CN105018678B - A kind of steel desulfurization agent and its sulfur method and method for making steel - Google Patents

A kind of steel desulfurization agent and its sulfur method and method for making steel Download PDF

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CN105018678B
CN105018678B CN201510470427.2A CN201510470427A CN105018678B CN 105018678 B CN105018678 B CN 105018678B CN 201510470427 A CN201510470427 A CN 201510470427A CN 105018678 B CN105018678 B CN 105018678B
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steel
desulfurization
tfe
vanadium
vanadium extraction
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CN105018678A (en
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张国东
王大鹏
董诗朋
李澍
范富华
冯晓明
谢勇
丁闯
张帆
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Chengde Jianlong Special Steel Co Ltd
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Chengde Jianlong Special Steel Co Ltd
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Abstract

The invention provides a kind of steel desulfurization agent and its sulfur method and method for making steel, the desulfurizing agent is made up of by the weight of each raw material and molten iron than mainly the following raw material:1 2kg/tFe fluorite;8 9kg/tFe lime;0.25 3.3kg/tFe aluminum shot and/or AD powder;The method for making steel, using the process route of desulfurization after first vanadium extraction.Described desulfurizing agent can carry out deoxidation while desulfurization to half steel, significantly alleviate refining desulfuration pressure, the content of sulphur in finished steel is reduced to less than 0.002%, and the desulfurizing agent composition is simple, easy to use;Described method for making steel completely eliminates the contaminated problem of vanadium slag.

Description

A kind of steel desulfurization agent and its sulfur method and method for making steel
Technical field
The invention belongs to iron and steel smelting technology field, more particularly to a kind of steel desulfurization agent and its sulfur method and steel-making side Method.
Background technology
Iron ore containing vanadium is after smelting into vanadium-bearing hot metal, it usually needs first carries out vanadium extraction, then could be made steel.Vanadium titanium magnetic Iron ore has huge reserves in China as a kind of important iron ore containing vanadium.Climbing steel, holding steel, elder brother's steel and Wei Gangdeng enterprises is all Smelted using vanadium titano-magnetite.The molten iron that vanadium titano-magnetite blast furnace process goes out content of vanadium compared with common molten iron is high, and vanadium It is a kind of important resource, therefore necessary vanadium extraction before molten iron-steelmaking, produce vanadium slag.At present, the producer of vanadium slag is produced both at home and abroad Method is more, mainly has New Zealand's ladle to blow vanadium technique, South Africa shaking ladle process for extracting vanadium and the vanadium extraction by converter blowing of Russia and China Technique etc., other process for extracting vanadium also include v-bearing steel slag vanadium extraction and process for extracting vanadium from stone coal etc., wherein it is optimal with vanadium extraction by converter blowing technique, Technical-economic index is best.
In vanadium extraction from hot metal semisteel smelting enterprise, generally using molten iron pretreatment desulfurizing technique outside stove, and desulfurizing iron (KR/ injections)-vanadium extraction by converter blowing-pneumatic steelmaking-LF/VD (ladle refining/vacuum refining)-continuous casting route, desulfurizing iron is using single Blow granular magnesium, granular magnesium, pulverized limestone and meet injection or molten iron KR stirring techniques.
For most of steel, S belongs to harmful element, and severe exacerbation steel quality is segregated in steel, is significantly dropped under high temperature Low steel plasticity, cause " hot-short " phenomenon of steel.As client requires more and more higher to steel quality, therefore to harmful member in steel Plain S contents are also more and more lower, and steel low-sulfur steel less than 0.010% containing S has accounted for industrially developed country's steel demand at present More than the 50% of amount, and sulfur content is also significantly increased in the demand of 0.001%-0.003% ultralow-sulfur steel.
However, the use of desulfurizing agent can usually pollute the vanadium slag of converter extracting vanadium production.To solve this problem, CN 103194567 A disclose a kind of smelting process of iron ore containing vanadium.The smelting process includes the following steps that order is carried out:Adopt With blast furnace process iron ore containing vanadium, vanadium-bearing hot metal is obtained;Vanadium extraction by converter blowing is carried out to vanadium-bearing hot metal, respectively obtains half steel and vanadium slag;It is right The half steel carries out KR desulfurization or blowing desulfurization, wherein, the half steel temperature control is 1350-1400 DEG C.Using blast-melted The process route of KR methods desulfurization after first vanadium extraction, completely eliminates the contaminated problem of vanadium slag from production line.Using first vanadium extraction The steel that afterwards prepared by the process route of KR methods desulfurization, its sulfur content need further to reduce.
At present, existing Many researchers are studied the desulfurizing agent used in steelmaking process.Such as CN 102108429A Disclose one kind and be used for pneumatic steelmaking deoxidization desulfuration agent, it is made up of following raw materials according:Calcium carbonate mineral matter 35%, carborundum 6%th, kaolin 15%, clinker 8%, surplus are scrap iron and steel cuttings;Above-mentioned raw materials are granulated, granularity 0-30mm, its Chemical composition is:Si 52%, Ca 9%, Ba 15%, Sr 5%, C≤0.36%, S≤0.024%, P≤0.01%, surplus For Fe.The A of CN 103103312 disclose a kind of semisteel desulfurizing agent and the sulfur method using the desulfurizing agent.The half steel desulfurization The mass percent of each composition is in agent:CaF 27-15%, Mg1%-8%, remaining is CaO and inevitable impurity;It is described Sulfur method carries out desulfurization using KR methods, and used desulfurizing agent uses above-mentioned semisteel desulfurizing agent.CN 102776328A are public A kind of preparation method of the ladle slag modifier of hypoxemia low-sulfur high-nitrogen steel is opened:By electrolytic aluminium ash and calcium oxide and fluorite press than Example mixing, aluminium ash 30-40%;Calcium oxide 40-50%;Fluorite 10-15%, add bath of glass and be well mixed, be then pressed into ball, Through being drying to obtain finished product;Aluminium ash component weight % contents used are as follows:Aluminium ash:Al 5-10%, AlN 25-35%, Al2O335- 50%, SiO22-5%, NaCl 10-15%.But it is obvious not enough using the effect of desulfurizing agent desulfurization, and desulfurization pressure It is also very big.
The content of the invention
In view of the deficienciess of the prior art, it is an object of the invention to propose a kind of steel desulfurization agent and its sulfur method And method for making steel, the desulfurizing agent can make sulfur content in finished steel be reduced to less than 0.002%, and can significantly mitigate refining Desulfurization pressure.
To use following technical scheme up to this purpose, the present invention:
An object of the present invention is to provide a kind of steel desulfurization agent, the desulfurizing agent by each raw material and molten iron weight Than being mainly made up of the following raw material:
Fluorite 1-2kg/tFe
Lime 8-9kg/tFe
Aluminum shot and/or AD powder 0.25-3.3kg/tFe.
" kg/tFe " of the present invention refers to the quality (kg) of other materials added in molten iron per ton.
Fluorite (CaF in the steel desulfurization agent provided is provided2) content be 1-2kg/tFe, such as 1.2kg/tFe, 1.5kg/ TFe, 1.6kg/tFe, 1.7kg/tFe, 1.8kg/tFe or 1.9kg/tFe etc..
During steel desulfurization, the reaction that lime (CaO) participates in is CaO+ [S]=CaS+ [O], can from reaction equation Go out to add the progress that lime is advantageous to desulphurization reaction.But CaO addition is not The more the better, as CaO additions carry Height, clinker is caused to melt difficult, and then the viscosity of clinker rises, mobility is deteriorated, and result in the dynamic conditions of desulphurization reaction It is deteriorated, desulfurization degree declines.It is therefore preferable that lime adding amount is 8-9kg/tFe, such as 8.1kg/tFe, 8.2kg/tFe, 8.5kg/ TFe, 8.6kg/tFe, 8.7kg/tFe, 8.8kg/tFe or 8.9kg/tFe etc..
In steel-making, desulphurization reaction is a reduction reaction process, can be written as reaction equation:[S]+O2-=S2-+[O].This Invent in the desulfurizing agent provided and contain pure aluminum, and aluminium belongs to strong reductant, and electronics can be constantly provided in sweetening process, makes [S] reaction generation S2-.Therefore, pure aluminum addition molten iron can be significantly reduced to the oxygen content in molten iron, promote entering for desulphurization reaction OK, so as to improving desulfurization degree.The addition that aluminum shot and/or AD powder are selected from cost consideration is 0.25-3.3kg/tFe, such as 0.3kg/tFe、0.4kg/tFe、0.5kg/tFe、0.7kg/tFe、1.0kg/tFe、1.6kg/tFe、1.9kg/tFe、2.2kg/ TFe, 2.5kg/tFe, 3.0kg/tFe or 3.2kg/tFe etc..Preferably, 0.25-0.5kg/ is added into molten steel in sweetening process TFe aluminum shot or the 1.6-3.3kg/tFe AD powder containing 15wt% aluminum shots.
As preferable technical scheme, the desulfurizing agent is by the weight ratio of each raw material and molten iron mainly by the following raw material group Into:
Fluorite 1kg/tFe
Lime 9kg/tFe
Aluminum shot 0.25kg/tFe.
AD powder aluminium simple substance containing 15wt%, 20wt% or 30wt% on the basis of the weight of AD powder, it is described " wt% " is weight percentage.
The second object of the present invention is to provide a kind of semi-steel making sulfur method, and the sulfur method is using as described above Desulfurizing agent to molten iron carry out desulfurization.
The third object of the present invention is to provide a kind of method for making steel, and desulfurization after method for making steel elder generation vanadium extraction is described de- Sulphur uses KR Desulfurization by stirring method, and desulfurizing agent as described above is used during the KR Desulfurization by stirring method.
The KR Desulfurization by stirring method is:First add the fluorite and lime of formula ratio into the half steel obtained after vanadium extraction, then The aluminum shot and/or AD powder of formula ratio are added in whipping process.
Aluminum shot and/or the AD powder is to add while stirring in half steel.
The present invention is thoroughly eliminated using the process route of KR Desulfurization by stirring method after blast-melted first vanadium extraction from production line Vanadium slag contaminated problem;CaO and CaF is used in sweetening process2, and deoxidation is carried out using aluminum shot and/or AD powder, significantly subtract Light refining desulfuration pressure, makes the sulfur content of finished product steel grade be reduced to less than 0.002%.
The mixing speed of the KR Desulfurization by stirring method is 75-85r/min, such as 76r/min, 77r/min, 78r/min, 79r/ Min, 80r/min, 82r/min, 84r/min or 85r/min etc..
With the continuous increase of mixing speed, desulfurization degree gradually rises, and this is due to that stirring-head rotating speed improves, molten iron and slag The response area increase of son, equivalent to the dynamic conditions that the method using machinery improves reaction, promotes entering for desulphurization reaction OK, it is contemplated that molten iron is excessive and equipment situation, therefore mixing speed is controlled in 75-85r/min.
Preferably, the mixing time of the KR Desulfurization by stirring method is 15-20min, such as 16min, 17min, 18min, 19min Or 20min etc..
The vanadium extraction is carried out in converter, and the charge weight of molten iron is 68-70t, such as 68t, 69t or 70t in converter.Pass through The charge weight of control molten iron makes ton steel desulfurization deviation smaller, and under the conditions of ensuring identical mixing parametric, the mixing effect of molten iron It is unaffected.
Preferably, the duration of blast in vanadium extracting process is 4-5min, such as 4min, 4.5min or 5min.
Half Steel ladle clearance >=500mm after the vanadium extraction, such as 500mm, 550mm, 600mm, 650mm, 700mm or 800mm etc..
The temperature of the half steel obtained after the vanadium extraction is 1360-1400 DEG C, such as 1365 DEG C, 1370 DEG C, 1380 DEG C, 1385 DEG C, 1390 DEG C or 1395 DEG C etc..
Preferably, carry out KR Desulfurization by stirring method when half steel temperature be 1330-1370 DEG C, such as 1335 DEG C, 1340 DEG C, 1350 DEG C, 1355 DEG C, 1360 DEG C or 1365 DEG C etc..
The present invention is in steelmaking process, the temperature of half steel during by controlling the half steel temperature and KR Desulfurization by stirring method after vanadium extraction Degree ensure that the temperature requirement needed for desulphurization reaction.
Compared with prior art, beneficial effects of the present invention are:
Desulfurizing agent provided by the invention can carry out deoxidation while desulfurization to half steel, significantly alleviate refining desulfuration pressure Power, the content of sulphur in finished steel is reduced to less than 0.002%, thoroughly solve the technical problem that can not produce ultralow-sulfur steel, And desulfurizing agent composition is simple, easy to use;KR Desulfurization by stirring method after method for making steel elder generation provided by the invention vanadium extraction, production line On completely eliminate the contaminated problem of vanadium slag.
Embodiment
Technical scheme is further illustrated below by embodiment.
Embodiment 1
A kind of desulfurizing agent, the desulfurizing agent are made up of by the weight of each raw material and molten iron ratio the following raw material:
Fluorite 1kg/tFe
Lime 9kg/tFe
Aluminum shot 0.25kg/tFe.
A kind of method for making steel, desulfurization after method for making steel elder generation vanadium extraction, desulfurization use KR Desulfurization by stirring method.Wherein, vanadium extraction Carried out in converter, the charge weight of molten iron is 68t in converter, and half Steel ladle clearance is 800mm, and the duration of blast of vanadium extracting process is 5min, it is 1400 DEG C to control the half steel temperature obtained after vanadium extraction, and the temperature for carrying out half steel during KR Desulfurization by stirring method is 1370 DEG C, is stirred It is 85r/min to mix speed, mixing time 16min, first adds lime and the firefly of formula ratio during desulfurization into the half steel after vanadium extraction Stone, the aluminum shot of formula ratio is added in whipping process;Half steel after desulfurization obtains into by pneumatic steelmaking, refining and continuous casting again Product steel.
Carbon steel and middle-low alloy steel spark source atomic emission spectrometry analysis method (GB/ are utilized on direct-reading spectrometer T4336-2002 it is 0.001%) to determine sulfur content (weight percentage) in finished steel.
Embodiment 2
A kind of desulfurizing agent, the desulfurizing agent are made up of by the weight of each raw material and molten iron ratio the following raw material:
Fluorite 2kg/tFe
Lime 8kg/tFe
AD powder 3.3kg/tFe.
A kind of method for making steel, desulfurization after method for making steel elder generation vanadium extraction, desulfurization use KR Desulfurization by stirring method.Wherein, vanadium extraction Carried out in converter, the charge weight of molten iron is 70t in converter, and half Steel ladle clearance is 600mm, and the duration of blast of vanadium extracting process is 4.5min, it is 1390 DEG C to control the half steel temperature obtained after vanadium extraction, and the temperature for carrying out half steel during KR Desulfurization by stirring method is 1360 DEG C, Mixing speed is 75r/min, mixing time 20min, first added into the half steel after vanadium extraction during desulfurization formula ratio lime and Fluorite, the AD powder of formula ratio is added in whipping process;Half steel after desulfurization obtains by pneumatic steelmaking, refining and continuous casting again Finished steel.
Carbon steel and middle-low alloy steel spark source atomic emission spectrometry analysis method (GB/ are utilized on direct-reading spectrometer T4336-2002 it is 0.002%) to determine sulfur content (weight percentage) in finished steel.
Embodiment 3
A kind of desulfurizing agent, the desulfurizing agent are made up of by the weight of each raw material and molten iron ratio the following raw material:
Fluorite 1.5kg/tFe
Lime 8.5kg/tFe
Aluminum shot and AD powder 2.0kg/tFe.
A kind of method for making steel, desulfurization after method for making steel elder generation vanadium extraction, desulfurization use KR Desulfurization by stirring method.Wherein, vanadium extraction Carried out in converter, the charge weight of molten iron is 69t in converter, and half Steel ladle clearance is 500mm, and the duration of blast of vanadium extracting process is 4min, it is 1360 DEG C to control the half steel temperature obtained after vanadium extraction, and the temperature for carrying out half steel during KR Desulfurization by stirring method is 1330 DEG C, is stirred It is 80r/min to mix speed, mixing time 15min, first adds lime and the firefly of formula ratio during desulfurization into the half steel after vanadium extraction Stone, the aluminum shot and AD powder of formula ratio are added in whipping process;Half steel after desulfurization passes through pneumatic steelmaking, refining and continuous casting again Obtain finished steel.
Carbon steel and middle-low alloy steel spark source atomic emission spectrometry analysis method (GB/ are utilized on direct-reading spectrometer T4336-2002 it is 0.002%) to determine sulfur content (weight percentage) in finished steel.
Comparative example 1
The comparative example 1 is same as Example 1, and unique difference is to replace aluminum shot with calcium carbide.
After measured, sulfur content (weight percentage) is 0.015% in finished steel.
Comparative example 2
The comparative example 2 is same as Example 1, and unique difference is that aluminum shot is not contained in desulfurizing agent.
After measured, sulfur content (weight percentage) is 0.020% in finished steel.
Comparative example 3
The comparative example 3 is same as Example 1, and unique difference is that fluorite is not contained in desulfurizing agent.
After measured, sulfur content (weight percentage) is 0.022% in finished steel.
Comparative example 4
The comparative example 4 is same as Example 1, and unique difference is that lime is not contained in desulfurizing agent.
After measured, sulfur content (weight percentage) is 0.028% in finished steel.
Applicant states that the present invention illustrates the method detailed of the present invention, but not office of the invention by above-described embodiment It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implemented.Art Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention Addition, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and disclosing.

Claims (1)

1. a kind of method for making steel, desulfurization after method for making steel elder generation vanadium extraction, the desulfurization use KR Desulfurization by stirring method, its feature exists In using steel desulfurization agent during the KR Desulfurization by stirring method, the steel desulfurization agent is by each raw material and the weight ratio of molten iron It is made up of the following raw material:
Fluorite 1-2kg/tFe
Lime 8-8.9kg/tFe
Aluminum shot 0.25-0.4kg/tFe;
The duration of blast of the vanadium extraction is 4-5min;The half steel temperature obtained after the vanadium extraction is 1360-1395 DEG C;It is described to carry Vanadium is carried out in converter, and the charge weight of molten iron is 68-70t in converter;Half Steel ladle clearance >=500mm after the vanadium extraction, and ≤700mm;
The KR Desulfurization by stirring method is:The fluorite and lime of formula ratio are first added into the half steel obtained after vanadium extraction, then is being stirred During add formula ratio aluminum shot, the mixing speed is 75-79r/min;Mixing time is 16-20min, carries out KR stirrings The temperature of half steel is 1330-1340 DEG C during method desulfurization.
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CN112593048A (en) * 2020-12-09 2021-04-02 攀钢集团西昌钢钒有限公司 Semisteel desulfurization method

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