CN102199687A - RH vacuum treatment desulfurizing agent used for non-oriented electrical steel, preparation method thereof, and desulfurizing method using same - Google Patents
RH vacuum treatment desulfurizing agent used for non-oriented electrical steel, preparation method thereof, and desulfurizing method using same Download PDFInfo
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- CN102199687A CN102199687A CN201110105955XA CN201110105955A CN102199687A CN 102199687 A CN102199687 A CN 102199687A CN 201110105955X A CN201110105955X A CN 201110105955XA CN 201110105955 A CN201110105955 A CN 201110105955A CN 102199687 A CN102199687 A CN 102199687A
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Abstract
The invention relates to an RH vacuum treatment desulfurizing agent used for non-oriented electrical steel, a preparation method thereof, and a desulfurizing method using the same, belonging to the field of secondary refining of molten steel, so as to solve the problems that the RH vacuum treatment desulfurizing processes used for electrical steel in the prior art have serious erosion on refractory materials, high cost, slow melting speed and carburization risk to molten steel. The RH vacuum treatment desulfurizing agent used for non-oriented electrical steel is mainly composed of the following components: 50-60 weight parts of CaO, 10-25 weight parts of Al2O3 and 5-10 weight parts of CaF2. The invention also provides the preparation method of the RH vacuum treatment desulfurizing agent used for the non-oriented electrical steel, and the desulfurizing method using the RH vacuum treatment desulfurizing agent used for the non-oriented electrical steel. The RH vacuum treatment desulfurizing agent provided by the invention is mainly used for the RH vacuum treatment desulfurizing treatment of the non-oriented electrical steel.
Description
Technical field
The invention belongs to the molten steel furnace external refining field, be specifically related to non-oriented electrical steel RH vacuum-treat sweetening agent and preparation method thereof and sulfur method.
Background technology
Electrical steel is a kind of non-retentive alloy, and electrical sheet is a consumption maximum in the magneticsubstance, also is a kind of important energy saving type functional materials simultaneously, is key material indispensable in electric power, machinery, electronics and the war industry.Sulphur is a kind of deleterious element in non-oriented electrical steel, and the existence of sulphur not only can produce detrimentally affect to the processing characteristics of electrical steel, also can be to iron loss, and electromagnetic performance produces harm, when sulphur content iron loss of non-oriented electrical steel greater than 0.005% time obviously increases.Therefore, the content of strict control sulphur in non-oriented electrical steel.Because electrical steel is a ultra low-carbon steel, carbon content is extremely low in the steel, for guaranteeing RH vacuum decarburization effect, converter tapping all adopts not deoxidation or weak deoxidization technique, oxygen activity is higher in the molten steel, in follow-up refining process, be difficult to adopt equipments such as LF to carry out the dark desulfurization of molten steel, the control of sulphur can only rely on the dark desulfurization of molten iron substantially, molten iron sulphur is controlled in 0.003%, but be subjected to the influence of the sulphur that desulfurization residue and converter steelmaking process slag making materials bring into, the converter terminal sulphur content can surpass 0.005%, causes the electrical steel quality fluctuation thus.Therefore, be sulphur content in the stable control steel, adopt the important technology in the production of RH desulfurization becoming electrical steel.
The part producer of domestic production electrical steel carried out the research of RH desulfurization technology, and early stage RH sweetening agent substantially all adopts CaO-CaF
2Slag system, its CaF
2Content is up to 20%～40%, though effectively controlled sulphur content in the steel, sweetening agent is very big to the erosion of RH refractory materials, has reduced continuous processing power.For this reason, people have successively proposed multiple RH sweetening agent, and CN101134987 has proposed a kind of desulfurizing agent for non-oriented silicon steel, CaF in its sweetening agent component
2Weight percent is higher, reaches 15～30, does not break away from the vestige of early stage sweetening agent yet, and is bigger to the erosion of RH tubular stinger, and also with addition of the metal M g of weight percent 2～6, sweetening agent need carry out Passivation Treatment, sweetening agent complex manufacturing, cost height.Its weight percentages of components of the sweetening agent that proposes in CN101096720 CaO is 60～69%, Al
2O
3Be 1～5%, metal A l is 11～20%, and MgO is 5～10%, CaF
2Be 1～3%, and added B
2O
3And BaO, though can alleviate erosion to refractory materials, same cost is higher, and the danger of oriented molten steel carburetting.Patent CN1804055, CN1908197 and document [6] have proposed a kind of CaF that do not contain
2Sweetening agent, though this sweetening agent has alleviated the erosion of sweetening agent to the RH refractory materials, because of not containing CaF
2, and CaO/Al
2O
3＜1.7 is on the low side, and fusing is slow, will influence its sweetening effectiveness, is difficult to reach in the short treatment time sweetening effectiveness of expection, and CN1908197 has added 15～25% metal A l, product cost height simultaneously.Though the sweetening agent that CN10134806 proposed has also been emphasized CaF in the component
2Control, weight percent＜3%, but also added a certain amount of metal A l or BaCO
3, same cost is higher, and has the risk of molten steel carburetting.This shows that the ultra low-carbon steel RH sweetening agent that is proposed in current disclosed document or patent exists the RH refractory corrosion bigger, cost is higher, and fusing is slow, molten steel is had problems such as carburetting risk.
Summary of the invention
Bigger when the technical problem to be solved in the present invention is the electrical steel RH vacuum-treat desulfurization that exists in the prior art to refractory corrosion, cost is higher, and fusing is slow, molten steel is had the problem of carburetting risk.
The technical scheme that the present invention addresses the above problem provides a kind of non-oriented electrical steel RH vacuum-treat sweetening agent.This non-oriented electrical steel mainly consists of with RH vacuum-treat sweetening agent: CaO 50～60 weight parts, Al
2O
310～25 weight parts, CaF
25～10 weight parts.
Further, the granularity of above-mentioned sweetening agent is controlled at 3～15mm.Preferably, the granularity of above-mentioned sweetening agent is controlled at 3～8mm.
If have impurity in the sweetening agent, particularly some known obvious deleterious impurity of this area are controlled according to general knowledge and are got final product.Such as, require SiO
2≤ 10%, MgO≤5%, TiO
2≤ 2.0%, P≤0.08%, S≤0.08%.
The present invention also provides a kind of non-oriented electrical steel preparation method with RH vacuum-treat sweetening agent, at first with raw material quickened lime, calcium aluminate and fluorite fragmentation, then according to the component content of each raw material according to 50～60 parts of parts by weight CaO, Al
2O
310～25 parts, CaF
2Prepare for 5～10 parts, mix sweetening agent; The weight percent content of impurity is in the sweetening agent that makes: SiO
2≤ 10%, MgO≤5%, TiO
2≤ 2.0%, P≤0.08%, S≤0.08%.
Wherein, raw material granularity is controlled at 3～15mm during the raw material crushing described in the aforesaid method.
In addition, the present invention also provides a kind of method of non-oriented electrical steel RH vacuum-treat desulfurization, and sweetening agent of the present invention is added behind RH decarburization and deoxidation alloying by add-on 4-7 kg/ton molten steel.
Wherein, sweetening agent described in the aforesaid method is divided into two batches of addings, and first add-on is a 2-3 kg/ton molten steel, adds second batch behind molten steel circulation 1～3min, and its add-on is a 2-4 kg/ton molten steel, and molten steel recirculation 6～10min finishes desulfurization.
During sweetening agent is formed with CaF
2Parts by weight are controlled at 5～10, are significantly less than in traditional RH sweetening agent 20～40 content, have effectively alleviated the erosion of sweetening agent to refractory materials.With CaO, Al in the sweetening agent composition
2O
3, CaF
2Parts by weight be controlled at respectively in 50～60,10～25,5～10 the scope, the fusing point that makes sweetening agent has been guaranteed can melt rapidly after sweetening agent adds molten steel between 1280～1330 ℃.And need not be by adding B
2O
3, fusing assistant such as BaO solves because CaF
2Reduce the higher problem of bringing of sweetening agent fusing point.
Because electrical steel is a ultra low-carbon steel, carbon content is less than 0.005% in the steel, and carbon content is too high in the sweetening agent will cause molten steel carburetting.If add MgO, BaO in the sweetening agent, owing to all contain the carbon of some amount among raw material magnesia that these components adopt and the BaCO3, can cause in the sweetening agent carbon higher, thereby cause molten steel carburetting.For this reason, adopted carbon containing very low quickened lime, fluorite and calcium aluminate among the preparation method of the present invention, avoided molten steel carburetting thus as the sweetening agent raw material.The main chemical compositions Al of calcium aluminate
2O
3And CaO, the production method of calcium aluminate generally is in proportion with balling-up behind bauxite and the limestone crushing, is calcium aluminate at 1300 ℃ of calcination cooling back crushing packings, the steel-making deslagging agent is carried out company standard with calcium aluminate and is: Q/74362047-0001-2008.Product granularity is controlled at 3～15mm, is preferably 3～8mm, can enlarge the slag contact area, accelerate the fusing and the slagging speed of sweetening agent.Because adopting ore is raw material, must control impurity, wherein SiO
2, TiO
2, MgO belongs to and selects control, SiO
2Reactive aluminum in too high meeting and the steel, (be secondary oxidation usually in Iron and Steel Production, the too high reduction slag fluidity of MgO reduces speed of reaction, TiO to cause the scaling loss of molten steel Al
2Too highly also analogue can occur, and may cause occurring in the steel Ti and be mingled with, this three is brought into by raw material.P, S must control, and they can directly cause molten steel P, S to raise.
Sweetening agent be added in the RH deoxidation alloying after carry out, at this moment, oxygen activity is very low in the molten steel, need not to add noble metals such as Mg, Al and makes reductor.Therefore, do not add Mg, Al noble metal in the sweetening agent of the present invention, reduced the raw materials cost of sweetening agent, avoided Mg is carried out simultaneously the complicated technology of Passivation Treatment yet, simplified the production technique of sweetening agent, thereby reached the purpose that reduces the sweetening agent production cost.Adopt the mode that adds in two batches, and every batch added at interval the regular hour, avoided single batch of adding to cause the molten steel temperature drop excessive, sweetening agent melts, slagging is bad, the problem that desulfurization degree is low.
The present invention compared with prior art has following beneficial effect:
After adopting the technology of the present invention, can obtain 20～50% desulfurization degree at the RH refining process when producing non-oriented electrical steel, sulphur content is under 0.008% the condition before processing, handle back finished product sulphur content less than 0.005%, guaranteed the electromagnetic performance of electrical steel, reduce iron loss, thereby stablized quality product, improved the product lumber recovery.
Because the raw material type that the present invention adopts is less, and does not have precious metal and B such as Al, Mg
2O
3, fusing assistant such as BaO, raw materials cost is low, production technique is simple, the sweetening agent cost is low, and has avoided the carburetting to molten steel.
The present invention has reduced the CaF in the sweetening agent
2Content can alleviate the erosion of sweetening agent to the RH refractory materials, helps ensureing the continuous processing of RH, and the stove number waters in the company of improving electrical steel, reduces the electrical steel production cost.
Embodiment
Non-oriented electrical steel RH vacuum-treat sweetening agent.This non-oriented electrical steel mainly consists of with RH vacuum-treat sweetening agent: CaO 50～60 weight parts, Al
2O
310～25 weight parts, CaF
25～10 weight parts.
Further, the granularity of above-mentioned sweetening agent is controlled at 3～15mm.Preferably, the granularity of above-mentioned sweetening agent is controlled at 3～8mm.
If have impurity in the sweetening agent, particularly some known obvious deleterious impurity of this area are controlled according to general knowledge and are got final product.Such as, require SiO
2≤ 10%, MgO≤5%, TiO
2≤ 2.0%, P≤0.08%, S≤0.08%.
The present invention also provides a kind of non-oriented electrical steel preparation method with RH vacuum-treat sweetening agent, at first with raw material quickened lime, calcium aluminate and fluorite fragmentation, then according to the component content of each raw material according to 50～60 parts of parts by weight CaO, Al
2O
310～25 parts, CaF
2Prepare for 5～10 parts, mix sweetening agent; The weight percent content of impurity is in the sweetening agent that makes: SiO
2≤ 10%, MgO≤5%, TiO
2≤ 2.0%, P≤0.08%, S≤0.08%.
Wherein, raw material granularity is controlled at 3～15mm during the raw material crushing described in the aforesaid method.
In addition, the present invention also provides a kind of method of non-oriented electrical steel RH vacuum-treat desulfurization, and sweetening agent of the present invention is added behind RH decarburization and deoxidation alloying by add-on 4-7 kg/ton molten steel.
Wherein, sweetening agent described in the aforesaid method is divided into two batches of addings, and first add-on is 2～3 kg/ton molten steel, adds second batch behind molten steel circulation 1～3min, and its add-on is 2～4 kg/ton molten steel, and molten steel recirculation 6～10min finishes desulfurization.
The preparation of sweetening agent of the present invention: the mineral that can adopt pure compound or contain these compounds mix, if adopt pure compound, directly taking by weighing mixing gets final product, if adopt the mineral that contain these compounds, can adopt with quickened lime, calcium aluminate and fluorite is raw material, separated pulverizing, and control size is that 3～15mm is better.Composition requirement by sweetening agent of the present invention behind each determination of raw material component content is calculated content, and taking by weighing then stirs gets final product.In order to control SiO
2, MgO, TiO
2, P, S content, need to control to raw material.
Below, will be described in more detail the present invention by embodiment.
The preparation of embodiment 1 sweetening agent of the present invention
Quickened lime, calcium aluminate and fluorite is broken respectively, when broken raw material granularity is controlled at 5mm, detect the component content of each raw material, recording quickened lime mass percent component is CaO 85%, SiO
26%, MgO 6%, TiO
21.0%, P 0.07%, S 0.04%, calcium aluminate mass percent component is CaO 43%, Al
2O
338%, SiO
26%, TiO
22.5%, MgO 3.0%, P 0.05%, S 0.07%, fluorite mass percent component is CaF
285%, SiO
210%, P 0.02%, S 0.03%, TiO
20.5%, MgO 2.0%.Then according to the component content of each raw material according to 60 parts of parts by weight CaO, Al
2O
315 parts, CaF
210 parts of preparation sweetening agents, promptly calcium aluminate is got 40 weight parts, fluorite 10 weight parts, quickened lime 50 weight parts, and the impurity weight percent content is SiO in the sweetening agent at this moment
26.4%, MgO 4.4%, TiO
21.55%, P 0.057%, S 0.051% mix raw material stirring.
Method with reference to embodiment 1 makes following sweetening agent
Embodiment 2 uses sweetening agent desulfurization of the present invention
Molten steel enters the RH operation, S weight content 0.006% in the steel carries out carbonization treatment with the RH stove, treatment time 19min, C weight content 0.004%, add ferro-aluminum subsequently, ferrosilicon carries out deoxidation alloying, composition is adjusted in the steel grade limits, this moment oxygen activity be 0.0004%, behind deoxidation alloying, add the above-mentioned sweetening agent A that makes, add-on is 4 kg/ton molten steel, allows molten steel circulation 6min, finishes the vacuum desulfurization and handles.Carry out continuous casting then and sampling analysis tundish molten steel S weight content is 0.005%, the C weight content is 0.004%, and all the other compositions all meet the demands.
Embodiment 3 uses sweetening agent desulfurization of the present invention
Molten steel enters the RH operation, S weight content 0.007% in the steel carries out carbonization treatment with the RH stove, treatment time 19min, C weight content 0.004%, add ferro-aluminum subsequently, ferrosilicon carries out deoxidation alloying, composition is adjusted in the steel grade limits, this moment oxygen activity be 0.0004%, behind deoxidation alloying, add the above-mentioned sweetening agent B that makes, add-on is 7 kg/ton molten steel, allows molten steel circulation 10min, finishes the vacuum desulfurization and handles.Carry out continuous casting then and sampling analysis tundish molten steel S weight content is 0.005%, the C weight content is 0.004%, and all the other compositions all meet the demands.
Embodiment 4 uses sweetening agent desulfurization of the present invention
Molten steel enters the RH operation, S weight content 0.006% in the steel, carry out carbonization treatment with the RH stove, treatment time 19min, C weight content 0.003% adds ferro-aluminum, ferrosilicon carries out deoxidation alloying subsequently, composition is adjusted in the steel grade limits, this moment, oxygen activity was 0.0004%, added the above-mentioned sweetening agent C that makes behind deoxidation alloying, and first add-on is 2 kg/ton molten steel; Treat to add second crowd of sweetening agent C behind the molten steel circulation 3min, add-on is 2 kg/ton molten steel, after adding, allows molten steel circulation 6min, finishes the vacuum desulfurization and handles.Carry out continuous casting then and sampling analysis tundish molten steel S weight content is 0.004%, the C weight content is 0.003%, and all the other compositions all meet the demands.
Embodiment 5 uses sweetening agent desulfurization of the present invention
Molten steel enters the RH operation, S weight content 0.007% in the steel, carry out carbonization treatment with the RH stove, treatment time 19min, C weight content 0.003% adds ferro-aluminum, ferrosilicon carries out deoxidation alloying subsequently, composition is adjusted in the steel grade limits, this moment, oxygen activity was 0.0004%, added the above-mentioned sweetening agent D that makes behind deoxidation alloying, and first add-on is 3 kg/ton molten steel; Treat to add second crowd of sweetening agent D behind the molten steel circulation 1min, add-on is 4 kg/ton molten steel, after adding, allows molten steel circulation 10min, finishes the vacuum desulfurization and handles.Carry out continuous casting then and sampling analysis tundish molten steel S weight content is 0.0035%, the C weight content is 0.003%, and all the other compositions all meet the demands.
From the result of above embodiment as can be seen, adopt the content of S, C in the tundish finished product of the non-oriented electrical steel that method production provided by the invention obtains all to be controlled at lower level, molten steel carburetting phenomenon does not appear in sweetening process, can satisfy the specification of quality of steel fully.
Embodiment 6 uses sweetening agent desulfurization of the present invention
Molten steel enters the RH operation, S weight content 0.007% in the steel, carry out carbonization treatment with the RH stove, treatment time 19min, C weight content 0.003% adds ferro-aluminum, ferrosilicon carries out deoxidation alloying subsequently, composition is adjusted in the steel grade limits, this moment, oxygen activity was 0.0004%, added above-mentioned sweetening agent behind deoxidation alloying, and this sweetening agent takes by weighing CaO 55 weight parts, Al
2O
310 weight parts, CaF
29 weight parts mix arriving of preparation.First add-on is 3 kg/ton molten steel; Treat to add second batch of sweetening agent behind the molten steel circulation 1min, add-on is 4 kg/ton molten steel, after adding, allows molten steel circulation 10min, finishes the vacuum desulfurization and handles.Carry out continuous casting then and sampling analysis tundish molten steel S weight content is 0.004%, the C weight content is 0.003%, and all the other compositions all meet the demands.
Claims (7)
1. non-oriented electrical steel is characterized in that: mainly consist of CaO 50～60 weight parts, Al with RH vacuum-treat sweetening agent
2O
310～25 weight parts, CaF
25～10 weight parts.
2. non-oriented electrical steel according to claim 1 RH vacuum-treat sweetening agent, it is characterized in that: the granularity of described sweetening agent is controlled at 3～15mm.
3. non-oriented electrical steel is characterized in that with the preparation method of RH vacuum-treat sweetening agent: at first with raw material quickened lime, calcium aluminate and fluorite fragmentation, then according to the component content of each raw material according to 50～60 parts of parts by weight CaO, Al
2O
310～25 parts, CaF
2Prepare for 5～10 parts, mix sweetening agent; The weight percent content of impurity is in the sweetening agent that makes: SiO
2≤ 10%, MgO≤5%, TiO
2≤ 2.0%, P≤0.08%, S≤0.08%.
4. non-oriented electrical steel according to claim 3 is characterized in that: when broken raw material granularity is controlled at 3～15mm with the preparation method of RH vacuum-treat sweetening agent.
5. each described non-oriented electrical steel of claim 3～4 is with the sweetening agent of preparation method's preparation of RH vacuum-treat sweetening agent.
6. the method for non-oriented electrical steel RH vacuum-treat desulfurization is characterized in that: claim 1,2 or 5 each described sweetening agents are added behind RH decarburization and deoxidation alloying by add-on 4～7 kg/ton molten steel.
7. the method for non-oriented electrical steel RH vacuum-treat desulfurization according to claim 6, it is characterized in that: described sweetening agent is divided into two batches of addings, first add-on is 2～3 kg/ton molten steel, add second batch behind molten steel circulation 1～3min, its add-on is 2～4 kg/ton molten steel, molten steel recirculation 6～10min finishes desulfurization.
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Application publication date: 20110928 |