CN110964870B - Method for pre-desulfurizing molten iron of oil residue - Google Patents
Method for pre-desulfurizing molten iron of oil residue Download PDFInfo
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- CN110964870B CN110964870B CN201811138413.0A CN201811138413A CN110964870B CN 110964870 B CN110964870 B CN 110964870B CN 201811138413 A CN201811138413 A CN 201811138413A CN 110964870 B CN110964870 B CN 110964870B
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C1/00—Refining of pig-iron; Cast iron
- C21C1/02—Dephosphorising or desulfurising
- C21C1/025—Agents used for dephosphorising or desulfurising
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/04—Removing impurities by adding a treating agent
- C21C7/064—Dephosphorising; Desulfurising
- C21C7/0645—Agents used for dephosphorising or desulfurising
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)
Abstract
The invention discloses a method for pre-desulfurizing oil slag molten iron, which mainly solves the technical problems of difficult desulfurization, high magnesium powder consumption, low magnesium powder utilization rate and large slagging-off iron loss of the conventional composite blowing molten iron desulfurization process for desulfurizing molten iron with oil slag as molten iron. The technical scheme of the invention is as follows: a method for pre-desulphurizing molten iron with oil residues, comprising: determining the grade of the oil residue in the ladle; carrying out aluminum deoxidation on the molten iron slag in the ladle; and carrying out blowing desulfurization on the molten iron in the ladle. Compared with the process of adding magnesium powder, the method has the advantages that the utilization rate of the magnesium powder is improved from 20% to 51%; compared with the prior skimming process, the method reduces the skimming iron loss from 15.85 kg/ton iron to 10.25 kg/ton iron.
Description
Technical Field
The invention relates to a molten iron pretreatment technology, in particular to a method for pre-desulfurizing oil slag molten iron, belonging to the technical field of steel smelting and continuous casting.
Background
The torpedo car is a large-scale molten iron transporting device, can be used for transporting and storing molten iron, and has long heat preservation time; when in use, the hot metal ladle can replace a steel-making mixer and a common hot metal ladle car. The molten iron can also complete the operation processes of desulfurization and dephosphorization in the transportation process; in the ferrous metallurgy industry, a torpedo car is an indispensable transportation device.
In order to improve the steel-making yield and utilize the heat of the empty torpedo ladle, 5-10 tons of silicon steel sheets, crushed materials and other various waste steels are added into the torpedo ladle after the iron turning of the steel-making process is finished and in the process of returning to a blast furnace for iron receiving. In the process of blast furnace tapping and torpedo ladle molten iron transportation, FeO on the surface of the scrap steel, impurities brought by the scrap steel and molten iron react with each other, reaction products and unreacted impurities and blast furnace slag brought by the iron receiving process generate new molten iron slag, and the molten iron slag enters a ladle along with the molten iron during iron turning in the steel making process and floats to the surface of the molten iron. When the slag surface of the molten iron slag is locally blackened and crusted, and light micro bubbles at the non-crusted part of the molten iron slag are foamed, and the molten iron slag is easy to adhere to the wall of the ladle, the technical personnel refer to the molten iron slag as oil slag for convenient distinguishing; the oil residue can cause the difficulty of desulfurization of the composite blowing molten iron desulfurization process, the utilization rate of magnesium powder is obviously reduced, the weight percentage content of sulfur in the desulfurized molten iron is obviously higher, the desulfurization effect of the molten iron is unstable, the requirements on the components of steel are difficult to meet, secondary powder injection desulfurization is required, and the desulfurization period is prolonged.
At present, for common iron and steel enterprises, the average daily occurrence rate of the hot metal ladles containing oil slag in the hot metal ladles is 30 percent and is up to 80 percent, and aiming at the oil slag, a magnesium powder increasing process or a pre-slagging process is generally adopted, so that the problems of high magnesium powder consumption, large slagging iron loss and high hot metal pre-desulfurization cost exist, and the smelting of pure molten steel is greatly influenced.
Chinese patent publication No. CN102181608A discloses a modification process for blowing molten iron desulphurization slag, which utilizes a spray gun to spray fluidized lime and the like into molten iron in a post-blowing stage after the combined blowing of magnesium powder and fluidized lime is finished, wherein the spraying amount is 0.5-2.5 kg, so that the molten iron slag after the desulphurization is integrally modified, and the purpose is to improve the slag skimming effect and reduce the sulfur return amount of a converter. The patent does not relate to the modification of molten iron slag before desulfurization, and has no effect on recovering the desulfurization effect of magnesium powder and improving the utilization rate of the magnesium powder for the heat of oil slag.
Chinese patent publication No. CN1528919A discloses a method for desulfurizing molten iron by using an aluminum-containing calcium oxide-based desulfurizing agent, which adopts an aluminum-containing calcium oxide-based desulfurizing agent with CaF as a main component2、CaCO3Aluminum powder and Al2O3CaO, promoting the progress of the desulfurization reaction. The lime in the patent is a real desulfurizer and reacts with sulfur in molten iron, the principle is completely different from the desulfurization process of composite injection magnesium powder and lime powder, the purpose of adding aluminum powder is to react with desulfurization product oxygen, the aluminum powder is not used for molten iron slag modification, and the cost of the aluminum powder is very high.
Chinese patent publication No. CN104032096A discloses a desulfurization slag modifier and a method for desulfurizing molten iron, the desulfurization slag modifier adopted in the method contains corundum slag, sodium salt and fluorite, wherein the corundum slag is Al2O3、MgO、CaO、V2O5The sodium salt is Na2CO3NaCl and NaNO3One or more of the iron powder and the additive are added with 1.5-3 kg/ton of iron before powder injection desulfurization or in the process of powder injection desulfurization, so as to promote slag-iron separation and reduce slagging-off iron loss. The modifier ingredient CaO content of this patent is few, can not effectively improve the basicity of molten iron sediment before the desulfurization, promotes the powdered magnesium desulfurization effect, and the erosion rate of resistant material can be accelerated to the addition of fluorite simultaneously.
Chinese patent publication No. CN103820595A discloses a method for desulfurizing molten iron, which is characterized in that KR desulfurizing agent composed of lime and fluorite is added into a foundry ladle before turning iron, the weight of the KR desulfurizing agent is 2-4 kg/ton of iron, and the alkalinity of molten iron slag is increased from 1 to 4, so that the absorption of desulfurization products and the removal of desulfurization slag are facilitated. This patent is directed to pure granule magnesium desulfurization technology, and the desulfurization process does not spout lime powder, and its scheme is equivalent to move the lime powder in the compound jetting desulfurization technology to before turning over the iron, can't solve the desulfurization problem of oil slag heat, and the lime powder granularity is great simultaneously, and fluorite can accelerate the erosion rate of resistant material.
Chinese patent publication No. CN101358265A discloses a composite molten iron desulfurizer and a preparation method thereof, wherein the desulfurizer comprises CaO, TMg and CaC2、NaHCO3、Al、C、CaF2S, P, has the advantages of less slag, good desulphurization effect, low slagging-off iron loss and the like, and the purpose of adding the aluminum powder is to increase the activity of CaO in the desulfurizer and reduce the dosage of the CaO. However, the aluminum powder has high cost, needs to be added into a furnace when being mixed with lime powder and the like, has poor selectivity, and also contains fluorite.
Chinese patent publication No. CN101676410A discloses "aluminum slag, desulfurizing agent and desulfurizing method for desulfurizing high-silicon molten iron", the aluminum slag specially used for this purpose is composed of the following aluminum powder, alumina, fluorite powder, asphalt coke powder, etc., the purpose of the aluminum powder is to avoid the formation of high-melting-point silicate substances on the surface of lime, and to solve the problem of desulfurizing high-silicon abnormal molten iron. The method is only suitable for the KR desulfurization process, is not suitable for the desulfurization of the oil residue heat in the composite blowing desulfurization process, and has high aluminum powder cost.
The method has the advantages that the slag skimming effect and the desulfurization effect of the KR desulfurization process are improved, the problem of molten iron desulfurization of the oil slag heat in the magnesium powder-lime powder composite blowing desulfurization process is not solved, the used aluminum powder and lime are premixed in advance, the purpose of avoiding the formation of high-melting-point substances on the surface of the lime powder is high in cost and poor in selectivity, and the fluorite is added to accelerate the erosion speed of refractory materials.
The existing process for pre-desulfurizing the molten iron with the molten iron slag as the oil slag has the problems of unstable molten iron desulfurization, high magnesium powder consumption, large molten iron slagging iron loss and high molten iron pre-desulfurization cost.
Disclosure of Invention
The invention aims to provide a method for pre-desulfurizing oil-slag molten iron, which mainly solves the technical problems of difficult desulfurization, high magnesium powder consumption, low magnesium powder utilization rate and large slagging-off iron loss of the conventional composite blowing molten iron desulfurization process for desulfurizing molten iron with oil slag of molten iron.
The molten iron slag in the ladle is locally blackened and crusted, light micro bubbles are foamed at the position where the molten iron slag is not crusted, and the molten iron slag is easy to adhere to the ladle wall of the ladle and is also called as oil slag.
The oil residue molten iron refers to molten iron with oil residue as molten iron residue.
The slag column in the method is a liquid slag strip generated by the molten iron slag partially adhered to the mouth of the molten iron ladle under the action of gravity in the process of scraping the molten iron slag off the molten iron ladle by using a slag scraper.
The mild oil slag in the method refers to the molten iron slag when the length of the longest slag column in the slag columns formed in the slag skimming process is 10-15 cm.
The medium oil slag in the method refers to molten iron slag when the length of the longest slag column in slag columns formed in the slag skimming process is 16-20 cm.
The heavy oil slag in the method of the invention refers to the molten iron slag when the length of the longest slag column in the slag columns formed in the slag skimming process is more than 20 cm.
The binary alkalinity of the molten iron slag is the weight percentage content of CaO in the molten iron slag/SiO in the molten iron slag2The weight percentage content.
The technical scheme adopted by the invention is that the method for pre-desulfurizing the oil residue molten iron comprises the following steps:
1) determining the grade of oil slag in the ladle, conveying the ladle filled with molten iron to a molten iron slag skimming station, skimming the molten iron slag in the ladle for 1-3 times by using a skimming machine, and determining the grade of the oil slag according to the length value of the longest slag column;
2) carrying out aluminum deoxidation on the molten iron slag in the ladle, adding aluminum blocks into the molten iron in the ladle, wherein when the molten iron slag is light oil slag, the adding amount of the aluminum blocks is 0.044 kg/ton iron-0.069 kg/ton iron; when the molten iron slag is moderate oil slag, the adding amount of the aluminum blocks is 0.088 kg/ton iron-0.119 kg/ton iron; when the molten iron slag is heavy oil slag, the adding amount of the aluminum blocks is 0.150 kg/ton to 0.188 kg/ton of iron;
3) blowing and desulfurizing molten iron in a ladle, wherein in the blowing stage before molten iron desulfurization, fluidized lime powder is independently blown to the molten iron, the blowing speed of the fluidized lime powder is 60-80kg/min, and the flow rate of nitrogen blowing assisting gas is 0.7-1.0Nm3Min; when the molten iron slag is light oil slag, the addition amount of the fluidized lime powder is 1.05 kg/ton to 1.35 kg/ton of iron; when the molten iron slag is moderate oil slag, the addition amount of the fluidized lime powder is 1.45 kg/ton to 1.70 kg/ton of iron; when the molten iron slag is heavy oil slag, the addition amount of the fluidized lime powder is 1.85 kg/ton to 2.35 kg/ton of iron;
in the composite blowing stage, magnesium powder and fluidized lime powder are blown simultaneously, the blowing speed of the fluidized lime powder is 35kg/min to 45kg/min, the ratio of the blowing speed of the fluidized lime powder to the blowing speed of the magnesium powder is 3.0 to 4.5, and the flow rate of nitrogen blowing assistant is 0.7 to 1.0Nm3/min；
In the post-blowing stage, fluidized lime powder is independently blown, the addition amount of the fluidized lime powder is 0.15 kg/ton to 0.35 kg/ton of iron, the blowing speed of the fluidized lime powder is 18 to 35kg/min, and the flow rate of nitrogen blowing-assisted is 0.7 to 1.0Nm3/min。
Further, in the step 2), the aluminum block comprises the following chemical components in percentage by weight: more than or equal to 99.5 percent of Al, less than or equal to 0.22 percent of Si and less than or equal to 0.02 percent of Cu; the weight of the single aluminum block is 0.04-0.06 kg.
Further, in the step 3), the granularity of the fluidized lime powder is less than or equal to 0.05 mm.
Further, in the step 3), the granularity of the magnesium powder is 0.2-0.8 mm.
The method of the invention is based on the following studies of the applicant:
the weight percentage of FeO in the oil residue is 4-11%, and the binary alkalinity of the oil residue is 0.1-0.5; according to the desulfurization difficulty and the viscosity difference of the molten iron slag, the oil slag is divided into mild oil slag, moderate oil slag and severe oil slag. The weight percentage of FeO in the mild oil slag is 2.5-4.5%, and the binary alkalinity of the mild oil slag is 0.3-0.5; the weight percentage of FeO in the molten iron slag of the moderate oil slag is 5-7.5%, and the binary alkalinity of the molten iron slag is 0.15-0.3; the weight percentage content of FeO in the molten iron slag of the heavy oil slag is 8-11%, and the binary alkalinity of the molten iron slag is 0.1-0.15.
The method improves the desulfurization capability of the magnesium powder by adjusting the components of the molten iron oil residue to a normal level. The binary alkalinity of the oil residue is only 0.1-0.5, and SiO in the produced residue2Activity of (a) (SiO)2) Higher, large magnesium consumption and SiO2Reaction is carried out: (SiO)2)+[Mg]＝(MgO)+[Si](ii) a Meanwhile, the weight percentage of FeO in the oil residue is 4-11%, and Mg dissolved in molten iron can be oxidized: (FeO) + [ Mg]＝(MgO)+[Fe]Thereby causing the weight percentage of the dissolved magnesium in the molten iron to be reduced, and the reaction of the magnesium and the sulfur to be inhibited, resulting in abnormal desulfurization. The improvement is that aluminum blocks are added into the molten iron in the ladle before the molten iron is blown and desulfurized, and in the blowing stage before the molten iron is desulfurized, the aluminum blocks and the molten iron slag are fully contacted and partially dissolved in the molten iron under the stirring action of blowing-assisting nitrogen, so that 3(O) +2 Al is generated]＝(Al2O3) The oxygen in the molten iron and the molten iron slag is removed, the reducing atmosphere is improved, and the magnesium powder sprayed into the molten iron in the composite injection stage is prevented from being oxidized; secondly, the adding weight of fluidized lime powder is increased in the front blowing stage, and the fluidized lime powder is fully mixed and contacted with the molten iron slag under the action of nitrogen blowing and stirring assistance by utilizing the characteristics of fine particle size and large specific surface area, so that the slag forming speed is accelerated, the binary alkalinity of the molten iron slag is improved to 0.9-1, and on the one hand, the SiO can be greatly reduced2Activity of (1), (B), (C)2)+[Mg]＝(MgO)+[Si]On the other hand, the solubility of desulfurization products such as CaS, MgS and the like in the molten iron slag can be obviously improved, so that the reaction of magnesium and sulfur in the composite blowing stage is promoted, and the molten iron desulfurization effect is improved.
Compared with the prior art, the invention has the following positive effects:
1. the invention adopts the aluminum blocks and the fluidized lime powder to modify the molten iron oil residue, improves the desulfurization effect of the magnesium powder, has strong selectivity, simple and convenient operation and low labor intensity, and does not need equipment modification. 2. Compared with the process of adding magnesium powder, the method has the advantages that the utilization rate of the magnesium powder is improved from 20% to 51%; compared with the prior skimming process, the method reduces the skimming iron loss from 15.85 kg/ton iron to 10.25 kg/ton iron.
Detailed Description
The present invention will be further illustrated by the following specific examples, which are to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever.
In examples 1 to 4 of the present invention, the nominal capacity of the ladle for containing molten iron was 250 tons, and the flow rate of the nitrogen blowing assistance gas was 0.7Nm in the entire process3Min, the spraying weight of the fluidized lime powder after the composite spraying period is finished is 0.16 kg/ton iron and the weight of molten iron; in examples 1 to 4, the amount of the aluminum nuggets added was 45kg, 40kg, 25kg, and 15kg, respectively.
The molten iron parameters of the embodiment of the invention are shown in table 1, the blowing desulfurization process parameters are shown in table 2, and the desulfurization effect parameters are shown in table 3.
TABLE 1 molten iron parameters of examples of the present invention
TABLE 2 blowing desulfurization process parameters of the inventive examples
TABLE 3 desulfurization Effect parameters of examples of the present invention
In addition to the above embodiments, the present invention may have other embodiments. All technical solutions formed by adopting equivalent substitutions or equivalent transformations fall within the protection scope of the claims of the present invention.
Claims (4)
1. The method for pre-desulfurizing the oil slag molten iron is characterized by comprising the following steps of:
1) determining the grade of oil slag in the ladle, conveying the ladle filled with molten iron to a molten iron slag skimming station, skimming the molten iron slag in the ladle for 1-3 times by using a skimming machine, and determining the grade of the oil slag according to the length value of the longest slag column; the weight percentage content of FeO in the oil residue is 4-11%, and the binary alkalinity of the oil residue is 0.1-0.5;
2) carrying out aluminum deoxidation on the molten iron slag in the ladle, adding aluminum blocks into the molten iron in the ladle, wherein when the molten iron slag is light oil slag, the adding amount of the aluminum blocks is 0.044-0.069 kg/ton of iron; when the molten iron slag is moderate oil slag, the adding amount of the aluminum blocks is 0.088-0.119 kg/ton of iron; when the molten iron slag is heavy oil slag, the adding amount of the aluminum blocks is 0.150-0.188 kg/ton of iron; the mild oil slag is molten iron slag formed in the slag column in the slag skimming process when the length of the longest slag column is 10-15 cm, the weight percentage content of FeO in the molten iron slag is 2.5% -4.5%, and the binary alkalinity of the molten iron slag is 0.3-0.5; the moderate oil slag is molten iron slag formed in the slag column in the slag skimming process when the length of the longest slag column is 16-20 cm, the weight percentage content of FeO in the molten iron slag is 5.0% -7.5%, and the binary alkalinity of the molten iron slag is 0.15-0.30; the heavy oil slag is molten iron slag formed in the slag column in the slag skimming process when the length of the longest slag column is more than 20cm, the weight percentage content of FeO in the molten iron slag is 8-11%, and the binary alkalinity of the molten iron slag is 0.10-0.15;
3) blowing and desulfurizing molten iron in a ladle, wherein in the blowing stage before molten iron desulfurization, fluidized lime powder is independently blown to the molten iron, the blowing speed of the fluidized lime powder is 60-80kg/min, and the flow rate of nitrogen blowing assisting gas is 0.7-1.0Nm3Min; when the molten iron slag is light oil slag, the addition amount of the fluidized lime powder is 1.05-1.35 kg/ton of iron; when the molten iron slag is moderate oil slag, the addition amount of the fluidized lime powder is 1.45-1.70 kg/ton of iron; when the molten iron slag is heavy oil slag, the addition amount of the fluidized lime powder is 1.85-2.35 kg/ton of iron;
in the composite injection stage, magnesium powder and fluidized fossil are injected simultaneouslyThe spraying speed of the ash powder and the fluidized lime powder is 35-45kg/min, the ratio of the spraying speed of the fluidized lime powder to the spraying speed of the magnesium powder is 3.0-4.5, and the flow rate of the blowing-assisted nitrogen is 0.7-1.0Nm3/min；
In the post-blowing stage, fluidized lime powder is independently blown, the addition amount of the fluidized lime powder is 0.15-0.35 kg/ton iron, the blowing speed of the fluidized lime powder is 18-35kg/min, and the flow rate of the blowing-assisted nitrogen is 0.7-1.0Nm3/min。
2. The method for pre-desulfurizing the oil slag molten iron according to claim 1, wherein in the step 2), the aluminum blocks comprise the following chemical components in percentage by weight: more than or equal to 99.5 percent of Al, less than or equal to 0.22 percent of Si and less than or equal to 0.02 percent of Cu; the weight of the single aluminum block is 0.04-0.06 kg.
3. The method for pre-desulfurizing the molten iron with oil residues according to claim 1, wherein in the step 3), the particle size of the fluidized lime powder is less than or equal to 0.05 mm.
4. The method for pre-desulfurizing molten iron containing oil slag according to claim 1, wherein in the step 3), the particle size of the magnesium powder is 0.2-0.8 mm.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106591529A (en) * | 2016-11-28 | 2017-04-26 | 河钢股份有限公司承德分公司 | Ultra-low sulfur control method for hot metal pretreatment |
| CN106755738A (en) * | 2015-11-24 | 2017-05-31 | 上海梅山钢铁股份有限公司 | A kind of method for improving molten iron pretreatment desulfurizing pulvis deactivating magnesium powder utilization rate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106755738A (en) * | 2015-11-24 | 2017-05-31 | 上海梅山钢铁股份有限公司 | A kind of method for improving molten iron pretreatment desulfurizing pulvis deactivating magnesium powder utilization rate |
| CN106591529A (en) * | 2016-11-28 | 2017-04-26 | 河钢股份有限公司承德分公司 | Ultra-low sulfur control method for hot metal pretreatment |
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