Be the main method that middle vanadium iron is smelted at present; But this method complex manufacturing, smelting cycle is long, is difficult to produce high-quality vanadium iron.Relatively and right, the thermit reduction smelting cycle is about 1.5h, shortens greatly tap to tap time, can produce the vanadium iron of high-quality little carbon, but production cost is slightly high.
By its difference of using raw material, the thermit reduction smelting ferrovanadium can be divided into V
2O
5Thermit reduction and V
2O
3The electrit hot reducing method, it is excessive that the former reacts thermal value, and consumption aluminium is many, and cost is higher, and is prone to the splash phenomenon in the reaction process, has a strong impact on the recovery of vanadium.By contrast, with V
2O
3For raw material carries out the corresponding reduction of aluminium amount that the thermite reduction reaction is consumed, use V in theory
2O
3Smelting ferrovanadium compares V
2O
5Smelting ferrovanadium can be practiced thrift 40% aluminium, makes cost that bigger reduction arranged, and this also is V
2O
3The sharpest edges of smelting ferrovanadium.The contriver finds in application process, V
2O
3The electrit hot reducing method must be reinforced while switching on because reaction heat much smaller than the required heat of spontaneous reaction, must just can make this reaction row go down by external heat source, and whole smelting process all needs extraneous power supply to come additional heat, so V
2O
3Smelting ferrovanadium technology and V
2O
5Smelting ferrovanadium technology exists obviously different.The contriver also finds because V
2O
3Density is less, adopts powdery V
2O
3It is more serious to volatilize during smelting, influences the vanadium smelting direct yield, and because energising is longer tap to tap time, must strictly control manufacturing condition, exceeds standard easily otherwise smelt the middle vanadium iron carbon content that obtains, and influences the quality of vanadium iron.
So adopt two kinds of methods of vanadium iron in the thermite process production, a kind of energy surplus, a kind of energy shortage; The fusing point of slag is higher simultaneously, must reduce the content of vanadium in the slag through follow-up refining procedure, improves the recovery of vanadium; Make the technology even more complex, restricted the increase of middle vanadium iron output.Therefore, be necessary to study the method for vanadium iron in the electro-aluminothermic process smelting that a kind of smelting cycle is short, technological process is simple, the vanadium smelting recovery is high.
Summary of the invention
The technical problem that the present invention solved provides the method for vanadium iron in the high electro-aluminothermic process smelting of a kind of vanadium smelting recovery.Particularly, adopt V
2O
5And V
2O
3Mixture is a raw material, vanadium iron in smelting with electro-aluminothermic process, and step is following:
A, preparing bottom materials and major ingredient;
B, smelting initial stage, at first add bed material and smelt;
C, behind the bed material reacting balance, add major ingredient again;
D, refining.
Wherein, bed material is aluminium, V
2O
5, iron, lime; Major ingredient is V
2O
3, aluminium, V
2O
5, iron, lime, fluorite.
Preparing bottom materials should satisfy reaction fast fully, keeps higher reaction heat again, guarantees to form the molten bath.The bed material weight proportion is: V
2O
56.5-8.5 part, aluminium 3.5-4 part, lime 1.5-2 part, iron 2.5-3.5 part.
Theoretical consumption and reaction heat size according to the metallothermy reaction are confirmed the weight proportion relation between major ingredient: V
2O
520-40 part, V
2O
315-40 part, aluminium 23-28 part, lime 10-13 part, fluorite 4-5 part, iron 30-40 part.
Come out of the stove reverse mould, cooling, shrend alloy, vanadium iron finished product in conventional treatment processes such as break-iron, fragmentation, screening promptly get again after smelting end.
Method for smelting medium ferrovanadium among the present invention is earlier with aluminum shot, V
2O
5Be bed material, this reaction is violent, forms the molten bath at burner hearth bottom very soon, behind reacting balance, promptly in stove, adds V continuously
2O
5And V
2O
3Be main mixture, so both made full use of reaction heat, need not extraneous heat supply and smelt; Simplified technological process again; Simplify technological process, shortened to tap to tap time in the 1h, reduced slag viscosity; Smelt the low and vanadium smelting recovery height of comprehensive cost, the recovery steadily improves and reaches more than 96%.
Embodiment
Below through to the description of specific embodiment of the invention explanation but do not limit the present invention.
Method for smelting medium ferrovanadium is to adopt V among the present invention
2O
5And V
2O
3Mixture is a raw material, vanadium iron in smelting with electro-aluminothermic process, and step is following:
A, preparing bottom materials and major ingredient;
B, smelting initial stage, at first add bed material and smelt;
C, behind the bed material reacting balance, add major ingredient again;
D, refining.
Bed material is aluminium, V
2O
5, iron, lime, weight proportion is: V
2O
56.5-8.5 part, aluminium 3.5-4 part, lime (being CaO) 1.5-2 part, iron 2.5-3.5 part; Preferred V
2O
57.5 part, 3.85 parts in aluminium, 1.75 parts in lime, 3 parts of iron.
Major ingredient is V
2O
3, aluminium, V
2O
5, iron, lime, fluorite.Used aluminium, iron adopt aluminum shot and abrasive grit respectively, and weight proportion is: V
2O
520-40 part, V
2O
315-40 part, aluminium 23-28 part, lime 10-13 part, fluorite (are CaF
2) 4-5 part, iron 30-40 part.
Wherein, V in the major ingredient
2O
5With V
2O
3Weight proportion be V
2O
51-3 part, V
2O
31-3 part.
Used aluminium, iron adopt aluminum shot and abrasive grit respectively in bed material and the major ingredient.Lime can reduce the liquidus temperature and the viscosity of slag in the bed material, and iron and vanadium generate the fusing point that vanadium iron reduces alloy.
In the production preferably with V
2O
3Process pelletizing, so processing can solve V
2O
3Density is less, adopts powdery V
2O
3It is more serious to volatilize during smelting, influences the technical problem of vanadium smelting direct yield, and the pelletizing granularity is: 1mm～10mm, the pelletizing surface should be loose porous, has certain intensity, can not efflorescence behind the batch mixing.
Add fluorite in the major ingredient and can reduce slag viscosity and liquidus temperature, improve the smelting recovery of vanadium, the add-on of fluorite is the 10%-25% of aluminium amount, and granularity is 5mm～40mm.
Step B at first added bed material and smelts at the smelting initial stage, utilized the thermite reaction heat production, made it form the molten bath at burner hearth bottom, was beneficial to subsequent reactions;
Adopt the Al-Ca-Fe alloy refining during step D refining, and lower electrode energising striking insulation.The Al-Ca-Fe alloy that adds is refining agent, the Al-Ca-Fe alloy chemical ingredients by weight percentage: Al 45%～60%, Ca 15%～35%, surplus are iron and impurity; Foreign matter content is controlled to be: C≤0.05%, Si≤0.1%, P≤0.02%, S≤0.02%, Mn≤0.2%, impurity granularity are 1-3mm.The Al-Ca-Fe alloy granularity is controlled to be 1mm-40mm, if granularity is excessive, speed of response is slower, if undersized, scaling loss is bigger, and preferably its mean particle size is that the Al-Ca-Fe alloy of 5-30mm is preferable.The consumption of Al-Ca-Fe alloy too much can cause waste simultaneously, and being prone to increases production cost, and consumption is very few, then influences the smelting recovery of vanadium, and the add-on of general aluminium calcium iron is the 2%-6% of aluminum shot add-on;
Come out of the stove after smelt finishing, reverse mould, cooling, the shrend alloy, vanadium iron finished product in conventional treatment processes such as break-iron, fragmentation, screening promptly get again, the vanadium smelting recovery is up to more than 96%.
Embodiment 1
1, bed material proportioning: 75Kg V
2O
5, 38.5Kg Al, 17.5KgCaO, 30KgFe, bed material adds up to 161Kg.
2, major ingredient proportioning: 400Kg V
2O
5, 175Kg V
2O
3, 265Kg aluminum shot, 125Kg CaO, 50Kg CaF
2, 363Kg abrasive grit, 10Kg refining agent aluminium calcium iron.
Wherein, the chemical ingredients of Al-Ca-Fe alloy is by weight being Al 55, and Ca 25%, and surplus is iron and impurity.The foreign matter content of aluminium calcium iron is controlled to be: C≤0.05%, Si≤0.1%, P≤0.02%, S≤0.02%, Mn≤0.2%, granularity 1-3mm.
3, technological process: at first with V
2O
3Briquetting is then with aluminum shot, V
2O
5And V
2O
3Pelletizing, iron, lime, fluorite are raw material, adopt vanadium iron in the electro-aluminothermic process smelting.
A, smelting initial stage add bed material, with the magnesium chips striking of lighting or switch on, adopt thermite reaction to produce middle vanadium iron, and this reaction is violent, forms the molten bath at burner hearth bottom very soon, behind reacting balance, promptly in stove, adds V continuously
2O
5And V
2O
3Pelletizing is main major ingredient, the adjustment blanking velocity, and the assurance reaction in furnace leans on self-heating steadily to carry out.
After B, furnace charge added, the decline electrode and the striking of switching on added the Al-Ca-Fe alloy refining, the about 20min of energising insulation simultaneously, the smelting recovery of vanadium iron in carrying.
C, slag and alloy come out of the stove simultaneously after smelt finishing and pour ingot mould into, water filling is cooled off behind the about 30min of ingot mould cooling, and the shrend alloy is again through break-iron, fragmentation, screening, packing acquisition finished product.
Above-mentioned furnace charge obtains grade and is 49.6% FeV50 alloy 745Kg, alloy carbon content 0.15%, the residual vanadium 0.71% of lean slag, the vanadium smelting recovery 97.4% after smelting.
Embodiment 2
1, bed material proportioning: 75Kg V
2O
5, 38.5Kg Al, 17.5Kg CaO, 30Kg Fe, bed material adds up to 161Kg.
2, major ingredient proportioning: 300Kg V
2O
5, 300Kg V
2O
3, 260Kg aluminum shot, 123Kg CaO, 50Kg CaF
2, 375Kg abrasive grit, 10Kg refining agent aluminium calcium iron.
Wherein, the chemical ingredients of Al-Ca-Fe alloy is by weight being Al55%, and Ca 22%, and surplus is iron and impurity.The foreign matter content of aluminium calcium iron is controlled to be: C≤0.05%, Si≤0.1%, P≤0.02%, S≤0.02%, Mn≤0.2%, granularity 1-3mm.
3, technological process is basically with embodiment 1, and different is in stove, to add V continuously
2O
5And V
2O
3During the pelletizing mixture,, need the decline electrode striking additional heat of under low power, switching on if self-heating is not enough.After furnace charge adds, increase striking voltage, and add the Al-Ca-Fe alloy refining, the about 25min of energising insulation.
Above-mentioned furnace charge obtains grade and is 50.4% FeV50 alloy 766Kg, alloy carbon content 0.16%, the residual vanadium 0.81% of lean slag, the vanadium smelting recovery 96.9% after smelting.
Embodiment 3
1, bed material proportioning: V
2O
575Kg, Al 38.5Kg, CaO 17.5Kg, Fe 30Kg.Bed material adds up to 161Kg.
2, major ingredient proportioning: 240Kg V
2O
5, 360Kg V
2O
3, 230Kg aluminum shot, 110Kg CaO, 45KgCaF
2, 370Kg abrasive grit, 10Kg refining agent aluminium calcium iron.
Wherein, the chemical ingredients of Al-Ca-Fe alloy is by weight being Al 50%, and Ca 28%, and surplus is iron and impurity.The foreign matter content of aluminium calcium iron is controlled to be: C≤0.05%, Si≤0.1%, P≤0.02%, S≤0.02%, Mn≤0.2%, granularity 1-3mm.
3, technological process equally, is adding V continuously basically with embodiment 2 in stove
2O
5And V
2O
3During the pelletizing mixture,, need the decline electrode striking additional heat of under low power, switching on if self-heating is not enough.After furnace charge adds, increase striking voltage, and add the Al-Ca-Fe alloy refining, the about 25min of energising insulation.
Above-mentioned furnace charge obtains grade and is 50.1% FeV80 alloy 776Kg, alloy carbon content 0.18%, the residual vanadium 0.76% of lean slag, the vanadium smelting recovery 96.8% after smelting.
Technology of the present invention is simple, and on-the-spot transformation process is convenient, and feasibility is strong, and application prospect is wide.
Claims (7)
1. method for smelting medium ferrovanadium during electro-aluminothermic process prepares, it is characterized in that: it comprises the steps:
A, preparing bottom materials and major ingredient;
B, smelting initial stage, add and to light with magnesium chips behind the bed material or the striking of switching on is smelted;
C, behind the bed material reacting balance, add major ingredient again;
D, refining;
Wherein, bed material is aluminium, V
2O
5, iron, lime, weight proportion is: V
2O
56.5-8.5 part, aluminium 3.5-4 part, lime 1.5-2 part, iron 2.5-3.5 part;
Major ingredient is V
2O
3, aluminium, V
2O
5, iron, lime, fluorite, weight proportion is: V
2O
520-40 part, V
2O
315-40 part, aluminium 23-28 part, lime 10-13 part, fluorite 4-5 part, iron 30-40 part.
2. method for smelting medium ferrovanadium in the electro-aluminothermic process preparation according to claim 1 is characterized in that: with the V in the major ingredient
2O
3Process pelletizing.
3. method for smelting medium ferrovanadium in the electro-aluminothermic process preparation according to claim 1, it is characterized in that: steps A bed material weight proportion is: V
2O
57.5 part, 3.85 parts in aluminium, 1.75 parts in lime, 3 parts of iron.
4. according to method for smelting medium ferrovanadium in each described electro-aluminothermic process preparation of claim 1-3, it is characterized in that: adopt the Al-Ca-Fe alloy refining during step D refining, and lower electrode energising striking insulation.
5. method for smelting medium ferrovanadium in the electro-aluminothermic process according to claim 4 preparation is characterized in that: said Al-Ca-Fe alloy chemical ingredients by weight percentage: Al 45%～60%, Ca 15%～35%, surplus are iron and impurity; Foreign matter content is controlled to be: C≤0.05%, Si≤0.1%, P≤0.02%, S≤0.02%, Mn≤0.2%.
6. method for smelting medium ferrovanadium in the electro-aluminothermic process preparation according to claim 4, it is characterized in that: the said Al-Ca-Fe alloy granularity of step D is 1-30mm.
7. method for smelting medium ferrovanadium in the electro-aluminothermic process preparation according to claim 4, it is characterized in that: used aluminium is aluminum shot in bed material and the major ingredient, the said Al-Ca-Fe alloy add-on of step D is by weight the 2%-6% that counts the aluminum shot add-on.
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| CN102115821B (en) * | 2010-09-13 | 2013-01-23 | 攀钢集团钢铁钒钛股份有限公司 | Method for smelting ferrovanadium |
| CN102051518B (en) * | 2010-12-31 | 2012-06-27 | 攀钢集团钢铁钒钛股份有限公司 | Method for recycling fine ferrovanadium particles |
| CN102127640B (en) * | 2011-04-20 | 2012-10-17 | 攀枝花学院 | Method for producing moderate ferrovanadium |
| CN103045928A (en) * | 2012-12-31 | 2013-04-17 | 攀钢集团西昌钢钒有限公司 | Method for producing ferrovanadium by aluminothermic process |
| CN103397208B (en) * | 2013-07-11 | 2015-04-29 | 攀钢集团攀枝花钢铁研究院有限公司 | Process for smelting ferro-vanadium through electro-aluminothermic method |
| CN105018828B (en) * | 2015-08-13 | 2017-09-08 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind of preparation method of vanadium iron |
| CN105567966B (en) * | 2016-01-26 | 2017-09-08 | 攀钢集团攀枝花钢铁研究院有限公司 | Tumble the method for stove smelting ferrovanadium |
| CN106967917B (en) * | 2017-04-28 | 2019-03-19 | 攀钢集团研究院有限公司 | The control method of FeV80 alloy carbon content |
| CN107760887A (en) * | 2017-10-30 | 2018-03-06 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind of method that vanadium iron in low aluminium is smelted using stove of tumbling |
| CN107964599B (en) * | 2017-11-30 | 2020-02-04 | 攀钢集团攀枝花钢铁研究院有限公司 | Straight-barrel furnace ferrovanadium smelting method capable of improving vanadium yield |
| CN108300880B (en) * | 2018-02-02 | 2020-07-07 | 攀钢集团攀枝花钢铁研究院有限公司 | Preparation method of ferrovanadium alloy |
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