CN104073587B - The method of vanadium extraction by converter blowing - Google Patents
The method of vanadium extraction by converter blowing Download PDFInfo
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- CN104073587B CN104073587B CN201410347138.9A CN201410347138A CN104073587B CN 104073587 B CN104073587 B CN 104073587B CN 201410347138 A CN201410347138 A CN 201410347138A CN 104073587 B CN104073587 B CN 104073587B
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Abstract
The invention discloses a kind of method of vanadium extraction by converter blowing, described method comprises the top rifle pushing up the rifle oxygen blast stage and perform after the rifle oxygen blast stage of top and blows the inactive gas stage, wherein, the top rifle oxygen blast stage comprises: start, in the time of vanadium extraction blowing 210s ~ 270s, to use top rifle to converter molten pool oxygen blast in vanadium extraction blowing; Top rifle blows the inactive gas stage and comprises: in the time of vanadium extraction blow end point after the rifle oxygen blast stage of top, uses top rifle to blow inactive gas to converter molten pool; Described method also comprises: push up the rifle oxygen blast stage start time or before first refrigerant is joined converter molten pool, and vanadium extraction blowing 100s ~ 140s time second batch refrigerant is joined converter molten pool.According to the method for vanadium extraction by converter blowing of the present invention, the add-on of refrigerant in vanadium extraction converting process can be reduced.
Description
Technical field
The invention belongs to field of iron and steel smelting, specifically, the present invention relates to a kind of method of vanadium extraction by converter blowing.
Background technology
Vanadium extraction by converter blowing is blended in converter by vanadium-bearing hot metal, high speed pure oxygen jet is utilized to stir vanadium-bearing hot metal, by the silicon in molten iron, vanadium, manganese, titanium, iron be oxidized to stable oxide compound at least partially, the barium oxide combination of formation is called vanadium slag, and the molten iron after vanadium extraction is called half steel.Because the barium oxide proportion formed is less than half steel, utilize converter to flow in half cylinder of steel by half steel from tap hole, vanadium slag is stayed in stove, and half steel is as the raw material of lower operation converter steelmaking, and vanadium slag is poured in slag ladle from fire door, produces the raw material of vanadium goods as lower operation.
Vanadium extracting process is the oxidation reaction process of the elements such as iron in molten iron, vanadium, carbon, silicon, manganese, titanium, phosphorus, sulphur, the thermodynamics and kinetics condition when speed that the oxidizing reaction of these elements is carried out depends on the chemical composition of molten iron itself and blows vanadium.In oxygen gesture figure, carbon oxygen gesture line and vanadium oxygen gesture line have an intersection point, and the temperature that this point is corresponding is called carbon vanadium invert point, and lower than this temperature, vanadium has precedence over oxidation of coal, and higher than this temperature, carbon then has precedence over vanadium oxidation.Vanadium extraction is exactly the principle utilizing selective oxidation, adopts high speed pure oxygen jet to stir vanadium-bearing hot metal in top blown converter, the vanadium in molten iron is oxidized to a kind of physical-chemical reaction process of the stable barium oxide of high price.
The vanadium extraction by converter blowing operation of prior art mainly through refrigerant being added molten bath to control bath temperature below carbon vanadium invert point, thus reaches the object that vanadium protects carbon.But refrigerant main component is FeO, SiO
2deng, foreign matter content in vanadium slag can be caused when refrigerant add-on is excessive to rise, dilute the content of Vanadium in Vanadium Residue oxide compound; Bath temperature can be caused when refrigerant add-on is very few higher than carbon vanadium invert point, be unfavorable for the oxidation of vanadium, cause content of vanadium in molten steel higher, vanadium runs off serious.
Summary of the invention
One object of the present invention is the deficiency overcoming above-mentioned technology, provides a kind of and can reduce refrigerant add-on and improve the vanadium extraction by converter blowing method of Vanadium in Vanadium Residue recovery rate.
Another object of the present invention is the deficiency overcoming above-mentioned technology, provides a kind of vanadium extraction by converter blowing method that can improve the content of carbon in half steel.
Vanadium extraction by converter blowing method according to the present invention comprises the top rifle pushing up the rifle oxygen blast stage and perform after the rifle oxygen blast stage of top and blows the inactive gas stage, wherein, the top rifle oxygen blast stage comprises: start, in the time of vanadium extraction blowing 210s ~ 270s, to use top rifle to converter molten pool oxygen blast in vanadium extraction blowing; Top rifle blows the inactive gas stage and comprises: in the time of vanadium extraction blow end point after the rifle oxygen blast stage of top, uses top rifle to blow inactive gas to converter molten pool; Described method also comprises: push up the rifle oxygen blast stage start time or before first refrigerant is joined converter molten pool, and vanadium extraction blowing 100s ~ 140s time second batch refrigerant is joined converter molten pool; Wherein, refrigerant comprises at least one in cold pressing block, pig, iron scale and pellet, and cold pressing block is that converter dust-removing ash and/or iron scale are by the ball block of binding agent compression moulding.
According to exemplary embodiment of the present invention, when 115s ~ 125s is blown in vanadium extraction, second batch refrigerant can be joined converter molten pool.
According to exemplary embodiment of the present invention, first refrigerant add-on can be 9kg/t
molten iron~ 11kg/t
molten iron, second batch refrigerant add-on can be 11kg/t
molten iron~ 13kg/t
molten iron.
According to exemplary embodiment of the present invention, start, in the top rifle oxygen blast stage of vanadium extraction blowing 100s ~ 140s, top gun gun bit can be controlled at 1.5m ~ 1.8m in vanadium extraction blowing; Then, in the remaining time in the rifle oxygen blast stage of top, top gun gun bit can be controlled at 1.8m ~ 2.2m; On top, rifle blows in the inactive gas stage, can control top gun gun bit at 1.5m ~ 1.8m.
According to exemplary embodiment of the present invention, the oxygen flow in the rifle oxygen blast stage of top can be 22000m
3/ h ~ 24000m
3/ h, the rifle inactive gas flow blown in the inactive gas stage in top can be 22000m
3/ h ~ 24000m
3/ h.
According to exemplary embodiment of the present invention, all comprise FeO in cold pressing block, pig, iron scale and pellet, in refrigerant, the content of FeO can be not less than 50wt%.
According to exemplary embodiment of the present invention, refrigerant can comprise cold pressing block, and the granularity of cold pressing block can be 30mm ~ 70mm.
According to exemplary embodiment of the present invention, top blown converter or top and bottom combined blown converter can be used to carry out vanadium extraction blowing.
According to exemplary embodiment of the present invention, vanadium-bearing hot metal is the molten iron obtained after blast-furnace smelting containing coulsonite, described molten iron can comprise: the Ti of V, 0.19wt% of S, 0.3wt% of P, 0.06wt% of Mn, 0.60wt% of Si, 0.18wt% of C, 0.1wt% of 4.3wt% ~ 4.8wt% ~ 0.8wt% ~ 0.28wt% ~ 0.80wt% ~ 0.10wt% ~ 0.8wt% ~ 0.25wt%, all the other are iron and inevitable impurity.
According to exemplary embodiment of the present invention, the temperature of the vanadium-bearing hot metal before vanadium extraction blowing is 1280 DEG C ~ 1320 DEG C.
According to the method for vanadium extraction by converter blowing of the present invention, carry out the conversion of oxygen and nitrogen by reasonably controlled cooling model agent joining day and/or conservative control top rifle, significantly can reduce refrigerant add-on in vanadium extracting process and improve the recovery rate of the vanadium in the vanadium slag of blowing product.In addition, by conservative control top gun gun bit, select suitable refrigerant and/or determine the add-on of refrigerant, the carbon content in the half steel after bessemerizing vanadium extraction can also be improved.
Embodiment
The process for extracting vanadium of prior art mainly through refrigerant being added molten bath to be controlled by bath temperature below carbon vanadium invert point, thus reaches the object that vanadium protects carbon.But refrigerant main component is FeO, SiO
2deng, foreign matter content in vanadium slag can be caused when refrigerant add-on is excessive to rise, dilute the content of Vanadium in Vanadium Residue oxide compound; Bath temperature can be caused when refrigerant add-on is very few higher than carbon vanadium invert point, be unfavorable for the oxidation of vanadium, cause content of vanadium in molten steel higher, vanadium runs off serious.
The present invention is directed to the deficiencies in the prior art, provide a kind of method of vanadium extraction by converter blowing.Method according to the present invention comprises the top rifle pushing up the rifle oxygen blast stage and perform after the rifle oxygen blast stage of top and blows the inactive gas stage.Starting to be the top rifle oxygen blast stage in vanadium extraction blowing to the time of 210s ~ 270s (such as, 220s, 240s or 260s), mainly through performing top rifle oxygen blast to promote the oxidizing reaction of the vanadium in molten bath.For reducing the rising of bath temperature in top rifle oxygen blast phase process, start (namely in vanadium extraction blowing, rifle under oxygen rifle) time or 100s ~ 140s before and in vanadium extracting process time (such as, when 110s, 120s or 130s), respectively refrigerant is added molten bath, to guarantee to push up the FeO containing abundance in the irony first slag in the molten bath in rifle oxygen blast stage, be beneficial to the oxidizing reaction of the vanadium in molten iron.Top rifle to blow end point after the rifle oxygen blast stage of top blows the inactive gas stage, the main vanadium of lower aq in the FeO in the irony first slag pushing up the generation of rifle oxygen blast stage and half steel that relies on reacts, and half steel temperature is reduced to lower than carbon vanadium invert point from higher than carbon vanadium invert point gradually.Aforesaid operations not only significantly can reduce the add-on of refrigerant in vanadium extraction converting process, but also can improve the C content in the half steel of vanadium extraction terminal.
Vanadium extraction by converter blowing method of the present invention is specifically described below in conjunction with exemplary embodiment.
First, start, in the time of vanadium extraction blowing 210s ~ 270s (such as, 220s, 240s or 260s), to use top rifle to oxygen blast in the vanadium-bearing hot metal in molten bath in vanadium extraction blowing.Wherein, vanadium extraction blowing start (that is, rifle under oxygen rifle) time or forward direction molten bath add first refrigerant.Along with the reduction of (FeO) content in the rising of converter molten pool temperature and molten bath slag, when the 100s ~ 140s of vanadium extraction blowing, second batch refrigerant is added molten bath by (such as, when 110s, 120s or 130s).
Specifically, vanadium extraction by converter blowing process is the redox processes of the vanadium in vanadium-bearing hot metal and (FeO) in slag, and the oxidizing reaction rate of vanadium depends on the thermodynamics and kinetics condition in the chemical composition of vanadium-bearing hot metal itself and vanadium extraction reaction process.In oxygen gesture figure, the intersection point temperature (such as about 1361 DEG C) of carbon oxygen gesture line and vanadium oxygen gesture line is carbon vanadium invert point, but carbon vanadium invert point in actual vanadium extraction by converter blowing process can raise along with the increase of the rising of the concentration of the vanadium in molten iron and oxygen partial pressure, and reduce along with the reduction of the concentration of the vanadium in vanadium-bearing hot metal.When the temperature of vanadium-bearing hot metal is lower than carbon vanadium invert point, vanadium can have precedence over oxidation of coal, and when vanadium-bearing hot metal temperature is higher than carbon vanadium invert point, carbon then has precedence over vanadium oxidation.The process of vanadium extraction by converter blowing is exactly the principle utilizing selective oxidation, adopt top rifle winding-up pure oxygen jet to stir to change the thermodynamics and kinetics condition of vanadium-bearing hot metal in molten bath to vanadium-bearing hot metal, thus promote that the vanadium of the lower valency in vanadium-bearing hot metal is oxidized to the process of the oxide compound of the stable vanadium of high-valence state.
Start to vanadium extraction blowing 210s ~ 270s (such as in vanadium extraction blowing, 220s, 240s or 260s) time in, the elements such as the iron in vanadium-bearing hot metal, silicon, manganese, chromium can there is redox reaction and release of heat with (FeO) in slag at least partially, the heat of release can raise the temperature in molten bath, also reduces the rate of oxidation of vanadium simultaneously.Therefore, when vanadium extraction blowing starts (that is, rifle under oxygen rifle) or before first refrigerant is added molten bath to be used for reducing the initial temperature of vanadium-bearing hot metal, the vanadium extraction time of vanadium-bearing hot metal can be extended like this and improve the oxidation efficiency of vanadium.In addition, refrigerant is also for providing (FeO) to promote the carrying out of the oxidizing reaction of vanadium in the slag in molten bath.Refrigerant comprises cold pressing block, pig, iron scale and at least one in the pellet of blast furnace ironmaking, and wherein, cold pressing block is converter dust-removing ash and/or the iron scale ball block by binding agent compression moulding.
Along with the carrying out of vanadium extraction reaction, the oxidation of the elements such as the iron in vanadium-bearing hot metal, silicon, manganese, chromium impels bath temperature to raise.When the 100s ~ 140s of vanadium extraction blowing (such as, when 110s, 120s or 130s), preferably, when the 115s ~ 125s of vanadium extraction blowing (such as, during 120s), second batch refrigerant is added molten bath, the rising of the temperature of vanadium-bearing hot metal in vanadium extracting process can be reduced like this, the carbon avoiding bath temperature to cause higher than carbon vanadium invert point has precedence over vanadium oxidation, can also improve the content of the carbon in the half steel of the vanadium extraction product after vanadium extraction by converter blowing like this.In addition, add the content that second batch refrigerant can also improve (FeO) in the slag in molten bath, promote the carrying out of vanadium extraction reaction.
Vanadium-bearing hot metal according to the raw material as vanadium extraction by converter blowing of the present invention can for the molten iron obtained after blast-furnace smelting containing coulsonite.Described molten iron can comprise the Ti of V, 0.19wt% of S, 0.3wt% of P, 0.06wt% of Mn, 0.60wt% of Si, 0.18wt% of C, 0.1wt% of 4.3wt% ~ 4.8wt% ~ 0.8wt% ~ 0.28wt% ~ 0.80wt% ~ 0.10wt% ~ 0.8wt% ~ 0.25wt%, and all the other are iron and inevitable impurity.According to exemplary embodiment of the present invention, the temperature of the vanadium-bearing hot metal before vanadium extraction blowing can be 1280 DEG C ~ 1320 DEG C.
According to exemplary embodiment of the present invention, under the rifle of top, first refrigerant can be added to reduce the initial temperature of vanadium-bearing hot metal before rifle, improve the content of (FeO) in the vanadium extraction time of vanadium-bearing hot metal and the slag at vanadium extraction efficiency and raising vanadium extraction blowing initial stage.
According to exemplary embodiment of the present invention, the main component of refrigerant comprises FeO and SiO
2, the addition of refrigerant crosses the content that conference improves the impurity in slag, and the content of the impurity increased in slag dilutes the content of the barium oxide in slag; Refrigerant add-on is too small, can not reach the effect of cooling bath temperature, be unfavorable for the oxidation of vanadium, also increase the content of the vanadium in vanadium extraction product in half steel simultaneously, causes vanadium to run off serious.Because the vanadium-bearing hot metal temperature at initial stage of blowing is lower, now the addition of first refrigerant can be 9kg/t
molten iron~ 11kg/t
molten iron; Along with the rising of bath temperature, the addition of second batch refrigerant can be 11kg/t
molten iron~ 13kg/t
molten iron, bath temperature can be avoided like this higher than carbon vanadium invert point, promote the carrying out of the oxidizing reaction of vanadium, the addition of refrigerant can also be reduced like this, thus the foreign matter content reduced in slag and the content that improve the vanadium in slag.
According to exemplary embodiment of the present invention, preferably, vanadium extraction blowing start to vanadium extraction blowing 100 ~ 140s time in (such as, vanadium extraction blowing starts in the time of vanadium extraction blowing 120s), top gun gun bit can control at 1.5m ~ 1.8m, the stirring of oxygen jet to molten bath can be increased like this, promote the carrying out of the redox reaction of the vanadium in vanadium-bearing hot metal and (FeO) in slag.Along with the carrying out of the oxidizing reaction of vanadium, (FeO) content in slag reduces gradually, now can improve top gun gun bit to 1.8m ~ 2.2m and can keep this top gun gun bit to top the rifle oxygen blast stage terminate, to promote the oxidation of the Fe in molten bath, thus improve the carrying out of (FeO) content and promotion vanadium extraction reaction in slag.
According to exemplary embodiment of the present invention, the oxygen flow in the rifle oxygen blast stage of top can control at 22000m
3/ h ~ 24000m
3/ h, but the present invention is not limited to this.
According to exemplary embodiment of the present invention, all comprise FeO as in the cold pressing block of refrigerant, pig, iron scale and pellet, the FeO content in refrigerant can be not less than 50wt%.For providing a large amount of (FeO) to promote the carrying out that vanadium extraction is reacted in slag, can also reduce the add-on of refrigerant like this to reduce the foreign matter content in slag like this.
According to exemplary embodiment of the present invention, when refrigerant comprises cold pressing block, cold pressing block can be that the ball of 30mm ~ 70mm is block, but the present invention is not limited to this.
According to exemplary embodiment of the present invention, top blown converter or top and bottom combined blown converter can be used to carry out vanadium extraction blowing operation to vanadium-bearing hot metal.When using top and bottom combined blown converter to carry out vanadium extraction blowing operation to vanadium-bearing hot metal, at use top blow oxygen lance in molten bath during oxygen blast, can use end rifle in molten bath, blow inactive gas (such as, nitrogen or rare gas element) and molten bath is stirred.
Then, along with the carrying out of vanadium extraction reaction and the rising of bath temperature, when vanadium extraction blowing 210s ~ 270s, (such as, when 220s, 240s or 260s) is in the time of vanadium extraction blow end point, inactive gas (such as, nitrogen or rare gas element) is blown with top rifle.
Specifically, along with the reduction of the concentration of the vanadium in vanadium-bearing hot metal, the invert point of vanadium reduces, and bath temperature raises gradually and causes the rate of oxidation of vanadium to reduce, the rate of oxidation rising of carbon.When the 210s ~ 270s of vanadium extraction blowing (such as, when 220s, 240s or 260s), bath temperature now may a little more than carbon vanadium invert point, the carbon in vanadium-bearing hot metal can be taken off at this temperature in a large number to molten bath continuation oxygen blast, cause steel-making converter can not add steel scrap or cause converter steelmaking to occur deeply blowing, and vanadium extraction efficiency significantly reduces.In this case, top rifle oxygen blast is converted to top rifle to blow inactive gas (such as, nitrogen or rare gas element) and stir molten bath.Blowing inactive gas at top rifle carries out in the process of vanadium extraction operation to vanadium-bearing hot metal, and abundant (FeO) generated in slag mainly through the top rifle oxygen blast stage and the redox reaction of vanadium are to reach the object of vanadium extraction.When the 210s ~ 270s of vanadium extraction blowing (such as, when 220s, 240s or 260s), generate in converter molten pool slag abundant (FeO), by blowing inactive gas, stirring cooling is carried out to molten bath in this case, make bath temperature be reduced to below carbon vanadium invert point, thus the carrying out of (FeO) in slag and the redox reaction of vanadium can be promoted.In addition, use top rifle nitrogen blowing also to instead of refrigerant to reduce the add-on of refrigerant in bath temperature and reduction vanadium extraction by converter blowing converting process in (such as, when 220s, 240s or 260s) to the time of vanadium extraction blow end point when vanadium extraction blowing 210s ~ 270s.In the process that top rifle nitrogen flushing is stirred molten bath, along with the reduction gradually of bath temperature, in vanadium-bearing hot metal, the rate of oxidation of carbon also reduces gradually, and this just can improve the content of the carbon in the half steel in vanadium extraction product.In addition, top rifle nitrogen flushing also reduces the TFe content in slag, improves the Fe recovery rate of half steel.
According to exemplary embodiment of the present invention, when vanadium extraction blowing 210s ~ 270s (such as, when 220s, 240s or 260s) in the time of vanadium extraction blow end point, top gun gun bit can control at 1.5m ~ 1.8m, nitrogen can be increased like this to the stirring in molten bath to reduce bath temperature, promote the vanadium in vanadium-bearing hot metal and (FeO) redox reaction in slag, thus reach the object that vanadium protects carbon.
According to exemplary embodiment of the present invention, the flow that top rifle blows the inactive gas (such as, nitrogen or rare gas element) in inactive gas stage can be 22000m
3/ h ~ 24000m
3/ h, but the present invention is not limited to this.
As mentioned above, vanadium extraction by converter blowing method according to the present invention facilitates the rate of oxidation of vanadium, and (refrigerant add-on can be controlled in 25kg/t to reduce the add-on of refrigerant
ironbelow), and ensure that sufficient thermal source (C content in the half steel after vanadium extraction blowing can be controlled in more than 3.90%) for the converter smelting of half steel, improve the steel scrap consumption of half steel converter smelting.In addition, convert top rifle in the blowing later stage to by top rifle oxygen blast and blow inactive gas (such as, nitrogen or rare gas element) molten bath is stirred to (FeO) content reduced in slag, be conducive to slag sluicing system, and the iron in slag can settle down quickly after finishing blowing from slag, the content of the bright iron in slag and full iron is reduced, is conducive to the grade improving vanadium slag.
Although describe the method for vanadium extraction by converter blowing of the present invention with reference to specific embodiment, will be appreciated that the present invention is not limited to above embodiment.
Claims (6)
1. a method for vanadium extraction by converter blowing, is characterized in that, described method comprises the top rifle pushing up the rifle oxygen blast stage and perform after the rifle oxygen blast stage of top and blows the inactive gas stage,
Wherein, the top rifle oxygen blast stage comprises: start, in the time of vanadium extraction blowing 210s ~ 270s, to use top rifle to converter molten pool oxygen blast, and be 22000m by oxygen flux control in vanadium extraction blowing
3/ h ~ 24000m
3/ h, wherein, starts, in the top rifle oxygen blast stage of vanadium extraction blowing 100s ~ 140s, to control top gun gun bit at 1.5m ~ 1.8m in vanadium extraction blowing, in the remaining time then in the rifle oxygen blast stage of top, controls top gun gun bit at 1.8m ~ 2.2m;
Top rifle blows the inactive gas stage and comprises: in the time of vanadium extraction blow end point after the rifle oxygen blast stage of top, uses top rifle to blow inactive gas to converter molten pool, and is 22000m by the flow control of inactive gas
3/ h ~ 24000m
3/ h, wherein, on top, rifle blows in the inactive gas stage, controls top gun gun bit at 1.5m ~ 1.8m;
Described method also comprises: push up the rifle oxygen blast stage start time or before by 9kg/t
molten iron~ 11kg/t
molten ironfirst refrigerant join converter molten pool, and vanadium extraction blowing 115s ~ 125s time by 11kg/t
molten iron~ 13kg/t
molten ironsecond batch refrigerant join converter molten pool;
Wherein, refrigerant comprises at least one in cold pressing block, pig, iron scale and pellet, and cold pressing block is that converter dust-removing ash and/or iron scale are by the ball block of binding agent compression moulding.
2. the method for claim 1, is characterized in that, all comprises FeO in cold pressing block, pig, iron scale and pellet, and in refrigerant, the content of FeO is not less than 50wt%.
3. the method for claim 1, is characterized in that, refrigerant comprises cold pressing block, and the granularity of cold pressing block is 30mm ~ 70mm.
4. the method for claim 1, is characterized in that, uses top blown converter or top and bottom combined blown converter to carry out vanadium extraction blowing.
5. the method for claim 1, it is characterized in that, vanadium-bearing hot metal is the molten iron obtained after blast-furnace smelting containing coulsonite, described hot metal ladle contains: the Ti of V, 0.19wt% of S, 0.3wt% of P, 0.06wt% of Mn, 0.60wt% of Si, 0.18wt% of C, 0.1wt% of 4.3wt% ~ 4.8wt% ~ 0.8wt% ~ 0.28wt% ~ 0.80wt% ~ 0.10wt% ~ 0.8wt% ~ 0.25wt%, all the other are iron and inevitable impurity.
6. the method for claim 1, is characterized in that, the temperature of the vanadium-bearing hot metal before vanadium extraction blowing is 1280 DEG C ~ 1320 DEG C.
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| CN104673958B (en) * | 2015-03-16 | 2017-01-18 | 攀钢集团研究院有限公司 | Method for extracting vanadium and chromium by using top-bottom combined blowing converter |
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| CN104673956B (en) * | 2015-03-16 | 2017-01-18 | 攀钢集团研究院有限公司 | Method for extracting vanadium and chromium in converter |
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| 国内外氧气顶吹转炉提钒现状及对攀钢转炉提钒有关问题的探讨;潘树范;《钢铁钒钛》;19950331;第16卷(第1期);第6-16页、第31页 * |
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