CN1157486C - SYnthetic slag for reducing oxygen and sulfur content in molten steel and its slag making method - Google Patents
SYnthetic slag for reducing oxygen and sulfur content in molten steel and its slag making method Download PDFInfo
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- CN1157486C CN1157486C CNB021000840A CN02100084A CN1157486C CN 1157486 C CN1157486 C CN 1157486C CN B021000840 A CNB021000840 A CN B021000840A CN 02100084 A CN02100084 A CN 02100084A CN 1157486 C CN1157486 C CN 1157486C
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Abstract
The present invention relates to synthetic slag for reducing the contents of oxygen and sulfur in molten steel and a making method thereof, which belongs to the field of steel making production in metallurgical industry. The synthetic slag comprises the chemical components, in the proportion by weight, 2 to 15% of aluminum, 3 to 15% of cerium, 5 to 8% of magnesium, 2 to 10% of barium, 20 to 50% of calcium oxide, 10 to 48% of aluminum oxide, 2 to 10% of magnesia, 2 to 10% of sodium silicate and 2 to 8% of cellulose. The making method of the synthetic slag comprises the following steps: limestone, calcium fluoride or other high alkalinity materials are melted with flux into slag, and the slag is subsequently discharged and cooled to normal temperature. The present invention is characterized in that the slag, aluminum metallurgical slag and oxidized calcareous raw materials are all crushed into powder whose granularity is smaller than 0.5mm, the powder is subsequently mixed according to the proportion of 2 to 4: 2 to 6: 1 to 3, and the sodium silicate and the cellulose are simultaneously added; spherical synthetic slag whose diameter is from 10mm to 20mm is made after the powder is uniformly mixed, and the synthetic slag is dried at low temperature. Compared with the prior art, the slag has the characteristic of good use effect.
Description
Technical field
The invention belongs to the STEELMAKING PRODUCTION field in the ferrous metallurgy.Be applicable to that more preparation reduces the synthetic slag and the manufacture method thereof of oxygen, sulphur content in the steel.
Background technology
In the prior art, one of main task of STEELMAKING PRODUCTION is to remove phosphorus in the molten steel, sulphur, nitrogen, hydrogen, five kinds of impurity elements of oxygen.For example phosphorus can be removed in the process of hot metal pretreatment and steel-making, and gaseous impuritieies such as nitrogen, hydrogen can be controlled in the stove final vacuum is handled.And the sulphur in the molten steel must all must be removed in each link of STEELMAKING PRODUCTION such as hot metal pretreatment, steel-making decarburization and furnace rear refining.The steel water oxygen is then controlled in decarburization and stove aftertreatment.
Sulphur in the molten steel mainly is in iron manufacturing process, is brought in the metal by coke.Though all sulphur is removed in each link of smelting, the sulphur of final residual in molten steel will be stayed in the steel with the form of sulfide.Because the fusing point of sulfide is lower than steel, in the cast and the operation of rolling, easily cause the steel billet cracking, make difficult processing carrying out, sulfide also can make the atmospheric corrosion resistance of steel reduce in addition.Residual oxygen in molten steel, major part is brought into when oxidation is made steel, and reduce oxygen content in steel as much as possible has big difficulty.One of steel-making by combined-blown converter technology major function can reduce the oxygen level in the molten steel exactly.If the terminal point too high oxygen level in molten steel then will consume a large amount of iron alloys when deoxidation, also can form a large amount of deoxidation productss simultaneously.Enter in the slag if these deoxidation productss can not fully float, then finally have the partial oxidation thing and be mingled with and be left in the steel.In the reprocessing process of steel, these oxide inclusion can not be out of shape with the distortion of steel, and can form cavity and perishable source in steel, the work-ing life of having reduced steel.For example at the automobile industry steel, required at present oxygen content in steel should less than below the 10PPm, sulphur content is controlled at the standard of 10-20PPm scope, its reason is in order to prevent that erosion resistance and anti-punching performance that steel are in use produced from reducing phenomenon.In common process for making, some lime are thrown in employing in ladle in tapping process, purpose is to improve the basicity of slag and the ferric oxide in the dilution slag, simultaneously after finishing the molten steel alloying, throws in the final deoxygenation that molten steel is carried out in active metal such as a spot of aluminium to molten steel.The shortcoming of this method is that the lime that is added in the ladle is difficult to quick fusing, and sweetening effectiveness is very poor, and end-deoxidizers such as the aluminium that adds in molten steel have suitable part to remain in the molten steel, has formed oxide inclusion and the quality that has reduced steel.
At the problems referred to above, development in recent years the agent of synthetic slag liquid steel refining, its principle of work is to adopt the raw material have certain basicity and to contain multiple oxide compound, make have desulfurization, the synthetic slag refining agent of deoxygenation function net effect.This class synthetic slag refining agent is more effective than the sulphur and the oxygen that merely add in active metals such as lime and the aluminium control steel, and is greatly improved on efficient, and the product of deoxidation in the adsorbable molten steel, improves the knot cleanliness in the molten steel.This synthetic slag refining agent can be divided into three types of granulated slags, clinker, pre-melted slag.The principal feature of these three types of synthetic slag refining agents is respectively: (1) granulated slag, satisfactory raw material natural or that part is natural pulverized, sieves after, its abundant mixing is formed.The advantage of granulated slag is that production cost is lower, and energy consumption is less.Shortcoming is that dust is bigger in use, and burn-off rate is slow, granulated slag efflorescence of making moist easily in keeping and transportation, and burn-off rate is slow, and metallurgical effect is also undesirable.(2) clinker, satisfactory raw material natural or that part is natural pulverized, sieves after, behind its thorough mixing, carry out high temperature sintering, its sintering temperature is greater than 800 ℃.This sintering process makes and has begun fusing between the particle of this synthetic slag refining agent and formed integral body.The characteristics of this clinker are moisture-sensitive not, and dust is less in the use, and burn-off rate is also higher.But the production cost of this slag and energy consumption height are all higher.(3) production technique of pre-melted slag, pre-melted slag is that various starting material are melted in the smelting furnace of electrically heated or coke heating fully, treat that slag solidifies again after, again it is carried out fragmentation and is processed into finished product slag with certain granules degree.The characteristics of this pre-melted slag be not moisture-sensitive, be convenient to transportation, when using fusing fast and dust is few.But the production cost of this kind pre-melted slag is the highest and energy consumption is also very big.
Goal of the invention and content
The objective of the invention is to propose that a kind of burn-off rate is fast, result of use good and production cost and energy consumption is low, dust is few, be easy to keeping and transportation, and can reduce the synthetic slag and the slagging method thereof of oxygen in the molten steel, sulphur content.
According to purpose of the present invention, the synthetic slag of oxygen, sulphur content in the reduced molten steel that we proposed, mainly be utilize out steel reinforced concrete towards the time good dynamic conditions, fully react the easily reaction product of come-up that forms by elements such as sulphur, oxygen in synthetic slag and the steel.Slag system behind the synthetic slag upgrading also easily adsorbs the reaction product of come-up simultaneously, thereby it is got rid of from molten steel.The effect of the principle of work of employing synthetic slag of the present invention and deoxidation, desulfurization is mainly reflected in the oxidisability that reduces in molten steel and the ladle slag.For example the aluminium in this synthetic slag is the active metal, through being mixed with after the processing can with in the slag charge other become the phase-splitting solid solution, therefore avoid traditional aluminium block deoxidation to cause the shortcoming of major part a large amount of scaling loss on the molten steel face because of proportion is little, improved the metallic aluminium utilization ratio again effectively; On the other hand owing to the deoxidation products of solid solution metallic aluminium and activated processing, polynary low-melting other material polymerization, grow up to float and discharge the molten steel face, can avoid the aluminium block deoxidation easily to form single Al
2O
3Disperse is mingled with.For part in time the aluminium of reaction with the synthetic slag come-up after, can with tapping process in enter the hyperoxia voltinism converter terminal slag-metal reaction of ladle.This reaction can reduce the content of oxygen in the slag, improves the utilization ratio of deoxygenated alloy.Avoided of the secondary pollution of hyperoxia voltinism slag to molten steel is caused.The desulfurization principle of this synthetic slag can be found out according to the desulfurization chemical reaction formula:
, in ladle, behind the adding synthetic slag, increased (CaO) in the slag, reduced (FeO) content in the slag, promote steel, slag reaction forward to carry out.While is because of the Al of a large amount of activated processing in the synthetic slag
2O
3Form low-melting aluminum calcium salt with CaO, as 3CaOAl
2O
3And 12CaO7Al
2O
3, and can be rapidly combine with the slag brought in the tapping process, form the lower polynary slag system of fusing point.The new polynary slag system based on the calcium aluminate reducing slag that forms, fusing point is lower than the silicate slag system, and is better mobile, improved (S
2-) mass transfer velocity in slag, as (S
2-) at 12CaO7Al
2O
3Middle velocity of diffusion is at 2CaOSiO
2In 4 times.The CaS that is generated in the reaction formula can be moistening with calcium aluminate slag well, thereby be adsorbed and get rid of molten steel, reaches the purpose of desulfurization, clean molten steel.
According to above-mentioned principle, the composition that can reduce oxygen in the molten steel, sulphur content synthetic slag that we proposed is characterized in that the concrete chemical composition range of this synthetic slag is respectively (weight %): aluminium 2-15%; Cerium 3-15%; Magnesium 5-8%; Barium 2-10%; Calcium oxide 20-50%; Aluminum oxide 10-48%; Magnesium oxide 2-10%; Water glass 2-10%; Mierocrystalline cellulose 2-8%.
In the synthetic slag composition that can reduce oxygen in the molten steel, sulphur content proposed by the invention, the function of each chemical composition is mingled with agent, binding agent and peptizer by reductor, sweetening agent, absorption respectively and forms after mixing, wherein reductor includes elements such as aluminium, cerium, magnesium, barium, sweetening agent is a calcium oxide, the absorption inclusion aluminum oxide and calcium oxide etc. are arranged, binding agent is a water glass, and peptizer is a Mierocrystalline cellulose.
It is transformation to prior art that the one-tenth of synthetic slag of the present invention is grouped into, and for example in existing high alkalinity element, can come out the iron oxide reduction in the slag in these active metals, full iron in the slag is reduced and has very strong deoxidizing capacity.Simultaneously also because reaction is the diffusive deoxidation of carrying out in slag, institute forms inclusion so that deoxidation products can not remain in the steel.In synthetic slag of the present invention, be to adopt the nonferrous metallurgy slag as one of main raw material, because in coloured industry, there is a large amount of slags to go out of use, and in these slags, contain a large amount of aluminium, active metal such as cerium, magnesium, barium is to can be used as the synthetic slag raw material to be used.
The manufacture method that can reduce oxygen in the molten steel, sulphur content synthetic slag of the present invention is the production technique that adopts fritting-low-temperature sintering batch mixing and make ball, and the manufacturing process flow of this synthetic slag is: [sieving former fritting raw material]+[sieving former reductor powder] → [raw material mixing] → [multigraph press is made ball] → [oven dry of synthetic slag ball] → [packed for standby use].Therefore the manufacture method of synthetic slag of the present invention is with (weight %) Wingdale 30-50%; Lime 20-30%; The high basicity material of fluorite 10% and alumina 20-30% and 0-10% silica, after mixing, be dropped in the coke stove (electric arc furnace) and melt, temperature of fusion is at 1300-1600 ℃, it is stand-by to naturally cool to normal temperature after the slag that fusing is good is emitted by coke oven (electric arc furnace) slag notch, and the concrete preparation method who it is characterized in that this synthetic slag is (1), it is stand-by that slag is broken into the powder of granularity 〉=0.5mm; (2), it is stand-by that the nonferrous metallurgy slag that will smelt aluminium is broken into the powder of granularity 〉=0.5mm; (3), it is stand-by the calcium oxide raw material to be broken into the powder of granularity 〉=0.5mm; (4), with slag powder, nonferrous metallurgy pulverized slag material, the calcareous powder of calcium oxide by [(2-4): (2-6): (1-3)] batching, in batch mixing, should add (weight %) water glass 2-10%; Mierocrystalline cellulose 2-8% treats to make ball after mixed powder evenly, makes ball and can make ball on disc type is chosen shuttles machine, and spherical synthetic slag diameter should be in φ 10-20mm scope; (5), spherical synthetic slag is carried out oven drying at low temperature in rotary kiln, storing temperature is 100-200 ℃.
The synthetic slag that adopts the inventive method to produce, the slag system ingredient after residue adjustment is handled compares (Al in the slag with former slag
2O
3) content increase 15-20%, (FeO) total content reduces 10-15%, (MnO) slightly descend, other composition is constant substantially, by synthetic slag of the present invention to the slag upgrading after, the slag system interfacial tension increases, and helps the effect of steel, slag separation come-up discharge molten steel, has reduced to form the possibility of steel inclusion; Oxide inclusion, especially Al in next molten steel
2O
3It is good to be mingled with the calcium aluminate slag affinity, very easily in being adsorbed gathering, growing up and be easy to come-up and discharge molten steel.Because this slag system oxidisability is lower, can effectively prevent molten steel " secondary oxidation " simultaneously, the disperse oxide that reduces " secondary oxidation " formation is mingled with.
Adopt synthetic slag of the present invention and preparation method thereof compared with prior art, have the advantage of having gathered granulated slag, clinker, pre-melted slag three kinds of synthetic slag refining agents, and reduced the shortcoming of synthetic slag refining agent in the prior art, its contrast effect has:
(1) the inventive method is that the nonferrous metallurgy waste residue is processed into granulated slag as the raw material of forming synthetic slag, so this method promptly can utilization of waste material, and is beneficial to environment protection again.
(2) because the inventive method is to adopt a part of raw material of pre-melted slag as synthetic slag charge, has so not only reduced the fusing point and the production cost of synthetic slag, and also had the result of use of good desulfurization, deoxidation.
(3) in the method for the invention, with thorough mixing is even again behind the material screening, cause the ball of 10-20mm then.In actual use, reduce dust, improved the homogeneity of composition, reduced the temperature and time of heating, reduced energy consumption, but also reduced the moisture absorption in transportation, keeping process.
(4) ball-type synthetic slag of the present invention is carried out quick baking in rotary kiln, improved the intensity and the melting properties of synthetic slag.
Embodiment
The composition of synthetic slag and preparation method according to the present invention; we have made the synthetic slag charge of five kinds of proportioning components altogether; in order to contrast conveniently; we have also exemplified prior art synthetic slag scouring agent simultaneously; can find out that by contrast table synthetic slag of the present invention has good comprehensive to use and economical effectiveness, and be beneficial to environment protection again and also reduced in transportation, the moisture absorption and the efflorescence effect of synthetic slag in the process certainly.Each table is respectively in an embodiment of the present invention: table 1 is the composition comparison sheet of the embodiment of the invention and prior art; Table 2 is the preparation method and the characteristics contrast table of the embodiment of the invention and prior art; Table 3 is the result of use contrast table of the embodiment of the invention and prior art.Sequence number 1-5 is that the embodiment of the invention, sequence number 6-8 are prior art embodiment in each above-mentioned table.
The synthetic slag composition of table 1 embodiment of the invention and prior art is (weight %) relatively
| Project | The major ingredient of embodiment | |||||||
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | Example 8 | |
| Aluminium | 3 | 8 | 15 | 10 | 12 | 8 | 9 | 10 |
| Cerium | 15 | 5 | 3 | 6 | 8 | / | / | / |
| Magnesium | 5 | 6 | 5 | 6 | 8 | / | / | / |
| Barium | 10 | 3 | 2 | 4 | 4 | / | / | / |
| Aluminum oxide | 35 | 15 | 40 | 40 | 35 | 35 | 36 | 37 |
| Calcium oxide | 13 | 47 | 29 | 19 | 19 | 40 | 42 | 44 |
| Magnesium oxide | 10 | 2 | 2 | 5 | 5 | 2 | / | 2 |
Table 2 is the preparation method and the characteristics contrast of the embodiment of the invention and prior art
| The technology sequence number | Smelting temperature (℃) | Slag powder degree A, granularity (mm) | Nonferrous metallurgy slag B, granularity (mm) | Calcium oxide C, granularity (mm) | Mix powder ratio A: B: C | Water glass (weight %) | Mierocrystalline cellulose (weight %) | Make spherical diameter (mm) | Storing temperature (℃) |
| 1, synthetic slag of the present invention | 1450 | 0.4 | 0.4 | 0.3 | 3∶5∶2∶ | 7.5 | 5 | 14 | 110 |
| 2, synthetic slag of the present invention | 1520 | 0.5 | 0.4 | 0.4 | 4∶2∶2 | 4 | 5 | 19 | 140 |
| 3, synthetic slag of the present invention | 1395 | 0.25 | 0.3 | 0.3 | 2∶3∶1 | 9 | 7 | 12 | 110 |
| 4, synthetic slag of the present invention | 1490 | 0.15 | 0.2 | 0.5 | 4∶4∶2 | 8 | 4 | 14 | 115 |
| 5, synthetic slag of the present invention | 1420 | 0.4 | 0.3 | 0.2 | 3∶6∶3 | 3.5 | 3 | 16 | 120 |
| 6, granulated slag | / | / | / | / | / | / | / | / | / |
| 7, clinker | 800 | ≤10 | / | / | / | / | / | / | / |
| 8, pre-melted slag | 1580 | ≤10 | / | / | / | / | / | / | / |
Table 3 is the result of use contrast table of the embodiment of the invention and prior art
| Sequence number | Title | The preparation method | Deoxidation effect | Sweetening effectiveness | Cost | Application conditions | Metallurgical effect |
| 1 | Synthetic slag of the present invention | Pre-melt adds powder low temperature and makes ball | 10 | 31 | Lower | Well, dust is few | Good |
| 2 | Synthetic slag of the present invention | Pre-melt adds powder low temperature and makes ball | 23 | 45 | Lower | Well, dust is few | Good |
| 3 | Synthetic slag of the present invention | Pre-melt adds powder low temperature and makes ball | 45 | 52 | Lower | Well, dust is few | Good |
| 4 | Synthetic slag of the present invention | Pre-melt adds powder low temperature and makes ball | 30 | 53 | Lower | Well, dust is few | Good |
| 5 | Synthetic slag of the present invention | Pre-melt adds powder low temperature and makes ball | 30 | 55 | Lower | Well, dust is few | Good |
| 6 | Granulated slag | Manually, mechanically mixing | 10 | 8 | Low | Difference, dust is many | Difference |
| 7 | Clinker | The low-temperature sintering moulding | 15 | 15 | Lower | Better, dust is less | Better |
| 8 | Pre-melted slag | High temperature fritting moulding | 20 | 20 | High | Well, dust is few | Good |
Claims (2)
1, a kind of synthetic slag that can reduce oxygen in the molten steel, sulphur content is characterized in that the concrete chemical composition of forming this synthetic slag is respectively (weight %): aluminium 2-15%; Cerium 3-15%; Magnesium 5-8%; Barium 2-10%; Calcium oxide 20-50%; Aluminum oxide 10-48%; Magnesium oxide 2-10%; Water glass 2-10%; Mierocrystalline cellulose 2-8%.
2, a kind of manufacture method that can reduce oxygen in the molten steel, sulphur content synthetic slag as claimed in claim 1, this method is with (weight %) Wingdale 30-50%; Lime 20-30%; The high basicity material of fluorite 10% and alumina 20-30% and 0-10% silica, after mixing, be dropped in the coke stove and melt, temperature of fusion is at 1300-1600 ℃, and then will melt that to naturally cool to normal temperature after good slag is emitted by the coke oven slag notch stand-by, it is characterized in that the concrete preparation method of this synthetic slag is:
(1), it is stand-by slag to be broken into the powder of granularity 〉=0.5mm;
(2), it is stand-by that the nonferrous metallurgy slag that will smelt aluminium is broken into the powder of granularity 〉=0.5mm;
(3), it is stand-by the calcium oxide raw material to be broken into the powder of granularity 〉=0.5mm;
(4), by [(2-4): (2-6): (1-3)] blended simultaneously, should add (weight %) water glass 2-10% with slag powder, nonferrous metallurgy pulverized slag material, the calcareous powder of oxidation; Mierocrystalline cellulose 2-8% treats to make ball after mixed powder evenly, and spherical synthetic slag diameter should be in φ 10-20mm scope;
(5), spherical synthetic slag is carried out oven drying at low temperature in rotary kiln, storing temperature is 100-200 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021000840A CN1157486C (en) | 2002-01-17 | 2002-01-17 | SYnthetic slag for reducing oxygen and sulfur content in molten steel and its slag making method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021000840A CN1157486C (en) | 2002-01-17 | 2002-01-17 | SYnthetic slag for reducing oxygen and sulfur content in molten steel and its slag making method |
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| Publication Number | Publication Date |
|---|---|
| CN1377977A CN1377977A (en) | 2002-11-06 |
| CN1157486C true CN1157486C (en) | 2004-07-14 |
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|---|---|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100424196C (en) * | 2006-06-08 | 2008-10-08 | 鞍钢附企三炼钢修造总厂 | Lf furnace steel slag ball |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100436618C (en) * | 2005-07-11 | 2008-11-26 | 台州盛世环境工程有限公司 | Fusing agent used under high temperature fused state |
| CZ2007430A3 (en) * | 2007-06-25 | 2008-03-12 | Výzkumný ústav anorganické chemie, a. s. | Process for producing synthetic slag |
| FR2938530B1 (en) * | 2008-11-19 | 2011-07-29 | Kerneos | POROUS MAGNESIAN CLINKER, METHOD OF MANUFACTURE AND USE AS FLOW FOR PROCESSING STEEL DAIRY |
| CN102010926B (en) * | 2010-11-24 | 2012-06-06 | 南京钢铁股份有限公司 | Process for smelting and producing medium high carbon steel |
| TWI408237B (en) * | 2010-12-29 | 2013-09-11 | Univ Nat Chunghsing | Composition of de-sulfur agent for ladle furance of refining process and method for removing sulfur from the molten steel in ladle furnace |
| CN105177224A (en) * | 2015-10-05 | 2015-12-23 | 杭州碧清环保科技有限公司 | Desulfuration and deoxidization agent prepared by means of metal smelting waste and preparation method of desulfuration and deoxidization agent |
| CN111910047A (en) * | 2020-07-09 | 2020-11-10 | 山东钢铁股份有限公司 | Synthetic slag for smelting titanium-containing H-shaped steel and preparation method thereof |
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2002
- 2002-01-17 CN CNB021000840A patent/CN1157486C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100424196C (en) * | 2006-06-08 | 2008-10-08 | 鞍钢附企三炼钢修造总厂 | Lf furnace steel slag ball |
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| CN1377977A (en) | 2002-11-06 |
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