CN102251068A - Vanadium-extracting cooling agent and preparation method thereof - Google Patents
Vanadium-extracting cooling agent and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a vanadium-extracting cooling agent, belonging to the field of iron and steel smelting and providing the vanadium-extracting cooling agent taking steel-making cutting slag and vanadium-extracting sludge as raw materials. The vanadium-extracting cooling agent comprises the following raw materials: 25-35 percent by weight of steel-making cutting slag, 20-35 percent by weight of vanadium-extracting sludge, 5-10 percent by weight of iron ore concentrate, 30-35 percent by weight of steel-making iron scale and 3-7 percent by weight of steel-making binding agent, wherein the content of TFe in the steel-making cutting slag is not less than 61 percent by weight; in the vanadium-extracting sludge, the content of TFe is not less than 67 percent by weight, the content of P is not more than 0.07 percent by weight and the content of S is not more than 0.7 percent by weight; in the iron ore concentrate, the content of TFe is not less than 62 percent by weight, the content of P is not more than 0.007 percent by weight and the content of S is not more than 0.3 percent by weight; in the steel-making iron scale, the content of TFe is not less than 63 percent by weight, the content of P is not more than 0.02 percent by weight and the content of S is not more than 0.03 percent by weight. The vanadium-extracting cooling agent disclosed by the invention has the advantages of low cost, high resource utilization rate, favorable cooling effect, and the like.
Description
Technical field
The present invention relates to a kind of vanadium extraction by converter blowing with refrigerant and preparation method thereof, belong to field of iron and steel smelting.
Background technology
China is vanadium titano-magnetite big country, climb steel, hold steel, enterprises such as elder brother's steel, prestige steel adopt vanadium titano-magnetite to smelt, the molten iron that the vanadium titano-magnetite blast-furnace smelting goes out is compared the content of vanadium height with common molten iron, and vanadium is a kind of important resource, therefore vanadium slag is produced in necessary vanadium extraction before the molten iron-steelmaking.At present, the production method of producing vanadium slag both at home and abroad is more, mainly contains New Zealand's hot metal ladle and blows vanadium technology, South Africa shaking ladle process for extracting vanadium, Russia and Chinese vanadium extraction by converter blowing technology etc., and other process for extracting vanadium also comprises v-bearing steel slag vanadium extraction, process for extracting vanadium from stone coal etc.Wherein with vanadium extraction by converter blowing technology optimum, technico-economical comparison is best.
The production technique of vanadium extraction by converter blowing is mainly updated this technology by adding refrigerant, control process temperature and duration of blast both at home and abroad at present.The Converter Oxigen Blowing vanadium extraction is an exothermic process, silicon [Si], manganese [Mn], vanadium [V], carbon element oxidations such as [C] are rapidly heated the molten bath, and [Si], [Mn] oxidation occur in before [V] oxidation, vanadium extraction can not suppress its reaction, and [C], [V] invert point are greatly about about 1385 ℃, therefore to obtain the high oxidation rate and [V] the high recovery rate of [V], must be in the reaction process by adding vanadium-raising cooling agent, the control bath temperature makes it to approach [C], [V] below the invert point, reaches the purpose that carbon is protected in vanadium extraction.The terminal point half steel temperature of vanadium extraction is unsuitable too high, and the vanadium extraction process is oxidized to the master with vanadium early stage, and the later stage is reduced to the master with vanadium, is that vanadium is reduced to the master but blow the vanadium process.So what adopt when cooling is to add refrigerant to make molten iron temperature drop to suitable scope, by the control to duration of blast and process temperature, with the vanadium oxidation in the half steel, improves recovery rate in the converter smelting.
The cooling of molten iron is the emphasis that vanadium extraction by converter blowing is produced.The cooling of molten iron mainly is to add refrigerant in molten iron, and refrigerant commonly used at present has: common iron ore, cooled agglomerated pellet, steel scrap, iron scale and high-grade ore.Climbing steel vanadium employing iron scale, ferric oxide ball and cooled agglomerated pellet is refrigerant, after cooling system improves, and v slag grade 〉=17.5%, the residual vanadium of half steel≤0.04%, vanadium recovery 〉=80.0%.
Refrigerant commonly used at present generally adopts fine iron breeze, iron scale etc. to produce for raw material, CN1789435 discloses a kind of vanadium extraction from hot metal control calcium refrigerant and vanadium extraction from hot metal control calcium technology, the chemical ingredients of its vanadium-raising cooling agent (wt%) is: iron scale 56-60%, fine iron breeze 30-40%, wedding agent 5-10%, this refrigerant can increase the extraction yield and the v slag grade of vanadium, stablizes the vanadium slag calcium oxide content.CN100582248 discloses a kind of vanadium-raising cooling agent and preparation method thereof and using method, this refrigerant with iron scale or vanadium extraction mud, contain the vanadium iron concentrate, wedding agent is a raw material production, contains the ferriferous oxide of 80%-95%, the SiO of 3-6%
2, 0.1-0.6% V
2O
5, 1-3%MgCl
2
The present inventor has carried out a large amount of research to vanadium extraction by converter blowing with refrigerant.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of vanadium extraction by converter blowing refrigerant, and this refrigerant is a main raw material with steel-making cutting slag.
Technical scheme of the present invention is:
Vanadium-raising cooling agent, its raw material consists of: steel-making cutting slag 25～35wt%, vanadium extraction mud 20～35wt%, fine iron breeze 5～10wt%, steel-making iron scale 30～35wt%, steel-making wedding agent 3～7wt%; Wherein, TFe content 〉=61wt% in the described steel-making cutting slag; TFe content 〉=67wt% in the described vanadium extraction mud, P content≤0.07wt%, S content≤0.7wt%; TFe content 〉=62wt% in the described fine iron breeze, P content≤0.007wt%, S content≤0.3wt%; TFe content 〉=63wt% in the described steel-making iron scale, P content≤0.02wt%, S content≤0.03wt%.
Preferably, described steel-making wedding agent is at least a in cement, wilkinite, starch, water glass, the high-aluminium vanadine.
The present invention also provides the preparation method of above-mentioned vanadium-raising cooling agent, this method comprises, to make steel cutting slag, vanadium extraction mud, fine iron breeze, steel-making iron scale, steel-making wedding agent by mass ratio is: steel-making cutting slag 25～35wt%, vanadium extraction mud 20～35wt%, fine iron breeze 5～10wt%, steel-making iron scale 30～35wt%, steel-making wedding agent 3～7wt% add water and mix and stir, be pressed into pelletizing, drying makes the pelletizing water content promptly get vanadium-raising cooling agent less than 3% of pelletizing gross weight.
Preferably, among the preparation method of above-mentioned vanadium-raising cooling agent, described steel-making cutting slag, steel-making iron scale particle diameter are no more than 3mm.
Preferably, among the preparation method of above-mentioned vanadium-raising cooling agent, the ratio of the add-on of water and raw material gross weight is 3～5: 45～50, more preferably 3: 50.
The present invention further provides steel-making cutting slag in the purposes of making vanadium-raising cooling agent.
Concrete technical scheme is: will make steel cutting slag 25～35wt%, vanadium extraction mud 20～35wt%, fine iron breeze 5～10wt%, steel-making iron scale 30～35wt%, steel-making wedding agent 3～7wt% adds the water mixing and stirs, be pressed into pelletizing, drying makes the pelletizing water content promptly get vanadium-raising cooling agent less than 3% of pelletizing gross weight; Wherein, TFe content 〉=61wt% in the described steel-making cutting slag; TFe content 〉=67wt% in the described vanadium extraction mud, P content≤0.07wt%, S content≤0.7wt%; TFe content 〉=62wt% in the described fine iron breeze, P content≤0.007wt%, S content≤0.3wt%; TFe content 〉=63wt% in the described steel-making iron scale, P content≤0.02wt%, S content≤0.03wt%.
Preferably, above-mentioned steel-making cutting slag is in the purposes of making vanadium-raising cooling agent, and steel-making cutting slag, steel-making iron scale particle diameter are no more than 3mm.
Preferably, above-mentioned steel-making cutting slag is in the purposes of making vanadium-raising cooling agent, and the ratio of the add-on of water and raw material gross weight is 3～5: 45～50; The ratio of the add-on of water and raw material gross weight more preferably 3: 50.
Beneficial effect of the present invention:
The invention provides a kind of utilization steel-making cutting slag and vanadium extraction mud and prepare vanadium-raising cooling agent and preparation method thereof for main raw material.The vanadium-raising cooling agent that the present invention produced, ball shape is even, and intensity is (fall from the 2m height not broken) better, and a balling ratio is up to 85%, total iron content (TFe:Fe in the refrigerant of being made
2O
3+ FeO+MFe, TFe refer to full iron, i.e. the massfraction of ferro element in ore; MFe refers to Armco magnetic iron, has the massfraction of ferro element in ore of magnetic) reached more than 60%, it is few to contain compositions such as P, S, water, satisfies the requirement as vanadium-raising cooling agent fully.Carry out the vanadium-bearing hot metal vanadium extraction with vanadium-raising cooling agent of the present invention, compare with the refrigerant that adopts prior art: the relative minimizing of usage quantity of (1) refrigerant; (2) V in the vanadium slag
2O
5Content improves 0.5%-2%; (3) recovery rate of vanadium improves 6%～8%.In addition, vanadium-raising cooling agent of the present invention has advantages such as cost is low, production technique is simple, resource utilization is high, good cooling results; Cutting slag and vanadium extraction mud that the present invention not only can produce the steel plant continuous casting workshop fully effectively utilize, save cost, and can adapt to the vanadium extraction by converter blowing production requirement fully.
Description of drawings
Fig. 1 is the production process route of embodiment of the invention vanadium-raising cooling agent.
Embodiment
Vanadium-raising cooling agent, its raw material consists of: steel-making cutting slag 25～35wt%, vanadium extraction mud 20～35wt%, fine iron breeze 5～10wt%, steel-making iron scale 30～35wt%, steel-making wedding agent 3～7wt%;
Wherein, TFe content 〉=61wt% in the described steel-making cutting slag; TFe content 〉=67wt% in the described vanadium extraction mud, P content≤0.07wt%, S content≤0.7wt%; TFe content 〉=62wt% in the described fine iron breeze, P content≤0.007wt%, S content≤0.3wt%; TFe content 〉=63wt% in the described steel-making iron scale, P content≤0.02wt%, S content≤0.03wt%.
Steel-making cutting slag among the present invention is meant: the steel plant continuous casting workshop in order to obtain the continuously cast bloom of certain-length, uses flame cutter that continuously cast bloom is cut when producing, and the solid scoriform material that is produced during cutting is called steel-making cutting slag.
Vanadium extraction mud among the present invention is meant: in the vanadium extraction by converter blowing process, a large amount of oxygen owing in converter extracting vanadium, jetted, produced a large amount of waste gas behind the oxygen reaction, for these waste gas are effectively handled, steel mill takes these gases away by exhaust equipment, in this process, the solid granule that gas is taken away can form a kind of gunk when carrying out wet dedusting, and this material just is called vanadium extraction mud.
Steel-making iron scale among the present invention is meant: the converter steelmaking oxidation shell of iron scale from steel rolling and casting process generation, its main component is a ferric oxide.The ferric oxide micromicro improves slag fluidity, also helps dephosphorization, and can lower the temperature.
Preferably, described steel-making wedding agent is at least a in cement, wilkinite, starch, water glass, the high-aluminium vanadine.
The present invention also provides the preparation method of above-mentioned vanadium-raising cooling agent, this method comprises, to make steel cutting slag, vanadium extraction mud, fine iron breeze, steel-making iron scale, steel-making wedding agent by mass ratio is: steel-making cutting slag 25～35wt%, vanadium extraction mud 20～35wt%, fine iron breeze 5～10wt%, steel-making iron scale 30～35wt%, steel-making wedding agent 3～7wt% add water and mix and stir, be pressed into pelletizing, drying makes the pelletizing water content promptly get vanadium-raising cooling agent less than 3% of pelletizing gross weight.
The pelletizing shape can be spherical in the aforesaid method, also can be elliposoidal, and is preferred spherical, is convenient to blanking.Why need to suppress balling-up, be because in the vanadium extraction by converter blowing production process, using ventilation installation to bleed always from fire door, and refrigerant also is to add from fire door, if do not suppress balling-up, powder can be communicated with gas and taken away a part together in adition process, not only influence the wet dedusting of gas, but also influence the utilization ratio of material.In addition, because moisture is excessive, the dangerous phenomenon of big spray in the possible producer, so pelletizing requires to be dried to the moisture content requirement less than 3% of pelletizing gross weight in the aforesaid method.
Preferably, among the preparation method of above-mentioned vanadium-raising cooling agent, steel-making cutting slag, steel-making iron scale particle diameter are no more than 3mm, main because when being pressed into the pelletizing refrigerant after above-mentioned raw materials will being mixed, if particle diameter too conference influences balling ratio, therefore steel-making cutting slag, steel-making iron scale particle diameter are no more than 3mm.
Preferably, among the preparation method of above-mentioned vanadium-raising cooling agent, the ratio of the add-on of water and raw material gross weight is 3～5: 45～50; Preferred, the ratio of the add-on of water and raw material gross weight is 3: 50.Add the water-wet raw material during batch mixing, make raw material contain certain moisture, thereby can better combine, improve the intensity of balling ratio and ball with wedding agent.
The present invention further provides steel-making cutting slag in the purposes of making vanadium-raising cooling agent.
Concrete technical scheme is: will make steel cutting slag 25～35wt%, vanadium extraction mud 20～35wt%, fine iron breeze 5～10wt%, steel-making iron scale 30～35wt%, steel-making wedding agent 3～7wt% adds the water mixing and stirs, be pressed into pelletizing, drying makes the pelletizing water content promptly get vanadium-raising cooling agent less than 3% of pelletizing gross weight; Wherein, TFe content 〉=61wt% in the described steel-making cutting slag; TFe content 〉=67wt% in the described vanadium extraction mud, P content≤0.07wt%, S content≤0.7wt%; TFe content 〉=62wt% in the described fine iron breeze, P content≤0.007wt%, S content≤0.3wt%; TFe content 〉=63wt% in the described steel-making iron scale, P content≤0.02wt%, S content≤0.03wt%.
Preferably, above-mentioned steel-making cutting slag is in the purposes of making vanadium-raising cooling agent, and steel-making cutting slag, steel-making iron scale particle diameter are no more than 3mm.
Preferably, above-mentioned steel-making cutting slag is being made vanadium extraction by converter blowing with in the purposes of refrigerant, and the ratio of the add-on of water and raw material gross weight is 3～7: 45～50; The ratio of the add-on of water and raw material gross weight more preferably 3: 50.
In order to understand the present invention better, further specify the present invention below in conjunction with embodiment.
The one-tenth of the raw material index of grading is as shown in table 1 among the present invention, has listed total iron (TFe) content in the steel-making cutting slag in the table respectively; Total iron (TFe) content in the vanadium extraction mud, phosphorus (P) content, sulphur (S) content; Total iron (TFe) content in the iron ore concentrate, phosphorus (P) content, sulphur (S) content; Total iron (TFe) content, phosphorus (P) content, sulphur (S) content and the used steel-making wedding agent of steel-making iron scale.
With steel-making cutting slag listed in the table 1, the broken also screening of steel-making iron scale obtains the powder that particle diameter is no more than 3mm, to make steel then and cut slag, vanadium extraction mud, fine iron breeze, the steel-making iron scale, the steel-making wedding agent is pressed certain mass than batching, the material that will prepare is put into mixer mixing stirring afterwards, add entry in the whipping process, after stirring raw material being sent into ball press suppresses, the raw material of balling-up does not return in the ball press hopper, the wet bulb group that the is pressed into natural air drying in the iron railings hopper of packing into is dried to water content and promptly gets vanadium extraction by converter blowing refrigerant of the present invention less than 3% of pelletizing gross weight; The performance of concrete proportioning raw materials, processing parameter and gained refrigerant is as shown in table 2, and concrete production process route as shown in Figure 1.
The present invention is also to being that the vanadium-raising cooling agent (being called cooled agglomerated pellet) that raw material (promptly do not add steel-making cutting slag) is made is studied with iron scale, vanadium extraction mud, powdered iron ore, wedding agent, and the refrigerant and the cooled agglomerated pellet refrigerant that will utilize technical solution of the present invention (embodiment of the invention 1,3,5) to obtain are used for vanadium extraction by converter blowing technology, under all identical situation of other processing condition such as adding opportunity, adding mode, the add-on of two class refrigerants, add V in the vanadium slag that obtains after the refrigerant vanadium extraction
2O
5The recovery rate of content, vanadium, TFe content are as shown in table 3; The concrete proportioning of cooled agglomerated pellet is as shown in table 4.
The raw material and the index of correlation thereof of table 1 preparation vanadium-raising cooling agent
The preparation condition of table 2 vanadium-raising cooling agent and performance
Annotate: the spherical vanadium extraction by converter blowing of above-mentioned 6 embodiment gained is even with the equal shape of refrigerant.
Table 3 vanadium-raising cooling agent working conditions and result of use thereof
The raw material of table 4 cooled agglomerated pellet and proportioning
As seen from the above table, utilize steel-making cutting slag to prepare vanadium-raising cooling agent, not only make steel-making cutting slag recycling economy utilize, and: the usage quantity of (1) refrigerant reduces relatively; (2) V in the vanadium slag
2O
5Content improves 1%-2%; (3) recovery rate of vanadium improves 0.5%～2%.In addition, report among the patent application CN100582248 to contain preparation of vanadium iron fine ore and iron scale and wedding agent and the refrigerant that forms of compacting, it is used for vanadium extraction from hot metal, V in the gained vanadium slag
2O
5Content is 15.93～17.11%, and the recovery rate of gained vanadium is 77.1～78.2%.As fully visible, the vanadium-raising cooling agent of the present invention's preparation not only can utilize vanadium extraction mud and steel-making cutting slag recycling economy, and has improved the utilization ratio of vanadium resource.
Claims (10)
1. vanadium-raising cooling agent is characterized in that, its raw material consists of: steel-making cutting slag 25～35wt%, vanadium extraction mud 20～35wt%, fine iron breeze 5～10wt%, steel-making iron scale 30～35wt%, steel-making wedding agent 3～7wt%;
Wherein, TFe content 〉=61wt% in the described steel-making cutting slag; TFe content 〉=67wt% in the described vanadium extraction mud, P content≤0.07wt%, S content≤0.7wt%; TFe content 〉=62wt% in the described fine iron breeze, P content≤0.007wt%, S content≤0.3wt%; TFe content 〉=63wt% in the described steel-making iron scale, P content≤0.02wt%, S content≤0.03wt%.
2. vanadium-raising cooling agent according to claim 1 is characterized in that, described steel-making wedding agent is at least a in cement, wilkinite, starch, water glass, the high-aluminium vanadine.
3. the preparation method of claim 1 or 2 described vanadium-raising cooling agents, it is characterized in that, this method comprises, with described steel-making cutting slag, vanadium extraction mud, fine iron breeze, steel-making iron scale, the wedding agent of making steel by mass ratio be: steel-making cutting slag 25～35wt%, vanadium extraction mud 20～35wt%, fine iron breeze 5～10wt%, steel-making iron scale 30～35wt%, steel-making wedding agent 3～7wt% add the water mixing and stir, be pressed into pelletizing, drying makes the pelletizing water content promptly get vanadium-raising cooling agent less than 3% of pelletizing gross weight.
4. the preparation method of vanadium-raising cooling agent according to claim 3 is characterized in that, the particle diameter of described steel-making cutting slag, steel-making iron scale is no more than 3mm.
5. according to the preparation method of claim 3 or 4 described vanadium-raising cooling agents, it is characterized in that the ratio of the add-on of water and raw material gross weight is 3～5: 45～50.
6. the preparation method of vanadium-raising cooling agent according to claim 5 is characterized in that, the ratio of the add-on of water and raw material gross weight is 3: 50.
7. steel-making cutting slag is in the purposes of making vanadium-raising cooling agent.
8. steel-making cutting slag according to claim 7 is in the purposes of making vanadium-raising cooling agent, it is characterized in that, to make steel cutting slag 25～35wt%, vanadium extraction mud 20～35wt%, fine iron breeze 5～10wt%, steel-making iron scale 30～35wt%, steel-making wedding agent 3～7wt% adds water and mixes and stir, be pressed into pelletizing, drying makes the pelletizing water content promptly get vanadium-raising cooling agent less than 3% of pelletizing gross weight;
Wherein, TFe content 〉=61wt% in the described steel-making cutting slag; TFe content 〉=67wt% in the described vanadium extraction mud, P content≤0.07wt%, S content≤0.7wt%; TFe content 〉=62wt% in the described fine iron breeze, P content≤0.007wt%, S content≤0.3wt%; TFe content 〉=63wt% in the described steel-making iron scale, P content≤0.02wt%, S content≤0.03wt%.
9. steel-making cutting slag according to claim 8 is characterized in that in the purposes of making vanadium-raising cooling agent the cutting slag of making steel, steel-making iron scale particle diameter are no more than 3mm.
According to Claim 8 or 9 described steel-making cutting slags in the purposes of making vanadium-raising cooling agent, it is characterized in that the ratio of the add-on of water and raw material gross weight is 3～5: 45～50; Be preferably 3: 50.
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| CN102586538A (en) * | 2012-02-20 | 2012-07-18 | 攀钢集团攀枝花钢铁研究院有限公司 | Vanadium extraction coolant and preparation method thereof |
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| CN103468855A (en) * | 2013-09-30 | 2013-12-25 | 攀钢集团攀枝花钢钒有限公司 | Rotating furnace coolant, preparing method thereof and use method thereof |
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| CN104878222A (en) * | 2015-06-09 | 2015-09-02 | 钢铁研究总院 | Hot-metal-ladle vanadium extraction method |
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| CN103468855B (en) * | 2013-09-30 | 2015-04-22 | 攀钢集团攀枝花钢钒有限公司 | Rotating furnace coolant, preparing method thereof and use method thereof |
| CN104878222A (en) * | 2015-06-09 | 2015-09-02 | 钢铁研究总院 | Hot-metal-ladle vanadium extraction method |
| CN110904346A (en) * | 2019-12-17 | 2020-03-24 | 攀枝花钢城集团有限公司 | Sodium-containing vanadium extraction coolant and preparation method and application thereof |
| CN111910041A (en) * | 2020-08-25 | 2020-11-10 | 承德建龙特殊钢有限公司 | Vanadium extraction coolant and preparation method thereof |
| CN111996333A (en) * | 2020-08-28 | 2020-11-27 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for reducing oxidation of magnesia carbon brick of electric furnace |
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