WO2023233450A1 - 冷却液及び鋼板の冷却方法 - Google Patents

冷却液及び鋼板の冷却方法 Download PDF

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WO2023233450A1
WO2023233450A1 PCT/JP2022/021889 JP2022021889W WO2023233450A1 WO 2023233450 A1 WO2023233450 A1 WO 2023233450A1 JP 2022021889 W JP2022021889 W JP 2022021889W WO 2023233450 A1 WO2023233450 A1 WO 2023233450A1
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Prior art keywords
coolant
weight
steel plate
cooling
ions
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PCT/JP2022/021889
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English (en)
French (fr)
Japanese (ja)
Inventor
寛和 古瀬
貴司 中野
康介 稲葉
Original Assignee
Ｐｒｉｍｅｔａｌｓ Ｔｅｃｈｎｏｌｏｇｉｅｓ Ｊａｐａｎ株式会社
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Priority to PCT/JP2022/021889 priority Critical patent/WO2023233450A1/ja
Priority to JP2024524516A priority patent/JPWO2023233450A1/ja
Publication of WO2023233450A1 publication Critical patent/WO2023233450A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/52—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
    • C21D9/54—Furnaces for treating strips or wire
    • C21D9/56—Continuous furnaces for strip or wire
    • C21D9/573—Continuous furnaces for strip or wire with cooling
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/24—Cleaning or pickling metallic material with solutions or molten salts with neutral solutions

Definitions

  • the present disclosure relates to a cooling liquid and a method for cooling a steel plate.
  • high-temperature steel plates may be cooled down.
  • Patent Document 1 describes that in a continuous heat treatment line for steel strips, the steel strips are cooled by spraying a liquid or a gas-liquid mixed fluid onto the steel strips before performing hot-dip metal plating treatment.
  • a substance having pickling properties against metal oxides such as iron oxide is used as the cooling fluid.
  • At least one embodiment of the present invention provides a cooling liquid and a cooling liquid capable of cooling a steel plate while effectively suppressing corrosion of equipment and steel plates and generation of an oxide film on the surface of the steel plate.
  • the purpose is to provide a method for cooling steel plates.
  • the cooling liquid includes: A cooling liquid for cooling a steel plate, a first ion that can be converted in a solution into a first substance that generates a reducing gas upon decomposition; a second ion capable of reacting with iron oxide to form an iron-containing ionic compound; including;
  • the concentration of the first ions in the coolant is 0.5% by weight or more and 6% by weight or less,
  • the concentration of the second ions in the coolant is 1.0% by weight or more and 28% by weight or less.
  • a method for cooling a steel plate includes: A cooling method for cooling a steel plate, the method comprising: The method includes a step of supplying the above-mentioned cooling liquid to the steel plate to cool the steel plate.
  • a cooling liquid and a method for cooling a steel plate that can cool a steel plate while effectively suppressing corrosion of equipment and steel plates and generation of oxide film on the surface of the steel plate. provided.
  • FIG. 1 is a schematic diagram showing a continuous heat treatment facility as an example of an apparatus to which a cooling liquid or a cooling method according to some embodiments is applied.
  • FIG. 1 is a schematic configuration diagram of an example of an apparatus to which a cooling liquid or a cooling method according to some embodiments is applied, and is a diagram showing a continuous heat treatment equipment 100 for continuously heat treating steel plates.
  • the continuous heat treatment equipment 100 shown in FIG. 1 includes a continuous annealing furnace 10 for continuously annealing a strip-shaped steel plate S, and the continuous annealing furnace 10 includes a preheating zone 12, a heating zone 14, and a cooling zone 16. and, including.
  • a plurality of conveyance rolls 18 are provided in the preheating zone 12, the heating zone 14, and the cooling zone 16, and by applying tension to the steel plate S via the conveyance rolls 18, the conveyance speed (line speed) according to this tension is adjusted.
  • the steel plate S is conveyed.
  • the preheating zone 12 is provided on the upstream side of the heating zone 14 and the cooling zone 16 in the conveying direction of the steel sheet S, and in order to suppress the temperature variation of the steel sheet S at the entrance of the heating zone 14, the preheating zone 12 is provided before entering the heating zone 14.
  • the steel plate S is preheated by a burner (not shown) or the like.
  • the heating zone 14 is provided downstream of the preheating zone 12 and upstream of the cooling zone 16 in the conveyance direction of the steel plate S, and is configured to heat the steel plate S with a burner or the like (not shown).
  • the temperature of the heating zone 14 can be adjusted, for example, by increasing or decreasing the amount of fuel supplied to the burner.
  • the cooling zone 16 is located downstream of the preheating zone 12 and the heating zone 14 in the conveyance direction of the steel sheet S, and sprays cooling fluid onto the surface of the steel sheet S heated in the heating zone 14 by cooling means such as a cooling nozzle 22. It is configured to slowly or rapidly cool the steel plate S by attaching the steel plate S.
  • a reducing or non-oxidizing gas may be supplied into the continuous annealing furnace 10.
  • the steel plate S is annealed by passing through the above-mentioned pre-heating zone 12, heating zone 14, and cooling zone 16.
  • the steel plate S annealed in the continuous annealing furnace 10 may be sent to a continuous plating treatment facility 30.
  • the continuous plating treatment facility 30 is a facility for continuously plating the steel sheet S, and includes a pot 32 (molten metal pot) that forms a plating bath 34 of molten metal, and a sink roll provided inside the pot 32. 36, and a wiping nozzle 38 for adjusting the amount of plating solution (molten metal) attached to the steel plate S.
  • the molten metal stored as a plating solution inside the pot 32 may include zinc, aluminum, or an alloy containing zinc or aluminum.
  • the steel sheet S annealed in the continuous annealing furnace 10 is placed between the outlet of the continuous annealing furnace 10 and the pot 32 while being given tension by the bridle roll 20 provided at the outlet of the continuous annealing furnace 10. It is led to a plating bath 34 of molten metal through a snout 24 .
  • the cooling fluid used to cool the steel plate S includes the cooling liquid described below. You can stay there.
  • the cooling means may be configured to supply a cooling liquid described below or a mixed fluid of the cooling liquid and gas to the surface of the steel plate S by the cooling means.
  • cooling liquid and cooling method according to some embodiments may be applied to processes other than the continuous annealing process in the steel plate manufacturing process. That is, the cooling liquid and cooling method according to some embodiments may be used to cool the steel plate S in equipment other than the continuous annealing furnace 10.
  • the coolant includes a first ion that can be converted in solution to a first substance that generates a reducing gas upon decomposition, and a first ion that can react with iron oxide to form an iron-containing ionic compound. 2 ions.
  • the concentration of the first ions in the coolant is from 0.5% by weight to 6% by weight, and the concentration of the second ions in the coolant is from 1.0% by weight to 28% by weight. Note that the coolant contains water.
  • the concentration of ions herein is the concentration at room temperature (25° C.).
  • the coolant according to the above-described embodiment contains the above-described first ions, reducing gas is generated by decomposition of the first substance in the coolant. Therefore, during cooling of the steel sheet S using the cooling liquid, the oxidation reaction of iron on the surface of the steel sheet S can be suppressed, thereby preventing the formation of an oxide film (scale, iron oxide) on the surface of the steel sheet S. Can be suppressed. Further, since the cooling liquid according to the above-described embodiment contains the above-mentioned second ions, even if an oxide film (iron oxide) is generated on the surface of the steel plate S during cooling of the steel plate S using the cooling liquid.
  • an ionic compound is formed by reaction with the second ion iron oxide, and the oxide film (iron oxide) can be dissolved and removed.
  • the concentration of the first ions is 0.5% by weight or more, and the concentration of the second ions is 1.0% by weight or more, so these effects can be easily obtained.
  • the concentration of the first ions in the cooling liquid according to the above-described embodiment is 6% by weight or less and the concentration of the second ions is 28% by weight or less, the cooling liquid is evaporated and concentrated during cooling of the steel sheet. Remaining of solute components on the surface can be suppressed.
  • the concentration of the first ions is 0.5% by weight or more and 6% by weight or less
  • the concentration of the second ions is 1.0% by weight or more and 28.0% by weight or less. Therefore, the pH tends to be higher than that of an acidic liquid (for example, hydrochloric acid) used for pickling the steel sheet S. Therefore, corrosion of the equipment and the steel plate S due to adhesion of the cooling liquid can be suppressed. Therefore, according to the cooling liquid according to the above-described embodiment, the steel plate S can be cooled while effectively suppressing corrosion of the equipment and the steel plate S, and generation of an oxide film on the surface of the steel plate S.
  • an acidic liquid for example, hydrochloric acid
  • the total concentration of the first ions and the second ions in the coolant may be 2.0% by weight or more and 33.0% by weight or less.
  • the total concentration of the first ions and the second ions is 2.0% by weight or more, the effect of suppressing the formation of an oxide film on the surface of the steel sheet S is relatively high. Further, since the above-mentioned total concentration is 33.0% by weight or less, the pH tends to be higher than that of an acidic liquid (such as hydrochloric acid) used for pickling the steel sheet S. Therefore, corrosion of the equipment and the steel plate S can be effectively suppressed, and the formation of an oxide film on the surface of the steel plate S can be effectively suppressed.
  • an acidic liquid such as hydrochloric acid
  • the first ion is an ion that can be transformed in solution into a first substance that generates a reducing gas upon decomposition.
  • the reducing gas is, for example, hydrogen (H 2 ) gas.
  • the first ion may be an ion containing a nitrogen atom (N).
  • the first ion may be an ion containing a nitrogen atom (N) and a hydrogen atom (H).
  • the first ion is, for example, ammonium ion (NH 4 + ), hydrazine ion (N 2 H 5 + or N 2 H 6 + ), or alcohol amine ion (for example, ethanolamine ion or triethanolamine). ion, etc.).
  • Ammonium ions as the first ions can be changed into ammonia (NH 3 ; first substance) in the solution (coolant). Furthermore, ammonia generates hydrogen gas, which is a reducing gas, by decomposition.
  • ammonia and ammonium ions exist in a state of ionization equilibrium in the solution.
  • the ammonia dissolved in the solution is decomposed according to the following formula (B) to generate hydrogen gas.
  • hydrogen gas which is a reducing gas, can be generated in the coolant containing ammonium ions.
  • the hydrazine ion as the first ion can be changed into hydrazine (N 2 H 4 ; first substance) in the solution (coolant). Moreover, hydrazine generates hydrogen gas, which is a reducing gas, when decomposed.
  • Ions of alcohol amines as the first ions can be changed into alcohol amines (first substance) in the solution (coolant). Further, alcohol amines generate hydrogen gas, which is a reducing gas, when decomposed.
  • the coolant containing the first ions is, for example, a first substance corresponding to the first ions (such as ammonia corresponding to ammonia as the first ion) or an ionic compound (salt) containing the first ions dissolved in water. You can get it by doing so.
  • the first substance is a substance obtained by changing the first ion in a solution, and is a substance that decomposes to generate a reducing gas.
  • the first substance may be a nitrogen compound containing a nitrogen atom.
  • the first substance may be a compound containing a nitrogen atom and a hydrogen atom.
  • the first substances corresponding to the above-mentioned first ions, ammonium ion, hydrazine ion, and alcohol amine ion are ammonia, hydrazine, and alcohol amine, respectively.
  • These first substances are compounds containing nitrogen atoms and hydrogen atoms, respectively.
  • the concentration of ammonium ions in the coolant may be 0.5% by weight or more and 5.3% by weight or less. If the concentration of ammonium ions in the cooling liquid is within this range, the pH of the cooling liquid tends to be higher than that of an acidic liquid (such as hydrochloric acid) used for pickling the steel sheet S. Therefore, corrosion of the equipment and the steel plate S due to adhesion of the cooling liquid can be effectively suppressed.
  • an acidic liquid such as hydrochloric acid
  • the coolant may include ammonia. That is, the coolant may be water with ammonia dissolved therein.
  • the coolant containing ammonia can be obtained by mixing water with ammonia water having a predetermined concentration in which ammonia is dissolved in advance.
  • the first ions in the coolant are ammonium ions.
  • the ammonia concentration in the coolant may be 1.8% by weight or more and 4.5% by weight or less. If the ammonia concentration in the cooling liquid is within this range, the pH of the cooling liquid tends to be higher than that of an acidic liquid (such as hydrochloric acid) used for pickling the steel sheet S. Therefore, corrosion of the equipment and the steel plate S due to adhesion of the cooling liquid can be effectively suppressed.
  • an acidic liquid such as hydrochloric acid
  • the second ion is an ion that can react with iron oxide to form an ionic compound containing iron.
  • the ionic compound may be a complex.
  • Ionic compounds containing iron are generally soluble in water. That is, iron oxide can be dissolved by causing the second ion to react with iron oxide.
  • the second ion is, for example, an organic acid ion (for example, acetate ion (CH 3 COO ⁇ ), etc.), an ionized amino acid (for example, glycine ionized (H 3 + NCH 2 COO ⁇ ), etc.), or a sulfate ion (SO 4 2- ) or chloride ion ( Cl- ).
  • organic acid ion for example, acetate ion (CH 3 COO ⁇ ), etc.
  • an ionized amino acid for example, glycine ionized (H 3 + NCH 2 COO ⁇ ), etc.
  • SO 4 2- sulfate ion
  • Cl- chloride ion
  • an organic acid ion (R-COO - ) as a second ion is generated when an organic acid is ionized in an aqueous solution (cooling liquid), but as shown in reaction formula (C) below, it is produced by ionization with iron oxide.
  • the reaction produces an organic acid salt of iron (R-COOFe).
  • Organic acid salts of iron eg iron acetate
  • sulfate ion (SO 4 2- ) as the second ion is generated by ionization of sulfate (for example, ammonium sulfate) in an aqueous solution (cooling liquid), but as shown in reaction formula (D) below, , produces iron sulfate (FeSO 4 ) by reaction with iron oxide.
  • Sulfate of iron (ferrous sulfate) is soluble in water.
  • the coolant containing the second ions can be obtained, for example, by dissolving in water a substance that can change into the second ions in a solution.
  • the second ion is an organic acid ion (such as acetic acid ion), an ionized amino acid (such as ionized glycine), a sulfate ion, or a chloride ion
  • the coolant containing the second ion is an organic acid (such as acetic acid ion). ), amino acids (such as glycine), sulfuric compounds, or chlorides in water.
  • the concentration of sulfate ions in the coolant may be 1.5% by weight or more and 14.0% by weight or less. If the concentration of sulfate ions in the cooling liquid is within this range, the pH of the cooling liquid tends to be higher than that of an acidic liquid (such as hydrochloric acid) used for pickling the steel sheet S. Therefore, corrosion of the equipment and the steel plate S due to adhesion of the cooling liquid can be effectively suppressed.
  • an acidic liquid such as hydrochloric acid
  • the concentration of acetate ions in the coolant may be 7.2% by weight or more and 17.8% by weight or less. If the concentration of acetate ions in the cooling liquid is within this range, the pH of the cooling liquid tends to be higher than that of an acidic liquid (such as hydrochloric acid) used for pickling the steel sheet S. Therefore, corrosion of the equipment and the steel plate S due to adhesion of the cooling liquid can be effectively suppressed.
  • an acidic liquid such as hydrochloric acid
  • the concentration of ionized glycine in the coolant may be 1.0% by weight or more and 10.0% by weight or less. If the concentration of ionized glycine in the coolant is within this range, the pH of the coolant tends to be higher than that of an acidic liquid (such as hydrochloric acid) used for pickling the steel sheet S. Therefore, corrosion of the equipment and the steel plate S due to adhesion of the cooling liquid can be effectively suppressed.
  • an acidic liquid such as hydrochloric acid
  • the coolant may include ammonium sulfate. That is, the coolant may be water in which ammonium sulfate is dissolved. In this case, the first ion in the coolant is ammonium ion and the second ion is sulfate ion.
  • the ammonium sulfate concentration in the coolant may be 2.0% by weight or more and 19.3% by weight or less. If the ammonium sulfate concentration in the cooling liquid is within this range, the pH of the cooling liquid tends to be higher than that of an acidic liquid (such as hydrochloric acid) used for pickling the steel sheet S. Therefore, corrosion of the equipment and the steel plate S due to adhesion of the cooling liquid can be effectively suppressed.
  • an acidic liquid such as hydrochloric acid
  • the coolant may include ammonium chloride. That is, the coolant may be water in which ammonium chloride is dissolved. In this case, the first ion in the coolant is an ammonium ion and the second ion is a chloride ion.
  • the ammonium sulfate concentration in the coolant may be 1.5% by weight or more and 15.7% by weight or less. If the ammonium chloride concentration in the cooling liquid is within this range, the pH of the cooling liquid tends to be higher than that of an acidic liquid (such as hydrochloric acid) used for pickling the steel sheet S. Therefore, corrosion of the equipment and the steel plate S due to adhesion of the cooling liquid can be effectively suppressed.
  • an acidic liquid such as hydrochloric acid
  • the pH of the coolant is 5 or higher. In some embodiments, the pH of the coolant may be greater than or equal to 5 and less than or equal to 14.
  • the pH of the cooling liquid is higher than the pH of the acidic liquid (such as hydrochloric acid) used for pickling the steel sheet S. Therefore, corrosion of the equipment and the steel plate S due to adhesion of the cooling liquid can be effectively suppressed. Therefore, the steel plate S can be cooled while effectively suppressing corrosion of the equipment and the steel plate S and generation of an oxide film on the surface of the steel plate S.
  • the acidic liquid such as hydrochloric acid
  • the coolant according to some embodiments can be obtained by dissolving a solute from which the first ion or the second ion is derived in water.
  • a coolant containing ammonium ions as the first ions can be obtained by dissolving ammonia or aqueous ammonia in water.
  • a cooling liquid containing acetate ion or ionized glycine as the second ion can be obtained by dissolving acetate ion or glycine in water.
  • a coolant containing ammonium ions as the first ions and sulfate ions as the second ions can be obtained by dissolving ammonium sulfate in water.
  • a method for cooling a steel plate includes a step of cooling the steel plate by supplying the above-mentioned cooling liquid to the surface of the steel plate.
  • the above-mentioned cooling liquid may be supplied to cool the steel plate during the annealing process of the steel plate.
  • the annealing treatment of the steel plate can be performed using, for example, the continuous annealing furnace 10 described above.
  • the cooling liquid can be supplied to the surface of the steel sheet S using, for example, cooling means (cooling nozzle 22, etc.) provided in the cooling zone 16 of the continuous annealing furnace 10 described above.
  • the steel plate is cooled using the above-mentioned cooling liquid under relatively high-temperature conditions where corrosion is likely to occur. Therefore, under such conditions, the steel plate can be cooled while effectively suppressing corrosion of the equipment and the steel plate and generation of an oxide film on the surface of the steel plate.
  • the temperature of the steel plate may be lowered by 300°C or more while supplying the cooling liquid to the steel plate.
  • the steel plate is cooled using the above-mentioned cooling liquid under relatively high-temperature conditions where corrosion is likely to occur. Therefore, under such conditions, the steel plate can be cooled while effectively suppressing corrosion of the equipment and the steel plate and generation of an oxide film on the surface of the steel plate.
  • Cooling liquids of Examples 1 to 25 shown in Tables 1 and 2 were prepared and tested and evaluated as described below.
  • the cooling liquids of Examples 4 to 25 contained the solutes (ammonia, ammonium sulfate, ammonium chloride, acetic acid and/or glycine) listed in Tables 1 and 2, respectively, to the concentrations listed in Tables 1 and 2. It was prepared by dissolving it in water. Note that the cooling liquids in Examples 1 to 3 are water that does not contain solutes.
  • the steel plate sample Before heating the steel plate sample to 800°C, the steel plate sample is grayish white, and when heated to 800°C (with an oxide film formed), the surface of the steel plate sample becomes dark gray. It is. Therefore, it can be determined by visual inspection whether the oxide film remains or has decreased.
  • Example 1 to 25 The evaluation results for Examples 1 to 25 are shown in Tables 1 and 2.
  • the evaluation result was A, and the oxide film on the surface of the steel plate sample was clearly reduced compared to before immersion in the coolant. Therefore, it has been found that by cooling the steel plate using the cooling fluids according to these examples, the oxide film on the steel plate can be removed or the formation of the oxide film can be suppressed.
  • Examples 1 to 3 which are comparative examples of the present invention
  • the appearance observation (visual observation) of the samples showed that most of the oxide film remained. Therefore, it has been found that the cooling fluids according to these examples cannot effectively remove the oxide film or effectively suppress the formation of the oxide film.
  • the oxide film was removed to some extent in the appearance observation (visual observation) of the samples, but as a result of EDS analysis, nitrogen (N) peaks were observed on the surface of the samples. was observed, indicating that the sample surface was nitrided.
  • the cooling fluid according to the embodiment of the present invention can effectively suppress the formation of an oxide film and corrosion on the surface of a steel plate during cooling of the steel plate.
  • the cooling liquid includes: A cooling liquid for cooling a steel plate, a first ion that can be converted in a solution into a first substance that generates a reducing gas upon decomposition; a second ion capable of reacting with iron oxide to form an iron-containing ionic compound; including;
  • the concentration of the first ions in the coolant is 0.5% by weight or more and 6% by weight or less,
  • the concentration of the second ions in the coolant is 1.0% by weight or more and 28% by weight or less.
  • the coolant in (1) above contains the above-mentioned first ions, reducing gas is generated by decomposition of the first substance in the coolant. Therefore, during cooling of the steel plate using the cooling liquid, the oxidation reaction of iron on the surface of the steel plate can be suppressed, thereby suppressing the formation of an oxide film (iron oxide) on the surface of the steel plate.
  • the cooling liquid in (1) above contains the above-mentioned second ions, even if an oxide film (iron oxide) is formed on the surface of the steel plate during cooling of the steel plate using the cooling liquid, the second ion The oxide film (iron oxide) can be dissolved and removed by the reaction between ions and iron oxide.
  • the cooling liquid of the above (1) has a first ion concentration of 0.5% by weight or more and a second ion concentration of 1.0% by weight or more, these effects are likely to be obtained.
  • the concentration of the first ion is 6% by weight or less and the concentration of the second ion is 28% by weight or less, so the surface of the steel material is It is possible to suppress the solute components from remaining in the water.
  • the concentration of the first ion is 0.5% by weight or more and 6% by weight or less
  • the concentration of the second ion is 1.0% by weight or more and 28.0% by weight or less.
  • the steel plate can be cooled while effectively suppressing corrosion of the equipment and the steel plate and generation of an oxide film on the surface of the steel plate.
  • a total concentration of the first ions and the second ions in the coolant is 2.0% by weight or more and 33.0% by weight or less.
  • the total concentration of the first ions and the second ions is 2.0% by weight or more, the effect of suppressing the formation of an oxide film on the surface of the steel sheet is relatively high. Further, since the above-mentioned total concentration is 33.0% by weight or less, the pH tends to be higher than that of an acidic liquid used for pickling steel plates. Therefore, it is possible to effectively suppress corrosion of equipment and steel plates, and also to effectively suppress the formation of oxide films on the surfaces of steel plates.
  • the first substance includes a nitrogen compound.
  • the first substance that generates a reducing gas (hydrogen gas, etc.) by decomposition contains a nitrogen compound, the pH of the coolant in which the first substance is dissolved tends to increase. Therefore, corrosion of equipment and steel plates due to adhesion of coolant can be effectively suppressed.
  • the first substance includes ammonia, hydrazine, or alcohol amines.
  • the first substance that generates a reducing gas upon decomposition contains ammonia, hydrazine, or alcohol amines
  • the pH of the coolant in which the first substance is dissolved tends to increase. Therefore, corrosion of equipment and steel plates due to adhesion of coolant can be effectively suppressed.
  • ammonia, hydrazine, or alcohol amines are the first substances that generate hydrogen (H 2 ) gas, which is a reducing gas, when decomposed.
  • the second ions include organic acid ions, ionized amino acids, sulfate ions, or chloride ions.
  • the first ion includes ammonium ion
  • the concentration of the ammonium ions in the coolant is 0.5% by weight or more and 5.3% by weight or less.
  • hydrogen gas which is a reducing gas
  • ammonium ion concentration in the cooling liquid is 0.5% by weight or more and 5.3% by weight or less
  • the pH tends to be higher than that of an acidic liquid used for pickling steel sheets. Therefore, corrosion of equipment and steel plates due to adhesion of coolant can be effectively suppressed.
  • the second ion includes a sulfate ion
  • the concentration of the sulfate ions in the coolant is 1.5% by weight or more and 14.0% by weight or less.
  • the cooling liquid contains ammonia
  • the concentration of ammonia in the coolant is 1.8% by weight or more and 4.5% by weight or less.
  • the coolant includes ammonium sulfate;
  • concentration of ammonium sulfate in the coolant is 2.0% by weight or more and 19.3% by weight or less.
  • hydrogen gas which is a reducing gas
  • hydrogen gas is generated by the decomposition of ammonia converted from ammonium ions in the solution. Oxidation reactions can be suppressed by hydrogen gas.
  • sulfate ions are present in the solution, even if an oxide film (iron oxide) is formed on the surface of the steel plate during cooling of the steel plate using a cooling liquid, the reaction with the sulfate ions will cause an oxide film (iron oxide) to form on the surface of the steel plate. ) can be removed by dissolving. Therefore, the formation of an oxide film on the surface of the steel sheet can be effectively suppressed.
  • the ammonium sulfate concentration in the cooling liquid is 2.0% by weight or more and 19.3% by weight or less, the pH tends to be higher than that of an acidic liquid used for pickling steel sheets. Therefore, corrosion of equipment and steel plates due to adhesion of coolant can be effectively suppressed.
  • the coolant includes ammonium chloride,
  • the concentration of ammonium chloride in the cooling liquid is 1.5% by weight or more and 15.7% by weight or less.
  • hydrogen gas which is a reducing gas
  • hydrogen gas is generated by the decomposition of ammonia converted from ammonium ions in the solution. Oxidation reactions can be suppressed by hydrogen gas.
  • chloride ions are present in the solution, even if an oxide film (iron oxide) is formed on the surface of the steel plate during cooling of the steel plate using a cooling liquid, the oxide film (iron oxide) will form due to the reaction with the chloride ions. Iron oxide) can be dissolved and removed. Therefore, the formation of an oxide film on the surface of the steel sheet can be effectively suppressed.
  • the ammonium chloride concentration in the cooling liquid is 1.5% by weight or more and 15.7% by weight or less, the pH tends to be higher than that of an acidic liquid used for pickling steel sheets. Therefore, corrosion of equipment and steel plates due to adhesion of coolant can be effectively suppressed.
  • the second ion includes an acetate ion
  • the concentration of the acetate ions in the coolant is 7.2% by weight or more and 17.8% by weight or less.
  • the acetate ions are present in the solution, even if an oxide film (iron oxide) is formed on the surface of the steel plate during cooling of the steel plate using a cooling liquid, the acetate ions and Through this reaction, the oxide film (iron oxide) can be dissolved and removed as iron acetate. Therefore, the formation of an oxide film on the surface of the steel sheet can be effectively suppressed. Further, since the acetate ion concentration in the cooling liquid is 7.2% by weight or more and 17.8% by weight or less, the pH tends to be higher than that of an acidic liquid used for pickling steel sheets. Therefore, corrosion of equipment and steel plates due to adhesion of coolant can be effectively suppressed.
  • the second ion includes ionized glycine
  • the concentration of the ionized glycine in the coolant is 1.0% by weight or more and 10.0% by weight or less.
  • the ionized glycine exists in the solution, even if an oxide film (iron oxide) is formed on the surface of the steel plate during cooling of the steel plate using a cooling liquid, the ionized glycine By reacting with glycine, the oxide film (iron oxide) can be dissolved and removed as an ionic compound with ionized glycine. Therefore, the formation of an oxide film on the surface of the steel sheet can be effectively suppressed. Further, since the concentration of ionized glycine in the cooling liquid is 1.0% by weight or more and 10.0% by weight or less, the pH tends to be higher than that of an acidic liquid used for pickling steel sheets. Therefore, corrosion of equipment and steel plates due to adhesion of coolant can be effectively suppressed.
  • the pH of the coolant is 5 or more.
  • the pH of the cooling liquid is 5 or more, so the pH is higher than that of an acidic liquid used for pickling steel plates. Therefore, corrosion of equipment and steel plates due to adhesion of the cooling liquid can be effectively suppressed. Therefore, the steel plate can be cooled while effectively suppressing corrosion of the equipment and the steel plate and generation of an oxide film on the surface of the steel plate.
  • a method for cooling a steel plate according to at least one embodiment of the present invention includes: A cooling method for cooling a steel plate, the method comprising: A step of cooling the steel plate by supplying the cooling liquid according to any one of (1) to (13) above to the steel plate is provided.
  • the coolant contains the above-mentioned first ions
  • reducing gas is generated by decomposition of the first substance in the coolant. Therefore, during cooling of the steel plate using the cooling liquid, the oxidation reaction of iron on the surface of the steel plate can be suppressed, thereby suppressing the formation of an oxide film (iron oxide) on the surface of the steel plate.
  • the cooling liquid contains the above-mentioned second ions, even if an oxide film (iron oxide) is formed on the surface of the steel plate during cooling of the steel plate using the cooling liquid, Also, the oxide film (iron oxide) can be dissolved and removed by reaction with the second ion.
  • the concentration of the first ions is 0.5% by weight or more and 6% by weight or less
  • the concentration of the second ions is 1.5% by weight or more and 28.0% by weight or less. It has a higher pH than the acidic liquid used for pickling steel sheets. Therefore, corrosion of equipment and steel plates due to adhesion of the cooling liquid can be suppressed. Therefore, according to the method (14) above, the steel plate can be cooled while effectively suppressing the corrosion of the equipment and the steel plate and the formation of an oxide film on the surface of the steel plate.
  • the temperature of the steel plate is lowered by 300° C. or more while supplying the cooling liquid.
  • the steel plate is cooled using the above-mentioned cooling liquid under conditions where corrosion is likely to occur at a relatively high temperature. Therefore, under such conditions, the steel plate can be cooled while effectively suppressing corrosion of the equipment and the steel plate and generation of an oxide film on the surface of the steel plate.
  • the cooling method includes: adding at least one of ammonia, ammonium sulfate, acetic acid or glycine to water to obtain the cooling liquid; In the cooling step, the cooling liquid is supplied to the steel plate to cool the steel plate.
  • a cooling liquid can be easily obtained by adding ammonia, ammonium sulfate, acetic acid, or glycine to water.
  • expressions expressing shapes such as a square shape or a cylindrical shape do not only mean shapes such as a square shape or a cylindrical shape in a strict geometric sense, but also within the range where the same effect can be obtained. , shall also represent shapes including uneven parts, chamfered parts, etc.
  • the expressions "comprising,””including,” or “having" one component are not exclusive expressions that exclude the presence of other components.

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  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
PCT/JP2022/021889 2022-05-30 2022-05-30 冷却液及び鋼板の冷却方法 WO2023233450A1 (ja)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61201737A (ja) * 1985-03-04 1986-09-06 Nippon Steel Corp 表面特性の良好な冷延鋼帯の製造方法
JPS63192820A (ja) * 1987-02-06 1988-08-10 Sumitomo Metal Ind Ltd 鋼材の冷却方法
JPS6442521A (en) * 1987-08-07 1989-02-14 Sumitomo Metal Ind Method for cooling metal
JPH01139728A (ja) * 1987-11-26 1989-06-01 Sumitomo Metal Ind Ltd 化成処理性に優れた連続焼鈍冷延鋼板の冷却処理方法
JPH01156429A (ja) * 1987-12-11 1989-06-20 Sumitomo Metal Ind Ltd 連続焼鈍冷延鋼板の冷却処理方法
JPH02170925A (ja) * 1988-12-21 1990-07-02 Sumitomo Metal Ind Ltd 連続焼鈍冷間圧延鋼板の製造方法
CN107881295A (zh) * 2017-11-18 2018-04-06 蚌埠中梁机械科技有限公司 一种铸铁模具的表面处理方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61201737A (ja) * 1985-03-04 1986-09-06 Nippon Steel Corp 表面特性の良好な冷延鋼帯の製造方法
JPS63192820A (ja) * 1987-02-06 1988-08-10 Sumitomo Metal Ind Ltd 鋼材の冷却方法
JPS6442521A (en) * 1987-08-07 1989-02-14 Sumitomo Metal Ind Method for cooling metal
JPH01139728A (ja) * 1987-11-26 1989-06-01 Sumitomo Metal Ind Ltd 化成処理性に優れた連続焼鈍冷延鋼板の冷却処理方法
JPH01156429A (ja) * 1987-12-11 1989-06-20 Sumitomo Metal Ind Ltd 連続焼鈍冷延鋼板の冷却処理方法
JPH02170925A (ja) * 1988-12-21 1990-07-02 Sumitomo Metal Ind Ltd 連続焼鈍冷間圧延鋼板の製造方法
CN107881295A (zh) * 2017-11-18 2018-04-06 蚌埠中梁机械科技有限公司 一种铸铁模具的表面处理方法

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