CN100500913C - Low-manganese low- sulfur raw material ferroferrite for amorphous usage and method of production - Google Patents
Low-manganese low- sulfur raw material ferroferrite for amorphous usage and method of production Download PDFInfo
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Abstract
The invention discloses a non-crystal low-manganese and low-sulfur pure ion and manufacturing method, which comprises the following parts: 0.03-0.07% C, 0.10-2.0% Si, 0.03-0.06% Mn, not more than 0.02% P, not more than 0.005% S, not more than 0.02% Al, not more than 0.008% Sn and not more than 0.01% Ti. The manufacturing procedure comprises the following steps: adopting melted iron to predispose; reducing S content in the melted iron; blowing in the rotary furnace; removing carbon and manganese through double-slag method or multiple slaggings; proceeding LF refining; casting in the square blank; using FeSi, Al or individual Al to predeoxidize; blowing and stirring in the whole procedure; dispersing through ferrosilicium and rankinite to deoxidize and desulfurize deeply; reducing Al; heating; feeding calcium line after stirring; casting; obtaining iron blank.
Description
Technical field
The invention belongs to the metallic substance preparation field, particularly a kind of low composition violent, the low-sulfur pure iron as raw material designs and production method, is particularly useful for the production of non-crystaline amorphous metal and associated materials.
Background technology
Pure iron as raw material is the basic material of exploitation iron and steel novel material, and along with the kind increase of novel material and the rising of output in recent years, the research and development of pure iron as raw material also come into one's own day by day with application.Regulation according to national standard (GB9971-88), the main application of pure iron as raw material and chemical ingredients such as table 1, the pure iron as raw material composition is because there is very big-difference in the difference of application conditions, for this reason, the trade mark of all corresponding foundation oneself of domestic main manufacturing enterprise, as paper " current situation and development of Taiyuan Iron and Steel Co. pure iron as raw material " (Zhang Yubin, " Taiyuan Iron and Steel Co. science and technology " the 1st phase in 2002, the 6th～9 page) report, Taiyuan Iron and Steel Co. group has developed ultra-low carbon high-purity series raw material pure iron, its trade mark is respectively YT00, YT0 (table 2) has further improved C on the basis of national standard, P, S purity.In the practical application since pure iron as raw material to relate to element many, each element component content purity differs, the material of institute's melting requires also inconsistent to each composition of pure iron as raw material, therefore these brands and specification can't satisfy market demand fully at present.
Table 1 YT series pure iron chemical ingredients (GB9971-88)
The part high-purity raw pure iron of table 2 Taiyuan Iron and Steel Co. group exploitation
According to the difference of non-ferro element removal technology, can tentatively the pure iron element be divided three classes: the first kind is C, gas, adopts the vacuum-treat degree of depth to remove; Second class is Mn, P, S etc., removes in antivacuum smelting process; The 3rd class is Cu, Cr, Ni, Sn, Ti etc., and its content depends mainly on the raw material situation.The applicating and exploitation of pure iron as raw material mainly carries out around first kind element especially C at present, and when smelting ultrapure pure iron (C≤0.025%), vacuum-treat becomes main smelting means.Report in the paper " current situation and development of Taiyuan Iron and Steel Co. pure iron as raw material " (" Taiyuan Iron and Steel Co. science and technology " the 1st phase in 2002), adopt when Taiyuan Iron and Steel Co. is smelted YT01, YT00, YT0 series product that hot metal pretreatment is taken off S, bessemerized, the technological process of production of RH vacuum refinement, continuous casting, wherein RH mainly is in order to carry out dark decarburization.Small-scale pure iron production technique has other vacuum apparatus of employing, paper " smelting technology of ultrapure technically pure iron is inquired into " (Cai Yongcheng, " iron and steel " 2000 the 35th volume second phases, the 16th～18 page) report that the Fushun special steel utilizes 20t electric arc furnace and the ultrapure technically pure iron of 30t VHD/VOD refining furnace three process exploitations, main component C 0.0020%-0.006%, Mn 0.02-0.06%, Si0.02-0.045%, Si 0.0010-0.0017%, P 0.0024-0.0035%; This paper reports that also the Great Wall special steel utilizes electric arc furnace and vacuum induction furnace to produce the technically pure iron of the high cleanliness of C 0.0033%, S 0.0025%, P 0.0028%; Obviously, vacuum-treat has also increased the manufacturing cost of pure iron as raw material when carrying out dark decarburization.In the patent about pure iron, more is the report of exploitation electrical pure iron both at home and abroad, and it requires C≤0.010%.Patent of invention (the application number 200510048127.1 of Taiyuan Iron ﹠ Steel's application, applying date 2005.11.25) disclose " method for manufacturing electromagnetic pure iron cold-rolled sheet material with low coercive force and high magnetoconductivity ", it passes through hot metal pretreatment, top and bottom combined blown converter smelting and vacuum refinement, the composition of finished product molten steel is: C≤0.010%, Si≤0.10%, Mn≤0.20%, P≤0.015%, S≤0.010%, Al=0.50%～0.80%, [O], [N]＜40ppm, Japanese Patent JP5306437 exploitation pure iron is as magneticsubstance, and composition is C≤0.005%, Si≤0.02%, Mn≤0.15%, P≤0.015%, S≤0.003%, Al≤0.01%, N≤0.005%, Mg0.001-0.015%; Pure iron composition C≤0.02% of patent JP1139739 exploitation, Si≤0.3%, Mn≤0.5%, P≤0.01%, S≤0.01%.All these flow processs adopt converter smelting final vacuum processing carrying out decarburization.
In actual applications, because the progress of novel material smelting technique has significantly reduced the carburetting of fusion process, make some materials to pure iron as raw material and do not require very low C content, require 0.025≤C≤0.07% as amorphous with pure iron as raw material, and the second dvielement Mn, low (Mn≤0.04% of S content, S≤0.05%), the 3rd dvielement Sn, (Ti≤0.01% such as Ti, Sn≤0.008%) super low loading, adopt conventional bof process can carry out the control of carbon, but because to Mn, S, Sn, elements such as Ti are had relatively high expectations, and existing smelting technology can not meet the needs of production.The smelting of such pure iron need be selected the few molten iron of residual element for use, in smelting process, need to adopt suitable bessemerize, furnace outer refining process, fully carry out demanganize and desulfurization and just can achieve the goal.
Summary of the invention
The objective of the invention is to obtain the production technique of this pure iron as raw material simultaneously in order to design the composition of a kind of amorphous with low manganese, low-sulfur pure iron as raw material, this pure iron as raw material is applicable to the production of non-crystaline amorphous metal and associated materials.
In order to achieve the above object, the present invention is achieved in that
One aspect of the present invention has provided a kind of amorphous with hanging down manganese, low-sulfur pure iron as raw material, its composition is by weight percentage: C 0.03-0.07%, Si 0.10-2.0%, Mn 0.03-0.06%, P≤0.02%, S≤0.005%, Al≤0.02%, Sn≤0.008%, Ti≤0.01%, all the other are Fe.
The product of this pure iron as raw material is continuous casting square billet or bar.
Another aspect of the present invention has provided the production method of a kind of above-mentioned amorphous with low manganese, low-sulfur pure iron as raw material, and comprise following antivacuum smelting step: hot metal pretreatment-bessemerize-LF refining-continuous casting becomes base.
Bessemerize and/or the LF refinement step comprises the slagging process of high Si.
Bessemerize and take repeatedly deslagging in the step.
S, P are reduced in the hot metal pretreatment step control molten iron: S≤0.02%, P≤0.04%.
The first time or preceding twice deslagging of bessemerizing in the process are carried out under 1420 ℃ of-1560 ℃ of temperature condition.
Bessemerize the step control quantity of slag＜6 kilogram/ton steel down.
Bessemerizing tapping process adopts Al or Al to add low-carbon (LC) FeSi to carry out pre-deoxidation; The refining final deoxygenation adopts CaSi or CaSi to add low-carbon (LC) FeSi.In case Mn in anti-avulsion oxygen and the refining procedure molten steel and C content increase.
Adopt the LF refining furnace to carry out dark desulfurization, make S in the molten steel≤0.005%.
A third aspect of the present invention has provided the purposes of a kind of amorphous with low manganese, low-sulfur pure iron as raw material: the melting raw material that is used for non-crystaline amorphous metal.
In sum, according to above-mentioned purpose, the needs that the present invention produces according to non-crystaline amorphous metal improve respectively this pure iron as raw material composition and production method.
Improved pure iron as raw material composition
Determine that pure iron as raw material composition range of the present invention is as shown in table 3, composition characteristic is embodied in the strictness control of low-carbon (LC), low-sulfur, low manganese and residual element.
Table 3 pure iron as raw material composition of the present invention claimed range (wt.%)
| C | Si | Mn | P | S | Al | Cu | Ti | Sn | |
| Scope | 0.03-0.07 | 0.1-2.0 | 0.03-0.06 | ≤0.02 | ≤0.005 | ≤0.02 | ≤0.025 | ≤0.01 | ≤0.008 |
Compared with prior art, the improvement of the present invention's key aspect composition is:
Si 0.1-2.0%: the present invention is because technology determines that the content of Si should be at 0.1-2.0%.And the content requirement to Si in the prior art is lower, paper " current situation and development of Taiyuan Iron and Steel Co. pure iron as raw material " (Zhang Yubin for example, " Taiyuan Iron and Steel Co. science and technology " the 1st phase in 2002, the 6th～9 page) report, the Si content of its trade mark YT00, YT0 is respectively 0.05%, 0.03%, general requirement 0.02-0.05%, because in the existing production technology, owing to bessemerize decarburization, low Si content is inevitable, the requirement that low simultaneously Si content also is existing pure iron composition; The Si content that the present invention obtains is higher, is the needs of deoxidation in steel making on the one hand, the pure iron as raw material of the high Si content that obtains on the other hand, the add-on of Si in the time of can reducing smelting amorphous alloy.
Relevant smelting technology
According to the carbon content characteristics, adopt adopting non-vacuum process, so that old process hot metal pretreatment-bessemerize-LF refining-billet continuous casting production technique is a support, molten iron is carried out pre-treatment reduce S content in the molten iron, the full molten iron of converter or add steel scrap less, can use the few molten iron of residual element or the pig iron to do raw material, the double slag process or the slag that repeatedly inclines are adopted in steel-making, the first time or preceding twice deslagging of bessemerizing in the process are carried out under lower temperature condition, as 1420 ℃-1560 ℃, with MnO in a large amount of removal slags.The dark decarburization of converter, demanganize adopt two pushing off the slag to operate during converter tapping, strict control is the quantity of slag down, by MnO content in dilution, the reduction slag, reduce the molten steel Mn content of converter tapping; The described following quantity of slag of wanting strict control converter tapping process of bessemerizing, the following quantity of slag is less than 6 kilograms of steel per ton, in case MnO is reduced in a large number in anti-avulsion oxygen and the refining procedure slag, causes the Mn in the molten steel to increase.The first time or preceding twice deslagging of bessemerizing in the process should be carried out under lower temperature condition, as 1420 ℃-1560 ℃, with MnO in a large amount of removal slags.Converter smelting tapping process employing Al or Al add low-carbon (LC) FeSi and carry out pre-deoxidation;
Adopt the LF refining furnace to carry out dark desulfurization, make S in the molten steel≤0.005%.Adopt FeSi, Al behind the stove or carry out pre-deoxidation with Al separately, the refining final deoxygenation adopts CaSi or CaSi to add low-carbon (LC) FeSi.In case the Mn in anti-avulsion oxygen and the refining procedure molten steel and C content increase, omnidistance bottom blowing is stirred, and the diffusive deoxidation of refining procedure silico-calcium is carried out dark desulfurization, fallen Al, intensification; Soft stirring is set off after feeding silicon-calcium wire, and continuous casting becomes continuously cast bloom.Product form can be the continuous casting square billet of various size, also can be rolled into the bar of all size.
Pure iron as raw material state: as cast condition blank or bar.
Characteristics of the present invention are:
1) the invention provides the composition range that a class is hanged down the pure iron as raw material of C, low Mn, low S, be characterized in 0.03≤C≤0.07%, 0.03%≤Mn≤0.06%, 0.1%≤Si≤2.0%, S≤0.005%, Al≤0.02%, Ti≤0.01%, Sn≤0.008%.
2) the present invention is strict to going into the stove furnace charge, and molten iron is pretreated low-sulfur molten iron, does not add or adds steel scrap less, avoids residual element such as Sn, Ti, Cu excessive.
3) converter operation adopts two slag technologies, can according to circumstances implement twice or repeatedly deslagging MnO content in the dilution converter slag during production.
4) the present invention adopts the common process flow process, the dark decarburization of converter, and dark desulfurization is carried out in the LF refining.
5) low-sulfur of the present invention, low manganese pure iron as raw material are recommended to do raw material form with continuous casting material.
Compared with prior art, beneficial effect of the present invention is to provide a kind of low violent, low-sulfur pure iron as raw material, and Si content is higher simultaneously, can satisfy the application of producing non-crystaline amorphous metal and associated materials.
Embodiment
Describe the specific embodiment of the present invention in detail below in conjunction with embodiment, but the specific embodiment of the present invention is not limited to embodiment.
Embodiment 1:
Present embodiment production amorphous of the present invention is with hanging down S, low Mn pure iron as raw material, and present embodiment comprises following processing step:
One, hot metal pretreatment
Molten iron passes through the magnesium desulfurization, goes into the stove hot metal composition and is: Si 0.40%, P 0.04%, S0.02%, Mn 0.3%.
Two, bessemerize
1. go into the stove furnace charge and all adopt molten iron, 90 tons of converter capacities.
2. adopt double-slag operation, first slag chargeization is good, pours out 2/3 slag, slag making again then, final slag composition CaO 42%, MgO 11%, SiO
210%, P
2O
51.2%, MnO 1.5%, T
Fe20%.
3. tapping temperature is 1630 ℃, terminal point composition: C 0.035%, and Si 0.001%, and Mn 0.04%, and S 0.012%, and P 0.009%.
4. two pushing off the slag operations are taked in tapping, and tapping process adds ferrosilicon, Al ingot, and ladle is omnidistance behind the stove stirs.
Three, LF refining
1. deoxidization desulfuration: adopt FeSi, silico-calcium to carry out diffusive deoxidation, keep the white slag time greater than 20min.Top slag ingredient CaO 51%, Al
2O
318%, SiO
28%, MgO 8%, FeO 0.4%.
2. Argon stirs: refining is adopted big Argon stirring intensity in earlier stage, and the middle and later periods suitably reduces stirring intensity; Soft blow time 〉=10min.
3. terminal point composition:
| Element | C | Si | Mn | P | S | Al | Sn | Ti |
| Content, % | 0.04 | 0.4 | 0.04 | 0.01 | 0.005 | 0.008 | 0.002 | 0.003 |
4. heating: 4 ℃/min of heat-up rate, 1620 ℃ of tapping temperature first bags connect 1600 ℃ of casting ladles.
Four, billet continuous casting
1. big bag adopts the long nozzle protection, and crystallizer adopts submerged nozzle, carries out the full guard cast.
2. 1560 ℃ of tundish temperatures, pulling rate 2.2m/min.
3. pour into 130mm * 130mm * 6m continuously cast bloom.
Under the present invention instructed, present embodiment adopted the common process route, produced the pure iron as raw material continuous cast billet of low-sulfur, low manganese in hot metal pretreatment-bessemerize-LF refining-continuous small-billet casting technological process of production, satisfied the application of producing non-crystaline amorphous metal.
Embodiment 2:
One, hot metal pretreatment
Molten iron is through after the magnesium desulfurization, goes into the stove composition to be: Si 0.55%, P 0.035%, S 0.01%, Mn 0.15%.
Two, bessemerize
1. converter capacity is 120 tons, and going into the stove furnace charge is 120 tons of molten iron, 5 tons of steel scraps, and the steel scrap main component is: P 0.04%, S 0.035%, Mn 0.25%.
2. adopt three slag making, first slag chargeization is good, pours out 1/2 slag, and slag making again then after second batch of slag chargeization is intact, is poured out 1/2 slag, makes new slag again, final slag composition CaO45%, MgO 9%, SiO
211.5%, P
2O
51.3%, MnO 1.3%, T
Fe23.5%.
3. tapping temperature is 1640 ℃, terminal point composition: C 0.032%, and Si＜0.001%, Mn 0.035%, and S 0.015%, and P 0.01%.
4. two pushing off the slag operations are taked in tapping, and tapping process adds ferrosilicon, and aluminum steel is fed at the Argon station behind the stove, and ladle is omnidistance to be stirred.
Three, LF refining
1. deoxidization desulfuration: adopt FeSi, silico-calcium to carry out diffusive deoxidation, keep the white slag time greater than 20min.Final slag composition CaO 48%, Al
2O
320%, SiO
212%, MgO 7%, FeO 0.6%.
2. Argon stirs: refining is adopted big Argon stirring intensity in earlier stage, and the middle and later periods suitably reduces stirring intensity; After feeding the CaSi line, soft blow time 〉=10min.
3. terminal point composition:
| Element | C | Si | Mn | P | S | Al | Sn | Ti |
| Content, % | 0.042 | 0.38 | 0.038 | 0.012 | 0.004 | 0.006 | 0.004 | 0.002 |
4. heating: 4 ℃/min of heat-up rate, 1620 ℃ of tapping temperature first bags connect 1600 ℃ of casting ladles.
Four, billet continuous casting
1. big bag adopts the long nozzle protection, and crystallizer adopts submerged nozzle, carries out the full guard cast.
2. 1560 ℃ of tundish temperatures, pulling rate 2.0m/min.
3. pour into 150mm * 150mm * 6m continuously cast bloom.
Claims (10)
1. an amorphous is with hanging down manganese, low-sulfur pure iron as raw material, and it is characterized in that: its composition is by weight percentage: C 0.03-0.07%, Si 0.10-2.0%, Mn 0.03-0.06%, P≤0.02%, S≤0.005%, Al≤0.02%, Sn≤0.008%, Ti≤0.01%, all the other are Fe.
2. pure iron as raw material according to claim 1 is characterized in that: its product is continuous casting square billet or bar.
3. an amorphous is characterized in that with the production method of low manganese, low-sulfur pure iron as raw material:
1) composition of pure iron is by weight percentage: C 0.03-0.07%, and Si 0.10-2.0%, Mn 0.03-0.06%, P≤0.02%, S≤0.005%, Al≤0.02%, Sn≤0.008%, Ti≤0.01%, all the other are Fe;
2) production method comprises following antivacuum smelting step: hot metal pretreatment-bessemerize-LF refining-continuous casting becomes base.
4. production method according to claim 4 is characterized in that: described bessemerizing taked repeatedly deslagging in the step.
5. production method according to claim 4 is characterized in that: S, P are reduced in the described hot metal pretreatment step control molten iron: S≤0.02%, P≤0.04%.
6. production method according to claim 6 is characterized in that: the first time or preceding twice deslagging of bessemerizing in the process are carried out under 1420 ℃ of-1560 ℃ of temperature condition.
7. production method according to claim 4 is characterized in that: the described step control quantity of slag＜6 kilogram/ton steel down of bessemerizing.
8. production method according to claim 4 is characterized in that: bessemerize tapping process and adopt Al or Al to add low-carbon (LC) FeSi to carry out pre-deoxidation; The refining final deoxygenation adopts CaSi or CaSi to add low-carbon (LC) FeSi, in case Mn in anti-avulsion oxygen and the refining procedure molten steel and C content increase.
9. production technique according to claim 4 is characterized in that: adopt the LF refining furnace to carry out dark desulfurization, make S in the molten steel≤0.005%.
10. an amorphous is characterized in that: the melting raw material that is used for non-crystaline amorphous metal with the purposes of hanging down manganese, low-sulfur pure iron as raw material.
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| CN104264053B (en) * | 2014-08-29 | 2016-06-15 | 武汉钢铁(集团)公司 | The neodymium iron boron production method of pure iron as raw material bar |
| CN105986053A (en) * | 2015-02-13 | 2016-10-05 | 鞍钢股份有限公司 | Method for producing industrial pure iron |
| CN106811567B (en) * | 2015-12-02 | 2018-08-03 | 鞍钢股份有限公司 | Method for producing low manganese steel |
| CN106367553B (en) * | 2016-09-05 | 2019-02-15 | 攀钢集团攀枝花钢铁研究院有限公司 | Titanium slag furnace by-product smelting low carbon ingot iron and its method |
| CN108559905A (en) * | 2018-03-09 | 2018-09-21 | 邢台钢铁有限责任公司 | High amorphized silicon pure iron as raw material and its production method |
| CN109290537B (en) * | 2018-10-17 | 2021-02-09 | 安阳钢铁股份有限公司 | Production method of pure iron billet serving as raw material |
| CN109797266A (en) * | 2019-01-14 | 2019-05-24 | 包头钢铁（集团）有限责任公司 | A kind of production method producing ingot iron using the high ferrous manganese ore of high phosphorus as raw material |
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