CN102477509B - Preparation method of medium ferrovanadium - Google Patents
Preparation method of medium ferrovanadium Download PDFInfo
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- CN102477509B CN102477509B CN 201010575462 CN201010575462A CN102477509B CN 102477509 B CN102477509 B CN 102477509B CN 201010575462 CN201010575462 CN 201010575462 CN 201010575462 A CN201010575462 A CN 201010575462A CN 102477509 B CN102477509 B CN 102477509B
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Abstract
The invention provides a preparation method of medium ferrovanadium. The method comprises the following steps of: contacting a vanadium-extracting lixivium with a water-soluble ferric salt; controlling the pH value of a reaction system to be in a range of 1.8-2.8 through adding calcium hydroxide and/or calcium oxide in the contact process; carrying out solid-liquid separation on a product obtained after contact so as to obtain a solid containing ferric vanadate and calcium vanadate; calcining and dewatering the obtained solid and then evenly mixing the solid with aluminum powder, calcium oxide and magnesium oxide; and smelting the evenly mixed mixture in an induction furnace to obtain medium ferrovanadium. The method provided by the invention is a medium ferrovanadium preparation method which is simple in production process and low in cost.
Description
Technical field
The present invention relates to a kind of preparation method of middle vanadium iron.
Background technology
Vanadium iron is mainly as the alloy addition of making steel.After adding vanadium iron in steel, can significantly improve hardness, intensity, toughness, the wear resistance of steel.Vanadium iron is usually used in carbon steel, low alloy steel, strength steel, high quality steel, tool steel and Cast Iron Production.
At present, smelting ferrovanadium mainly contains the methods such as vanadous oxide, Vanadium Pentoxide in FLAKES, ferric vandate and the smelting of vanadic acid calcium both at home and abroad.Wherein, take vanadous oxide and Vanadium Pentoxide in FLAKES as the raw material smelting ferrovanadium, adopt silicothermic process, thermite process or carbothermy to obtain qualified middle vanadium iron product.But vanadous oxide and Vanadium Pentoxide in FLAKES normally extract from the sodium roasting vanadium-extracting leach liquor, and pilot process is complicated, and produces reluctant acid ammoniated wastewater, and production cost is high.
CN101104891A has introduced a kind of ferrous iron and precipitated ferric vandate from low vanadium solution, then utilize the ferric vandate preparation to contain the method for vanadium iron, in this method, vanadium directly obtains ferric vandate with the ferrous iron precipitation, contain vanadium, iron and oxygen element in throw out, can be directly used in vanadium iron smelts, simplified technique, ammonium salt-containing not in the waste water that obtains has reduced production cost.What but this method adopted is the ferrous iron precipitation, because ferrous iron has reductibility, can with the vanadium extraction leach liquor in V
5+And Cr
6+React, form V
4+, Cr
3+And Fe
3+, in adding alkali adjusting pH value 5-6 process, except forming the ferric vandate precipitation, also can form VO (OH)
2, Cr (OH)
3, Fe (OH)
3, Fe (OH)
2Deng throw out, the precipitated product complicated component causes washing and filtration difficulty, simultaneously impurity Cr (OH)
3Entering throw out can make and bring impurity Cr in the vanadium iron smelting process into.
CN101100720A has introduced the technique with smelting vanadium iron from calcium vanadate, and its method is that vanadic acid calcium, aluminium powder, irony material are added according to certain ratio, and energising is smelted and made ferro-vanadium.This method has been saved the production link of vanadium oxide, has avoided the problem of the acid ammonium salt waste water that vanadium oxide production brings, and slag fluidity is good, but this method quantity of slag is large, and need to add in addition iron powder, and production process is controlled complicated.
Summary of the invention
To the objective of the invention is the problem that exists in the vanadium iron smelting technology in existing in order overcoming, to provide a kind of production technique simple, low a kind of of cost method of vanadium iron in preparation from the vanadium extraction leach liquor.
The invention provides a kind of preparation method of middle vanadium iron, the method comprises the vanadium extraction leach liquor is contacted with water-soluble trivalent ferric salt, remain in the 1.8-2.8 scope by the pH value that adds calcium hydroxide and/or calcium oxide to control reaction system in contact process, product after contact obtains containing the solid of ferric vandate and vanadic acid calcium through solid-liquid separation, with this solid of obtaining after calcined dehydration, mix with aluminium powder, calcium oxide, magnesium oxide again, this mixture that mixes is smelted in induction furnace obtained middle vanadium iron.
Middle vanadium iron preparation method of the present invention compared with prior art has following advantage.
1) in the present invention, ferric vandate is the FeVO4xH2O of crystal habit, and deposition rate is high, and product is easy to washing and filters;
2) can regulate the pH value by adding milk of lime, milk of lime is cheap, is easy to save cost; And do not produce ammoniated wastewater, in the vanadium iron smelting process, the quantity of slag is few, has reduced subsequent treatment cost; Need not add iron powder or vanadium oxide, save the cost of raw material.
3) contain calcium in solid product, be evenly distributed, be conducive to the carrying out of smelting, the add-on of step compounding process lime after saving simultaneously.
Embodiment
The invention provides a kind of preparation method of middle vanadium iron, the method comprises the vanadium extraction leach liquor is contacted with water-soluble trivalent ferric salt, remain in the 1.8-2.8 scope by the pH value that adds calcium hydroxide and/or calcium oxide to control reaction system in contact process, product after contact obtains containing the solid of ferric vandate and vanadic acid calcium through solid-liquid separation, with this solid of obtaining after calcined dehydration, mix with aluminium powder, calcium oxide, magnesium oxide again, this mixture that mixes is smelted in induction furnace obtained middle vanadium iron.
In the present invention, described vanadium extraction leach liquor can be for adopting the prepared various vanadium extraction leach liquors of method well known in the art.The sodium vanadium extraction leach liquor that for example can prepare for the method for vanadium slag sodium roasting-water logging.Preferably, the vanadium concentration in described vanadium extraction leach liquor can be 20-30g/L.
In the present invention, the chemical equation that relates in each stage is as follows:
The vanadium extraction leach liquor is contacted with water-soluble trivalent ferric salt, remains in the 1.8-2.8 scope by the pH value that adds calcium hydroxide and/or calcium oxide to control reaction system in contact process, generate the reaction of precipitation:
2VO
3 -+Ca(OH)
2→Ca(VO
3)
2↓+2OH
-
Fe
3++VO
3 -+2.5H
2O＝FeVO
4·1.5H
2O↓+2H
+
With the ferric vandate calcined dehydration:
FeVO
4·1.5H
2O＝FeVO
4+1.5H
2O↑
Solid and aluminium powder, calcium oxide, the magnesium oxide of ferric vandate and vanadic acid calcium are mixed, and smelting obtains middle vanadium iron in induction furnace:
3FeVO
4+8Al＝3FeV+4Al
2O
3
3Ca(VO
3)
2+10Al＝5Al
2O
3+6V+3CaO
In the present invention, the consumption of described water-soluble trivalent ferric salt can be selected according to the content of vanadium in the vanadium extraction leach liquor.Particularly, can be in v element and ferro element, in the vanadium in described vanadium extraction leach liquor and water-soluble trivalent ferric salt, the mol ratio of iron is 1: 1.05-1.5; Under the prerequisite that the assurance reaction is carried out smoothly, taking cost into account, be preferably in v element and ferro element, in the vanadium in described vanadium extraction leach liquor and water-soluble trivalent ferric salt, the mol ratio of iron is 1: 1.1-1.3.
In the present invention, by the vanadium extraction leach liquor is contacted with water-soluble trivalent ferric salt, keep within the specific limits by the pH value that adds calcium hydroxide and/or calcium oxide to control reaction system in contact process, thereby precipitin reaction is carried out.Wherein, the temperature that above-mentioned vanadium extraction leach liquor contacts with water-soluble trivalent ferric salt can be 50-105 ℃, and the time of contact can be 50-180 minute; Being preferably the temperature that the vanadium extraction leach liquor contacts with water-soluble trivalent ferric salt is 80-100 ℃, and the time of contact is 60-120 minute.
The pH value of above-mentioned reaction system generally remains in the 1.8-2.8 scope, and the pH value that is preferably above-mentioned reaction system remains in the 2-2.5 scope.Method in the pH value of controlling reaction system can be the whole bag of tricks known in the field.The present invention is preferably the pH value that adopted the pH acidometer to come the assaying reaction system every 5-15 minute, judges the amount of interpolation calcium hydroxide and/or calcium oxide according to measured value, thereby the pH value that makes reaction system is in specialized range.Described calcium hydroxide can be for solid, can be also aqua calcis, is preferably solid, because the milk of lime cost is low, and from considering economically, milk of lime more preferably.When adding above-mentioned calcium oxide, calcium oxide first with reaction system in the water reaction generate calcium hydroxide, then participate in reaction and regulate the pH value by calcium hydroxide.
In the present invention, described water-soluble trivalent ferric salt can be various water-soluble trivalent iron salts known in the field.Be preferably the large trivalent iron salt of solubleness in water, particularly, can be iron(ic) chloride and/or iron nitrate.
In the present invention, the product after described contact obtains containing the solid of ferric vandate and vanadic acid calcium through solid-liquid separation.Described solid-liquid separation can be the whole bag of tricks known in the field.Such as the method such as filtering, centrifugal.The present invention is preferably filtration.Also comprise a small amount of water glass, Calucium Silicate powder and water in the solid that solid-liquid separation obtains.
In the present invention, the method also comprises washs filtering the resulting solid that contains ferric vandate and vanadic acid calcium, and the solvent of described washing is water, and the consumption of water can be selected according to specific circumstances.Generally, the consumption of water can be the 80-90% of the volume of reaction system.
In the present invention, the solid that will contain ferric vandate and vanadic acid calcium is calcined, to remove the water of being combined with ferric vandate in the ferric vandate hydrate.The condition of described calcining can be various conditions known in those skilled in the art.It is 500-600 ℃ that the present invention is preferably calcining temperature, and the time is 2-3 hour.
In the present invention, the solid after calcined dehydration and aluminium powder, calcium oxide, magnesium oxide are mixed, then this mixture that mixes is smelted in induction furnace obtained middle vanadium iron.Wherein, solid after calcined dehydration and aluminium powder, calcium oxide, magnesian usage ratio, can be for the described solid after the calcined dehydration of 100 weight parts as benchmark, described and aluminium powder, calcium oxide, when magnesium oxide mixes, the add-on of aluminium powder is that the add-on of 42-44 weight part, calcium oxide is that 7-10 weight part, magnesian add-on are the 4-5 weight part.The condition of described smelting can be various conditions known in the field.The temperature of for example smelting is 1800-1900 ℃, and the time of smelting is 60-90 minute.
The present invention will be described in detail by the following examples, but the present invention is not limited in following embodiment.
Vanadium extraction leach liquor in following examples: carry out sodium roasting vanadium-extracting according to the method described in " external vanadium metallurgical " (metallurgical industry press, published 121 pages in 1985), obtain the sodium roasting vanadium-extracting leach liquor.
Vanadium concentration (in Vanadium Pentoxide in FLAKES) adopts chemical titration to measure, concrete grammar is: accurately pipette sample 10ml, add 50ml water, slowly inject 10ml sulfuric acid, heating for dissolving, cooling, add 4 0.1% phenylanthranilic acid ethanolic solns, be titrated to solution with 0.1mol/L ferrous sulfate standardized solution and become bright green by red-purple.Then the ferrous sulfate volume of using according to titration and the volume of concentration and the solution of getting calculate vanadium concentration.
The vanadiumcontent of middle vanadium iron adopts GB/T 8704.5-1994 vanadium iron chemical analysis method potentiometric determination vanadium amount.
Embodiment 1
The present embodiment is used for the preparation method of explanation vanadium iron.
the vanadium extraction leach liquor that is 25g/L with 1L vanadium concentration is heated to 100 ℃, then according to Fe: the mol ratio of V=1.1 adds iron nitrate in solution, stir, reacted 60 minutes, adopt milk of lime to regulate the pH value in reaction process, make the pH value stabilization in the 2.0-2.1 scope, the reaction complete after with the gained solution filter, use the quick washing of water of 800ml to obtain containing ferric vandate and vanadic acid calcium solid, with the solid that obtains, dry, calcining dehydration in 2 hours under 500 ℃, obtain ferric vandate and vanadic acid calcium solid mixture 80g, then add aluminium powder 33.6g, calcium oxide 5.6g part, magnesium oxide 3.2g, fully mix, putting into induction furnace smelts, be warming up to 1800 ℃, keep molten state, react after 60 minutes, stop energising, naturally cooling, can obtain middle vanadium iron 47.2g, contain vanadium 50.3 % by weight.
Embodiment 2
The present embodiment is used for the preparation method of explanation vanadium iron.
the vanadium extraction leach liquor that is 30g/L with the vanadium concentration of 1L is heated to 80 ℃, then according to Fe: the mol ratio of V=1.2 adds iron(ic) chloride in solution, stir, reacted 80 minutes, adopt calcium hydroxide to regulate the pH value in reaction process, make the pH value stabilization at 2.3-2.4, the reaction complete after with the gained solution filter, use the quick washing of water of 900ml to obtain containing ferric vandate and vanadic acid calcium solid, with the solid that obtains, dry, in 560 ℃ of calcinings dehydration in 2.5 hours, obtain ferric vandate and vanadic acid calcium solid mixture 95g, then add aluminium powder 39.9g, calcium oxide 7.6g part, magnesium oxide 4.8g, fully mix, putting into induction furnace smelts, be warming up to 1850 ℃, keep molten state, react after 75 minutes, stop energising, naturally cooling, can obtain vanadium iron in 55.7g, contain vanadium 50.1 % by weight
Embodiment 3
The present embodiment is used for the preparation method of explanation vanadium iron.
the vanadium extraction leach liquor that is 27g/L with 1L vanadium concentration is heated to 90 ℃, then according to Fe: the mol ratio of V=1.3 adds iron nitrate in solution, stir, reaction 1h, adopt milk of lime to regulate the pH value in reaction process, make the pH value stabilization at 2.4-2.5, the reaction complete after with the gained solution filter, use 800ml to wash fast and obtain containing ferric vandate and vanadic acid calcium solid, with gained ferric vandate and vanadic acid calcium solid, dry, in 600 ℃ of calcinings dehydration in 3 hours, obtain ferric vandate and vanadic acid calcium solid mixture 86g, then add aluminium powder 37.8g, calcium oxide 8.2g part, magnesium oxide 3.9g, fully mix, putting into induction furnace smelts, be warming up to 1900 ℃, keep molten state, react after 90 minutes, stop energising, naturally cooling, can obtain vanadium iron in 50.6g, containing vanadium is 50.2 % by weight.
Embodiment 4
The present embodiment is used for the preparation method of explanation vanadium iron.
Adopt vanadium iron in the method preparation in embodiment 1, different is that milk of lime is replaced with calcium oxide.Obtain vanadium iron in 49.3g, containing vanadium is 49.8 % by weight.
Claims (10)
1. the preparation method of vanadium iron in a kind, the method comprises the vanadium extraction leach liquor is contacted with water-soluble trivalent ferric salt, remain in the 1.8-2.8 scope by the pH value that adds calcium hydroxide and/or calcium oxide to control reaction system in contact process, product after contact obtains containing the solid of ferric vandate and vanadic acid calcium through solid-liquid separation, with this solid of obtaining after calcined dehydration, mix with aluminium powder, calcium oxide, magnesium oxide again, this mixture that mixes is smelted in induction furnace obtained middle vanadium iron.
2. method according to claim 1, wherein, the temperature that described vanadium extraction leach liquor contacts with water-soluble trivalent ferric salt is 50-105 ℃, the time of contact is 50-180 minute.
3. method according to claim 2, wherein, the temperature that described vanadium extraction leach liquor contacts with water-soluble trivalent ferric salt is 80-100 ℃, the time of contact is 60-120 minute.
4. method according to claim 1, wherein, the pH value of described reaction system remains in the 2-2.5 scope.
5. the described method of any one according to claim 1-4, wherein, in v element and ferro element, in the vanadium in described vanadium extraction leach liquor and water-soluble trivalent ferric salt, the mol ratio of iron is 1: 1.05-1.5.
6. method according to claim 5, wherein, in v element and ferro element, in the vanadium in described vanadium extraction leach liquor and water-soluble trivalent ferric salt, the mol ratio of iron is 1: 1.1-1.3.
7. the described method of any one according to claim 1-4, wherein, described water-soluble trivalent ferric salt is iron(ic) chloride and/or iron nitrate.
8. method according to claim 1, wherein, the temperature of described calcined dehydration is 500-600 ℃, the time is 2-3 hour.
9. according to claim 1 or 8 described methods, wherein, described solid after the calcined dehydration of 100 weight parts is as benchmark, described and aluminium powder, calcium oxide, when magnesium oxide mixes, the add-on of aluminium powder is that the add-on of 42-44 weight part, calcium oxide is that 7-10 weight part, magnesian add-on are the 4-5 weight part, the temperature of described smelting is 1800-1900 ℃, and the time of smelting is 60-90 minute.
10. method according to claim 1, wherein, in described vanadium extraction leach liquor, vanadium concentration is 20-30g/L.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101104891A (en) * | 2007-08-10 | 2008-01-16 | 三穗县恒峰矿业有限公司 | Method for preparing vanadium-iron from low-vanadium solution |
| CN101693932A (en) * | 2009-10-19 | 2010-04-14 | 攀钢集团攀枝花钢钒有限公司 | Method for producing ferrovanadium |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101104891A (en) * | 2007-08-10 | 2008-01-16 | 三穗县恒峰矿业有限公司 | Method for preparing vanadium-iron from low-vanadium solution |
| CN101693932A (en) * | 2009-10-19 | 2010-04-14 | 攀钢集团攀枝花钢钒有限公司 | Method for producing ferrovanadium |
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