CN104862442A - Method for extracting vanadium through combined blown converter - Google Patents
Method for extracting vanadium through combined blown converter Download PDFInfo
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- CN104862442A CN104862442A CN201510207916.9A CN201510207916A CN104862442A CN 104862442 A CN104862442 A CN 104862442A CN 201510207916 A CN201510207916 A CN 201510207916A CN 104862442 A CN104862442 A CN 104862442A
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Abstract
The invention relates to the field of steel smelting, and discloses a method for extracting vanadium through a combined blown converter. The method comprises the steps of mixing molten iron in the combined blown converter and further comprises the steps of blowing oxygen to the molten iron through an oxygen gun in the blowing stage, and blowing carbon monoxide or mixed gas of the carbon monoxide and nitrogen to the molten iron through a converter bottom air brick. According to the method, the carbon monoxide or the mixed gas of the carbon monoxide and the nitrogen is blown into the molten iron through the converter bottom air brick, a certain amount of carbon monoxide is added into the molten iron, the redox equilibrium relation among C, CO and CO2 is utilized for reducing the use number of cooling agents, and meanwhile reducing the oxygenation efficiency of carbon, the oxygenation efficiency of the vanadium is improved, the utilization rate of resources is optimized, and the vanadium extraction production cost is reduced.
Description
Technical field
The present invention relates to field of iron and steel smelting, particularly, relate to a kind of method of combined blown converter vanadium extraction.
Background technology
Vanadium (V) is a kind of transiting group metal elements, and under vanadium metal normal temperature, chemical property is more stable, more active under high temperature.The valence electron structure of vanadium atom is 3d
34s
2, be typical valence variation element, five valence electrons can participate in into key, have+2 ,+3 ,+4 and+5 valence states.Under different oxygen partial pressure and temperature, the stable compound of vanadium is also different, wherein, is conducive to the stable existence of trivalent vanadium oxide compound by reducing oxygen partial pressure raising temperature.In addition, vanadium also has multiple non-stoichiometric oxide, available general formula V
no
2n-1the oxide compound of the same clan that (3≤n≤9) represent.At V
2o
4and V
2o
5between, there will be a known V
3o
5, V
3o
7, V
4o
7, V
4o
9, V
5o
9, V
6o
11, V
6o
13deng oxide compound.Industrial barium oxide mainly V
2o
3, VO
2and V
2o
5, wherein V
2o
5particularly important.
Vanadium has excellent intensity, hardness and antifatigue effect because of it, and is widely used in the fields such as iron and steel, chemical industry, aviation.The vanadium of about 84% is dissolved in steel as alloying element and forms VC and VN in iron and steel, to play crystal grain thinning, suppresses bainite and pearlitic growth to increase the effect of martensite intensity, thus the hardness of raising steel, intensity, toughness and wear resistance.Containing the product of vanadium with vanadium iron and VN for mainization crystal grain.Vanadium is used for non-ferrous alloy mainly with the structured material that V-Al system alloy is representative, as alloys such as excellent high temperature Aircraft Structure Materials Ti-6Al-4V, Ti-8Al-1V-Mo and Ti-6Al-6V-2Sn.Vanadium product for chemical field mainly contains V
2o
5, NH
4vO
3, V
2o
3, VOCl
3and VCl
4deng, as the electrode materials of catalyzer, tinting material, high capacity cell.It is worth mentioning that the multivalent state due to vanadium, vanadium is used as anode material of lithium battery or is developed to the energy storage devices such as ultracapacitor, has the advantages such as charging is rapid, specific energy is high, cheap, has much application prospect.In addition, the vanadium product of about 2% is also applied to the fields such as medicine, protective material and thin-film material.Now there are some researches show that vanadium compound has the effect of para-insulin, can promote the synthesis of liver starch and muscle glycogen, suppression hepatic glycogenolytic is glucose, promotes the synthesis of fat and suppresses fatty decomposition.Generally speaking, vanadium and vanadium product are widely used for improving material property or accelerating chemical reaction course mainly as additive.
Vanadium resource is as a kind of scarce resource important in the world, and without the vanadium minerals can adopted separately, it disperses in the distribution of occurring in nature very much, and main association is in sulphur navajoite VS
2or V
2s
5, plumbous navajoite (or claim vanadinite) Pb
5(VO
4)
3c, vanadium marble KV
2(AlSi
2o
10) (OH)
2, potassium vanadate uranium ore K
2(UO
2) (VO
4)
23H
2in the mineral such as O and vanadium titano-magnetite.The total reserves of whole world vanadium is 6,300 ten thousand tons, and workable reserves is 1,020 ten thousand tons.Raw material type for vanadium extraction is a lot, and the vanadium of 88% obtains from vanadium titano-magnetite in the world, and all the other vanadium extraction raw materials have bone coal, spent catalyst, oil lime-ash, yeath etc.Because of vanadium raw materials kind, mineral characteristic and wherein content of vanadium differ greatly, from also varied containing the technological process control extracting vanadium vanadium material, mainly contain pyrometallurgical smelting, wet-leaching and pyrogenic process-wet method combined extraction process.
1. pyrometallurgical smelting
Usually be main raw material with vanadium titano-magnetite, obtain vanadium-bearing hot metal by blast furnace or other ironmaking flow process, then in converter, be blown into oxygen make vanadium oxidization enrichment in metal in slag.Obtain containing V when adopting duplex to bessemerize
2o
5the vanadium slag of 8 ~ 20% and the half steel containing C about 3.6%, obtain when adopting single converter slag-making to blow containing V
2o
5the v-bearing steel slag of 2 ~ 5% and molten steel.The vanadium slag obtained or v-bearing steel slag carry out subsequent extracted through the mode of roasting-leaching or directly leaching.Along with steel-making and the demand for development of process for extracting vanadium, also occur direct in converter, add sodium carbonate blowing, obtained Vanadium and half steel, reach the object removing p and s in molten iron simultaneously.
2. wet-leaching
This kind of technique is comparatively applicable to the waste prodss such as spent catalyst, flying dust and oil lime-ash, also have be applied in bone coal on a small quantity, the raw ore such as vanadium titano-magnetite, but exist with the trivalent vanadium form of indissoluble because wherein vanadium is all main, directly leach compared with pyrometallurgical smelting and pyrogenic process-wet method combined extraction process rate of recovery lower.The technique directly leached at present mainly contains acidleach, alkali leaching, Bioleaching, pressurized acid leaching etc.R.Navarro compares acidleach and alkali leaching oil flying dust process for extracting vanadium, although thinking that NaOH leaches leaching yield is 61% have more selectivity lower than acidleach for magnesium-yttrium-transition metal compound, obtains adjusting pH to be that 8 precipitations add NH again except after Al containing vanadium solution
4cl to pH 5 just precipitablely obtains vanadium product, and deposition rate reaches 99%.D.Mishra adopts a kind of lithotrophic bacteria-sulfur oxidizing bacterium process spent catalyst, by promoting growth and the two-step pretreatment of sulfur oxidizing bacterium, V leaching rate can be made to reach 94.8%; Li etc. [17] are after the method exploring oxidizing roasting-pressurized acid leaching, normal pressure acidleach, take pressurized acid leaching extracting vanadium from stone coal V leaching rate can be brought up to 76% and the reaction times short, compare 70% of normal pressure acidleach 50% and roasting-extract technology to have and improve significantly, but this technique is higher to equipment requirements.The techniques such as precipitation-calcining, solvent extraction-back extraction are generally taked to obtain final vanadium product after vanadium being leached into solution.
3. pyrogenic process-wet method combined extraction
Because V in raw ore exists mainly with more stable trivalent vanadium form, usually need its roasting under oxidizing atmosphere to be changed into high price compound and be beneficial to leach.For the bone coal resource of China, its vanadium resource total amount of containing accounts for 87% of the total vanadium in the whole nation, vanadium grade is 0.13 ~ 1.2%, and the pyrogenic process-wet method combined extraction process of development has traditional sodium-salt calcination-water logging, blank roasting-acidleach (alkali leaching), few salt roasting-circulating leaching and calcium salt roasting-acidleach (alkali leaching) etc.Although sodium-salt calcination technique has the advantages such as maturing temperature is low, the time is short, its rate of recovery is low, produce a large amount of obnoxious flavour as HCl and Cl
2just gradually by few salt roasting or calcium salt roasting replace.
At present, the production method producing vanadium slag in world wide is more, mainly contain New Zealand's hot metal ladle and blow vanadium technique, South Africa shaking ladle process for extracting vanadium, Russia and Chinese vanadium extraction by converter blowing technique etc., other process for extracting vanadium also comprises v-bearing steel slag vanadium extraction, process for extracting vanadium from stone coal etc.Wherein most main flow is vanadium extraction by converter blowing technique, and its treatment capacity is maximum.Vanadium extraction by converter blowing technology is developed by Russia's (USSR (Union of Soviet Socialist Republics)), and exploitation is main afterwards applies in Iron And Steel Company of Nizhni Tagil.Iron And Steel Company of Nizhni Tagil (hereinafter referred to as lower steel) is built in 1940, started in 1964 with the vanadium of blast-furnace smelting KOH-KAE card nail (unit of length) admire magnetite produce vanadium-bearing hot metal.The said firm carries out the exploration of blowing pig iron containing vanadium novel method from nineteen fifty-seven, and the duplex practice vanadium extraction of vanadium extraction by converter blowing one converter steelmaking studied by units such as Ural ferrous metallurgy institutes is made steel and succeeded.On the basis that 10t experimental converter makes a search, build up 100t converter in November, 1963 again, and carry out first commerical test, confirm the reasonableness adopting oxygen vanadium extraction from molten iron.The typical process of recommending is as follows: converter loads molten iron 115 ~ 120t, loads the solid pig iron of 12% in advance, the iron scale of 5%, oxygen purity 9.2%, oxygen supply intensity 150 ~ 200m
3/ min, oxygen pressure 0.98 ~ 1.45MPa, spray gun height 0.7 ~ 1.5m, adopts 3 hole shower nozzles, duration of blast 8 ~ 12min.When molten bath containing vanadium higher than 0.04% time, re-blow.Result confirms the high-level efficiency with oxygen vanadium extraction, and can realize the degree of depth and remove vanadium, vanadium oxidation ratio reaches 92% ~ 94%.
1978, lower steel, in order to the throughput of equilibrium steel-making and steel rolling and the demand that meets vanadium slag, extended into 160t original 3 130t converters, newly build up again the 4th 160t converter the end of the year 1979, and adopt four to blow three dutys, i.e. a block converter vanadium extraction, two block converter steel-making, the maintenance of another seat is stand-by.In industrialness running, enable oxygen coverter vanadium extraction automation control system, carried out remaining slag operation technique.Concrete technology flow process is: the vanadium-bearing hot metal shipped from blast furnace plant, first pour the even hot metal composition of hot metal mixer and temperature into, pour molten iron into iron ladle from hot metal mixer again, transport to the workplatform of converter workshop section, with crane, molten iron is blended into converter extracting vanadium, then according to molten iron temperature and silicon content, hopper adds oxidation one refrigerant steel rolling iron sheet 70 ~ 80kg/tFe in converter, and then fall oxygen rifle and start oxygen blast, oxygen rifle height starts as 2.0m, be down to 1.0m subsequently, oxygen supply intensity is about 300m
3/ min, when in molten iron during silicone content height, whole smelting phase rifle position all keeps lower limit.In oxygen blowing process, part be melted in carbon in molten iron and most of slag making element all oxidized.Half steel temperature rises to 1340 ~ 1410 DEG C from 1230 ~ 1260 DEG C simultaneously, 2.8% ~ 3.6% is dropped at molten iron carbon content, content of vanadium drops to after 0.04%, lift oxygen rifle and stop oxygen blast, half steel is poured into half cylinder of steel, vanadium slag is poured into slag ladle or stay (during remaining slag operation) in converter.Then half cylinder of steel filling half steel is transported to converter workshop section, half steel is blended into steel-making converter and smelts.
From the beginning of the sixties, China once Shoudu Iron and Steel Co, Tang Gang, on steel, climb steel, hold and the top-blown oxygen converter of steel and Ma Gang carries out too much item half industry and type approval test, achieve a large amount of testing datas.Hold the 20t top-blown oxygen converter formally input vanadium extraction production in 1988 that steel two is made steel.China's top-blown oxygen converter vanadium extraction oxygen pressure-controlled is at 0.53 ~ 0.7MPa, and oxygen-consumption is 16.37 ~ 25.0m
3/ t; Pig, iron scale, ore, acid pellet, useless vanadium slag and high-carbon steel scrap is adopted to make refrigerant, half Carbon Content Of Steel is 3.17% ~ 3.95%, residual vanadium amount is 0.06% ~ 0.11%, half steel temperature is 1347 ~ 1420 DEG C, vanadium oxidation ratio is 68.9% ~ 87.81%, and vanadium recovery is 74.82% ~ 78.65%.But because starting material conditional fluctuation is large, operating procedure is unstable, lacks effective terminal point control means in addition, makes to blow vanadium index and also owe desirable, especially vanadium oxidation ratio and the rate of recovery, also larger with steel gap under Russia.
China climbs steel and has carried out vanadium extraction by converter blowing type approval test in 1986 ~ 1987 years, select vanadium extraction scheme provide foundation for climbing steel the second stage of the project, the invaluable experience for vanadium extraction by converter blowing productive accumulation.Hold steel and carry out the test of oxygen coverter top-bottom blowing vanadium extracting in 1993.Vanadium extraction technico-economical comparison is improved comprehensively.Ma Gang started to build 30t converter extracting vanadium in nineteen ninety.1993, hold steel and transform 1# bottom blowing system for converter, airing system changes single nitrogen blowing into by hydrogen, nitrogen two-way.Bottom-blown air brick is made up of magnesite refractory, inside sets 4 internal diameters as the stainless steel tube of 2mm.This bottom-blowing device is utilized to do the vanadium extraction test of top bottom blowing.Blowing the independent top blast of oxygen supply pressure ratio again to decrease, is 0.6 ~ 0.85MPa, rifle position 0.8 ~ 1.lm, oxygen supply intensity 1.9 ~ 2.5m
3/ mint.
Bottom blowing gas intensity is 0.03 ~ 0.06m
3/ mint, flow is 72 ~ 150Nm
3/ h.Test acid pellet and make refrigerant containing vanadium iron block, add-on is depending on molten iron temperature and Si, Ti content, and pelletizing add-on is 5% ~ 8% of iron water amount, and iron block add-on is 15% ~ 20%.Result shows, top and bottom complex blowing technique is obviously better than single Top Blown Process.Combined blowing process blowing is steady, slagging is fast, sticky rifle, the sticky furnace bottom of refrigerant; Half Carbon Content Of Steel on average improves 0.36%, and residual vanadium reduces by 0.017%, vanadium slag V
2o
5improve 0.2%, TFe and reduce by 4.34%, the oxidation ratio of vanadium improves 3.05%; Oxygen blow duration shortens 1 ~ 2min.Meanwhile, when terminal vanadium slag is crossed rare, independent bottom blowing nitrogen 1.5 ~ 2.0min, can make bits retrogradation, and TFe reduces by 3.28% ~ 5.93%, V
2o
5improve 0.77% ~ 1.73%.
In order to reduce vanadium extraction production cost further, reduce the oxidation ratio of carbon, improve the oxidation ratio of vanadium, research staff also needs the method improving above-mentioned vanadium extraction by converter blowing further.
Summary of the invention
The object of this invention is to provide a kind of method of combined blown converter vanadium extraction, the method is conducive to, while the oxidation ratio of the oxidation ratio improving vanadium, reduction carbon, reducing vanadium extraction production cost.
To achieve these goals, the invention provides a kind of method of combined blown converter vanadium extraction, the method comprises and is blended in described combined blown converter by molten iron, the method is also included in the blowing stage by oxygen rifle to oxygen blast in described molten iron, is blown the mixed gas of carbon monoxide or carbon monoxide and nitrogen by furnace bottom gas permeable brick in described molten iron.
The method of a kind of combined blown converter vanadium extraction of technique scheme, by blowing the mixed gas of carbon monoxide or carbon monoxide and nitrogen in described molten iron from furnace bottom gas permeable brick, introduces a certain amount of carbon monoxide, utilizes C, CO and CO in molten iron
2between redox equilibrium relation, while the consumption reducing refrigerant, reduce the oxidation ratio of carbon, the oxidation ratio improving vanadium, optimize resource utilization ratio and reduce vanadium extraction production cost.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
Propose as background technology part, in order to vanadium extraction production cost can be reduced further, reduce the consumption of refrigerant, reduce the oxidation ratio of carbon, improve the oxidation ratio of vanadium, improve the utilization ratio of resource, research staff also needs the method improving vanadium extraction by converter blowing further.
For this reason, in the typical embodiment of one of the present invention, provide a kind of method of combined blown converter vanadium extraction, the method comprises and is blended in combined blown converter by molten iron, also be included in the blowing stage by oxygen rifle to oxygen blast in molten iron, in molten iron, blown the mixed gas of carbon monoxide or carbon monoxide and nitrogen by furnace bottom gas permeable brick.
Aforesaid method blows the mixed gas of carbon monoxide or carbon monoxide and nitrogen in molten iron by furnace bottom gas permeable brick, introduce a certain amount of carbon monoxide, utilize C, CO and CO in molten iron
2between redox equilibrium relation, while the consumption reducing refrigerant, reduce the oxidation ratio of carbon, the oxidation ratio improving vanadium, optimize resource utilization ratio and reduce vanadium extraction production cost.
Identical with the prior art introduced in background technology, aforesaid method provided by the present invention also comprises non-blowing stage and blowing stage.Wherein the non-blowing stage refers to that oxygen rifle does not carry out the oxygen supply stage; During the blowing stage refers to oxygen supply by lance.Wherein, in the non-blowing stage, by furnace bottom gas permeable brick to nitrogen blowing in molten iron; The air supply intensity of nitrogen is 0.15-0.25m
3/ mint.
Preferably, in aforesaid method, 1-1.5min before the blowing stage terminates, terminated to the blowing stage, and by furnace bottom gas permeable brick, to nitrogen blowing in molten iron, (preferred air supply intensity is 0.15-0.25m
3/ mint).In this approach by 1-1.5min before the blowing stage terminates by furnace bottom gas permeable brick to nitrogen blowing in molten iron, be on the one hand conducive to the oxidation ratio better reducing carbon, improve the oxidation ratio of vanadium, also help on the other hand and carries out continuous seepage, raise the efficiency.
Aforesaid method provided by the present invention, as long as in the blowing stage, the mixed gas blowing carbon monoxide or carbon monoxide and nitrogen by furnace bottom gas permeable brick in described molten iron just can realize reducing the oxidation ratio of carbon, the object of the oxidation ratio of raising vanadium.But, in order to reduce the oxidation ratio of carbon better, improve the oxidation ratio of vanadium, in the preferred embodiment of the present invention, the molten iron temperature >1340 DEG C in combined blown converter is blended in aforesaid method, and Si content >0.25wt.% and/or Mn content >0.20wt.% and/or carbon content >3.4wt.% in molten iron.The temperature of molten iron be blended in combined blown converter by control and the content of Si and/or Mn and/or C, be conducive to while shortening duration of blast, realizes the oxidation ratio reducing carbon further, the object of the oxidation ratio of raising vanadium.
Those skilled in the art can with reference to the ordinary method adjustment temperature of molten iron of the prior art and the content of Si and/or Mn and/or C, be blended in combined blown converter by satisfactory molten iron again, the methods for the adjustment temperature of molten iron and the content of Si and/or Mn and/or C will repeat no more in the present invention.
In the preferred embodiment of the present invention, particular requirement is not had, with reference to ordinary method of the prior art for by furnace bottom gas permeable brick to the air supply intensity of air feed in molten iron.In the preferred embodiment of the present invention, the air supply intensity of nitrogen is preferably at 0.2m
3/ below mintFe, the air supply intensity of the mixed gas of carbon monoxide or carbon monoxide and nitrogen is preferably 0.1-0.5m
3/ mintFe.By controlling the air supply intensity of gas with various, being conducive to the whipping force improving converting process, and then reducing oxidation of coal rate.
State on the invention method in molten iron, blow the mixed gas of carbon monoxide and nitrogen by furnace bottom gas permeable brick time, particular requirement is not had, as long as be wherein mixed with carbon monoxide just can realize object of the present invention for both ratios in the mixed gas of carbon monoxide and nitrogen.But in the preferred embodiment of the present invention, the volume ratio of carbon monoxide and nitrogen is preferably 0.1-0.5:1.By both limited proportions within the scope of this, be conducive to better realizing reducing oxidation of coal rate and reducing furnace temperature amount, reduce the effect of the relative usage of refrigerant.
In the present invention, in order to reduce the oxidation ratio of carbon better, improve the oxidation ratio of vanadium, in the preferred embodiment of the present invention, aforesaid method is comprised by oxygen rifle oxygen blown step in molten iron: early stage oxygen rifle is placed in the first rifle position at air feed; Mid-term oxygen rifle is placed in the second rifle position at air feed; And in the air feed later stage, oxygen rifle being placed in the first rifle position, the first rifle position is higher than the second rifle position.In the method, mentioned air feed early stage, air feed mid-term and air feed later stage be all with respect to air feed from oxygen rifle to the mixed gas of oxygen blast gas and carbonic acid gas in molten iron during (namely blowing the stage).The method, by the position of oxygen rifle to the different air feed phasic change of oxygen blast in molten iron oxygen rifle, while reduction furnace temperature amount, can reduce the oxidation ratio of carbon.
Preferably, the shower nozzle being positioned at the oxygen rifle of the first rifle position is 1.7-1.9m higher than the distance of the liquid level of molten iron; The shower nozzle being positioned at the oxygen rifle of the second rifle position is 1.5-1.7m higher than the distance of the liquid level of molten iron; More preferably, the first rifle position is relative to the second high 0.1-0.3m in rifle position.
State on the invention in method and do not have particular requirement for by oxygen rifle to the duration in oxygen blast air feed early stage and air feed later stage in molten iron, as long as in the position of different air feed phasic change oxygen rifle, just can reach while reduction furnace temperature amount, reduce the effect of the oxidation ratio of carbon.In the preferred embodiment of the present invention, the air feed duration in earlier stage of aforesaid method is 0.5-1.0min, and the duration in air feed later stage is 1-1.5min, and is 5-12min by oxygen rifle total duration of oxygen blown step in molten iron, is preferably 5-6min.By air feed early stage and the duration in air feed later stage, and total duration is limited in above-mentioned scope, is conducive to better reducing furnace temperature amount, and the oxidation ratio of minimizing carbon.
State on the invention method by oxygen rifle in molten iron in oxygen blown step, the air supply intensity for oxygen rifle does not have particular requirement, with reference to ordinary method.In the preferred embodiment of the present invention, the air supply intensity of described oxygen rifle is 2.0-3.0m
3/ mintFe.The air supply intensity of oxygen rifle is limited within the scope of this, is conducive to, while the oxidation ratio ensureing vanadium, reducing the oxidation ratio of carbon.
In the preferred embodiment of the present invention, aforesaid method is also included in the step that the blowing stage adds vanadium-raising cooling agent in molten iron.Preferably, the step of adding vanadium-raising cooling agent in molten iron comprises: after being lighted a fire by oxygen rifle, add the vanadium-raising cooling agent of 10%-30% in molten iron; Blowing adds the vanadium-raising cooling agent of 20%-50% after starting 1-2min in molten iron; Before finishing blowing during 1.5-3min, in molten iron, add remaining vanadium-raising cooling agent.In the present invention by adding vanadium-raising cooling agent in the blowing stage to gradation in molten iron, be conducive to the furnace temperature adjusting combined blown converter, to improve vanadium oxidation ratio.
Operable vanadium-raising cooling agent includes but not limited to one or more the combination in pig, refrigerant, iron scale, ore in the present invention; Preferably, the add-on of described vanadium-raising cooling agent is below 25Kg/tFe.
In the present invention by adopting the method for above-mentioned combined blown converter vanadium extraction, effectively can be reduced in the furnace temperature of combined blown converter in vanadium extracting process, when the add-on of vanadium-raising cooling agent is 16-22Kg/tFe (compared with prior art reducing by 5 ~ 10kg/tFe), vanadium extraction by converter blowing terminal temperature stability contorting just can be made at about 1380 DEG C, optimize the utilization ratio of resource and reduce vanadium extraction production cost.
Below by embodiment 1-7 and will contrast as example 1-2 describes the present invention.
One, raw material explanation
The molten iron used in following embodiment 1-7 and comparative example 1-2 is from vanadium titano-magnetite blast-furnace smelting.The composition of this molten iron is as shown in table 1:
Table 1
Two, embodiment and comparative example
Embodiment 1
Be blended in 200t combined blown converter after above-mentioned molten iron 1 is heated to 1345 DEG C, in the non-blowing stage, in described molten iron, blow N by furnace bottom gas permeable brick
2(nitrogen), air supply intensity is 0.0010m
3/ mintFe.
In the blowing stage, in described molten iron, blow O by oxygen rifle
2(air supply intensity of oxygen rifle is 3.5m
3/ mintFe), (carbon monoxide, air supply intensity is 0.1m in described molten iron, to blow CO by furnace bottom gas permeable brick
3/ mintFe), and before the refining stage terminates 1.5min, terminate to the described blowing stage, by furnace bottom gas permeable brick, to nitrogen blowing in described molten iron, (air supply intensity is 0.2m
3/ mintFe).In the above-mentioned blowing stage, in molten iron, blow O by oxygen rifle
2process (total duration 6min) in, air feed early stage (0.5min) oxygen rifle is placed in the first rifle position (shower nozzle of oxygen rifle and the difference of altitude of molten iron level are 1.8m); Mid-term oxygen rifle is placed in the second rifle position (shower nozzle of oxygen rifle and the difference of altitude of molten iron level are 1.6m) at air feed; And in the air feed later stage (1.5min), oxygen rifle is returned to the first rifle position, complete the blowing to molten iron;
In the above-mentioned blowing stage, after being lighted a fire by oxygen rifle, in molten iron, first add the described vanadium-raising cooling agent of 10kg/tFe; After blowing starts 2min, in molten iron, add the described vanadium-raising cooling agent of 10kg/tFe; Before finishing blowing during 2min, add remaining described vanadium-raising cooling agent in molten iron, vanadium-raising cooling agent is pig, and total amount is below 25kg/tFe.
In the present invention by adopting the method for above-mentioned combined blown converter vanadium extraction, effectively can be reduced in the furnace temperature of combined blown converter in vanadium extracting process, when the add-on of vanadium-raising cooling agent is 18-25Kg/tFe (compared with prior art reducing by 5 ~ 10kg/tFe), vanadium extraction by converter blowing terminal temperature stability contorting just can be made at about 1380 DEG C, optimize the utilization ratio of resource and reduce vanadium extraction production cost.
Embodiment 2
Be blended in 200t combined blown converter after above-mentioned molten iron 2 is heated to 1350 DEG C, in the non-blowing stage, in described molten iron, blow N by furnace bottom gas permeable brick
2(nitrogen), air supply intensity is 0.0015m
3/ mintFe.
In the blowing stage, in molten iron, blow O by oxygen rifle
2(air supply intensity of oxygen rifle is 2.0m
3/ mintFe), in described molten iron, blow CO (carbon monoxide) and N by furnace bottom gas permeable brick
2mixed gas (CO and N
2volume ratio be 0.3:1, air supply intensity is 0.5m
3/ mintFe).In the above-mentioned blowing stage, after the composition and temperature that detect molten iron are reached above-mentioned requirements, in molten iron, blowing O by oxygen rifle
2process (total duration 6min) in, air feed early stage (0.5min) oxygen rifle is placed in the first rifle position (shower nozzle of oxygen rifle and the difference of altitude of molten iron level are 1.9m); Mid-term oxygen rifle is placed in the second rifle position (shower nozzle of oxygen rifle and the difference of altitude of molten iron level are 1.6m) at air feed; And in the air feed later stage (1min), described oxygen rifle is returned to the first rifle position, complete the blowing to molten iron.
In the above-mentioned blowing stage, after being lighted a fire by oxygen rifle, in molten iron, first add the described vanadium-raising cooling agent of 5kg/tFe; After blowing starts 1min, in molten iron, add the described vanadium-raising cooling agent of 15kg/tFe; Before finishing blowing during 3min, add remaining described vanadium-raising cooling agent in molten iron, vanadium-raising cooling agent is pig, and total amount is 25kg/tFe.
Embodiment 3
Be blended in 120t combined blown converter after above-mentioned molten iron 3 is heated to 1355 DEG C, in the non-blowing stage, in described molten iron, blow N by furnace bottom gas permeable brick
2(nitrogen), air supply intensity is 0.0010m
3/ mintFe.
In the blowing stage, in described molten iron, blow O by oxygen rifle
2(air supply intensity is 2.5m
3/ mintFe), in described molten iron, blow CO (carbon monoxide) and N by furnace bottom gas permeable brick
2mixed gas (CO and N
2volume ratio be 0.5:1, air supply intensity is 0.3m
3/ mintFe).
In the above-mentioned blowing stage, after the composition and temperature that detect molten iron are reached above-mentioned requirements, in described molten iron, blow O by oxygen rifle
2process (total duration 5min) in, air feed early stage (1min) oxygen rifle is placed in the first rifle position (shower nozzle of oxygen rifle and the difference of altitude of molten iron level are 1.7m); Mid-term oxygen rifle is placed in the second rifle position (shower nozzle of oxygen rifle and the difference of altitude of molten iron level are 1.5m) at air feed; And in the air feed later stage (1.5min), oxygen rifle is returned to the first rifle position, complete the blowing to molten iron;
In the above-mentioned blowing stage, after being lighted a fire by oxygen rifle, in molten iron, first add the described vanadium-raising cooling agent of 12kg/tFe; After blowing starts 1.5min, in molten iron, add the described vanadium-raising cooling agent of 8kg/tFe; Before finishing blowing during 1min, add remaining described vanadium-raising cooling agent in molten iron, vanadium-raising cooling agent is pig, and total amount is 21kg/tFe.
Embodiment 4
Extraction vanadium method: with reference to embodiment 2, difference is, blows CO (carbon monoxide) and N by furnace bottom gas permeable brick in described molten iron
2mixed gas (CO and N
2volume ratio be 0.1:1, air supply intensity is 0.5m
3/ mintFe).
Embodiment 5
Extraction vanadium method: with reference to embodiment 2, difference is, blows CO (carbon monoxide) and N by furnace bottom gas permeable brick in described molten iron
2mixed gas (CO and N
2volume ratio be 0.5:1, air supply intensity is 0.5m
3/ mintFe).
Embodiment 6
Extraction vanadium method: with reference to embodiment 2, difference is, is blended in combined blown converter after above-mentioned molten iron 2 is heated to 1335 DEG C.
Embodiment 7
Extraction vanadium method: with reference to embodiment 2, wherein difference is, blows CO (carbon monoxide) and N by furnace bottom gas permeable brick in described molten iron
2mixed gas (CO and N
2volume ratio be 50:1, air supply intensity is 0.5m
3/ mintFe).
Comparative example 1
Above-mentioned molten iron 1 is heated to 1340 DEG C to be blended in 200t combined blown converter, in the non-blowing stage, blows N by furnace bottom gas permeable brick in described molten iron
2(nitrogen), air supply intensity is 0.0010m
3/ mintFe, completes the interpolation of described vanadium-raising cooling agent (pig, add-on is 19Kg/tFe) in the 2min before the blowing stage.
In the blowing stage, in described molten iron, blowing O by oxygen rifle
2(air supply intensity of oxygen rifle is 2.0m
3/ mintFe), in molten iron, blow N by furnace bottom gas permeable brick
2(air supply intensity is 0.2m
3/ mintFe).Wherein, in molten iron, O is blown by oxygen rifle
2process (total duration 5min) in, air feed early stage (1min) oxygen rifle is placed in the first rifle position (shower nozzle of oxygen rifle and the difference of altitude of molten iron level are 1.9m); Mid-term oxygen rifle is placed in the second rifle position (shower nozzle of oxygen rifle and the difference of altitude of molten iron level are 1.6m) at air feed; And in the air feed later stage (1.5min), described oxygen rifle is returned to the first rifle position, complete the blowing to molten iron.
Comparative example 2
Above-mentioned molten iron 1 is heated to 1320 DEG C to be blended in 120t combined blown converter, in the non-blowing stage, blows N by furnace bottom gas permeable brick in described molten iron
2(nitrogen), air supply intensity is 0.0010m
3/ mintFe, completes the interpolation of vanadium-raising cooling agent (pig, add-on is 19Kg/tFe) in the 2min before the blowing stage.
In the blowing stage, in molten iron, blowing O by oxygen rifle
2(air supply intensity of oxygen rifle is 1.8m
3/ mintFe), in molten iron, blow N by furnace bottom gas permeable brick
2(air supply intensity is 0.25m
3/ mintFe).Wherein, in molten iron, O is blown by oxygen rifle
2process (total duration 5min) in, air feed early stage (1.5min) oxygen rifle is placed in the first rifle position (shower nozzle of oxygen rifle and the difference of altitude of molten iron level are 1.8m); Mid-term oxygen rifle is placed in the second rifle position (shower nozzle of oxygen rifle and the difference of altitude of molten iron level are 1.5m) at air feed; And in the air feed later stage (1min), described oxygen rifle is returned to the first rifle position, complete the blowing to molten iron.
Three, test
(1), test event and method
The oxidation ratio of vanadium: measuring method is chemical analysis;
The oxidation ratio of carbon: measuring method is chemical analysis.
(2), test result: as shown in table 2.
Table 2
| Embodiment is numbered | Vanadium-raising cooling agent add-on (kg/tFe) | Vanadium oxidation ratio (%) | Oxidation of coal rate (%) |
| Embodiment 1 | 22 | 91.03 | 11.46 |
| Embodiment 2 | 25 | 89.68 | 12.22 |
| Embodiment 3 | 21 | 91.68 | 11.27 |
| Embodiment 4 | 20 | 90.31 | 10.39 |
| Embodiment 5 | 18 | 91.36 | 10.28 |
| Embodiment 6 | 22 | 91.02 | 10.32 |
| Embodiment 7 | 16 | 91.54 | 14.26 |
| Comparative example 1 | 32 | 84.36 | 15.71 |
| Comparative example 2 | 28 | 83.47 | 16.18 |
From content in table 2, adopt the embodiment 1-7 of method provided by the present invention compared with documents 1-2, in the process of vanadium extraction, while the consumption obviously reducing refrigerant, reduce the oxidation ratio of carbon, improve the oxidation ratio of vanadium, as can be seen here, extraction vanadium method provided by the present invention optimizes the utilization ratio of resource and reduces vanadium extraction production cost.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each the concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode.In order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (10)
1. the method for a combined blown converter vanadium extraction, described method comprises and is blended in described combined blown converter by molten iron, it is characterized in that, described method is also included in the blowing stage by oxygen rifle to oxygen blast in described molten iron, is blown the mixed gas of carbon monoxide or carbon monoxide and nitrogen by furnace bottom gas permeable brick in described molten iron.
2. method according to claim 1, wherein, 1-1.5min before the described refining stage terminates, terminated, by furnace bottom gas permeable brick to nitrogen blowing in described molten iron to the described blowing stage.
3. method according to claim 1, wherein, be blended into the molten iron temperature >1340 DEG C in described combined blown converter, and Si content >0.25wt% and/or Mn content >0.20wt% and/or carbon content >3.4wt% in molten iron.
4. method as claimed in any of claims 1 to 3, wherein, the air supply intensity of described nitrogen is at 0.2m
3/ below mintFe, the air supply intensity of the mixed gas of described carbon monoxide or carbon monoxide and nitrogen is 0.1-0.5m
3/ mintFe.
5. method as claimed in any of claims 1 to 3, wherein, the volume ratio of carbon monoxide and nitrogen described in the mixed gas of described carbon monoxide and nitrogen is 0.1-0.5:1.
6. method as claimed in any of claims 1 to 3, wherein, describedly to be comprised to oxygen blown step in described molten iron by oxygen rifle: early stage described oxygen rifle is placed in the first rifle position at air feed; Mid-term described oxygen rifle is placed in the second rifle position at air feed; And in the air feed later stage, described oxygen rifle being placed in described first rifle position, described first rifle position is higher than described second rifle position;
Preferably, the shower nozzle being positioned at the oxygen rifle of described first rifle position is 1.7-1.9m higher than the distance of the liquid level of described molten iron; The shower nozzle being positioned at the oxygen rifle of described second rifle position is 1.5-1.7m higher than the distance of the liquid level of described molten iron;
Preferably, described first rifle position is relative to the described second high 0.1-0.3m in rifle position.
7. method according to claim 6, wherein, the duration in described air feed early stage is 0.5-1.0min, and the duration in described air feed later stage is 1-1.5min, is 5-12min by oxygen rifle to total duration of oxygen blown step in described molten iron.
8. method as claimed in any of claims 1 to 3, wherein, the described oxygen rifle that passes through is in oxygen blown step in described molten iron, and the air supply intensity of described oxygen rifle is 2.0-3.0m
3/ mintFe.
9. method as claimed in any of claims 1 to 3, wherein, described method is also included in the step that the described blowing stage adds vanadium-raising cooling agent in described molten iron,
Preferably, the step of adding vanadium-raising cooling agent in described molten iron comprises:
After being lighted a fire by oxygen rifle, in molten iron, add the described vanadium-raising cooling agent of 10%-30%;
After blowing starts 1-2min, in molten iron, add the described vanadium-raising cooling agent of 20%-50%;
1.5-3min before finishing blowing, adds remaining described vanadium-raising cooling agent in molten iron.
10. method according to claim 9, wherein, described vanadium-raising cooling agent is one or more the combination in pig, refrigerant, iron scale, ore;
Preferably, the add-on of described vanadium-raising cooling agent is below 25Kg/tFe.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107904349A (en) * | 2017-11-29 | 2018-04-13 | 攀钢集团西昌钢钒有限公司 | A kind of top and bottom combined blown converter extraction vanadium method |
| CN109722499A (en) * | 2019-02-28 | 2019-05-07 | 攀钢集团攀枝花钢钒有限公司 | Vanadium extraction by converter blowing oxygen nitrogen is mixed to blow air supply method |
| CN111334639A (en) * | 2020-04-14 | 2020-06-26 | 西安建筑科技大学 | Method for promoting vanadium extraction and carbon conservation by using CO |
| CN112522467A (en) * | 2020-11-30 | 2021-03-19 | 攀钢集团攀枝花钢铁研究院有限公司 | Converter sectional bottom blowing CO2Method for extracting vanadium |
| CN115821070A (en) * | 2022-12-06 | 2023-03-21 | 中国科学院过程工程研究所 | Method for extracting vanadium by oxidizing molten iron |
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| CN103981322A (en) * | 2014-05-05 | 2014-08-13 | 攀钢集团攀枝花钢铁研究院有限公司 | Top-bottom combined blowing converter vanadium extraction method |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107904349A (en) * | 2017-11-29 | 2018-04-13 | 攀钢集团西昌钢钒有限公司 | A kind of top and bottom combined blown converter extraction vanadium method |
| CN109722499A (en) * | 2019-02-28 | 2019-05-07 | 攀钢集团攀枝花钢钒有限公司 | Vanadium extraction by converter blowing oxygen nitrogen is mixed to blow air supply method |
| CN109722499B (en) * | 2019-02-28 | 2021-02-09 | 攀钢集团攀枝花钢钒有限公司 | Converter vanadium extraction oxygen nitrogen mixed blowing gas supply method |
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| CN112522467A (en) * | 2020-11-30 | 2021-03-19 | 攀钢集团攀枝花钢铁研究院有限公司 | Converter sectional bottom blowing CO2Method for extracting vanadium |
| CN115821070A (en) * | 2022-12-06 | 2023-03-21 | 中国科学院过程工程研究所 | Method for extracting vanadium by oxidizing molten iron |
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