CN102417950A - Seamless calcium line and preparation method thereof - Google Patents
Seamless calcium line and preparation method thereof Download PDFInfo
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- CN102417950A CN102417950A CN2011103838939A CN201110383893A CN102417950A CN 102417950 A CN102417950 A CN 102417950A CN 2011103838939 A CN2011103838939 A CN 2011103838939A CN 201110383893 A CN201110383893 A CN 201110383893A CN 102417950 A CN102417950 A CN 102417950A
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Abstract
The invention relates to a seamless calcium line and a preparation method thereof. The seamless calcium line which is a line body formed by wrapping a solid calcium core with a shell is characterized in that: the shell is a seamless steel shell, and the weight ratio of the solid calcium core to the seamless shell in the line body of each unit length is 1:2.3-5.7. The seamless calcium line of the invention has the following advantages: the rigidity of the calcium line is high, so the line can be fed to deep parts of a steel ladle, splashing can be alleviated or avoided, calcium can be uniformly distributed in the steel ladle, the calcium line usage efficiency is greatly improved, the calcium recovery rate is improved 2-5 times, and the inclusion removal effect is good; and the feeding amount of a core wrapping line is reduced, the calcium processing time is saved, the temperature loss in the molten steel calcium processing process is reduced, and the molten steel nitrogen and oxygen increasing case in the molten steel processing process are effectively improved. The seamless calcium line produced with the technology of the invention has the advantages of high efficiency, low cost, and easy enforcement and popularization.
Description
Technical field
The present invention relates to the liquid steel refining technical field, be specifically related to a kind of seamless calcium line and preparation method thereof.
Background technology
Wire-feeding technique is the new liquid steel refining technology that after the technology of dusting, grows up.Exactly with steel liquid deoxidation, desulfurization, carburetting, be mingled with sex change, the required material of trimming and process thread (solid wire or fill the bag core suede of relevant pulvis), use the mechanical forces of feeding wire machine it passed through a kind of new-type secondary refining techniques that the molten steel face reaches the molten steel deep with certain speed.With other secondary refining technology compared with techniques of particularly dusting; Have that alloy receives that De Fenggao, accurate composition control, equipment are simple, less investment, process safety are reliable, the molten steel cooling less, do not have an advantage such as environmental pollution; Thereby since the mid-1970s exploitation, obtained application more and more widely abroad.Existing steel-making and casting use cored-wire to be mostly powder core normal packet heart yearn.
The general belt steel thickness of existing cored-wire is 0.4～0.6mm, and the fastening uncinus is 4 times of belt steel thickness.And need higher wire-feeding velocity just can make the optimum depth of line feeding ladle, and speed should be controlled at 160～300m/min, can not feed ladle bottom and splash easily because of its band steel is thin, and band steel cracking phenomena is arranged, and calcium can not be evenly distributed in ladle.Traditional Ca-Si cored-wire, Ca-Al cored-wire receive production technique to influence the yield instability of Ca, are unfavorable for the control to steel quality.
The pure calcium core-spun yarn of seamless real core has the seam product relatively, and production technique is complicated, and the domestic enterprise that can produce is less, and majority still is in development.And utilize the existing processes technology to be difficult to bear larger-diameter solid calcium line, and thinner solid calcium line needs very high wire-feeding velocity, causes its off-position in ladle wayward.Current, smelter presses for the pure calcium core-spun yarn of larger-diameter seamless real core and improves the quality of liquid steel refining, and reduces production costs accordingly.
Summary of the invention
The technical problem that the present invention will solve provides a kind ofly can slow down the molten steel splash, improve the calcium recovery, go to be mingled with effective seamless calcium line, and discloses a kind of method for preparing larger-diameter seamless solid calcium line.
For solving the problems of the technologies described above, the technical scheme that the present invention adopts is:
A kind of seamless calcium line is the line body that is formed by shell parcel solid calcium sandwich layer at least, and said shell is seamless box hat, and the weight ratio of solid calcium sandwich layer and seamless box hat is 1:2.3～5.7 in this line body in the unit length.
Said line body diameter 9～12mm, solid calcium sandwich layer 50～70g/m, seamless box hat weighs 230～350g/m.
Said seamless box hat is processed through hight frequency welding by the low-carbon steel band.
Said solid calcium sandwich layer outside surface is coated with passivation film.
The preparation method of above-mentioned seamless calcium line may further comprise the steps:
(1) with calcium metal in vacuum oven after the heating and melting, vacuum pouring becomes calcium pump, again calcium pump is heated to 365～380 ℃ after, push or/and be drawn into the calcium heart yearn of certain diameter;
(2) getting mild-carbon steel strip coats above-mentioned calcium heart yearn palintrope volume and is shaped to pipe;
(3) closely weld together with the faying flange of hight frequency welding method above-mentioned pipe; And air-cooled or contactless water-cooled is carried out in the joint portion after butt welding connects immediately; Used high frequency frequency is 300～450KHz during hight frequency welding, 3 °～5 ° of V-type angular apertures, and welding temperature is at 1380～1500 ℃; Welding pressure 19.6～29.4 Mpa, welding speed 15～20m/min; Above-mentioned ratio-frequency welding has outstanding advantage: 1) weldering speed is high, and this is that the welding zone rate of heating is exceedingly fast, and can not produce " skip welding " owing to the electric energy high concentration; 2) heat affected zone is little, and this is that the workpiece autorefrigeration is strong, so the heat affected zone is narrow and difficult generation oxidation, thereby can obtain the weld seam of favorable tissue and performance, can not produce burning and not weld penetration phenomenon because weldering speed is high; 3) preweld cleaning can be carried out in surface, place to be welded.
(4) burr at excision solder bond position, again after shaping, stretch processing seamless calcium line.
In said step (3), hight frequency welding is carried out under atmosphere of inert gases.
In said step (1), the calcium heart yearn outside surface of moulding is carried out Passivation Treatment:
Calcium heart yearn outside surface in moulding evenly applies one deck passivator at least; And after leaving standstill 5～15min; Behind 110～120 ℃ of down dry 0.5～1h, promptly form passivation film, said passivator is pressed by Hydrocerol A, oxalic acid, water: the weight ratio of 4～8:1～2:20 is formed.
Can carry out passivation through following method: apply evenly at least at the calcium heart yearn outside surface of moulding that the doping of one deck silicone oil boils the additive that forms, this passivator is not introduced impurity constituents such as metallic element yet, and raw materials cost is cheap is easy to get.
Can delay the gasification rate of calcium metal after the surface passivation of calcium heart yearn, phenomenon is seethed on the slag surface when significantly reducing line feeding, improves the recovery of calcium greatly.
The present invention has actively useful effect:
1. the band steel is thick, rigidity is high, can feed more deep branch of ladle, slows down or avoids splash; And make calcium can be evenly distributed in ladle, and increasing substantially the service efficiency of calcium line, the recovery of calcium can improve 2～5 times; And it is better to go to be mingled with effect, and the yield rate of steel is increased to more than 99% by 96%.
2. can reduce the feed quantity of cored-wire, practice thrift the calcium treatment time, reduce the temperature loss in the molten steel calcium treating processes, and effectively improved molten steel nitrogen pick-up, oxygenation situation in the molten steel treating processes.
3. utilize the efficient of the seamless calcium line of explained hereafter of the present invention high, cost is low, and is easy to implement to promote; Significantly improve iron and steel output and quality after promoting the use of, reduce steel-making cost, by 10 yuans per ton; Then the whole nation is produced 10 yuan=5,000,000,000 yuan of 500,000,000 tons of *, obvious social benefit per year.
Description of drawings
Fig. 1 is the middle bag yield comparison diagram of various cored-wires.
Embodiment
Used raw material etc. if no special instructions, is commercially available among the following embodiment; Method therefor is ordinary method if no special instructions.
1 one kinds of seamless calcium lines of embodiment; Be the line body (diameter 10mm) that forms by shell parcel solid calcium sandwich layer; Its shell is to process seamless box hat by the low-carbon steel band through hight frequency welding, and the weight ratio of solid calcium sandwich layer and seamless box hat is 1:3.5 in this line body in the unit length, solid calcium sandwich layer 60g/m; And solid calcium sandwich layer outside surface is coated with passivation film, the heavy 300g/m of seamless box hat.
The preparation method of above-mentioned seamless calcium line may further comprise the steps:
(1) with calcium metal (Ca content >=98%) in vacuum oven after the heating and melting; Vacuum pouring becomes calcium pump; After again calcium pump being heated to 365～380 ℃, push or/and be drawn into the calcium heart yearn of certain diameter, evenly apply one deck passivator (pressed by Hydrocerol A, oxalic acid, water: the weight ratio of 6:1:20 is formed) at the calcium heart yearn outside surface of moulding; And after leaving standstill 15min, promptly form passivation film behind the dry 1h of baking down in 115 ℃;
(2) getting mild-carbon steel strip coats above-mentioned calcium heart yearn and is shaped to cylindric pipe after shaper twists;
(3) make the above-mentioned induction coil that is enclosed with the pipe of calcium heart yearn through high-frequency welding equipment; Near the induction coil magnetic field produces inductive current through steel band edge, and steel band edge is owing to the resistance heat that self-resistance produces is heated, and the steel band edge of heating forms weld seam through the extrusion roll extruding; And the joint portion after butt welding connects is immediately carried out air-cooled fast; Used high frequency frequency is 350KHz during hight frequency welding, and the V-type angular aperture is 3 °, and welding temperature is at 1400 ℃; Welding pressure 25.5Mpa, welding speed 18m/min;
(4) burr at excision solder bond position, again after shaping, stretch processing seamless calcium line.
2 one kinds of seamless calcium lines of embodiment; Be the line body (diameter 9mm) that forms by shell parcel solid calcium sandwich layer; Its shell is to process seamless box hat by the low-carbon steel band through hight frequency welding, and the weight ratio of solid calcium sandwich layer and seamless box hat is 1:4.0 in this line body in the unit length, solid calcium sandwich layer 55g/m; And solid calcium sandwich layer outside surface is coated with passivation film, the heavy 310g/m of seamless box hat.Its preparation method is basically with embodiment 1.
The seamless calcium line application test of embodiment 3 certain steel mill
Cold rolling base-material with production flow line steel 1.245mb is a research object; Employing hello calcium content is 28% Ca-Si cored-wire, Ca-Al respectively; Cored-wire and embodiment 1 said seamless calcium line carry out molten steel calcium to be handled, and the data comparison is carried out in the variation of the processing parameter of processes such as the composition check after each is handled, cast situation, metallurgical analysis, analyzes the yield of Ca in the molten steel under respectively handling; And the variation of control steel inclusion type, quantity, improve the effect of aspect such as molten steel flow property.
1. the physicals of alloy wire
Table 1 Ca-Si line technology index
Table 2 Ca-Al line technology index
The technical indicator of used seamless calcium line is seen embodiment 1.
(2) experimental procedure
1. the high calcium line feed quantity of Theoretical Calculation
Through the content of calcium metal in the known high calcium line, get under the state through Theoretical Calculation in the stabilized steel water yield and in steel, to feed 120 seamless calcium lines, can guarantee in the steel calcium contents at 30～35PPm, and reach the requirement of Ca/Als=0.12 in the steel.The Theoretical Calculation foundation:
Alloy amount=molten steel amount * actual value/(alloying element content * yield)
Utilize the appointed condition of LF refining furnace double at the scene in the actual production; Dispose high calcium core-spun yarn at 1# line feeding station respectively; 2# line feeding station configuration Ca-Si line, Ca-Al line, each station experimentizes, and whole process is carried out data tracking; Through the physical and chemical inspection feedback, can obtain actual molten steel calcium content and cast situation and metallurgical effect.
2. experiment condition
Molten steel amount: 80T ± 3; Calcium silk feeding time: the phase that restores after white slag forms carries out calcium and handles; ALs:0.015 in the steel～0.040%; Feeding wire speed: 2.5～3.0m/s (adjusting at any time) according to on-the-spot cored-wire thawing situation and molten steel splash effect; Wire feeder: the feeding wire machine conduit is adjusted into 1.5m from liquid steel level; The molten steel soft blow time: more than the assurance >=8min; Sample time: feed silk back 3min.
(3) experiment effect analysis
1. on-site operational data
Table 3 silicon-calcium wire, aluminium calcium line simultaneous test process data
Calcium line experimentation data that table 4 is seamless
2. calcium yield comparison: through spectrum physico-chemical analysis data; Can draw after used seamless calcium line feed quantity is adjusted; (being adjusted into 100mm by 1400mm) still satisfied the requirement of molten steel calcium treatment process, and the yield height of calcium is respectively in the steel: average 41.3%, the 2nd average 38.8% (the reaching as high as 53.4%) of test of the 1st test, the 3rd test average 34.8%; Do contrast experiment's the average yield 8.6%, 6.9% of the average yield 15.3%:Ca-Al line of Ca-Si line,, satisfy technical requirements up to 3～5 times.
3. pour into a mould situation: owing to prevent that sulphur content is too high in the steel, calcium is handled the back and is produced the easy blocking mouth of a river in a large amount of CaS casting process, and the molten steel sulphur content that test is this time produced all is controlled at below 0.005%; Reached processing requirement, through continuous casting feedback information in casting process, big Baogang flows smooth and easy under water; Mold liquid level is stable, and water-coating port is observed from change, and the inner no abnormal thing of smooth surface gathers; Can judge the treatment stage of LF refining furnace calcium the Al of deoxidation products bunch shape in the steel
20
3Fully combine in CaO, formed liquid calcium-aluminate, just 12CaO-7Al
2O
3Fusing point is 1415 ℃, passes through not blockage phenomenon of the mouth of a river smoothly.
(4) calcium is handled metallurgical effect
Carrying out in the steel that calcium handles mainly is the defective that overcomes aluminium deoxidation, changes the shape of steel inclusion, and (changing into spherical by a bunch shape, strip) inclusion changes the calcium-aluminate that contains Ca, (12Ca.7AL into
20
3) its inside is Ca-AL
20
3. the outside is CaS-Mn-AL mutually
20
3. along with the content of calcium in the steel increases, manganese sulfide almost disappears, and it is liquid under the steel-making temperature that its fusing point is 1450 ℃, and makes its come-up through stirring a little less than the oxygen blast, thereby reduces harmful element in the steel, makes the molten steel purity higher, and the inside and outside quality reaches specification of quality.
Through can judge the metallurgical effect of this test example 1 said seamless calcium line to 10 stove steel metallurgical analysis, the metallographic result specifically sees table 5.
Table 5 metallographic result
From the metallographic result comparison of two kinds of cored-wires, can find out the metallurgical effect after high calcium core-spun yarn is handled molten steel, be superior to the Ca-Si line.
(5) above-mentioned test shows:
1. traditional Ca-Si cored-wire, Ca-Al cored-wire receive production technique to influence the yield instability of Ca, and (the Ca-Si cored-wire fluctuates between 10.5%～21.2%, and the Ca-Al cored-wire fluctuates between 5.4%～10.7%) is unfavorable for the control to steel quality; 2. the seamless calcium line yield of the present invention is high, and fluctuation range is less, and yield is relatively stable; 3. from the inclusion level although, carry out calcium with the seamless calcium line of the present invention and handle, the inclusion rank is lower, and with the processing of traditional C a-Si line, the inclusion rank is apparently higher than seamless calcium line; 4. because the yield of seamless calcium line [Ca] is high, can reduces the feed quantity of cored-wire, thereby practice thrift the calcium treatment time; Reduced the temperature loss in the molten steel calcium treating processes; And effectively improved the molten steel nitrogen pick-up in the molten steel treating processes, oxygenation.
The seamless calcium line (embodiment 2) that embodiment 4 certain steel mill supplied the prosperous calcium industry of the crowd of Gongyi City ltd during March 16～31 days March in 2011 in 2011 has carried out enlarging on probation, and 11.06 tons altogether, it is qualified that composition is chemically examined in inspection, and the result is following:
Table 6 is seamless, and the calcium line composition constitutes
| Chemical ingredients | Ca | Al | Mg |
| Standard-required (%) | ≥98.0 | ≤0.8 | ≤1.0 |
| Assay (%) | 98.9 | 0.4 | 0.5 |
This is seamless calcium line enlarges and on probationly is arranged in the RH stove and carries out, and main steel grade is Q460C-1, E36N, S355J-2, Q370R-2 etc.Concrete trial state is seen table 1.The yield that among Fig. 1 is embodiment 2 said seamless calcium lines and calcium iron wire etc. compares.From Fig. 1, can find out, use seamless calcium line, the average calcium yield of middle bag is 31.61%, improves 25.57% than the calcium iron wire.The economic comparison of seamless calcium line and calcium iron wire (bag calcium contents same case in changing into) is seen table 8, uses seamless calcium line, and 11.3 yuan of ton wire costs reduce 0.2 yuan than the calcium iron wire.But obtaining that same yield is counted as by 6.04% originally is 1/5 of calcium iron wire.
The concrete applicable cases of the seamless calcium line of table 7
The economic comparison of seamless calcium line of table 8 and calcium iron wire
| The line kind | Line feeding length (m) | Molten steel amount (t) | Linear density (g/m) | Middle bag calcium contents (%) | Middle bag calcium yield (%) | Ton wire consumption (kg) | The same period silk thread price (unit/t) | Silk thread cost (unit/t steel) | Obtain the contrast of same yield (6.04%) cost |
| The calcium iron wire | 470.40 | 155.68 | 425.0 | 0.0017 | 6.04 | 1.28 | 8800.0 | 11.3 | 1 |
| Seamless calcium line | 150.00 | 153.01 | 380.0 | 0.0017 | 31.61 | 0.37 | 30000.0 | 11.1 | 1/5 |
In sum, the average calcium yield of bag is 31.61% in the above-mentioned seamless calcium line, and is high by 25.57% than the calcium iron wire; Use embodiment 2 said seamless calcium lines, 11.1 yuan of ton wire costs reduce 0.2 yuan than the calcium iron wire.But obtaining that same yield is counted as by 6.04% originally is 1/5 of calcium iron wire.
Change each the concrete numerical parameter in the foregoing description, or material composition be equal to replacement, can form a plurality of concrete embodiment, be common variation range of the present invention, detail no longer one by one at this.
Claims (7)
1. a seamless calcium line is the line body that is formed by shell parcel solid calcium sandwich layer at least, it is characterized in that said shell is seamless box hat, and the weight ratio of solid calcium sandwich layer and seamless box hat is 1:2.3～5.7 in this line body in the unit length.
2. seamless calcium line according to claim 1 is characterized in that, said line body diameter 9～12mm, and solid calcium sandwich layer 50～70g/m, seamless box hat weighs 230～350g/m.
3. seamless calcium line according to claim 1 is characterized in that, said seamless box hat is processed through hight frequency welding by the low-carbon steel band.
4. seamless calcium line according to claim 1 is characterized in that, said solid calcium sandwich layer outside surface is coated with passivation film.
5. the preparation method of the said seamless calcium line of claim 1 may further comprise the steps:
(1) with calcium metal in vacuum oven after the heating and melting, vacuum pouring becomes calcium pump, again calcium pump is heated to 365～380 ℃ after, push or/and be drawn into the calcium heart yearn of certain diameter;
(2) getting mild-carbon steel strip coats above-mentioned calcium heart yearn palintrope volume and is shaped to pipe;
(3) closely weld together with the faying flange of hight frequency welding method above-mentioned pipe; And air-cooled or contactless water-cooled is carried out in the joint portion after butt welding connects immediately; Used high frequency frequency is 300～450KHz during hight frequency welding, 3 °～5 ° of V-type angular apertures, and welding temperature is at 1380～1500 ℃; Welding pressure 19.6～29.4 Mpa, welding speed 15～20m/min;
(4) burr at excision solder bond position, again after shaping, stretch processing seamless calcium line.
6. according to the preparation method of the said seamless calcium line of claim 5, it is characterized in that in said step (3), hight frequency welding is carried out under atmosphere of inert gases.
7. according to the preparation method of the said seamless calcium line of claim 5, it is characterized in that, in said step (1), the calcium heart yearn outside surface of moulding carried out Passivation Treatment:
Calcium heart yearn outside surface in moulding evenly applies one deck passivator at least; And after leaving standstill 5～15min; Behind 110～120 ℃ of down dry 0.5～1h, promptly form passivation film, said passivator is pressed by Hydrocerol A, oxalic acid, water: the weight ratio of 4～8:1～2:20 is formed.
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| CN102653808A (en) * | 2012-05-07 | 2012-09-05 | 上海盛宝冶金科技有限公司 | Seamless aluminum-containing core-spun yarn |
| CN102676739A (en) * | 2012-05-07 | 2012-09-19 | 上海盛宝冶金科技有限公司 | Seamless aluminum-containing core spun yarn |
| CN102719609A (en) * | 2012-06-26 | 2012-10-10 | 巩义市众鑫钙业有限公司 | Seamless aluminum calcium iron wire and preparation method thereof |
| CN102748578A (en) * | 2012-07-09 | 2012-10-24 | 巩义市众鑫钙业有限公司 | Seamless ferroaluminum wire and preparation method thereof |
| CN103234771A (en) * | 2013-03-19 | 2013-08-07 | 内蒙古包钢钢联股份有限公司 | Sampling, sample preparation and determination method of high calcium wire |
| CN103525976A (en) * | 2012-07-01 | 2014-01-22 | 秦皇岛北方管业有限公司 | Solid metal cored wire and preparation method thereof |
| WO2015192348A1 (en) * | 2014-06-19 | 2015-12-23 | 巩义市众鑫钙业有限公司 | Welded calcium core wire and application method thereof in molten steel refining |
| CN105695662A (en) * | 2015-03-27 | 2016-06-22 | 马鞍山市兴达冶金新材料有限公司 | Production method of passivated pure calcium core-spun yarn |
| CN108588328A (en) * | 2018-04-20 | 2018-09-28 | 无锡市伟达包芯线厂 | A kind of alloying pellet welding core-spun yarn production technology |
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| CN102653808A (en) * | 2012-05-07 | 2012-09-05 | 上海盛宝冶金科技有限公司 | Seamless aluminum-containing core-spun yarn |
| CN102719609A (en) * | 2012-06-26 | 2012-10-10 | 巩义市众鑫钙业有限公司 | Seamless aluminum calcium iron wire and preparation method thereof |
| CN102719609B (en) * | 2012-06-26 | 2014-06-25 | 巩义市众鑫钙业有限公司 | Seamless aluminum calcium iron wire and preparation method thereof |
| CN103525976A (en) * | 2012-07-01 | 2014-01-22 | 秦皇岛北方管业有限公司 | Solid metal cored wire and preparation method thereof |
| CN102748578B (en) * | 2012-07-09 | 2016-02-24 | 巩义市众鑫钙业有限公司 | Seamless ferroaluminum wire and preparation method thereof |
| CN102748578A (en) * | 2012-07-09 | 2012-10-24 | 巩义市众鑫钙业有限公司 | Seamless ferroaluminum wire and preparation method thereof |
| CN103234771A (en) * | 2013-03-19 | 2013-08-07 | 内蒙古包钢钢联股份有限公司 | Sampling, sample preparation and determination method of high calcium wire |
| WO2015192348A1 (en) * | 2014-06-19 | 2015-12-23 | 巩义市众鑫钙业有限公司 | Welded calcium core wire and application method thereof in molten steel refining |
| CN106170566A (en) * | 2014-06-19 | 2016-11-30 | 巩义市众鑫钙业有限公司 | Welding calcium core-spun yarn and the application process in liquid steel refining thereof |
| CN106170566B (en) * | 2014-06-19 | 2019-03-19 | 巩义市众鑫钙业有限公司 | Weld calcium core-spun yarn and its application method in liquid steel refining |
| CN105695662A (en) * | 2015-03-27 | 2016-06-22 | 马鞍山市兴达冶金新材料有限公司 | Production method of passivated pure calcium core-spun yarn |
| CN105695662B (en) * | 2015-03-27 | 2017-06-30 | 马鞍山市兴达冶金新材料有限公司 | A kind of production method for being passivated pure calcium core-spun yarn |
| CN108588328A (en) * | 2018-04-20 | 2018-09-28 | 无锡市伟达包芯线厂 | A kind of alloying pellet welding core-spun yarn production technology |
| CN108588328B (en) * | 2018-04-20 | 2019-12-24 | 无锡市伟达新材料科技有限公司 | Alloy particle welding cored wire production process |
| CN108823345A (en) * | 2018-06-29 | 2018-11-16 | 山东国益新材料有限公司 | One kind being used for the pretreated magnesium iron core-spun yarn of molten iron and production method |
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