CN102312049A - Desulfurizing agent suitable for high-aluminum silicon steel and preparation method thereof - Google Patents
Desulfurizing agent suitable for high-aluminum silicon steel and preparation method thereof Download PDFInfo
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- CN102312049A CN102312049A CN2010102156637A CN201010215663A CN102312049A CN 102312049 A CN102312049 A CN 102312049A CN 2010102156637 A CN2010102156637 A CN 2010102156637A CN 201010215663 A CN201010215663 A CN 201010215663A CN 102312049 A CN102312049 A CN 102312049A
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Abstract
The invention provides a desulfurizing agent suitable for high-aluminum silicon steel and a preparation method thereof. The desulfurizing agent comprises the following components: 75-80 percent of calcium oxide (CaO), 10-15 percent of aluminum oxide (Al2O3), 3-6 percent of magnesium oxide (MgO), 3-6 percent of magnesium chloride (MgCl2), not greater than 1.5 percent of silicon dioxide (SiO2), not greater than 0.02 percent of all titanium (Ti) and not greater than 0.02 percent of all carbon (C). The preparation method comprises the following steps: (1) weighing the raw materials: 72-77 percent of CaO, 8-13 percent of Al2O3 and 10-20 percent of binder; (2) respectively crushing the CaO and the Al2O3 into particles of which the particle sizes are less than 0.1mm; (3) heating the CaO to 120-150 DEG C, and carrying out spray treatment on the CaO particles by using silicone oil so as to form a protective film; (4) mixing the CaO and the Al2O3 with the binder; and (5) pressing into balls by using a ball press, and drying and packaging. The desulfurizing agent provided by the invention is easy to store, has high desulfurizing rate and low environmental pollution and has low corrosion on the refractory of a vacuum slot body; in the desulfurizing process, the molten steel carburetion and titanizing can be controlled to be under 5ppm; and the desulfurizing rate can reach at least 50 percent on the premise of not increasing the refining time.
Description
Technical field
The invention belongs to steel-making SECONDARY REFINING IN A VACUUM CHAMBER field, relate in particular to a kind of high alumina silicon steel with RH vacuum-treat sweetening agent and preparation method thereof.
Background technology
Silicon steel is a kind of electrotechnical steel, with the iron core of well behaved siliconized plate making X-former, motor, can not only save the energy, reduces iron loss, and can also reduce sound pollution.The core technology of its steelmaking process is the abundant removal of harmful element and the reasonable control of its inclusion.Sulphur is a kind of harmful elements as far as most steel grades, molten steel is carried out the domestic method that desulfurization is a sulphur content in the control steel at the RH refining process.
60～seventies of last century, the RH device obtained developing rapidly.Its major function is the degassing, alloying, chemical heat, removal inclusion, desulfurization etc.Wherein powder injection desulphurization such as has fast, stablizes at advantage, but its equipment cost is higher with running cost, and sweetening effectiveness is not obvious deeply.Relevant references has " Shanghai metal "-2005 27 volumes 4 phase 54-57 pages or leaves " powder injection desulphurization in the molten steel RH refining process ".Because powder injection desulphurization has the problem that investment is big, environment is poor, running cost is high, therefore at present domestic normal the employing is the mode desulfurization that the top adds sweetening agent in the vacuum tank, and this method has advantage easy and simple to handle, that cost is low.Relevant references has " iron and steel "-2005 year 40 volume 11 phase 27-29 pages or leaves " the dark desulfurization of RH-KTB pre-melted slag is put into practice ".
(application number: CN200910076729.6) disclose a kind of sweetening agent that is applicable to that chute adds, this sweetening agent composition is the patent of " pre-melted slag deep desulfuration method in a kind of RH vacuum oven " by name: CaO:55～60%, Al
2O
3: 15～25%, SiO
2: 2～8%, MgO:0～5%, S:0～0.06, moisture: 0～0.5%, impurity: 0～1.89%; Be weight percentage.But this sweetening agent is not described the content of titanium and carbon, if this sweetening agent is used for the silicon steel desulfurization, causes that very easily carbon and titanium content exceed standard in the steel.SiO in this sweetening agent in addition
2Content also higher, SiO
2Content be 2～8%, add the SiO that silicon steel forms in RH vacuum-treat process
2, aggravated erosion to magnesium chromium firebrick on the RH vacuum treatment installation, seriously restricted the work-ing life of treatment unit.The patent of by name " vacuum refining agent and preparation method thereof " (application number: CN200610020000.3) disclose high to inclusion content in the molten steel in the soft steel production processes such as non orientating silicon steel, oriented silicon steel, the slag oxidisability is strong, the characteristics of slag unstable properties; The composition (weight percent %) of having formulated the RH vacuum refining agent is: CaO 32～45%, Al
2O
3: 25～36%, Al:15～25%, CaF
2: 0～8%, SiO
2: 0～8%, full C:0～0.18, all the other are impurity.In the above-mentioned patent, the effect of molten steel desulfurizing has been played in the adding of low-carbon (LC) fritting thing calcium aluminate, and the adding of metallic aluminium has the effect of deoxidation of molten steel.Though this patent shortcoming is that wherein fluorite can reduce the refining agent fusing point, plays the effect of quick slagging, simultaneously also strengthened slag to the equipment work lining refractories erosion.The sweetening agent of this invention is not described titanium content equally, is prone to cause that titanium content exceeds standard in the steel.(application number: CN200510023269.2) composition of disclosed RH vacuum treatment deep desulfurization pre-melted slag is (weight percent %) to the patent of " used for ultra-low-carbon steel RH vacuum treatment deep desulfurization pre-melted slag and preparation method thereof " by name: CaO:48～56%, Al
2O
3: 33～43%, MgO:0.2～5.0%, SiO
2: 2.5～6.0%, TiO
2≤1.9%, carbon≤0.05%, all the other are impurity.Above-mentioned pre-melted slag in the preparation, in order to reduce titanium and the content of carbon in the pre-melted slag, raw material is fine Wingdale and high-purity Al
2O
3Powder, but full titanium is not explained because the aluminium reducing that the titanium of all valence states and form all possibly contained in the aluminium silicon steel in the sweetening agent is a titanium, thereby causes that titanium content exceeds standard in the steel.SiO in this sweetening agent in addition
2Content also higher, SiO
2Content be 2.5～6.0%, add the SiO that silicon steel forms in RH vacuum-treat process
2, can aggravate erosion equally to magnesium chromium firebrick on the RH vacuum treatment installation.On the other hand, Al in this sweetening agent
2O
3Content also higher, Al
2O
3Content be 33～43%, contain aluminium silicon steel and when adopting aluminium deoxidation, can generate more Al
2O
3, make Al in the slag
2O
3Content raises, and is unfavorable for forming low-melting calcium aluminate, causes desulfurization performance to descend.
Above-mentioned sweetening agent is pre-melted desulfurizing agent, and the preparation sweetening agent need be used corresponding fritting treatment facility, when fritting is handled, can cause the pollution of sweetening agent itself, also can reduce the activity of main desulfurization thing phase (CaO).
(application number: CN200610030597.X) disclosed non-pre-melted desulfurizing agent is applicable to the desulfurization of RH vacuum to the patent of " a kind of desulfurizing agent for non-oriented silicon steel " by name, and composition is (weight percent %): CaO:45～58%, Al
2O
3: 8～23%, CaF
2: 15～30; SiO
2: 3～8%; Mg:2～6%; C≤0.015%.This sweetening agent is not described the content of titanium, if this sweetening agent is used for the desulfurization of high alumina silicon steel, causes that very easily carbon and titanium content exceed standard in the steel.SiO in this sweetening agent in addition
2Content also higher, SiO
2Content be 3～8%, be used for the silicon steel desulfurization and be prone to the erosion of aggravation magnesium chromium firebrick on the RH vacuum treatment installation.Though the fluorite in the sweetening agent can reduce the refining agent fusing point, play the effect of quick slagging, simultaneously also strengthened slag to the equipment work lining refractories erosion.
As stated, existing sweetening agent can not satisfy the requirement that contains the desulfurization of aluminium silicon steel, can cause in the use molten steel carburetting, increase the titanium phenomenon, simultaneously also consider to contain the Al that generates in the aluminium silicon steel refining process
2O
3And SiO
2Effect on Performance to slag.
Summary of the invention
The objective of the invention is to overcome the deficiency that above-mentioned prior art exists; Characteristics to high alumina silicon steel; Provide that a kind of slagging speed is fast, desulfurization degree is high, pollution is little; Molten steel recarburization with increase titanium and can both be controlled at below the 5ppm, and the anti-material of vacuum trough body is corroded little vacuum smelting desulfurizing agent and preparation method thereof.
The present invention is achieved in that this sweetening agent composition weight percent that is applicable to high alumina silicon steel is: CaO:75%～80%, Al
2O
3: 10%～15%, MgO:3%～6%, MgCl
2: 3%～6%, SiO
2≤1.5%, full Ti≤0.02%, full C≤0.02%, said full Ti refers to the whole Ti content in the sweetening agent, said full C refers to the whole C content in the sweetening agent.
The present invention is applicable to that the preparation method of high alumina silicon steel sweetening agent comprises the following steps: 1. to take by weighing raw material by following weight percent: CaO:72%～77%, Al
2O
3: 8%～13%, sticker: 10%～20%, said sticker is the mixture of Natural manganese dioxide, magnesium chloride and water, its weight ratio is 1: 1: 1.5; 2. with CaO and Al
2O
3Be broken into the particle of particle diameter respectively less than 0.1mm; 3. for preventing that CaO from reducing activity because of suction, CaO is heated to 120～150 ℃, to the processing of spraying of CaO particle, to form protective membrane, described silicone oil accounts for 3%～4% of CaO gross weight with silicone oil, and the thickness of said CaO surface protection film is 5～10 μ m; 4. with CaO, Al
2O
3Mix with sticker, mixing time is 2～4 hours; 5. use pressure>=500Kg/cm
2The pair roller ball press be pressed into pelletizing, and under 130～160 ℃ of temperature, dry so that organic composition volatilizees fast, discharge micro-moisture simultaneously, answer sealed damp-proof during packing.
Basic thought of the present invention is that the raw material of preparing sweetening agent selects high-quality CaO and Al for use
2O
3, among the said high-quality CaO CaO content greater than 98%, said high-quality Al
2O
3Middle Al
2O
3Content is brought impurity element into to avoid raw material, like titanium, carbon and silicon-dioxide etc. greater than 98%.Sweetening agent need not fritting, has not only practiced thrift cost but also has not fallen the activity of CaO.On the other hand; Be prone to generate the characteristics of aluminum oxide and silicon oxide when containing aluminium silicon steel deoxidation alloying; Suitably reduce aluminum oxide and silica content in the sweetening agent, the sweetening power decline that prevents to cause because of aluminum oxide in the slag and silica content are too high in the refining process and to the erosion of refractory brick.
The purpose that the present invention adds CaO is, CaO helps desulfurization, but simple CaO fusing point is higher, it with contain the Al that generates in the aluminium silicon steel fusion process
2O
3And SiO
2And the Al that contains of sweetening agent itself
2O
3In conjunction with after, can generate the lower slag of fusing point, help desulfurization.But too much CaO can make the slag fluidity variation, even crust, is unfavorable for desulfurization.So the amount with addition of CaO is to take into account the characteristics that contain aluminium silicon steel, the content range of CaO is between 72%～77%.Add Al
2O
3Purpose be: an amount of Al
2O
3Can improve the flowing property of slag, consider to contain in the aluminium silicon steel fusion process to generate Al
2O
3Characteristics, so the content of aluminum oxide is controlled between 8%～13%.Sticker is the mixture of Natural manganese dioxide, magnesium chloride and water, and the weight ratio of Natural manganese dioxide, magnesium chloride and water is 1: 1: 1.5, and the sticker add-on accounts for 10～20% of total material total amount.This sticker with can generate Natural manganese dioxide after high-temperature molten steel contacts, Natural manganese dioxide has provide protection to magnesium chromium firebrick on the RH vacuum treatment installation.The raw materials mix time should be more than 2 hours, and to guarantee abundant mixing, mixing time is long, consume human and material resources.
The sweetening agent of the present invention not only content of titanium, carbon is extremely low, and has rodent dioxide-containing silica also extremely low to magnesium chromium firebrick on the RH vacuum treatment installation, and transportation compares with desulfurizer powder when using, and environmental pollution is little.Also consider to contain the Al that generates in the aluminium silicon steel refining process simultaneously
2O
3And SiO
2To the Effect on Performance of slag, during the preparation sweetening agent, guarantee to contain higher CaO content and lower Al in the sweetening agent
2O
3Content.
Sweetening agent of the present invention has the preservation of being easy to, desulfurization degree is high, environmental pollution is little; The anti-material of vacuum trough body is corroded little characteristics; When melting contains aluminium silicon steel, can guarantee that molten steel recarburization is controlled at below the 5ppm in the whole sweetening process simultaneously, the titanium that increases of molten steel also is controlled at below the 5ppm; Under the prerequisite that does not increase refining time, desulfurization degree can reach more than 50%.
Embodiment
Through embodiment the present invention is done further description below.
The embodiment of the invention is carried out selection, preparation and melting as follows:
(1) raw material is selected high-quality CaO (containing CaO is more than 98%) and high-quality Al for use
2O
3(contain Al
2O
3Be more than 98%).
(2) take by weighing raw material by following weight percent: CaO:72%～77%, Al
2O
3: 8%～13%, sticker: 10%～20%, sticker is the mixture of Natural manganese dioxide, magnesium chloride and water, the weight percent of Natural manganese dioxide, magnesium chloride and water is 1: 1: 1.5.With CaO and Al
2O
3Put into crusher respectively and carry out grinding and processing, be broken into the particle of particle diameter less than 0.1mm.
(3) for preventing that CaO from reducing activity because of suction, adopt silicone oil to processings of spraying of CaO particle, to form protective membrane, spraying is heated to 120 ℃～150 ℃ with CaO before handling, and sprinkling silicone oil accounts for 3%～4% of total CaO weight.
(4) with CaO and Al
2O
3Mix with sticker, mixing time is 2～4 hours.
(5) adopt pressure>=500Kg/cm
2The pair roller ball press be pressed into the pelletizing product.
(6) pelletizing oven dry, the packing, for use to suppressing.Bake out temperature volatilizees organic composition between 130～160 ℃ fast, discharges micro-moisture simultaneously.Note sealing during packing, guard against damp during preservation.
Embodiment of the invention sweetening agent material rate is seen table 1.
The proportioning raw materials (wt%) of table 1 embodiment of the invention sweetening agent
| The sweetening agent raw material | CaO | Al 2O 3 | Sticker |
| Embodiment 1 | 75 | 13 | 12 |
| Embodiment 2 | 73 | 11 | 16 |
| Embodiment 3 | 72 | 10 | 18 |
Embodiment of the invention sweetening agent chemical ingredients is seen table 2.
The chemical ingredients (wt%) of table 2 embodiment of the invention sweetening agent
| The sweetening agent component | CaO | Al 2O 3 | MgO | MgCl 2 | SiO 2 | Full Ti | Full C | Other impurity |
| Embodiment 1 | 79 | 13 | 3 | 3 | 1.0 | 0.01 | 0.02 | 0.97 |
| Embodiment 2 | 78 | 12 | 4 | 4 | 0.9 | 0.02 | 0.02 | 1.06 |
| Embodiment 3 | 77 | 11 | 5 | 5 | 1.1 | 0.02 | 0.01 | 0.87 |
The inventive embodiments sweetening agent is used for the RH refining process of high alumina silicon steel, and composition is seen table 3 before and after the molten steel desulfurizing.Visible from table 3, molten steel recarburization is controlled at below the 5ppm after desulfurization is handled, and molten steel increases titanium and is controlled at below the 5ppm, and desulfurization degree can reach more than 50%.After the testing identity desulfurization was handled, sweetening agent to the refractory loss on the RH vacuum treatment installation seldom.
Composition contrast (wt%) before and after table 3 molten steel desulfurizing
Claims (6)
1. a sweetening agent that is applicable to high alumina silicon steel is characterized in that this sweetening agent composition weight percent is: CaO:75%～80%, Al
2O
3: 10%～15%, MgO:3%～6%, MgCl
2: 3%～6%, SiO
2≤1.5%, full Ti≤0.02%, full C≤0.02%, said full Ti refers to the whole Ti content in the sweetening agent, said full C refers to the whole C content in the sweetening agent.
2. the said preparation method who is applicable to high alumina silicon steel sweetening agent of claim 1 is characterized in that comprising the following steps: 1. taking by weighing raw material by following weight percent: CaO:72%～77%, Al
2O
3: 8%～13%, sticker: 10%～20%, said sticker is the mixture of Natural manganese dioxide, magnesium chloride and water; 2. with CaO and Al
2O
3Be broken into the particle of particle diameter respectively less than 0.1mm; 3. CaO is heated to 120～150 ℃, with silicone oil to the processing of spraying of CaO particle, to form protective membrane; 4. with CaO, Al
2O
3Mix with sticker; 5. be pressed into pelletizing with ball press, and dry, pack.
3. the preparation method of sweetening agent according to claim 2, the weight ratio that it is characterized in that Natural manganese dioxide, magnesium chloride and water in the said sticker is 1: 1: 1.5.
4. the preparation method of sweetening agent according to claim 2 is characterized in that CaO content is greater than 98% among the said CaO; Said Al
2O
3Middle Al
2O
3Content is greater than 98%.
5. the preparation method of sweetening agent according to claim 2 is characterized in that said silicone oil accounts for 3%～4% of CaO gross weight, and the thickness of said CaO surface protection film is 5～10 μ m.
6. the preparation method of sweetening agent according to claim 2, the mixing time that it is characterized in that said raw material is 2～4 hours; The bake out temperature of said pelletizing is 130～160 ℃.
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| CN106521093A (en) * | 2016-12-08 | 2017-03-22 | 桂林加宏汽车修理有限公司 | Industrial desulfurizing agent |
| CN107837670A (en) * | 2017-12-12 | 2018-03-27 | 太原钢铁(集团)有限公司 | A kind of double alkali desulfurizing agents and preparation method thereof |
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