CN114622052A - Molten iron dephosphorization agent, preparation method thereof and molten iron dephosphorization method - Google Patents
Molten iron dephosphorization agent, preparation method thereof and molten iron dephosphorization method Download PDFInfo
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- CN114622052A CN114622052A CN202210275578.2A CN202210275578A CN114622052A CN 114622052 A CN114622052 A CN 114622052A CN 202210275578 A CN202210275578 A CN 202210275578A CN 114622052 A CN114622052 A CN 114622052A
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- molten iron
- dephosphorization
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 230
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 118
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 115
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000003723 Smelting Methods 0.000 claims abstract description 46
- 239000002994 raw material Substances 0.000 claims abstract description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001816 cooling Methods 0.000 claims abstract description 18
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 16
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 16
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 16
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 16
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 16
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 11
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 11
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- 238000010791 quenching Methods 0.000 claims description 19
- 230000000171 quenching effect Effects 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 33
- 239000011574 phosphorus Substances 0.000 abstract description 33
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 33
- 229910019142 PO4 Inorganic materials 0.000 abstract description 8
- 239000010452 phosphate Substances 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 5
- 229910001634 calcium fluoride Inorganic materials 0.000 abstract description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011737 fluorine Substances 0.000 abstract description 2
- 229910052731 fluorine Inorganic materials 0.000 abstract description 2
- 238000002844 melting Methods 0.000 abstract description 2
- 230000008018 melting Effects 0.000 abstract description 2
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 60
- 239000010439 graphite Substances 0.000 description 60
- 229910002804 graphite Inorganic materials 0.000 description 60
- 229910052751 metal Inorganic materials 0.000 description 32
- 239000002184 metal Substances 0.000 description 32
- 239000002893 slag Substances 0.000 description 25
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 13
- 239000000292 calcium oxide Substances 0.000 description 11
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 11
- 229910000831 Steel Inorganic materials 0.000 description 9
- 239000010959 steel Substances 0.000 description 9
- 229910052786 argon Inorganic materials 0.000 description 8
- 238000009614 chemical analysis method Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 8
- 239000010931 gold Substances 0.000 description 8
- 229910052737 gold Inorganic materials 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 229910000421 cerium(III) oxide Inorganic materials 0.000 description 6
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 4
- 235000011941 Tilia x europaea Nutrition 0.000 description 4
- 239000004571 lime Substances 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- 238000009628 steelmaking Methods 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229910052585 phosphate mineral Inorganic materials 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- 229910052776 Thorium Inorganic materials 0.000 description 2
- IKNAJTLCCWPIQD-UHFFFAOYSA-K cerium(3+);lanthanum(3+);neodymium(3+);oxygen(2-);phosphate Chemical group [O-2].[La+3].[Ce+3].[Nd+3].[O-]P([O-])([O-])=O IKNAJTLCCWPIQD-UHFFFAOYSA-K 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052590 monazite Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical compound [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- -1 rare earth phosphate Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Images
Classifications
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)
Abstract
The application provides a molten iron dephosphorizing agent, a preparation method thereof and a molten iron dephosphorizing method. The molten iron dephosphorization agent comprises the following components in percentage by mass: 59-65% of CaO and SiO2 19％‑24％、Fe2O3 10％‑14％、La2O3 1％‑4％、CeO21% -4% of other oxides and 1% -5%; the other oxide includes Al2O3And/or MgO. The preparation method of the molten iron dephosphorization agent comprises the following steps: mixing the raw materials, smelting under the protection of inert gas, and then cooling and crushing to obtain the molten iron dephosphorization agent. The molten iron dephosphorization method comprises the following steps: adding the molten iron dephosphorizing agent into the molten iron to carry out dephosphorization reaction. The molten iron dephosphorizing agent provided by the application has a low melting point, and does not need to add CaF2Fluxing and effectively avoiding CaF2Erosion of furnace lining and fluorine pollution; high phosphate capacity, high dephosphorization efficiency, and reduced dephosphorization agent in smelting processThe addition amount of the phosphorus removal agent reduces the dephosphorization cost.
Description
Technical Field
The application relates to the field of metallurgy, in particular to a molten iron dephosphorization agent, a preparation method thereof and a molten iron dephosphorization method.
Background
Phosphorus is a harmful element for most steel grades. The high phosphorus content in the steel can cause the cold brittleness of the steel, thereby affecting the mechanical property, welding property and the like of the steel. Therefore, it is necessary to control the phosphorus content during the smelting process.
In the blast furnace iron making process, almost all phosphorus in iron ore enters molten iron. With the decreasing supply of high-quality iron ore resources, most iron works begin to use low-grade medium-high phosphorus iron ore, resulting in the phosphorus content in the molten iron reaching 0.3% or more. In order to meet the requirements of users on high-purity and high-quality steel, phosphorus in the steel must be removed to be below 0.02%, and for ultra-low phosphorus steel, the phosphorus in the steel must be controlled to be below 0.005%. At present, a part of steel plants adopt two-step smelting, namely, molten iron is dephosphorized in one converter and then transferred to another converter for smelting. The dephosphorizing agents commonly adopted for dephosphorizing molten iron comprise a lime dephosphorizing agent and a soda dephosphorizing agent. The lime series dephosphorizing agent has low price and wide source and is widely applied to dephosphorization of molten iron; the soda dephosphorizing agent is expensive, easy to gasify and escape at high temperature, and low in utilization rate, and the furnace lining is easy to be corroded by the soda dephosphorizing agent, so that the use of the dephosphorizing agent is less.
Therefore, it is a hot point of research to develop a molten iron dephosphorizing agent with low dephosphorizing cost, large phosphate capacity and high dephosphorizing efficiency.
Disclosure of Invention
The present application is directed to a molten iron dephosphorizing agent, a method for preparing the same, and a method for dephosphorizing molten iron, which solve the above problems.
In order to achieve the purpose, the following technical scheme is adopted in the application:
a molten iron dephosphorization agent comprises the following components in percentage by mass:
CaO59％-65％、SiO219％-24％、Fe2O310％-14％、La2O31％-4％、CeO21% -4% and 1% -5% of other oxides;
the other oxide includes Al2O3And/or MgO.
Preferably, the molten iron dephosphorizing agent comprises the following components in percentage by mass:
CaO60％-62％、SiO219％-22％、Fe2O310％-12％、La2O32％-3％、CeO22% -3% and other oxides 1% -3%;
the other oxide includes Al2O3And/or MgO.
The application provides a preparation method of the molten iron dephosphorization agent, which comprises the following steps:
mixing the raw materials, smelting under the protection of inert gas, and then cooling and crushing to obtain the molten iron dephosphorization agent.
Preferably, the smelting temperature is 1480-1520 ℃ and the smelting time is 30-60 min.
Preferably, the cooling comprises:
cooling to 400-500 deg.c at 4-5 deg.c/min and water quenching.
Preferably, the particle size of the material obtained by crushing is 15 meshes-20 meshes.
Preferably, the alkalinity of the molten iron dephosphorization agent is 2-3.
Preferably, the purity of CaO in the raw materials is more than or equal to 98.0%; SiO 22The purity is more than or equal to 99.0 percent; fe2O3The purity is more than or equal to 99.0 percent; la2O3The purity is more than or equal to 99.0 percent; CeO (CeO)2The purity is more than or equal to 99.0 percent; al (Al)2O3The purity is more than or equal to 98.0 percent; the purity of MgO is more than or equal to 98.0 percent.
The application also provides a molten iron dephosphorization method, which comprises the following steps:
and adding the molten iron dephosphorizing agent into molten iron to perform dephosphorization reaction.
Preferably, the addition amount of the molten iron dephosphorization agent is 10-15% of the mass of the molten iron.
Compared with the prior art, the beneficial effect of this application includes:
the molten iron dephosphorizing agent, CaO and SiO2、Fe2O3、La2O3、CeO2And specific other oxides (Al)2O3And/or MgO), andusing La with higher optical basicity2O3And CeO2Replacing part of CaO. CeO (CeO)2Conversion to Ce under high temperature steelmaking conditions2O3And La2O3And PO4 3-Ion combination to generate rare earth phosphate (Ce, La, Nd, Th) [ PO ] with stable property4]Exerting La under the condition of high-temperature steel making2O3And Ce2O3The thermodynamic effect of dephosphorization is achieved, and the phosphate capacity of the dephosphorization agent is remarkably improved; the molten iron dephosphorizing agent has low melting point, and does not need to add CaF2Fluxing and effectively avoids CaF2Erosion of furnace lining and fluorine pollution; the molten iron dephosphorizing agent has large phosphate capacity and high dephosphorizing efficiency, can reduce the adding amount of the dephosphorizing agent in the smelting process, and reduces the dephosphorizing cost.
The preparation method of the molten iron dephosphorization agent is simple to operate.
The molten iron dephosphorization method provided by the application has the advantages that the molten iron dephosphorization agent is used for dephosphorization, the dephosphorization effect is good, and the cost is low.
Drawings
To more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments are briefly described below, and it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope of the present application.
FIG. 1 shows a dephosphorization apparatus used in examples and comparative examples;
FIG. 2 is a graph showing the effect of dephosphorization in examples and comparative examples.
Reference numerals:
1-upper layer graphite crucible; 2-lower layer graphite crucible; 3-molten iron dephosphorizing agent; 4-small holes; 5-a graphite stopper rod; 6-molten iron.
Detailed Description
The terms as used herein:
"prepared from … …" is synonymous with "comprising". As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having," "contains" or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of … …" excludes any non-specified element, step, or component. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of … …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when the range "1 ~ 5" is disclosed, the ranges described should be construed to include the ranges "1 ~ 4", "1 ~ 3", "1 ~ 2 and 4 ~ 5", "1 ~ 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
In these examples, the parts and percentages are by mass unless otherwise indicated.
"part by mass" means a basic unit of measure indicating a mass ratio of a plurality of components, and 1 part may represent any unit mass, for example, 1g or 2.689 g. If we say that the part by mass of the component A is a part by mass and the part by mass of the component B is B part by mass, the ratio of the part by mass of the component A to the part by mass of the component B is a: b. alternatively, the mass of the A component is aK and the mass of the B component is bK (K is an arbitrary number, and represents a multiple factor). It is unmistakable that, unlike the parts by mass, the sum of the parts by mass of all the components is not limited to 100 parts.
"and/or" is used to indicate that one or both of the illustrated conditions may occur, e.g., a and/or B includes (a and B) and (a or B).
A molten iron dephosphorization agent comprises the following components in percentage by mass:
CaO59％-65％、SiO219％-24％、Fe2O310％-14％、La2O31％-4％、CeO21% -4% and 1% -5% of other oxides;
the other oxide includes Al2O3And/or MgO.
In an optional embodiment, the molten iron dephosphorizing agent comprises the following components in percentage by mass:
CaO60％-62％、SiO219％-22％、Fe2O310％-12％、La2O32％-3％、CeO22% -3% and other oxides 1% -3%.
Optionally, the molten iron dephosphorization agent is calculated by mass percent, and the content of CaO is 59%, 60%, 61%, 62%, 63%, 64%, 65% or any value between 59% and 65%; SiO 22May be 19%, 20%, 21%, 22%, 23%, 24% or any value between 19% and 24%; fe2O3May be present in an amount of 10%, 11%, 12%, 13%, 14% or any value between 10% and 14%; la2O3The content of (b) may be 1%, 2%, 3%, 4% or any value between 1% and 4%; CeO (CeO)2The content of (b) may be 1%, 2%, 3%, 4% or any value between 1% and 4%; the content of the other oxides may be 1%, 2%, 3%, 4%, 5% or any value between 1% and 5%.
The application provides a preparation method of the molten iron dephosphorization agent, which comprises the following steps:
mixing the raw materials, smelting under the protection of inert gas, and then cooling and crushing to obtain the molten iron dephosphorization agent.
In an alternative embodiment, the temperature of the smelting is 1480-1520 ℃ and the time is 30-60 min.
Optionally, the smelting temperature may be any value between 1480 ℃, 1490 ℃, 1500 ℃, 1510 ℃, 1520 ℃ or 1480 ℃ to 1520 ℃, and the time may be any value between 30min, 40min, 50min, 60min or 30min to 60 min.
In an alternative embodiment, the cooling comprises:
cooling to 400-500 deg.c at 4-5 deg.c/min and water quenching.
Optionally, the temperature reduction is any value of 400 ℃, 410 ℃, 420 ℃, 430 ℃, 440 ℃, 450 ℃, 460 ℃, 470 ℃, 480 ℃, 490 ℃, 500 ℃ or between 400 ℃ and 500 ℃.
In an alternative embodiment, the particle size of the material obtained by the pulverization is 15 mesh to 20 mesh.
Optionally, the particle size of the crushed material may be any value between 15 mesh, 16 mesh, 17 mesh, 18 mesh, 19 mesh, 20 mesh or 15 mesh and 20 mesh.
In an alternative embodiment, the basicity of the molten iron dephosphorizing agent is 2-3.
In an optional embodiment, the purity of CaO in the raw material is more than or equal to 98.0 percent; SiO 22The purity is more than or equal to 99.0 percent; fe2O3The purity is more than or equal to 99.0 percent; la2O3The purity is more than or equal to 99.0 percent; CeO (CeO)2The purity is more than or equal to 99.0 percent; al (Al)2O3The purity is more than or equal to 98.0 percent; the purity of MgO is more than or equal to 98.0 percent.
One of the most common rare earth phosphate minerals in nature is monazite, also known as monazite, whose main chemical component is (Ce, La, Nd, Th) [ PO4]The rare earth phosphate mineral is stable in property, and the activity of the rare earth phosphate mineral in slag is low. On the other hand, CaO has an optical basicity of 1, and a rare earth oxide La2O3And Ce2O3The optical basicity of (a) is higher than that of CaO, and is 1.18 and 1.23 respectively. Thus, La is used2O3And Ce2O3The partial replacement of CaO in the lime series dephosphorization agent can improve the phosphate capacity of the dephosphorization agent, and has good thermodynamic conditions for dephosphorization. Ce2O3At room temperatureCeO with poor stability at room temperature2Can be converted into Ce under high-temperature steelmaking conditions2O3. Thus, the present application employs La2O3And CeO2Part replaces CaO, and exerts La under the condition of high-temperature steelmaking2O3And Ce2O3The dephosphorization thermodynamic effect is feasible and innovative.
The application also provides a molten iron dephosphorization method, which comprises the following steps:
and adding the molten iron dephosphorizing agent into molten iron to perform dephosphorization reaction.
In an optional embodiment, the amount of the dephosphorizing agent added to the molten iron is 10-15% of the mass of the molten iron.
Optionally, the addition amount of the molten iron dephosphorization agent is 10%, 11%, 12%, 13%, 14%, 15% or any value between 10% and 15% of the molten iron mass.
Embodiments of the present application will be described in detail below with reference to specific examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present application and should not be construed as limiting the scope of the present application. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
The embodiment provides a molten iron dephosphorization agent, which comprises the following components in percentage by mass:
CaO59％、SiO221％、Fe2O312％、La2O33％、CeO 23% and Al2O32％。
The preparation method of the molten iron dephosphorization agent comprises the following steps:
step one, drying raw materials, weighing according to requirements, and uniformly mixing;
step two, putting the uniformly mixed raw materials into a smelting furnace for smelting at the temperature of 1490 ℃ for 50min, and simultaneously carrying out argon protection;
and step three, cooling to 400 ℃ at the speed of 5 ℃/min after smelting, taking the smelted slag system out of the smelting furnace, quenching with water, and mechanically crushing the slag system to obtain the molten iron dephosphorization agent.
The dephosphorizing agent after the mechanical crushing in the third step is 16 meshes.
Dephosphorizing molten iron by using the dephosphorizing agent, which comprises the following steps:
as shown in fig. 1, a molten iron dephosphorization experiment is performed by using a double-layer graphite crucible, wherein the double-layer graphite crucible comprises an upper layer graphite crucible 1 and a lower layer graphite crucible 2, and the lower layer graphite crucible 2 is used for containing metal iron blocks; the upper layer graphite crucible 1 is used for containing a molten iron dephosphorizing agent 3. A small hole 4 is arranged at the bottom of the upper layer graphite crucible 1, a graphite stopper rod 5 is arranged in the small hole 4, and after the dephosphorizing agent is completely melted, the graphite stopper rod 5 is pulled out so that the melted dephosphorizing agent flows into the lower layer graphite crucible 2 to carry out the dephosphorization reaction of molten iron.
In this example, a double-layer graphite crucible having a lower layer containing 400g of metallic iron blocks and an upper layer containing 42g of dephosphorizing agent was placed in a thermostatic zone of a tubular electric furnace and kept at 1550 ℃ for 30min so as to completely melt the raw materials. The stopper rod is then pulled out so that the dephosphorizing agent in the upper graphite crucible 1 flows into the molten iron 6 in the lower graphite crucible 2, at which time a timer is started. And (4) after the dephosphorization reaction time reaches 16min, quickly taking out the double-layer graphite crucible and placing the double-layer graphite crucible in water for quenching. And (4) separating the slag from the gold, and measuring the phosphorus content in the metal sample by using a chemical analysis method. The initial phosphorus content of the metal iron block is 0.43 percent, the phosphorus content of the metal sample after dephosphorization by the dephosphorizing agent is 0.21 percent, and the dephosphorization rate is 51.16 percent.
Example 2
The embodiment provides a molten iron dephosphorization agent, which comprises the following components in percentage by mass:
CaO61％、SiO221％、Fe2O310％、La2O32％、CeO22％、Al2O32% and MgO 2%.
The preparation method of the molten iron dephosphorization agent comprises the following steps:
step one, drying raw materials, weighing according to requirements, and uniformly mixing;
step two, putting the uniformly mixed raw materials into a smelting furnace for smelting at 1500 ℃ for 55min, and simultaneously carrying out argon protection;
and step three, cooling to 400 ℃ at the speed of 4 ℃/min after smelting, taking the smelted slag system out of the smelting furnace, quenching with water, and mechanically crushing the slag system to obtain the molten iron dephosphorization agent.
The dephosphorizing agent after the mechanical crushing in the third step is 18 meshes.
Dephosphorizing molten iron by using the dephosphorizing agent, which comprises the following steps:
in this example, the same dephosphorization apparatus as in example 1 was used. The double-layer graphite crucible with the lower layer filled with 400g of metal iron blocks and the upper layer filled with 42g of dephosphorization agent is placed at a constant temperature zone of a tubular electric furnace, and the temperature is kept at 1550 ℃ for 30min, so that the raw materials are completely melted. The graphite stopper rod 5 is then pulled out so that the dephosphorizing agent in the upper graphite crucible 1 flows into the molten iron 6 in the lower graphite crucible 2, at which time a timer is started. And (4) after the dephosphorization reaction time reaches 16min, quickly taking out the double-layer graphite crucible and placing the double-layer graphite crucible in water for quenching. And (4) separating the slag from the gold, and measuring the phosphorus content in the metal sample by using a chemical analysis method. The initial phosphorus content of the metal iron block is 0.43 percent, the phosphorus content of the metal sample after dephosphorization by the dephosphorizing agent is 0.22 percent, and the dephosphorization rate is 48.84 percent.
Example 3
The embodiment provides a molten iron dephosphorization agent, which comprises the following components in percentage by mass:
CaO64％、SiO222％、Fe2O310％、La2O31％、CeO21% and MgO 2%.
The preparation method of the molten iron dephosphorization agent comprises the following steps:
step one, drying raw materials, weighing according to requirements, and uniformly mixing;
step two, putting the uniformly mixed raw materials into a smelting furnace for smelting at 1500 ℃ for 60min, and simultaneously carrying out argon protection;
and step three, cooling to 400 ℃ at the speed of 5 ℃/min after smelting, taking the smelted slag system out of the smelting furnace, quenching with water, and mechanically crushing the slag system to obtain the molten iron dephosphorization agent.
The dephosphorizing agent after the mechanical crushing in the third step is 19 meshes.
Dephosphorizing molten iron by using the dephosphorizing agent, which comprises the following steps:
in this example, the same dephosphorization apparatus as in example 1 was used. And (3) placing the double-layer graphite crucible with the lower layer containing 400g of metal iron blocks and the upper layer containing 42g of dephosphorization agent at a constant temperature zone of a tubular electric furnace, and preserving heat for 30min at the temperature of 1550 ℃ so as to completely melt the raw materials. The graphite stopper rod 5 is then pulled out so that the dephosphorizing agent in the upper graphite crucible 1 flows into the molten iron 6 in the lower graphite crucible 2, at which time a timer is started. And (4) after the dephosphorization reaction time reaches 16min, quickly taking out the double-layer graphite crucible and placing the double-layer graphite crucible in water for quenching. And (4) separating the slag from the gold, and measuring the phosphorus content in the metal sample by using a chemical analysis method. The initial phosphorus content of the metal iron block is 0.43 percent, the phosphorus content of the metal sample after dephosphorization by the dephosphorizing agent is 0.24 percent, and the dephosphorization rate is 44.19 percent.
Comparative example 1
A dephosphorizing agent for molten iron dephosphorization comprises the following main components:
CaO62％、SiO223％、Fe2O313% and Al2O32％。
The dephosphorizing agent is prepared according to the preparation method in example 1, that is, the method comprises the following steps:
step one, drying raw materials, weighing according to requirements, and uniformly mixing;
step two, putting the uniformly mixed raw materials into a smelting furnace for smelting at the temperature of 1490 ℃ for 50min, and simultaneously carrying out argon protection;
and step three, cooling to 400 ℃ at the speed of 5 ℃/min after smelting, taking the smelted slag system out of the smelting furnace, quenching with water, and mechanically crushing the slag system to obtain the dephosphorizing agent.
The dephosphorizing agent after the mechanical crushing in the third step is 16 meshes.
In this comparative example, the same dephosphorization apparatus as in example 1 was employed. The double-layer graphite crucible with the lower layer filled with 400g of metal iron blocks and the upper layer filled with 42g of dephosphorization agent is placed at a constant temperature zone of a tubular electric furnace, and the temperature is kept at 1550 ℃ for 30min, so that the raw materials are completely melted. The graphite stopper rod 5 is then pulled out so that the dephosphorizing agent in the upper graphite crucible 1 flows into the molten iron 6 in the lower graphite crucible 2, at which time a timer is started. And (4) after the dephosphorization reaction time reaches 16min, quickly taking out the double-layer graphite crucible and placing the double-layer graphite crucible in water for quenching. And (4) separating the slag from the gold, and measuring the phosphorus content in the metal sample by using a chemical analysis method. The initial phosphorus content of the metal iron block is 0.43 percent, the phosphorus content of the metal sample after dephosphorization by the dephosphorizing agent is 0.39 percent, and the dephosphorization rate is 9.30 percent.
Comparative example 2
A dephosphorizing agent for molten iron dephosphorization comprises the following main components:
CaO63％、SiO221％、Fe2O312％、Al2O32% and MgO 2%.
The dephosphorizing agent is prepared according to the preparation method in example 2, that is, the method comprises the following steps:
step one, drying raw materials, weighing according to requirements, and uniformly mixing;
step two, putting the uniformly mixed raw materials into a smelting furnace for smelting at 1500 ℃ for 55min, and simultaneously carrying out argon protection;
and step three, cooling to 400 ℃ at the speed of 4 ℃/min after smelting, taking the smelted slag system out of the smelting furnace, quenching with water, and mechanically crushing the slag system to obtain the dephosphorizing agent.
The dephosphorizing agent after the mechanical crushing in the third step is 18 meshes.
In this comparative example, the same dephosphorization apparatus as in example 1 was employed. The double-layer graphite crucible with the lower layer filled with 400g of metal iron blocks and the upper layer filled with 42g of dephosphorization agent is placed at a constant temperature zone of a tubular electric furnace, and the temperature is kept at 1550 ℃ for 30min, so that the raw materials are completely melted. The graphite stopper rod 5 is then pulled out so that the dephosphorizing agent in the upper graphite crucible 1 flows into the molten iron 6 in the lower graphite crucible 2, at which time a timer is started. And (4) after the dephosphorization reaction time reaches 16min, quickly taking out the double-layer graphite crucible and placing the double-layer graphite crucible in water for quenching. And (4) separating the slag gold, and measuring the phosphorus content in the metal sample by using a chemical analysis method. The initial phosphorus content of the metal iron block is 0.43 percent, the phosphorus content of the metal sample after dephosphorization by the dephosphorizing agent is 0.40 percent, and the dephosphorization rate is 6.98 percent.
Comparative example 3
The dephosphorizing agent for molten iron dephosphorization comprises the following main components in percentage by weight:
CaO65％、SiO223％、Fe2O310% and MgO 2%.
The dephosphorizing agent is prepared according to the preparation method in example 3, that is, the method comprises the following steps:
step one, drying raw materials, weighing according to requirements, and uniformly mixing;
step two, smelting the uniformly mixed raw materials in a smelting furnace at 1500 ℃ for 60min and simultaneously carrying out argon protection;
and step three, cooling to 400 ℃ at the speed of 5 ℃/min after smelting, taking the smelted slag system out of the smelting furnace, quenching with water, and mechanically crushing the slag system to obtain the molten iron dephosphorization agent.
The dephosphorizing agent after the mechanical crushing in the third step is 19 meshes.
In this comparative example, the same dephosphorization apparatus as in example 1 was employed. The double-layer graphite crucible with the lower layer filled with 400g of metal iron blocks and the upper layer filled with 42g of dephosphorization agent is placed at a constant temperature zone of a tubular electric furnace, and the temperature is kept at 1550 ℃ for 30min, so that the raw materials are completely melted. The graphite stopper rod 5 is then pulled out so that the dephosphorizing agent in the upper graphite crucible 1 flows into the molten iron 6 in the lower graphite crucible 2, at which time a timer is started. And after the dephosphorization reaction time reaches 16min, quickly taking out the double-layer graphite crucible and placing the double-layer graphite crucible in water for quenching. And (4) separating the slag from the gold, and measuring the phosphorus content in the metal sample by using a chemical analysis method. The initial phosphorus content of the metal iron block is 0.43 percent, the phosphorus content of the metal sample after dephosphorization by the dephosphorizing agent is 0.39 percent, and the dephosphorization rate is 9.30 percent.
Comparative example 4
The dephosphorizing agent for molten iron dephosphorization comprises the following main components in percentage by weight:
CaO61％、SiO221％、Fe2O312％、CeO22％、Al2O32% and MgO 2%.
The dephosphorizing agent is prepared according to the preparation method in example 2, that is, the method comprises the following steps:
step one, drying raw materials, weighing according to requirements, and uniformly mixing;
step two, putting the uniformly mixed raw materials into a smelting furnace for smelting at 1500 ℃ for 55min, and simultaneously carrying out argon protection;
and step three, cooling to 400 ℃ at the speed of 4 ℃/min after smelting, taking the smelted slag system out of the smelting furnace, quenching with water, and mechanically crushing the slag system to obtain the dephosphorizing agent.
The dephosphorizing agent after the mechanical crushing in the third step is 18 meshes.
In this comparative example, the same dephosphorization apparatus as in example 1 was employed. The double-layer graphite crucible with the lower layer filled with 400g of metal iron blocks and the upper layer filled with 42g of dephosphorization agent is placed at a constant temperature zone of a tubular electric furnace, and the temperature is kept at 1550 ℃ for 30min, so that the raw materials are completely melted. The graphite stopper rod 5 is then pulled out so that the dephosphorizing agent in the upper graphite crucible 1 flows into the molten iron 6 in the lower graphite crucible 2, at which time a timer is started. And (4) after the dephosphorization reaction time reaches 16min, quickly taking out the double-layer graphite crucible and placing the double-layer graphite crucible in water for quenching. And (4) separating the slag from the gold, and measuring the phosphorus content in the metal sample by using a chemical analysis method. The initial phosphorus content of the metal iron block is 0.43 percent, the phosphorus content of the metal sample after dephosphorization by the dephosphorizing agent is 0.37 percent, and the dephosphorization rate is 13.95 percent.
Comparative example 5
A dephosphorizing agent for molten iron dephosphorization comprises the following main components:
CaO61％、SiO221％、Fe2O312％、La2O32％、Al2O32% and MgO 2%.
The dephosphorizing agent is prepared according to the preparation method in example 2, that is, the method comprises the following steps:
step one, drying raw materials, weighing according to requirements, and uniformly mixing;
step two, putting the uniformly mixed raw materials into a smelting furnace for smelting at 1500 ℃ for 55min, and simultaneously carrying out argon protection;
and step three, cooling to 400 ℃ at the speed of 4 ℃/min after smelting, taking the smelted slag system out of the smelting furnace, quenching with water, and mechanically crushing the slag system to obtain the dephosphorizing agent.
The dephosphorizing agent after the mechanical crushing in the third step is 18 meshes.
In this comparative example, the same dephosphorization apparatus as in example 1 was employed. And (3) placing the double-layer graphite crucible with the lower layer containing 400g of metal iron blocks and the upper layer containing 42g of dephosphorization agent at a constant temperature zone of a tubular electric furnace, and preserving heat for 30min at the temperature of 1550 ℃ so as to completely melt the raw materials. The graphite stopper rod 5 is then pulled out so that the dephosphorizing agent in the upper graphite crucible 1 flows into the molten iron 6 in the lower graphite crucible 2, at which time a timer is started. And (4) after the dephosphorization reaction time reaches 16min, quickly taking out the double-layer graphite crucible and placing the double-layer graphite crucible in water for quenching. And (4) separating the slag gold, and measuring the phosphorus content in the metal sample by using a chemical analysis method. The initial phosphorus content of the metal iron block is 0.43 percent, the phosphorus content of the metal sample after dephosphorization by the dephosphorizing agent is 0.37 percent, and the dephosphorization rate is 13.95 percent.
FIG. 2 is a graph showing the comparison of the dephosphorization effect of the dephosphorization agent in examples 1, 2 and 3 and comparative examples 1, 2, 3, 4 and 5. As can be seen from FIG. 2, La was used2O3And Ce2O3Part of the calcium oxide substitutes CaO in the lime dephosphorizing agent, and the dephosphorizing effect of the dephosphorizing agent can be obviously improved.
Finally, it should be noted that: the above embodiments are only used for illustrating the technical solutions of the present application, and not for limiting the same; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present application.
Moreover, those skilled in the art will appreciate that while some embodiments herein include some features included in other embodiments, rather than other features, combinations of features of different embodiments are meant to be within the scope of the application and form different embodiments. For example, in the claims above, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the application and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art that is already known to a person skilled in the art.
Claims (9)
1. The molten iron dephosphorization agent is characterized by comprising the following components in percentage by mass:
CaO59％-65％、SiO219％-24％、Fe2O310％-14％、La2O31％-4％、CeO21% -4% and 1% -5% of other oxides;
the other oxide includes Al2O3And/or MgO.
2. The dephosphorizing agent for molten iron of claim 1, comprising, in mass percent:
CaO60％-62％、SiO219％-22％、Fe2O310％-12％、La2O32％-3％、CeO22% -3% and other oxides 1% -3%.
3. A method for preparing the dephosphorizing agent for molten iron according to claim 1 or 2, which comprises:
mixing the raw materials, smelting under the protection of inert gas, and then cooling and crushing to obtain the molten iron dephosphorization agent.
4. The preparation method of claim 3, wherein the smelting temperature is 1480-1520 ℃ and the time is 30-60 min.
5. The method of manufacturing according to claim 3, wherein the cooling comprises:
cooling to 400-500 deg.c at 4-5 deg.c/min, and quenching with water.
6. The method according to claim 3, wherein the particle size of the pulverized material is 15 to 20 mesh.
7. The manufacturing method according to any one of claims 3 to 6, wherein the basicity of the molten iron dephosphorizing agent is 2 to 3.
8. A method for dephosphorizing molten iron is characterized by comprising the following steps:
the dephosphorization agent for molten iron according to claim 1 or 2 is added to molten iron to conduct dephosphorization.
9. The method for dephosphorization of molten iron according to claim 8, wherein said molten iron dephosphorization agent is added in an amount of 10% -15% by mass of molten iron.
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| CN115341056A (en) * | 2022-08-22 | 2022-11-15 | 河北濡春新能源集团有限公司 | Rare earth nano metallurgy smelting agent |
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