CN103540711A - Method for simultaneously removing sulfur and phosphorus from semi-steel - Google Patents
Method for simultaneously removing sulfur and phosphorus from semi-steel Download PDFInfo
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- CN103540711A CN103540711A CN201310502990.4A CN201310502990A CN103540711A CN 103540711 A CN103540711 A CN 103540711A CN 201310502990 A CN201310502990 A CN 201310502990A CN 103540711 A CN103540711 A CN 103540711A
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Abstract
The invention provides a method for simultaneously removing sulfur and phosphorus from semi-steel. The method comprises the following steps sequentially carried out on a semi-steel sulfur removal station: carrying out first-stage injection on the semi-steel by using a sulfur removal oxygen lance, wherein an injection material is injection-assisted powder taking an inert gas as a carrier; carrying out second-stage injection on the semi-steel by using the sulfur removal oxygen lance, wherein an injection material is a mixture of the injection-assisted powder taking the inert gas as the carrier and passivating magnesium powder; carrying out third-stage injection on the semi-steel by using the sulfur removal oxygen lance, wherein the injection material is the injection-assisted powder taking the inert gas as the carrier, the semi-steel is molten iron obtained after vanadium is extracted from vanadium-containing molten iron by using a converter, and the injection-assisted powder is prepared from 55-80 parts by weight of passivating lime, 5-15 parts by weight of ferric oxide and 20-30 parts by weight of sodium oxide. The method has the advantages that the semi-steel without the vanadium can be simultaneously subjected to pretreating sulfur and phosphorus removal; the corrosion on a lining of a vanadium extracting converter can be avoided, and meanwhile, the content of sodium in vanadium residues can be reduced.
Description
Technical field
The invention belongs to semisteel smelting technical field after vanadium extraction, specifically, relate to a kind of method that half steel that vanadium-bearing hot metal is obtained after vanadium extraction aftertreatment carries out desulfurization simultaneously and dephosphorization.
Background technology
Conventionally, phosphorus, sulphur are the harmful elements in most steel grades.In recent years, along with developing rapidly of science and technology, Cryogenic Steel, marine steel, anti-hydrogen induced cracking steel and part slab steel, both required extremely low sulphur content, also requires phosphorus content <0.01% or 0.005% in steel.As everyone knows, sulphur content directly affects the use properties of steel, and in steel, the too high meeting of sulphur content causes the hot workability of steel to degenerate, and causes " hot-short " of steel; In addition, also can obviously reduce the welding property of steel, cause hot cracking; The plasticity of steel is also along with the remarkable variation of increase of sulphur content; In pure iron or siliconized plate, sulphur content is high, and hysteresis loss increases.So desulfurization becomes one of major objective in smelting iron and steel.
And desulfurizing iron is considered to alleviate the metallurgy load of blast furnace, converter, the main method of the economic target that develops skill, also becomes the requisite technique means of smelting low-sulfur Clean Steel.Since the eighties in 20th century, for the pre-dephosphorization problem of molten iron, also various treatment processs have been developed, the most representative have two kinds: a kind of is to carry out dephosphorization in containing the hot metal ladle of molten iron or fish torpedo ladle, another kind is in converter, to carry out dephosphorization of molten iron pre-treatment, and these two kinds of methods have all obtained industrial application.Hot metal ladle or fish torpedo ladle dephosphorization mainly contain that temperature drop is large, splash especially severe again during oxygen blast compensation temperature drop, and the molten iron treatment time is long affects the problems such as production direct motion, and applicable cases is undesirable.And the pre-dephosphorization of converter has been realized commercial scale production in Japan and the iron and steel enterprise of Korea S, Chinese Baosteel, Wuhan Iron and Steel Plant etc., when producing Low-phosphorus Steel, adopt the duplex dephosphorized technique smelting of twin furnace, and molten steel [P] can be down to 0.003%～0.008% from 0.08%, and effect is good.
Publication number is that the patent documentation of CN102796840A discloses refrigerant and production method, converter dephosphorization extraction vanadium method for a kind of converter dephosphorization vanadium extraction, described converter dephosphorization vanadium extraction comprises the following steps by the production method of refrigerant: sodium salt particle, iron scale particle, bauxitic clay fine powder and water are mixed, form compound; Through ball press, compound is pressed into bead; Baking bead, to remove moisture, obtains cooled agglomerated pellet finished product.Advantage of the present invention comprises: can in vanadium extraction by converter blowing process, realize vanadium extraction and dephosphorization simultaneously; Simple to operate; Impact on existing process for extracting vanadium and half steel quality is less; Dephosphorization efficiency is high, can guarantee the production efficiency of converter extracting vanadium.In addition, the present invention can move forward to converter extracting vanadium by the part dephosphorization task of steel-making converter, realizes the low-cost converter steelmaking of half steel, is convenient to obtain composition, molten steel that temperature is qualified.
Publication number be the patent documentation of CN101215619A disclose a kind of from vanadium-bearing hot metal vanadium extraction and dephosphorization method and utilize the process for making of the method, described from vanadium-bearing hot metal the method for vanadium extraction and dephosphorization comprise: vanadium-bearing hot metal is being carried out in the process of oxygen supply blowing, in described molten iron, add vanadium extraction and dephosphorization agent and refrigerant, described vanadium extraction and dephosphorization agent is Na
2cO
3, after blowing, obtain vanadium slag and low-phosphorous half steel.The method can extracted the Dephosphorization of vanadium, thereby can not only guarantee effective extraction of vanadium, and can effectively remove the phosphorus in molten iron.
Yet, method in above-mentioned two patent documentations is all that to take the compound of sodium be dephosphorizing agent, and in converter extracting vanadium, carry out dephosphorization, although this can play certain dephosphorization effect, it is larger to lining erosion that but the compound of sodium joins in converter, affect life of converter, can increase the sodium content in vanadium slag simultaneously, unfavorable to the production of follow-up vanadium goods.
Summary of the invention
The object of the invention is to solve at least one in above-mentioned prior art problem.
For example, one of object of the present invention is to provide a kind of and can carries out to half steel after vanadium extraction the method for desulfurization simultaneously and desulfurization.
The invention provides a kind of method to half steel while desulfurization dephosphorization.Described method is included in half steel desulfurization station following steps in sequence: with desulfurization oxygen rifle, half steel is carried out to first stage winding-up, its injection material blows pulvis for usining rare gas element as helping of carrier; With desulfurization oxygen rifle, half steel is carried out to subordinate phase winding-up, its injection material blows pulvis and deactivating magnesium powder mixture for usining rare gas element as helping of carrier; With desulfurization oxygen rifle, half steel is carried out to phase III winding-up, its injection material blows pulvis for usining rare gas element as helping of carrier, wherein, described half steel is the molten iron of vanadium-bearing hot metal gained after vanadium extraction by converter blowing, described in help and blow pulvis by passive lime, the ferric oxide of 5～15 parts and the sodium oxide of 20～30 parts of 55～80 parts are made by weight.
Compared with prior art, beneficial effect of the present invention comprises: can carry out while pretreatment desulfurizing and dephosphorization to the half steel after vanadium extraction; Simple to operate, do not need to build in addition related facility and equipment, do not extend activity time; Can reduce converter steelmaking supplementary product onsumption; Can avoid the erosion of converter extracting vanadium furnace lining, can reduce sodium content in vanadium slag simultaneously.
Embodiment
Hereinafter, in connection with exemplary embodiment, describe the method to half steel while desulfurization dephosphorization of the present invention in detail.
For example, containing vanadium iron ore deposit (, vanadium titano-magnetite) vanadium-bearing hot metal of gained after blast-furnace smelting, need to carry out extraction smelting of vanadium and hot metal pretreatment.Contriver finds: vanadium-bearing hot metal is for example processed, after (, vanadium extraction by converter blowing is smelted) through vanadium extraction, and the constituent contents such as silicomanganese vanadium are less, and phosphorus sulphur content is substantially constant; In addition, the half steel temperature after vanadium extraction is between 1350～1400 ℃, just in time in dephosphorization optimum temperature range.Therefore, contriver has proposed the method to half steel while desulfurization dephosphorization at half steel desulfurization station.
According to an illustrative embodiment of the invention to half steel simultaneously the method for desulfurization dephosphorization be included in half steel desulfurization station following steps in sequence: with desulfurization oxygen rifle, half steel is carried out to first stage winding-up, its injection material is to using rare gas element to blow pulvis as helping of carrier; With desulfurization oxygen rifle, half steel is carried out to subordinate phase winding-up, its injection material blows pulvis and deactivating magnesium powder mixture for usining rare gas element as helping of carrier; With desulfurization oxygen rifle, half steel is carried out to phase III winding-up, its injection material blows pulvis for usining rare gas element as helping of carrier, wherein, described half steel is the molten iron of vanadium-bearing hot metal gained after vanadium extraction by converter blowing, described in help and blow pulvis by passive lime, the ferric oxide of 5～15 parts and the sodium oxide of 20～30 parts of 55～80 parts are made by weight.Here, deactivating magnesium powder is sweetening agent, helps the passive lime (CaO) blowing in pulvis to react with [S] in half steel and generates CaS.For method of the present invention, help the winding-up amount of blowing pulvis and deactivating magnesium powder to determine according to the phosphorus sulphur content in half steel.In addition, preferably, described in help blow pulvis can be by passive lime, the ferric oxide of 7～13 parts and the sodium oxide of 22～28 parts of 60～75 parts are made by weight.
In another exemplary embodiment of the present invention, to half steel simultaneously the method for desulfurization dephosphorization on the basis of above-mentioned exemplary embodiment, also comprise the first stage is jetted in step and helps the winding-up amount of blowing pulvis, in subordinate phase winding-up step, helping to blow in the winding-up amount of pulvis and phase III winding-up step helps the winding-up amount of blowing pulvis to control respectively as helping 5%～10% of the always winding-up amount of pulvis of blowing, 70%～80% and 15%～25%, and first stage winding-up step, in subordinate phase winding-up step and phase III winding-up step, help the winding-up amount sum of blowing pulvis to be the always winding-up amount of pulvis of blowing that helps.In the method for the invention, first stage winding-up is mainly that the sulphur in half steel is removed, and the high desulfurization kinetics condition of sulphur content in this stage is good; Subordinate phase adopts mixed injection, is mainly to utilize the strong sweetening effectiveness of magnesium to carry out desulfurization; Phase III is mainly that the phosphorus in half steel is removed.Preferably, in the step of subordinate phase winding-up, will help the ratio that blows the straying quatity of pulvis and the straying quatity of deactivating magnesium powder to control as 5:1～7:1.Can make like this condition of slag good, easily remove, the phosphorus sulfur capacity of slag is high, is easy to phosphorus sulphur and controls.
In addition, preferably, the distance between desulfurization oxygen rifle and half steel liquid level is controlled as 50cm～100cm, can further be improved like this winding-up effect of desulfurization oxygen rifle.
In another exemplary embodiment of the present invention, to the half steel while, the method for desulfurization dephosphorization realizes in the following ways.
After vanadium extraction by converter blowing finishes, the half steel of not desulfurization, dephosphorization is transported to desulfurization station.Before desulfurization, will help respectively blow pulvis, deactivating magnesium powder is encased in different batch cans, batch can adopts drying nitrogen sealing, when spray gun to be desulfurization is down to half steel liquid level 50cm～100cm, starts take nitrogen and blows pulvis as carrier winding-up helps, spouting velocity is 30～55kg/min, and 0.5～2min jets; Then, employing helps blows the mode desulfurization dephosphorization that pulvis and deactivating magnesium powder are jetted simultaneously, after meeting desulfurization requirement, deactivating magnesium powder winding-up amount closes deactivating magnesium powder feed bin valve, for example, in this stage, the injecting velocity of deactivating magnesium powder can be 6～10kg/min, the winding-up time can be 8～15min, helps the ratio that blows the straying quatity of pulvis and the straying quatity of deactivating magnesium powder to control as 5:1～7:1; Next, continuing jets to help blows pulvis 0.5～2min, and spouting velocity is 30～55kg/min, then promotes spray gun, stops winding-up after spray gun leaves half steel liquid level.
In exemplary embodiment of the present invention, in passive lime, the quality percentage composition of CaO can be preferably more than 85% for more than 80%, and to reach better sweetening effectiveness, the granularity of passive lime is preferably <1.5mm.Deactivating magnesium powder grade can be >90%, and density is generally 0.88～0.98g/cm
3, granularity is <2mm preferably; More preferably, the weight that 2% and the granularity that the weight that in deactivating magnesium powder, granularity is greater than the part of 1.2mm is no more than deactivating magnesium powder total amount is less than the part of 0.15mm is not more than 10% of deactivating magnesium powder total amount.The grade of ferric oxide (powder) can be >90%, granularity can be <0.5mm, preferably, the weight that 80% and the granularity that the weight that in croci, granularity is less than the part of 0.075mm is not less than croci total amount is less than the part of 0.25mm should be not less than 98% of croci total amount.The grade of sodium oxide can be >95%, granularity can be <0.5mm, preferably, the weight that 80% and the granularity that the weight that in sodium oxide, granularity is less than the part of 0.075mm is not less than sodium oxide total amount is less than the part of 0.25mm is not less than 98% of sodium oxide total amount.Can further improve dephosphorization and sweetening effectiveness like this.Yet, the invention is not restricted to this, for example, in the situation that the granularity of passive lime, deactivating magnesium powder, brown iron oxide, sodium oxide is not more than 2mm, all can reach good desulfurization and dephosphorization effect.
In order to understand better the present invention, below in conjunction with concrete example, it is further described.
Example 1
Adopt passive lime, iron scale powder, sodium oxide to help and blow agent as raw material production, wherein, passive lime 65%, iron scale 15%, sodium oxide 20%.Before desulfurization, will help respectively blow pulvis, deactivating magnesium powder is encased in different batch cans, batch can adopts drying nitrogen sealing.
After vanadium extraction by converter blowing finishes, the half steel of the not desulfurization phosphorus obtaining is transported to desulfurization station after converter extracting vanadium is processed.Wherein, the C content of half steel is that 3.61%, P content is that 0.068%, S content is 0.065%.
Spray gun to be desulfurization starts take nitrogen and blows pulvis as carrier winding-up helps while being down to half steel liquid level 50cm, spouting velocity is 42kg/min, winding-up 0.5min.Then, adopt to help and blow the mode desulfurization dephosphorization that pulvis and deactivating magnesium powder are jetted simultaneously, the injecting velocity of deactivating magnesium powder is 8.5kg/min, and the winding-up time is 15min, helps the ratio that blows the straying quatity of pulvis and the straying quatity of deactivating magnesium powder to control as 5:1.Next, continuing jets to help blows pulvis 1min, and spouting velocity is 44kg/min, then promotes spray gun, stops winding-up after spray gun leaves half steel liquid level.
After testing, in the half steel after above-mentioned processing, phosphorus content is 0.039%, and dephosphorization rate reaches 43.28%, and sulphur content is 0.011%, and desulfurization degree reaches 83.08%.
Example 2
Adopt passive lime, iron scale powder, sodium oxide to help and blow agent as raw material production, wherein, passive lime 65%, iron scale 5%, sodium oxide 30%.Before desulfurization, will help respectively blow pulvis, deactivating magnesium powder is encased in different batch cans, batch can adopts drying nitrogen sealing.
After vanadium extraction by converter blowing finishes, the half steel of the not desulfurization phosphorus obtaining is transported to desulfurization station after converter extracting vanadium is processed.Wherein, the C content of half steel is that 3.84%, P content is that 0.070%, S content is 0.54%.
Spray gun to be desulfurization starts take nitrogen and blows pulvis as carrier winding-up helps while being down to half steel liquid level 100cm, spouting velocity is 39kg/min, winding-up 1min.Then, adopt to help and blow the mode desulfurization dephosphorization that pulvis and deactivating magnesium powder are jetted simultaneously, the injecting velocity of deactivating magnesium powder is 9kg/min, and the winding-up time is 13min, helps the ratio that blows the straying quatity of pulvis and the straying quatity of deactivating magnesium powder to control as 7:1.Next, continuing jets to help blows pulvis 2min, and spouting velocity is 38kg/min, then promotes spray gun, stops winding-up after spray gun leaves half steel liquid level.
After testing, in the half steel after above-mentioned processing, phosphorus content is 0.036%, and dephosphorization rate reaches 48.57%, and sulphur content is 0.009%, and desulfurization degree reaches 83.33%.
The present invention can (for example carry out while desulfurization and dephosphorization to half steel, dephosphorization rate can reach more than 40%, even more than 45%, desulfurization degree can reach more than 80%), thereby can provide low-phosphorous sulphur half steel for steel-making converter, dephosphorization task while having alleviated steel-making converter smelting molten steel, for the few slag steel-making of low phosphorus steel by smelting and realization creates conditions.In addition, the present invention also has simple to operate, does not need to build in addition related facility and equipment, does not extend activity time, to reducing converter steelmaking supplementary product onsumption, has played the good advantages such as effect.In addition, the present invention can also avoid the erosion to converter extracting vanadium furnace lining, can reduce sodium content in vanadium slag simultaneously.
Although described the present invention in conjunction with exemplary embodiment above, those of ordinary skills should be clear, in the situation that do not depart from the spirit and scope of claim, can carry out various modifications to above-described embodiment.
Claims (4)
1. the method to half steel while desulfurization dephosphorization, is characterized in that, described method is included in half steel desulfurization station following steps in sequence:
With desulphurization spray gun, half steel is carried out to first stage winding-up, its injection material blows pulvis for usining rare gas element as helping of carrier;
With desulphurization spray gun, half steel is carried out to subordinate phase winding-up, its injection material blows pulvis and deactivating magnesium powder mixture for usining rare gas element as helping of carrier;
With desulphurization spray gun, half steel is carried out to phase III winding-up, its injection material blows pulvis for usining rare gas element as helping of carrier,
Wherein, described half steel is the molten iron of vanadium-bearing hot metal gained after vanadium extraction by converter blowing, described in help and blow pulvis by passive lime, the ferric oxide of 5～15 parts and the sodium oxide of 20～30 parts of 55～80 parts are made by weight.
2. the method to half steel while desulfurization dephosphorization according to claim 1, is characterized in that, in the step of described subordinate phase winding-up, will help the ratio that blows the straying quatity of pulvis and the straying quatity of deactivating magnesium powder to control as 5:1～7:1.
3. the method to half steel while desulfurization dephosphorization according to claim 1, is characterized in that, described method is 50cm～100cm by the distance between desulfurization oxygen rifle and half steel liquid level.
4. according to claim 1 the half steel method of desulfurization dephosphorization simultaneously be is characterized in that, described in help and blow pulvis by passive lime, the ferric oxide of 7～13 parts and the sodium oxide of 22～28 parts of 60～75 parts are made by weight.
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| CN104711396A (en) * | 2015-03-14 | 2015-06-17 | 内蒙古科技大学 | Method removing phosphorus and sulfur simultaneously and reserving niobium, vanadium, chromium and nickel for molten iron |
| CN105385809A (en) * | 2015-10-23 | 2016-03-09 | 首钢总公司 | Desulfurizing method for molten iron containing sulfur |
| CN107663560A (en) * | 2016-07-28 | 2018-02-06 | 上海梅山钢铁股份有限公司 | The control method of pulverized limestone dosage in a kind of magnesium-based composite blowing Desulphuring Process of Molten Iron |
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| CN104711396A (en) * | 2015-03-14 | 2015-06-17 | 内蒙古科技大学 | Method removing phosphorus and sulfur simultaneously and reserving niobium, vanadium, chromium and nickel for molten iron |
| CN104711396B (en) * | 2015-03-14 | 2017-01-18 | 内蒙古科技大学 | Method removing phosphorus and sulfur simultaneously and reserving niobium, vanadium, chromium and nickel for molten iron |
| CN105385809A (en) * | 2015-10-23 | 2016-03-09 | 首钢总公司 | Desulfurizing method for molten iron containing sulfur |
| CN107663560A (en) * | 2016-07-28 | 2018-02-06 | 上海梅山钢铁股份有限公司 | The control method of pulverized limestone dosage in a kind of magnesium-based composite blowing Desulphuring Process of Molten Iron |
| CN107663560B (en) * | 2016-07-28 | 2019-09-17 | 上海梅山钢铁股份有限公司 | The control method of pulverized limestone dosage in a kind of magnesium-based composite blowing Desulphuring Process of Molten Iron |
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