CN86106699A - The production method of vanadium slag - Google Patents
The production method of vanadium slag Download PDFInfo
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- CN86106699A CN86106699A CN86106699.5A CN86106699A CN86106699A CN 86106699 A CN86106699 A CN 86106699A CN 86106699 A CN86106699 A CN 86106699A CN 86106699 A CN86106699 A CN 86106699A
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Abstract
Vanadium slag with following ingredients and mineral composition is to produce with the vanadium iron of gaseous oxidant blowing certain ingredients.The composition of vanadium slag (% by weight) is: vanadium oxide-16～30, and silicon oxide-10～24, manganese oxide-6～14, chromic oxide-1～12, titanium oxide-6～14, calcium oxide-0.3～30.0, metallic iron-2～20, ferric oxide-all the other; The mineralogical composition of vanadium slag (% by weight) is: spinel-40～70, glass-2～10, pyroxene and peridotites one all the other, wherein spinel crystal grain has the geometrical shape of rule, grain-size is 25～80 microns.Resulting vanadium slag can be used for producing the product that contains vanadium, as Vanadium Pentoxide in FLAKES and contain the gold that contains of vanadium.
Description
The invention relates to a kind of metallurgical method, especially produce the method for vanadium slag about oxidation vanadium iron in top blast, bottom blowing or compound converter of blowing.
The resulting vanadium slag of oxidation vanadium iron is a raw material of producing Vanadium Pentoxide in FLAKES on converter or miscellaneous equipment, and this Vanadium Pentoxide in FLAKES mainly is to be used for producing vanadium iron and the higher alloy of other vanadiumcontent in ferrous metallurgy.
At the metal-iron of vanadium alloying, directly use the ratio of vanadium slag constantly to increase in the production of steel and alloy at present.
The purposes that depends on it for the specific requirement of the chemical ingredients of vanadium slag and mineralogical composition aspect.The vanadium slag that is used for producing Vanadium Pentoxide in FLAKES must satisfy the strictest requirement, therefore, according to the difference of selected Production Flow Chart, stipulate out its optimum concentration range to each composition of vanadium slag.
In the Soviet Union, develop a kind of method, can in the converter of bottom blowing air and oxygen, in oxygen top blown and compound converter of blowing, produce the vanadium slag of various compositions, and carried out gyp industrial production (referring to Soviet Union inventor certificate No.316727 C21 C5/28,1960; Soviet Union inventor certificate No.531861, C21 C7/00,1974; Soviet Union inventor certificate No.589258, C21 C5/28,1973).
The vanadium slag of Sheng Chaning contains (% by weight) in this way:
Ferric oxide-41.6 titanium oxide-7.4
Silicon oxide-16.4 chromic oxide-2.8
Vanadium oxide-15.8 calcium oxide-1.5
Manganese oxide-9.1 metallographic phase 8-12
Impurity (Mg O, Al
2O
3, R
2O)-surplus.
(referring to N.P.Lyakishev etc., " vanadium in the ferrous metallurgy ", metallurgical press, 1983, the 36 pages).
But the vanadium slag of this composition can not meet the demands far away.So need improve, requirement can further improve vanadium oxide, manganese oxide, the concentration of calcium oxide and other oxide compound.In this case, must make the composition of vanadium slag reach the better parameter of optimum value to guarantee that vanadium reclaims.
The pyrometallurgical processes that reclaims vanadium from titanomagnetite is to obtain vanadium slag in converter, this method has also been carried out industrialness production (referring to K.N.Sokolova in China, " production and the use of external vanadium ", the meeting newspaper that Chermet intormatsia association publishes, 1981,10, (894), 3-15 page or leaf).But, in the vanadium slag of Sheng Chaning, the content of vanadium is big not enough in this way, and also will consume a considerable amount of auxiliary reagents aborning.(% by weight) is as follows for above-mentioned vanadium slag composition: V
2O
5-10～15; FeO-33～45, TiO
2-8～13.5, SiO
2-7.6～35.4, MnO-2.7～5.7, CaO-0.9～1.5.The composition (% by weight) of producing the used iron material of this vanadium slag is: C-4.5, V-0.37, Si-0.2, Mn-0.21, P-0.05, S-0.05, Ti-0.12.
A kind of iron material (% by weight) C-3.95 that uses the way blowing following ingredients of top blowing oxygen in shaking ladle is arranged, V-1.10, Si-0.24, Ti-0.22, Mn-0.22, P-0.08, S-0.087, Cr-0.29, Cu-0.04, Ni-0.4 in the method for producing vanadium slag.The vanadium slag that obtains in this way contains (% by weight):
Vanadium oxide-27.8 silicon oxide-17.3
Ferric oxide-22.4 aluminum oxide-3.5
Calcium oxide-0.5 carbon-3.5
Magnesium oxide-0.3 impurity-surplus
(referring to " Journal of lron and Steel Inst. ", in April, 1970, the 340th page).
But, the vanadium slag of this composition also is ideal raw material for the production of Vanadium Pentoxide in FLAKES, because its production temperature condition (in 1180～1270 ℃ of scopes) can not produce enough vanadic spinels of big (size is greater than 50 microns) of granularity in vanadium slag, and this spinel vanadium slag is very loose when oxidizing roasting.
The principal character of producing the vanadium iron refining process of vanadium slag is that vanadium enters the recovery degree of vanadium slag, this rate of recovery has been meant how many vanadium are converted in the vanadium slag and has gone from iron, just the slag making degree of vanadium is meant that in addition the vanadium of producing with vanadium slag is with respect to its isolated amount from metal.From long-term practice, learn, the temperature of metal when the slag making degree of vanadium depends primarily on the vanadium removal end, and be in 93.4～93.5% these scopes.The method relevant (referring to " Journal of Iron and Steel Inst., ", in April, 1970, the 340th page) that provides among first numerical value of slag making degree and the SAR.In this method, the outlet temperature of metal is no more than 1300 ℃ (1270 ℃ more precisely).Second numerical value of above-mentioned slag making degree is to draw from the oxygen converter method of the Soviet Union.In this method, metal temperature was up to 1370 ℃ (referring to L.A.Smirnor, " metallurgical process of titanomagnetite ", this gram of Ural Si Weier Jean-Yves Le D NIICnermet press, Coll.No.18,58-76 page or leaf) when vanadium removal finished.
Further improve the temperature of iron,, under same working condition, can reduce the slag making degree of vanadium such as bringing up to 1400 ℃～1420 ℃.Because " residue " concentration of vanadium has been increased to 0.06～0.08%(average 0.07% in last metal), the slag making degree drops to 85%, that is to say, and contained vanadium has 15% to lose in the iron.
Therefore, just proposed such problem: the metal temperature when improving the vanadium removal end is the slag making degree of unlikely again reduction vanadium simultaneously.The solution of this problem will enlarge the refining process of iron significantly and improve the quality of the vanadium slag of producing.In vanadium slag was produced, the loss of the another kind of vanadium was the sort of consumption that vanadium slag is separated from metal when blowing iron is finished in converter.Under the identical situation of other condition, the size of these losses depends on the composition of vanadium slag, and (in the Soviet Union) loss is 5% at most, and is that 8.6%(is referring to the document of selecting in the SAR method).
So what the Soviet Union adopted produces in the method for vanadium slag in converter, the total losses of vanadium can reach 12.5% at most, and is 16% in the SAR method.
In order to reduce the loss of vanadium, suggestion is when separating vanadium slag from metal, in converter, after the melting once it is left to before the melting for the second time, (referring to " steel " magazine, N in 1976 o.7, Moscow, people's such as L.A.Smirnov article " improvement of vanadium iron production efficiency " 597-601 page or leaf).But, metal temperature was brought up under 1400 ℃ and the higher situation when this technology finished at vanadium removal, still can not reduce the loss of vanadium.
The objective of the invention is to propose a kind of method of producing vanadium slag with the vanadium iron oxidation, this method can improve the quality that reclaims the rate of recovery of vanadium and improve vanadium slag from iron.
Adopt a kind of method that can produce the vanadium slag with following chemical components and mineralogical composition just can achieve the above object, the chemical ingredients of this vanadium slag (% by weight) is:
Vanadium oxide 16～30
Silicon oxide 10～24
Manganese oxide 6～14
Chromic oxide 1～12
Calcium oxide 0.3～30.0
Titanium oxide 6～14.0
Metallic iron 2～20
Ferric oxide all the other
The mineralogical composition of this vanadium slag (% by weight) is:
Spinel 40～70
Glass 2～10
Pyroxene and peridotites all the other
Spinel particle has the geometrical shape of rule, and size is in 25～80 micrometer ranges, and this method comprises packs the vanadium iron with following ingredients (weight %) in the converter into:
Vanadium-0.35～0.90, chromium-0.03～0.42
Carbon-3.8～4.8, phosphorus-0.02～0.10
Silicon-0.05～0.35, copper-0.04～0.32
Manganese-0.12～0.35, nickel-0.04～0.32
Titanium-0.07～0.38, cobalt-0.001～0.12
Iron-all the other
Then add the ferruginous composition and/or the composition of fluxing again, blow with gaseous oxidant, speed is 1.5～3.0 meters
3/ ton divides (pressing oxygen calculates), begins oxygen blast when the iron temperature is 1180～1300 ℃, and stops oxygen blast when the iron temperature is 1400～1650 ℃, and the specific surface area in molten bath is a 0.13-0.30 rice
2/ ton is produced a kind of work in-process or steel and vanadium slag.
Produce the quality of vanadium slag in order to improve, reduce the consumption of molten iron, improve the recovery rate that vanadium enters the rate of recovery of vanadium slag and improves metal, when fusion process finishes, be preferably in the mixture that will have following ingredients (% by weight) before the oxygen blast and add on the surface of molten iron:
The heavy hydrocarbon 0.5～6.0 that contains vanadium
The magnetic part 5～20 of vanadium slag
Rolling mill scale all the other
This operative technique can make more vanadium enter among the vanadium slag.
In addition, in order further to reduce the consumption of molten iron, increase vanadium oxide in vanadium slag concentration and improve its microstructure, steel scrap is added in the converter before being preferably in the molten iron oxygen blast, addition is the 1-10% of weight of molten iron, adds the steel scrap of 4-10% later on once more at the 15-25% of oxygen blow duration.
Be mainly used to produce the pig iron that contains vanadium in order to make, the basicity of the vanadium slag of steel and alloy (directly using vanadium slag) remains on 1.0～1.4 the level, and the pig iron that preferably blows added 60～70% the calcium flux that contains in the past.
In order to reduce after the oxygen blowing pig iron content of ferric oxide in the vanadium slag, be with rare gas element blow resulting intermediates or steel.
Compare with production technology in the past according to the vanadium slag that method of the present invention is produced, have following advantage:
Under the vanadium removal temperature that improves, have anti-preferably chemical reaction ability, thereby can guarantee to have higher slag making degree above under 1400 ℃ the temperature;
Slag has best heterogencity (heterogenize), can guarantee that the loss of vanadium is no more than 5% when therefore separating vanadium slag from metal;
The loss of vanadium was no more than 5% when slag (fragmentation, sorting) was used in the preparation roasting;
When oxidizing roasting is produced Vanadium Pentoxide in FLAKES later on, when water logging and/or acidleach, attach " Cynders " and improved the rate of recovery of vanadium in the slag;
Make metal-pig iron, steel and alloy alloying with vanadium effectively,
An example of vanadium slag is a kind of and alkalimetal oxide and carbon bonded slag, and % counts the two and contains 1.5～9.0% and 0.1～2.0% respectively by weight,
The vanadium slag that contains alkalimetal oxide and carbon, advantage have been to improve the microstructure of vanadium slag, and in this case, the mean size of spinel crystal grain will increase, and this crystal grain be vanadium slag mainly contain the vanadium phase.The another one effect of the common influence of these compositions is to make spinel form the loose microstructure of a kind of porous.The back this point is very necessary, because in this case, increased because reacted surface is long-pending, spinel crystal grain decomposes in the oxidation-reduction process easily, not only on the surface of spinel crystal grain, and among hole, also forming a kind of cenotype, the recovery degree that the result enters in the finished product vanadium strengthens, and reclaims more fully.
To show more significantly in the detailed description that these advantages of the inventive method and other advantage are done below.
Vanadium slag with above-mentioned composition obtains by come the oxidation vanadium iron with gaseous oxidant.This composition that has been found that vanadium slag is to be determined by the chemical constitution of iron.And according to the present invention, the composition of this iron (% meter by weight) is as follows:
Vanadium-0.35-0.90, phosphorus-0.02-0.10
Carbon-3.8-4.8, copper-0.04-0.32
Silicon-0.05-0.35, nickel-0.04-0.32
Manganese-0.12-0.35, cobalt-0.001-0.12
Titanium-0.07-0.38, iron-surplus
Chromium-0.03-0.42,
Owing to suitably in stove, form the more caused known corresponding rules of carbon oxynitriding titanium when considering the melting titanomagnetite, working volume little (less than 1000 meters
3) iron of this composition of melting in the general blast furnace.
The variation of composition ratio had both made some compositions surpass prescribed value and all can produce disadvantageous effect as surpassing the limit of stipulating above in the raw material iron.
Therefore, if the content of vanadium reduces to the concentration that will reduce vanadium oxide in the vanadium slag below 0.35% in the iron, both made other composition all under lower limiting the quantity of, the concentration of above-mentioned vanadium oxide also can drop to below 16%, thereby is unfavorable for changing into the slag treatment process of Vanadium Pentoxide in FLAKES.Simultaneously, if the content of vanadium also is disadvantageous above 0.90% in the iron.Because when the content of vanadium is big like this, the ratio of vanadium oxide will be greater than 30% in the vanadium slag that is generated, and this can reduce the slag making degree of vanadium, and can reduce vanadium slag isolating ratio (because it has thickened) from metal, has therefore also just increased the loss of vanadium.
Be dissolved in silicon in the iron and the effect of manganese is by the afore mentioned rules amount: in the ferric oxide oxidation, they have formed a kind of flowable silicate composition of liquid state, and this is to contain that spinel begins to produce mutually and growth institute is indispensable.Silicone content in iron does not wish to surpass 0.35%, because when the content of vanadium in the iron is 0.35%, the ratio of vanadium oxide will reduce to below 16% of requirement.
Consider that according to same reason the allowed band of manganese content also will have certain restriction in the iron.
Contained chromium and the titanium that is in the specialized range can become the compound spinel fully in the Fe composition, thereby makes it have the performance of anti-chemical reaction preferably and can improve its fire performance.Composite spinelle has the performance of higher anti-chemical reaction, helps to make vanadium to be oxidized into vanadium slag more completely, reduces the loss of vanadium when isolating vanadium slag from metal, thereby has improved the rate of recovery of vanadium.
Dissolved copper, nickel and cobalt and improve the active effect of carbon and be to improve the ratio of ferric oxide and other slag making composition (comprising vanadium) institute oxygen consumed of being used in the iron, therefore can raise the efficiency undoubtedly, make the vanadium oxidation more abundant, and increase the rate of recovery of vanadium when slag making.
According to method of the present invention, will have vanadium iron that afore mentioned rules forms and pack in the converter, use a kind of gaseous oxidant (as oxygen) blow (oxidation) then.Temperature is in 1180～1300 ℃ of scopes when beginning to blow, and oxygen blast speed is 1.5～3.0 meters
3/ ton divides; When blowing stopped, temperature was at 1400～1650 ℃, and the specific surface area of weld pool surface is 0.13～0.30 meter
2/ ton.
These manufacturing parameter values can guarantee that the additive of fluxing in ferruginous additive (refrigerant) and/or the adding molten bath obtains fully and completely mixing, thereby strengthened the oxidation of vanadium, made the vanadium slag that obtains have desired chemistry and mineral composition and granulometric composition.Has required adsorptive power simultaneously for vanadium oxide; There is not the dead band in the lower floor of metal and the part of close furnace wall; Because the normal inspissation (boiling-down) of slag, make metal in the dreg be mingled with concentration and free iron oxide concentration reduces, seal the size increase that makes spinel crystal grain owing to form the best of silicate around spinel, these several advantages of back can be improved the efficient that becomes Vanadium Pentoxide in FLAKES precision work process subsequently from slag widely.More noticeable in addition is that the parameter area of afore mentioned rules might avoid content of vanadium to reduce along pool depth basically, and this also helps vanadium and enters in the vanadium slag and go.
Be noted that the main effect that stressed results above guaranteeing to obtain by the specific surface area of weld pool surface and oxygenant be blown into speed the two in conjunction with reaching.Any one parameter variation has exceeded the limit of stipulating above and all can produce disadvantageous effect.Therefore, when being reduced to, the specific surface area of weld pool surface is lower than 0.13 meter
2/ ton hour will reduce the slag making degree of vanadium significantly, especially is being higher than under 1330 ℃ the temperature all the more soly, also can reduce the quality (metal inclusion and free oxidation iron ratio increase, and the size of spinel crystal grain reduces) of the vanadium slag that produces in addition.Meanwhile, as the specific surface area of weld pool surface above 0.30 meter
2/ ton also can be unfavorable to the parameter of being considered, causes the part to depart from the required ratio of vanadium slag composition and metal ingredient.
When realizing the object of the invention, the initial temperature of iron also is very important.Temperature drops to the quality (ratio of metal inclusion and ferric oxide increases, and the spinel grain-size reduces) that will reduce vanadium slag below 1180 ℃ significantly, and this is undesirable.On the contrary,, will increase the degree that carbon is burnt at the very start widely, thereby suppress the oxidation of vanadium and reduce its slag making degree in blowing if the beginning temperature is increased to more than 1300 ℃.
Should see, according to method of the present invention, under the temperature more much higher (1400-1650 ℃), make the slag making degree very high (more than 90%) of vanadium, and metal temperature generally all is no more than 1350 ℃ under the identical situation of the slag making degree of method vanadium in the past than previous methods.Only be higher than the slag making degree of just finding vanadium in 1480 ℃ and be lower than 90% in temperature, but in 1480～1600 ℃ of temperature ranges, the slag making degree of vanadium is stabilized on 85～90% the level, and the slag making degree is increased to same numerical value (90% even higher) once more under 1600 ℃ the temperature being higher than.Can hang down to 0.01% in " remnants " concentration that carbon is lower than vanadium in 0.25% the metal this moment.
The temperature that improves metal when vanadium removal finishes is compared the composition that not only can improve resultant vanadium slag with method in the past, finish the rate of recovery that improves vanadium under the temperature at higher vanadium removal, and can improve the throughput (reaching 25～30 tons/minute) of steel-making widely.
When implementing method of the present invention, it is very suitable using the slag making mixture of the various waste materials that contain vanadium, has the magnetic part and the rolling mill scale of waste material that afore mentioned rules forms such as heavy oil and so on oils, vanadium slag.
This additive not only can make the vanadiumcontent of slag obviously improve owing to vanadium enters from the magnetic part of hydrocarbon polymer and vanadium slag (byproduct when producing Vanadium Pentoxide in FLAKES the oxidizing roasting process) in the slag, and add heavy hydrocarbon (as heavy oil) in the composition to according to the present invention, also the particle of rolling mill scale and vanadium slag magnetic part particulate material can be glued together, because of particle adheres to each other mutually, thereby form a kind of homogeneous body.So basically, avoid them when blowing, to be pulled away, and can improve its service efficiency.In addition, the liquid hydrocarbon of sneaking in mixture will be emitted a certain amount of additional heat with the oxygen reaction that is blown into the time, thereby improve metal temperature, quicken fusing and accelerate the mixture of fusing and the reaction between the metal.This might reduce the wear rate of molten iron, improves the utilization ratio of rolling mill scale and so on iron ore material, increases vanadium enters vanadium slag from molten iron ratio.
The raising of these parameters also is that this is that (Mechanical Crushing is pulverized and magneticseparation) obtains when preparing oxidizing roasting with vanadium for the production Vanadium Pentoxide in FLAKES owing to added the magnetic part of vanadium slag in mixture.It contains metallic particles, and its size has not very good isolating vanadium slag on these particulate surfaces in 0.1～20 millimeter scope.According to the particulate size, particulate slag making degree is 20～50%.The average chemistry of vanadium slag magnetic part (% by weight) composed as follows:
Metallic iron-50～80, MnO-1～3,
SiO
2-2～8, TiO
2-1～3, the iron in the oxide compound-5～20, P-0.03～0.05, S-0.02～0.03, C-0.1～2.0
Use this vanadium slag magnetic part also to have following benefit.Because its density is big (comparing with rolling mill scale), therefore in blowing, help the slag making composition to mix better with metal.
When the content of major ingredient in the mixture has exceeded the scope of regulation, will produce bad effect.
When the content of hydrocarbon polymer is lower than 0.5%, the effect of " moistening " can appear, but very little, and when the ratio of hydrocarbon polymer surpasses 6%, the obvious superheated phenomenon of vanadium slag will occur, this will produce deleterious effect, has adverse influence such as the wearing quality to the furnace lining of converter.
Vanadium slag magnetic part content is limited by its dissolution time in mixture, when its content greater than 20% the time, it will be stayed in the resulting vanadium slag, thereby unfavorable to its quality.If its content is less than 5%, then it has just become problem in the meaning that mixture exists.
In order further to improve the quality of vanadium slag, especially reduce the ununiformity of its both macro and micro, and for ratio that improves vanadium oxide and the consumption that reduces molten iron, preferably add the steel scrap of some amount, promptly before cast iron, add 1～4% steel scrap with iron ore material (as rolling mill scale).When so handling, before 15～25% back adding rolling mill scales through duration of blast, form a kind of mobile liquid acidic slag, it can make the rolling mill scale slag making well of adding, thereby reduces the amount of taking away.Secondly, it can change the dissolution mechanism of rolling mill scale, and this mainly is by making the rolling mill scale preliminarily solubilised in the silicate vanadium slag, reducing simultaneously among the degree and metal infiltration vanadium slag of metal drippage, so as to reducing the quantity of metal inclusion.
But, the basic result that adopts this technology is the both macro and micro ununiformity that reduces vanadium slag, and this is very important for using vanadium slag subsequently in the production of Vanadium Pentoxide in FLAKES.
Optimum implementation more of the present invention are as follows:
The embodiment I. the vanadium iron that will have a following ingredients is packed in the converter
The composition of vanadium iron (% by weight) is: C-4.2～4.4, Si-0.10～0.20, V-0.40～0.60, Ti-0.10～0.20, Mn-0.10～0.20, Cr-0.05～0.15, P-0.03～0.06, S-0.02～0.043, Cu-0.08～0.12, Ni-0.08～0.12, Co-0.001～0.12.The iron amount of adding should guarantee to account for 0.15～0.25 meter that weld pool surface amasss
2/ ton.
After the converter of packing into, the temperature of iron is 1270～1280 ℃.In order to form vanadium slag, use the slag making mixture of following composition (% by weight):
The heavy hydrocarbon 3.0～5.0 that contains vanadium
The magnetic part 15～20 of vanadium slag
The rolling mill scale surplus
Add the mixture of 40～90 kilograms of above-mentioned compositions in each ton molten iron.Begin oxygen blast after this mixture being added on the molten iron surface, oxygen supply speed is 1.8～2.2 meters
3/ ton divides.By water-cooled nozzle from the top oxygen blast after 7-10 minute, oxygen blast stops; This moment, the temperature of metal was 1420～1470 ℃, and its composition (% by weight) is: C-2.4～2.8, Si-trace; The Ti-trace; V-0.02～0.04, P-0.03～0.06, S-0.02～0.04, Cu-0.08～0.12, Ni-0.08～0.12, Co-0.001～0.11
Resulting intermediates metal is poured into a ladle by a hole, vanadium slag is stayed in the converter.
Subsequently, repeat above-mentioned operation, after oxygen blast is intact, with argon gas or any other rare gas element from pushing up or again the metal that contains vanadium slag being blown 1.0～2.0 minutes from the bottom.After finishing this operation, (% by weight) is as follows for the composition of metal: C-2.0～2.4, and V-0.03～0.04, P-0.02～0.06, S-0.02～0.035, the temperature of metal is 1420～1450 ℃.
Every melting is collected a vanadium slag later on twice, and metal is wherein poured out, and the composition of resulting vanadium slag (% by weight) is:
Vanadium oxide 22-26,
Silicon oxide 14-18,
Manganese oxide 8-10,
Chromic oxide 1-3,
Titanium oxide 6-10,
Calcium oxide 0.3-3.0
Ferric oxide all the other
(% by weight) is as follows in the mineral composition of this vanadium slag:
Spinel 55-65
Glass 5-7
Pyroxene and peridotites all the other
The crystal grain of vanadic spinel all has the geometrical shape of rule, and crystal grain is of a size of 30～60 microns.
The embodiment II. will have with the vanadium iron of the identical composition of embodiment I and pack in the same converter, carry out oxygen blast.Initial parameter is all the same, and different is before converter that molten iron is packed into, adds some steel scraps, and addition is an iron 40-50 kilogram steel scrap per ton, and 20%(4-5 minute of oxygen blow duration) after, adding rolling mill scale, add-on is 50-60 kilogram/ton.By nozzle with 2.2-2.8 rice
3/ ton speed top blowing oxygen stopped oxygen blast after 20-25 minute, and this moment, the temperature of metal was 1600～1650 ℃, and its composition (% by weight) is: C-0.05～0.25, V-0.01～0.03, P-0.03～0.06, S-0.02～0.03.
After the metal that obtains poured out, handle with the slag making mixture, and casting or in openhearth steelmaking, be used for replacing the pig iron.
The vanadium slag of producing with this embodiment has following composition (% by weight):
Vanadium oxide 24-28,
Silicon oxide 14-18,
Manganese oxide 8-12,
Titanium oxide 6-9,
Iron particle 2-5,
Magnesium oxide 3-6,
Ca, Al, the oxide compound 4-8 of Cr,
Ferric oxide all the other
(% by weight) is as follows for the mineral composition of vanadium slag:
Spinel 65～70
Glass 2～4
Pyroxene and peridotites all the other.
The crystal grain of vanadic spinel has the geometrical shape of rule, and it is of a size of 40～80 microns.
The vanadium slag of being produced can successfully be processed into Vanadium Pentoxide in FLAKES in the above-described embodiment, thereby has guaranteed the high target that vanadium reclaims in the finished product, but known vanadium slag has much bigger difficulty on producing.
For the ease of the present invention is understood better, now lift some specific embodiments so that the production process of various different components vanadium slags to be described.
Embodiment 1
84 tons of vanadium iron with following composition (% meter) are by weight packed in the converter: C-3.8, Si-0.35, V-0.35, Ti-0.07, Mn-0.12, Cr-0.03, P-0.02, Cu-0.04, Ni-0.04, Co-0.001.After the converter of packing into, the temperature of iron is 1300 ℃.
Then slag making mixture (refrigerant) is added in the converter, add-on is 40 kilograms/ton, (% by weight) is as follows for the composition of mixture: heavy hydrocarbon-6(2.4 kilogram/ton), the magnetic part of vanadium slag-20(8 kilogram/ton), rolling mill scale-74(29.6 kilogram/ton).
The oxygen-supplying amount of top blowing oxygen is 3 meters
3/ ton divides.The specific surface area on molten metal surface is 0.3 meter
2/ ton.
After oxygen blast finished, the temperature of metal was 1460 ℃, and wherein each component content (% by weight) is: C-2.6, Si-trace, V-0.012, Ti-trace, Mn-0.01, Cr-trace, P-0.02, Cu-0.04, Ni-0.04, Co-0.001.
The metal that obtains is poured in the ladle, and all slags are completely stayed in the converter.During then the molten iron of the same composition of handle was packed converter into, Intake Quantity was with for the first time identical.The speed and the blowing oxygen quantity of refrigerant of packing into also keeps identical.
When oxygen blast finished, the composition of metal (% by weight) was: C-2.5, and V-0.018, the Si-trace, the Ti-trace, Mn-0.01, the Cr-trace, P-0.02, Cu-0.04, Ni-0.04, Co-0.001.The temperature of metal is 1450 ℃.
A slag is collected in per twice melting later on, and (% by weight) is as follows for its composition:
Vanadium oxide 16
Silicon oxide 24
Manganese oxide 6
Chromic oxide 1
Titanium oxide 6
Calcium oxide 0.3
Iron granule 8
Ferric oxide all the other.
(% by weight) is as follows in its mineral composition:
Spinel 40,
Glass 2,
Pyroxene and peridotites 58.
Vanadic spinel crystal grain is of a size of 25～35 microns, and they have the geometrical shape of rule.
The slag making degree 95% of vanadium.Vanadium slag isolating ratio from metal is 95%.From iron to the slag, the rate of recovery of vanadium is 90.2%.
Embodiment 2
200 tons of vanadium iron with following composition (weight %) are packed in the converter: C-4.2, Si-0.21, V-0.46, Ti-0.18, Mn-0.22, Cr-0.08, P-0.06, Cu-0.14, Ni-0.16, Co-0.06.The temperature of molten iron is 1280 ℃.
Then the slag making mixture is added in the converter, add-on is 50 kilograms/ton, (% by weight) is as follows for the composition of mixture: heavy hydrocarbon-0.5(0.25 kilogram/ton), the magnetic part of vanadium slag-5.0(2.5 kilogram/ton), rolling mill scale-94.5(47.25 kilogram/ton).
The oxygen-supplying amount of top blowing oxygen is 2 meters
3/ ton divides.The specific surface area on molten metal surface is 0.13 meter
2/ ton.After oxygen blast finished, the temperature of metal was 1400 ℃, and wherein the content of vanadium is 0.028%, and the content of carbon is 2.8%.
The metal that obtains is poured in the ladle, and slag is then stayed in the converter so that carry out melting next time.
Carry out another time melting under same initial parameter condition, resulting metal temperature is 1410 ℃, and the content of vanadium is 0.026%, and carbon content is 2.7%.
Collected slag composition (% by weight) is after twice melting:
Vanadium oxide-20.4,
Silicon oxide-14.2,
Manganese oxide-10.4,
Chromic oxide-2.4,
Titanium oxide-8.6,
Calcium oxide-1.5,
Iron granule-10.2,
Ferric oxide-all the other.
(% by weight) is as follows in its mineral composition:
Spinel 55,
Glass 5,
Pyroxene and peridotites 40.
The vanadic spinel grain-size is 30～40 microns.Crystal grain is good crystal, has the geometrical shape of rule.
The slag making degree of vanadium is 94.3%.
Vanadium slag isolating ratio from metal is 93%.From iron to the slag, the rate of recovery of vanadium is 87.5%.
Embodiment 3
22 tons of vanadium iron with following composition (weight %) are packed in the converter: C-4.8, V-0.90, Si-0.05, Mn-0.15, Ti-0.18, Cr-0.42, P-0.10, Cu-0.32, Ni-0.32, Co-0.12.Pack into after the converter, the temperature of molten iron is 1180 ℃.
Before packing into iron in the converter, the agglomerate that contains vanadium is packed in the stove, Intake Quantity is 106 kilograms/ton.The specific surface area of weld pool surface is 0.24 meter
2/ ton.The oxygen supply speed of carrying out bottom blowing by " inner casing tube " nozzle is 2.5 meters
3/ ton divides.The wear rate of the protection Sweet natural gas that nozzle consumed is 10% of an oxygen supply speed in whole oxygen blast process.After oxygen blast finished, the temperature of metal was 1420 ℃; Wherein the content of vanadium and carbon (% by weight) is respectively 0.05% and 2.8%.
The metal that obtains is poured out, slag is partly stayed in the converter so that carry out melting next time.
Carry out another time melting under same initial parameter condition, the metal temperature that obtains is 1430 ℃, and the content of vanadium and carbon is identical with last time.
Twice melting (wherein once being a part) collected slag in back has following composition (% by weight):
Vanadium oxide-30,
Silicon oxide-10,
Manganese oxide-6.4,
Titanium oxide-7.4,
Chromic oxide-12,
Calcium oxide-2.1,
Iron granule-6.2,
Alkalimetal oxide-9.0,
Carbon-0.1,
Ferric oxide-all the other.
Its mineral composition (% by weight) is:
Spinel 70,
Glass 10,
Pyroxene and peridotites 20.
The size major part of vanadic spinel crystal grain is 30～50 microns; Crystal grain has the geometrical shape of rule.
The slag making degree of vanadium is 95%.The segregation ratio of slag is 97%.From iron to the slag, the total yield of vanadium is 92%.
Embodiment 4
22 tons of vanadium iron with following composition (% by weight) are packed in the converter: C-4.4, V-0.52, Si-0.08, Mn-0.27, Ti-0.32, Cr-0.42, P-0.06, Cu-0.07, Ni-0.21, Co-0.06.The temperature of iron is 1240 ℃.
Before converter that iron is packed into, the agglomerate that contains vanadium to be packed in the stove, Intake Quantity is 92 kilograms/ton.The specific surface area of weld pool surface is 0.24 meter
2/ ton.The speed of bottom blowing air (calculating according to oxygen) is 3 meters
3/ ton divides.
When blowing finished, the temperature of metal was 1410 ℃, and wherein the content of vanadium and carbon (% by weight) is respectively 0.03% and 2.6%.
The metal that obtains is poured out, and all slags are all stayed in the converter so that melting next time.
Collect slag in twice melting carrying out in succession under same parameter condition, after vanadium removal finished, vanadium in the metal and carbon content (% by weight) were respectively 0.03% and 2.6%.
The slag of collecting later on three meltings contains (% by weight):
Vanadium oxide-16.6,
Silicon oxide-12,
Manganese oxide-10,
Chromic oxide-12,
Titanium oxide-14,
Alkalimetal oxide-1.5,
Calcium oxide-0.8,
Carbon-2.0,
Iron granule-20,
Ferric oxide-all the other.
Slag has following mineral composition (% by weight):
Spinel 70
Glass 8
Pyroxene and peridotites 22
Spinel crystal grain is of a size of 25～45 microns; Crystal grain has the geometrical shape of rule.The slag making degree is 93.2%.The vanadium total amount that is recovered in the bits is 89.5%.
Embodiment 5
162 tons of vanadium iron are packed in the converter, and the composition of vanadium iron (% by weight) is: V-0.52, C-4.4, Si-0.14, Mn-0.18, Ti-0.18, Cr-0.03, P-0.04, Cu-0.12, Ni-0.18, Co-0.005.The temperature of iron is 1280 ℃ in the converter.
Add a kind of dreggy material on iron surface, (% by weight) is as follows for its composition: heavy hydrocarbon-4.2, and the magnetic part of vanadium slag-15, rolling mill scale-all the other.The consumption of this mixture is 62 kilograms/ton.Is 1.5 meters from the top to metallic surface oxygen supply speed by water-cooled nozzle
3/ ton divides.The specific surface area of metallic surface is 0.18 meter
2/ ton.
When blowing finished, the temperature of metal was 1470 ℃, and vanadium when vanadium removal finishes in the metal and carbon content (% by weight) are respectively 0.03% and 2.2%.
Metal is poured out, and slag is all stayed in the converter, and repeats the aforesaid operations process under same initial parameter condition.In the melting second time, the temperature of metal is 1480 ℃, and the content of vanadium is identical.Carbon content is reduced to 2.1%.
Collected vanadium slag has following composition (% by weight) from twice melting:
Vanadium oxide-25.6,
Silicon oxide-14.1,
Manganese oxide-8.4,
Titanium oxide-8.6,
Chromic oxide-1.4,
Calcium oxide-3.0,
Alkali-metal oxide compound-2.1,
Carbon-0.5,
Iron granule-8.4,
Ferric oxide-all the other.
Resulting slag has following mineral composition (% by weight):
Spinel 60
Glass 4
Pyroxene and peridotites 36
Spinel crystal grain is of a size of 40～60 microns.Crystalline crystal grain has the geometrical shape of rule.
Embodiment 6
Having similarly to Example 5 the vanadium iron of forming with 162 tons packs in the converter.The temperature of vanadium iron is 1275 ℃.Before casting, 6.5 tons of (4%) steel scraps are installed in the converter.
The oxygen supply speed of top blowing oxygen is 2.5 meters
3/ ton divides, and the specific surface area of metallic surface is 0.18 meter
2/ ton.
After 6 minutes (oxygen blow duration 25%), again the rolling mill scale of 7.2 tons (4.5%) is added on the metallic surface, and continues oxygen blast, oxygen supply speed is constant.
When blowing finished, the carbon content of metal was 0.12%, and vanadiumcontent is 0.01%, and the temperature of metal is 1650 ℃, and the slag making degree of vanadium is 98% in this embodiment.(% by weight) is as follows for the composition of vanadium slag:
Vanadium oxide-28.4,
Silicon oxide-18.1,
Manganese oxide-8.2,
Titanium oxide-10.8,
Chromic oxide-2.3,
Calcium oxide-1.4,
Iron granule-3.2,
Ferric oxide-all the other.
The mineral composition of vanadium slag remains unchanged, and spinel crystalline size is increased to 80 microns, and crystal grain has the border of the obvious cut-out of rule.
Staying a part of bits and under same parameter condition after the repetitive operation, the composition of vanadium slag and front once do not have great variation in melting next time.
Embodiment 7
Having the vanadium iron identical with 6 compositions with the foregoing description 5 with 162 tons packs in the converter.The temperature of vanadium iron is 1275 ℃.Before casting, in converter, add 1.6 tons of (1%) steel scraps.
The oxygen supply speed of top blowing oxygen is 2.5 meters
3/ ton divides, and the specific surface area of metallic surface is 0.20 meter
2/ ton.
After oxygen blast 3 minutes (oxygen blow duration 15%), add 9.6 tons of (6%) rolling mill scales, and continue oxygen blast.
When oxygen blast finished, the carbon content of metal was 0.62%, and vanadiumcontent is 0.04%, and the temperature of metal is 1580 ℃.The slag making degree of vanadium is 92.4%.The composition of vanadium slag (% by weight) is:
Vanadium oxide-27.8,
Silicon oxide-17.4,
Manganese oxide-8.0,
Titanium oxide-9.2,
Chromic oxide-3.1,
Calcium oxide-1.6,
Iron granule-3.6,
Ferric oxide-all the other.
The mineral composition of vanadium slag is identical, and spinel crystal grain has the shape of rule, size 60-80 micron.
The vanadium slag quality property retention of collecting behind two melting cycles is constant.
Embodiment 8
160 tons of vanadium iron identical with the foregoing description 7 compositions are packed under identical temperature in the converter.Before casting, 20 tons of steel scraps of interpolation and 1.4 tons of lime in the converter (melting total amount 60%), these lime are that melting is needed.Oxygen supply speed during oxygen blast is 3.0 meters
3/ ton divides, and the specific surface area on metal pool surface is 0.20 meter
2/ ton.When oxygen blast finished, the temperature of metal was 1620 ℃, and metal components (% by weight) is: C-0.28, V-0.04, P-0.026.(% by weight) is as follows for the composition of vanadium slag:
Vanadium oxide-20.2,
Calcium oxide-18.1,
Silicon oxide-17.9,
Iron particle-2,
The oxide compound of manganese, titanium, chromium, magnesium, iron-all the other.
The basicity of vanadium slag is 1.0.The slag making degree of vanadium is 92.5%.Part vanadium slag stays so that blow next time.
Embodiment 9
Basicity is that 1.4 vanadium slag is to produce under the parameter condition identical with embodiment 7 and embodiment 8, just will add 1.6 tons of lime (melting total amount consumed 70%) with steel scrap.(% by weight) is as follows for the composition of the vanadium slag that obtains like this:
Vanadium oxide-18.2,
Calcium oxide-30,
Silicon oxide-15,
Manganese oxide-10,
Chromic oxide-2.1,
Titanium oxide-9.6,
Iron particle-2,
Ferric oxide-all the other.
When operating end of processing under 1600 ℃ of temperature, the slag making degree of vanadium is 92.5%.
Embodiment 10
The identical vanadium iron top blowing oxygen of 20 tons of compositions and embodiment 7 of packing in a converter, oxygen supply speed is 1 meter
3/ ton divides; Simultaneously by (2 meters of bottom " inner casing tube " nozzle bottom blowings
3/ ton divides), the specific surface area of metallic surface is 0.3 meter
2/ ton.Watering before the cast iron, in converter, adding steel scrap (vanadium iron weight 10%) and Wingdale (melting total amount consumed 65%).
When oxygen blast finished, the basicity of vanadium slag was 1.2, and vanadium slag composition (% by weight) is:
Calcium oxide-30,
Silicon oxide-25,
Vanadium oxide-17.4,
Manganese, chromium, titanyl compound-18.4,
Iron particle-2.0,
Ferric oxide-all the other.
The temperature of metal is 1620 ℃, and carbon containing 0.44% contains vanadium 0.04% and phosphorous 0.028%.
Embodiment 11
20 tons of compositions and embodiment 7 identical vanadium iron are packed under same temperature in the converter.Oxygen blast speed is 3 meters
3/ ton divides, and the specific surface area on metal pool surface is 0.3 meter
2/ ton.
When metal carbon content under 1600 ℃ of temperature reaches after 0.3%, stop oxygen blast, then from the bottom blowing argon gas, blowing argon gas speed is 0.2 meter
3/ ton divides, and argon blowing time is 2 minutes.Vanadiumcontent when oxygen blast finishes in the metal is 0.04%, and after Argon, when carbon containing was 0.25%, the vanadiumcontent in the metal was increased to 0.05%.
Before Argon, (% by weight) is as follows for the composition of vanadium slag:
Vanadium oxide-24.8,
Silicon oxide-14.2,
Iron particle-3.6,
Calcium oxide-6.2,
Ferric oxide-24.2,
Manganese, chromium, titanyl compound-all the other.
After Argon, (% by weight) is as follows for the composition of vanadium slag:
Vanadium oxide-26.8,
Silicon oxide-14.1,
Iron particle-3.8,
Calcium oxide-6.4,
Ferric oxide-18.6,
Manganese, chromium, titanyl compound-all the other.
The slag yield of vanadium reaches 89.5%.
Claims (4)
1, a kind of method of producing vanadium slag, the composition of the vanadium slag of producing (% by weight) is:
Vanadium oxide 16～30,
Silicon oxide 10～24,
Manganese oxide 6～14,
Chromic oxide 1～12,
Titanium oxide 6～14,
Calcium oxide 0.3～30.0,
Metallic iron 2～20,
Ferric oxide all the other
The mineral composition of vanadium slag (% by weight) is:
Spinel 40～70
Glass 2～10
Pyroxene and peridotites all the other
Wherein spinel crystal grain has the geometrical shape of rule, is of a size of 25～80 microns, packs in the converter comprising the vanadium iron that will have following composition (% by weight):
Vanadium-0.35～0.90 chromium-0.03～0.42
Carbon-3.8～4.8 phosphorus-0.02～0.10
Silicon-0.05～0.35 bronze medal-0.04～0.32
Manganese-0.12～0.35 nickel-0.04～0.32
Titanium-0.07～0.38 cobalt-0.001～0.12
Iron-all the other,
Add flux material, with the gaseous oxidant said vanadium iron that blows, oxygen blast speed (by oxygen calculating) is 1.5～3.0 meters
3/ ton divides, and metal temperature is 1180～1300 ℃ during the beginning oxygen blast, and oxygen blast when finishing metal temperature be 1400～1650 ℃, the specific surface area on bath surface is 0.13～0.30 meter
2/ ton obtains a kind of intermediates, perhaps steel and vanadium slag.
2, in accordance with the method for claim 1, it is characterized in that before being blown in the vanadium iron that the slag making mixture that will have following composition (% by weight) is added in the vanadium iron and goes with oxygenant:
Heavy contains vanadium hydrocarbon polymer 0.5～60
The magnetic part 5～20 of vanadium slag
Rolling mill scale all the other.
3, in accordance with the method for claim 1, it is characterized in that adding steel scrap before the oxygen blast in vanadium iron, addition is 1～4% of a vanadium iron weight, adds rolling mill scale later at 15～25% of oxygen blow duration, and add-on % by weight counts 4.5～6.0%.
4, in accordance with the method for claim 1, utilize the calcareous additive of interpolation 60～70% that the basicity of vanadium slag is remained in 1.0～1.4 scopes when it is characterized in that oxygen blast.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN86106699.5A CN1006402B (en) | 1985-08-22 | 1986-09-27 | Process for ranadium residue |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/SU1985/000072 WO1987001136A1 (en) | 1985-08-22 | 1985-08-22 | Vanadium slag and method for obtaining it |
| CN86106699.5A CN1006402B (en) | 1985-08-22 | 1986-09-27 | Process for ranadium residue |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN86106699A true CN86106699A (en) | 1988-04-20 |
| CN1006402B CN1006402B (en) | 1990-01-10 |
Family
ID=25742250
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN86106699.5A Expired CN1006402B (en) | 1985-08-22 | 1986-09-27 | Process for ranadium residue |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1006402B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107312905A (en) * | 2017-07-03 | 2017-11-03 | 攀枝花学院 | A kind of high-grade vanadium slag and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1295116C (en) * | 2004-04-16 | 2007-01-17 | 武杰 | Method for producing box brine water (plaster) bean curd |
| CN1329530C (en) * | 2005-12-27 | 2007-08-01 | 河北滦河实业集团有限公司 | Molten iron vanadium-extracting calcium-controlling coolant and process therefor |
-
1986
- 1986-09-27 CN CN86106699.5A patent/CN1006402B/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107312905A (en) * | 2017-07-03 | 2017-11-03 | 攀枝花学院 | A kind of high-grade vanadium slag and preparation method thereof |
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| CN1006402B (en) | 1990-01-10 |
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