A method of inhibiting or eliminating steel ladle galling

Abstract

The application relates to a method for inhibiting or eliminating the adhesion of a steel ladle, belonging to the technical fields of steel metallurgy, comprehensive utilization of metallurgical resources and slag metallurgy. Specifically, a slagging agent is added into molten steel in a steel ladle to generate a slagging reaction with the ladle adhesion, a low-melting-temperature slag system is formed to inhibit or eliminate the adhesion, the slagging agent can also be sprayed on the surface of the ladle refractory material to inhibit or eliminate the ladle adhesion; one or more of the blast furnace slag, the refining slag, the electric furnace slag and the molten reduction slag is added into the empty ladle with the adhesion, and gas agitation is performed to promote the melting and elimination of the adhesion.

Description

Technical Field

[0001] This invention belongs to the fields of iron and steel metallurgy, metallurgical resource utilization and slag metallurgy technology, and specifically relates to a method for inhibiting or eliminating adhesions in molten steel ladles. Background Technology

[0002] In steel production, the ladle, as a container for holding molten steel, undertakes the fundamental task of transporting molten steel to subsequent processes, including continuous casting. During use, it has been observed that with increasing ladle age, deposits and crusts form on the surface of the refractory material around the ladle, at the slag line, and on the top. This reduces the volume of molten steel, decreases the total weight of the molten steel, affects the turning over of the ladle with residual slag, and impacts the quality of subsequent molten steel and the effectiveness of bottom blowing.

[0003] The causes of the adhering material in the molten steel ladle are as follows: ① High-calcium steel slag carried in by the molten steel, the main phase of which is dicalcium silicate with a high melting temperature; ② Adhering materials with high melting temperature formed by slag corrosion of the refractory materials in the molten steel ladle, including magnesium aluminum spinel, high alumina, high magnesium oxide, etc.

[0004] Phase analysis of the ladle binder shows that the binder is mainly composed of mineral phases with high melting temperatures. Under the conditions of molten steel temperature, it cannot melt away, which has an adverse effect on the volume of molten steel and subsequent processes.

[0005] Currently, in order to reduce the impact of binders, the main approach is to spray or add slag-reducing agents (calcium oxide and calcium fluoride) onto the surface of refractory materials. However, this approach has drawbacks such as high melting temperature and the addition of fluoride salts to the slag-reducing agents, which pollutes the environment. It cannot suppress or eliminate binders in molten steel ladles. Summary of the Invention

[0006] To address the severe problem of steel ladle adhesion, this invention provides a method for inhibiting or eliminating adhesion in steel ladles. The method involves: adding a slag-forming agent to the molten steel in the ladle, which reacts with the adhesion to form a slag system with a low melting temperature, thus inhibiting or eliminating the adhesion. The slag-forming agent can also be sprayed onto the surface of the refractory material of the steel ladle to inhibit or eliminate the adhesion. Then, one or more of the following are added to the empty ladle containing adhesion: blast furnace slag, refining slag, electric furnace slag, and molten reducing slag. Gas agitation promotes the dissolution and elimination of the adhesion.

[0007] The present invention provides a method for inhibiting or eliminating adhesions in molten steel ladles, comprising the following two methods:

[0008] Method A, which involves inhibiting the adhesion of substances to molten steel ladles, comprises the following steps:

[0009] (A-1) Add an inhibitor of ladle adhesion to the molten steel in the ladle (during the pouring of molten steel into the ladle) and / or to the empty ladle (after which molten steel is poured in);

[0010] (A-2) The inhibitor reacts directly with the binder in the molten steel ladle, melts, and forms and / or enters the low melting temperature slag, which is distributed on the surface of the molten steel.

[0011] (A-3) During the process of suppressing or melting the adhering material in the molten steel ladle, metallic steel is entrained in the adhering material and enters the molten steel.

[0012] Furthermore, the inhibitor in step A (A-1) of the method also has the effect of eliminating the steel ladle adhesions; the steel ladle adhesions are eliminated by the cyclical treatment process of steps (A-1) and (A-2), after which the steel ladle adhesions that have been formed disappear, and the number of cycles is 15-400 times.

[0013] Furthermore, in step (A-1) of method A, the method of adding the inhibitor is as follows: directly adding the inhibitor to the molten steel during the pouring process, and / or, adding the inhibitor to the bottom of the empty molten steel ladle before pouring in the molten steel, and / or, spraying it onto the refractory material surface on the inner wall of the empty molten steel ladle.

[0014] Furthermore, the empty molten steel ladle is a molten steel ladle that has been baked or poured out of the molten steel, and the temperature of the empty molten steel ladle is ≥700℃; the temperature of the molten steel in the molten steel ladle is ≥1400℃.

[0015] Furthermore, in step A (A-1) of the method, the inhibitor is a slag-forming agent, and the slag-forming agent is:

[0016] (aa)FeO; or;

[0017] (bb) One or more of FeO, MnO, CaO, Al2O3, and MgO are mixed and used with SiO2; or;

[0018] (cc) One or more of the following: ordinary blast furnace slag, refining slag, electric furnace smelting slag, and heavy metal smelting slag; or;

[0019] (dd)SiO2, CaO, Al2O3, FeO, MnO, MgO are mixed together and then mixed with one or more of ordinary blast furnace slag, refining slag, electric furnace smelting slag and heavy metal smelting slag.

[0020] Furthermore, the ordinary blast furnace slag, refining slag, electric furnace smelting slag, and heavy metal smelting slag are in a molten or cold state; the melting temperature of the low melting temperature slag in step A (A-2) of the method is ≤1400℃.

[0021] Furthermore, in step A (A-1) of the method, the ordinary blast furnace slag, refining slag, electric furnace smelting slag, and heavy metal smelting slag are desulfurized slags; the total sulfur content in the desulfurized slag is ≤0.35% by mass; and the TiO2 content in the ordinary blast furnace slag and electric furnace smelting slag is ≤3% by mass.

[0022] Furthermore, in step A (A-1) of the method, the amount of inhibitor added is: 5 kg ≥ 0.6 kg per ton of molten steel.

[0023] Furthermore, in step (A-2) of method A, the main crystalline phase in the low melting temperature slag is one or more of the following: olivine structure, ordinary blast furnace slag, FeO structure, and binary eutectic structure, excluding magnesium olivine structure; the melting temperature of the olivine is ≤1350℃; the melting temperature of the ordinary blast furnace slag structure is ≤1350℃.

[0024] Method B, which removes adhering substances from molten steel ladles, comprises the following steps:

[0025] (B-1) Mix one or more of the following: molten blast furnace slag, molten refining slag, electric furnace smelting slag, molten reduction slag, ferroalloy slag and heavy metal smelting slag, pour into an empty steel ladle with adhesive material, and introduce gas to agitate.

[0026] (B-2) The binder in the molten steel ladle gradually dissolves and enters one or more of the following: molten blast furnace slag, molten refining slag, electric furnace smelting slag, molten reduction smelting slag, ferroalloy slag, and heavy metal smelting slag. The steel entrained in the binder settles to the bottom, forming bottom-settled molten steel.

[0027] Furthermore, steps (B-1) and (B-2) are repeated multiple times to remove the adhering material from the molten steel ladle, with the number of cycles being 2-5 times.

[0028] Furthermore, in step B (B-1) of the method, the blast furnace slag is one or both of ordinary blast furnace slag and titanium-containing blast furnace slag, wherein the titanium-containing blast furnace slag contains TiO2 > 3%; the ordinary blast furnace slag contains TiO2 ≤ 3%; the molten blast furnace slag, molten refining slag, electric furnace smelting slag, molten reduction smelting slag, ferroalloy slag, and heavy metal smelting slag are in a molten or cold state; the molten blast furnace slag, molten refining slag, electric furnace smelting slag, and heavy metal smelting slag are in a molten or cold state. The temperature of one or more of the following mixed slags—molten reduction ironmaking slag, ferroalloy slag, and heavy metal smelting slag—is ≥1280℃. When the slag temperature is <1280℃, it is heated by an electric furnace. The molten blast furnace slag, molten refining slag, electric furnace smelting ironmaking slag, molten reduction ironmaking slag, ferroalloy slag, and heavy metal smelting slag are directly derived from blast furnaces, electric furnaces, molten reduction furnaces, and heavy metal smelting processes. The molten refining slag is directly derived from steel refining processes.

[0029] Furthermore, in step B (B-1) of the method, the gas is one or a mixture of two or more of oxygen, air, oxygen-enriched air, nitrogen, and argon; the gas introduced into the titanium-containing blast furnace slag is one or more of oxygen, air, and oxygen-enriched air.

[0030] Furthermore, the iron impurities in the molten blast furnace slag, molten refining slag, electric furnace smelting slag, molten reduction smelting slag, ferroalloy slag, and heavy metal smelting slag settle to the bottom of the molten steel ladle; the molten steel settling at the bottom of the molten steel ladle and the molten iron settling in the slag are directly returned to the converter or electric furnace.

[0031] Furthermore, the heavy metal smelting slag in methods A and B is pyrometallurgical slag of copper, lead, nickel, tin, and zinc.

[0032] Table 1. Chemical composition (%) of heavy metal pyrometallurgical slag (copper smelting slag)

[0033] FeO <![CDATA[Fe3O4]]> <![CDATA[SiO2]]> Other components 30.00～60.00 8.00～40.00 20.00～40.00 3.00～10.00

[0034] Table 2 Chemical composition (%) of heavy metal pyrometallurgical slag (nickel smelting slag

[0035] FeO <![CDATA[Fe3O4]]> <![CDATA[SiO2]]> Other components 25～50.00 6.00～25.00 28.00～40.00 6～12.00

[0036] Table 3 Chemical composition (%) of heavy metal pyrometallurgical slag (lead smelting slag)

[0037] FeO <![CDATA[Fe3O4]]> <![CDATA[SiO2]]> Other components 25.00～50.00 6.00～25.00 15.00～40.00 8.00～20.00

[0038] Table 4. Chemical composition (%) of heavy metal pyrometallurgical slag (tin smelting slag)

[0039] FeO <![CDATA[Fe3O4]]> <![CDATA[SiO2]]> Other components 25.00～50.00 6.00～25.00 15.00～42.00 3.00～18.00

[0040] Table 5. Chemical composition (%) of heavy metal pyrometallurgical slag (zinc smelting slag)

[0041] FeO <![CDATA[Fe3O4]]> <![CDATA[SiO2]]> Other components 20.00～50.00 6.00～30.00 7.00～40.00 3.00～18.00

[0042] Table 6 Chemical composition (%) of ordinary blast furnace slag

[0043] CaO <![CDATA[SiO2]]> MgO <![CDATA[Al2O3]]> Other components 35.00～46.00 33.00～45.00 4.00～10.00 4.00～16.00 3.00～7.00

[0044] Table 7 Chemical composition (%) of titanium-containing blast furnace slag

[0045] CaO <![CDATA[SiO2]]> MgO <![CDATA[Al2O3]]> <![CDATA[TiO2]]> Other components 26.00～32.00 24.00～28.00 4.00～10.00 4.00～10.00 6.00～25.00 3.00～6.00

[0046] Table 8 Chemical composition (%) of calcium aluminate refining slag (steelmaking)

[0047] CaO <![CDATA[SiO2]]> <![CDATA[Al2O3]]> Other components 44.00～50.00 3.00～5.00 40.00～45.00 1.00～5.00

[0048] Table 9 Chemical composition (%) of dicalcium silicate calcium refining slag (steelmaking)

[0049] CaO <![CDATA[SiO2]]> <![CDATA[Al2O3]]> Other components 55.00～62.00 23.00～30.00 7.00～9.00 1.00～5.00

[0050] Table 10 Chemical composition (%) of iron slag from electric furnace smelting

[0051] CaO <![CDATA[SiO2]]> MgO <![CDATA[Al2O3]]> Other components 20.00～46.00 33.00～48.00 3.00～12.00 3.00～12.00 1.00～8.00

[0052] The principle of this invention:

[0053] (1) In method A, the slag-forming agent itself is a slag system with a low melting temperature, or (inhibitor) reacts with the binder to form a slag system with a low melting temperature (MgO-CaO-Al2O3-SiO2, FeO-MgO-CaO-Al2O3-SiO2, FeO-MnO-MgO-CaO-Al2O3-SiO2, FeO-MgO-CaO-Al2O3-SiO2, etc., melting temperature ≦1350℃, olivine structure, or ordinary blast furnace slag structure, or other binary eutectic structure with a low melting temperature), which is distributed on the surface of molten steel to inhibit or eliminate the binder and play a role in heat preservation of molten steel.

[0054] In addition, FeO has a low melting point, which can lower the melting temperature of the slag system and melt the binder, thus facilitating the melting of the binder.

[0055] (2) Method A utilizes desulfurized ordinary blast furnace slag, refining slag, electric furnace smelting slag, and molten iron slag.

[0056] The low melting temperature of reducing slag iron slag and heavy metal smelting slag inhibits or eliminates adhering substances.

[0057] (3) Method B utilizes molten ordinary blast furnace slag, refined slag, electric furnace slag, and molten metal.

[0058] Reduced slag, ferroalloy slag, and heavy metal smelting slag have high physical heat, high chemical activity, or low melting temperature, resulting in slag-forming reactions that eliminate binders.

[0059] (4) Method B utilizes molten ordinary blast furnace slag, refining slag, electric furnace smelting slag, molten reduction slag and heavy metal smelting slag, and under stirring conditions, promotes the dissolution of the binder into the slag, thereby eliminating the binder.

[0060] Advantages and beneficial effects of the present invention:

[0061] (1) The raw materials and process costs are low, and no equipment investment is required. The low melting temperature slag formed and / or added plays a role in heat preservation of molten steel.

[0062] (2) Short process and low energy consumption are features of the present invention, which suppresses or eliminates adhesives with the fewest steps.

[0063] (3) Utilizing the high physical heat, high chemical activity or low melting temperature of ordinary blast furnace slag, refining slag, electric furnace smelting slag, molten reduction slag, ferroalloy slag and heavy metal smelting slag, no heating is required, energy consumption is low, carbon is low, and the effect of inhibiting or eliminating binders is good.

[0064] (4) A feature of this invention is that it can recover steel or iron from binders, blast furnace slag, electric furnace slag, molten reduction slag, refining slag and ferroalloy slag. Detailed Implementation

[0065] The technical solution of the present invention will be further described below through embodiments.

[0066] Example 1 (Method A slag-forming agent, aa)

[0067] During the pouring of molten steel into the ladle, FeO is added at a rate of 1.5 kg per ton of molten steel (700°C for an empty ladle, 1480°C for the molten steel inside). The binders in the molten steel react with the FeO to form a low-melting-point slag system (ferroolitic structure, melting point 1300°C), thus inhibiting the formation of the binders. Simultaneously, the low-melting-point slag covers the surface of the molten steel, providing insulation. During the process of inhibiting or melting the binders in the ladle, steel entrained within the binders is incorporated into the molten steel.

[0068] Comparative Example 1

[0069] Other conditions were the same as in Example 1, with the molten steel temperature in the ladle at 1390°C, which was insufficient to melt the adhesive.

[0070] Comparative Example 2

[0071] Other conditions are the same as in Example 1, with an addition amount of 0.5 kg per ton of molten steel, and the binder does not melt.

[0072] Example 2 (Method A slag-forming agent, bb)

[0073] A mixture of FeO and SiO2 (molar ratio 2:1, based on the fir olivine structure) is added to an empty ladle (temperature 780℃), followed by molten steel (temperature 1400℃), at a rate of 1.3 kg per ton of molten steel. The binders in the molten steel, FeO, and SiO2 react to form a low-melting-point slag system (fir olivine structure, low melting point slag temperature 1260℃), inhibiting binder formation. Simultaneously, the low-melting-point slag covers the surface of the molten steel, providing insulation. During the process of inhibiting or melting the binders in the ladle, steel entrained in the binders is introduced into the molten steel.

[0074] Comparative Example 3

[0075] Other conditions were the same as in Example 2, with the temperature of the empty steel tank at 690°C, which was insufficient to melt the adhesive.

[0076] Comparative Example 4

[0077] Other conditions were the same as in Example 2, but FeO was not added, so a low melting temperature slag could not be formed, and the binder could not be melted.

[0078] Example 3 (Method A slag-forming agent, bb)

[0079] A mixture of MgO-CaO-Al2O3-SiO2 (composition: basicity CaO / SiO2 = 1.10, MgO mass percentage 7%, Al2O3 mass percentage 10%, based on ordinary blast furnace slag structure) is added to an empty ladle (empty ladle temperature 750℃). Molten steel is then added, with the ladle temperature at 1490℃, at a rate of 2.5 kg / ton of molten steel. The binders in the molten steel, along with MgO, CaO, Al2O3, and SiO2, react to form a low-melting-point slag system (ordinary blast furnace slag structure, low-melting-point slag temperature 1350℃), inhibiting binder formation. Simultaneously, the low-melting-point slag covers the surface of the molten steel, providing insulation. During the process of inhibiting or melting the binders in the ladle, steel entrained in the binders is introduced into the molten steel.

[0080] Comparative Example 5

[0081] Other conditions were the same as in Example 3, but SiO2 was not added, so a low melting temperature slag (olivine or ordinary blast furnace slag structure) could not be formed, and the binder could not be melted.

[0082] Example 4 (Method A slag-forming agent, bb)

[0083] During the pouring of molten steel into the ladle, a mixture of FeO-MgO-CaO-Al2O3-SiO2 (composition: basicity CaO / SiO2 = 1.10, MgO mass percentage 5%, Al2O3 mass percentage 7%, FeO mass percentage 5%, based on the structure of ordinary blast furnace slag) is added to the ladle (molten steel temperature 1490℃, empty ladle temperature 750℃). The addition amount is 2.3 kg per ton of molten steel. The binders in the molten steel, FeO, MgO, CaO, Al2O3, and SiO2 react to form a low-melting-point slag system (ordinary blast furnace slag structure, low-melting-point slag temperature 1330℃), inhibiting the formation of binders. Simultaneously, the low-melting-point slag covers the surface of the molten steel, providing insulation. During the process of inhibiting or melting the binders in the ladle, steel entrained in the binders is introduced into the molten steel.

[0084] Example 5 (Method A slagging agent, bb)

[0085] A FeO-MgO-CaO-SiO2 mixture (composition, olivine structure, (FeO+MgO+CaO) / SiO2 (molar ratio) = 2:1, with MgO mass percentage 4% and CaO mass percentage 8%) is added to a ladle (molten steel temperature 1490℃, empty ladle temperature 750℃). The addition amount is 2.0 kg per ton of molten steel. The binders in the molten steel, MgO, CaO, and SiO2 react to form a low-melting-point slag system (olivine structure, low melting temperature slag 1310℃), inhibiting binder formation. Simultaneously, the low-melting-point slag covers the surface of the molten steel, providing insulation. During the process of inhibiting or melting the binders in the ladle, steel entrained in the binders is introduced into the molten steel.

[0086] Comparative Example 6

[0087] Other conditions are the same as in Example 5, but SiO2 is not added, so it is impossible to form an olivine phase or a common blast furnace slag structure, to form a low melting temperature slag, and to melt the binder.

[0088] Example 6 (Method A slagging agent, bb)

[0089] A FeO-MgO-SiO2 mixture (composition, olivine structure, (FeO+MgO) / SiO2 (molar ratio) = 2:1, with MgO mass percentage of 5%) is added to a ladle (molten steel temperature 1490℃, empty ladle temperature 750℃). The addition amount is 1.4 kg per ton of molten steel. The binders in the molten steel, MgO, and SiO2 react to form a low-melting-point slag system (magnesian olivine structure, low melting temperature slag 1300℃), inhibiting binder formation. Simultaneously, the low-melting-point slag covers the surface of the molten steel, providing insulation. During the process of inhibiting or melting the binders in the ladle, steel entrained in the binders is introduced into the molten steel.

[0090] Comparative Example 7

[0091] Other conditions were the same as in Example 6, except that FeO was not added and MgO was used instead of FeO to form a magnesium olivine phase, which could not form a low melting temperature slag and could not melt the binder.

[0092] Example 7 (Method A slagging agent, bb)

[0093] A FeO-CaO-SiO2 mixture (composition, olivine structure, (FeO+CaO) / SiO2 molar ratio = 2:1, with CaO mass percentage 10%) is added to a ladle (molten steel temperature 1490℃, empty ladle temperature 750℃). Then, molten steel is added at a rate of 1.4 kg per ton of molten steel. The binders in the molten steel, CaO, and SiO2 react to form a low-melting-point slag system (calcium-iron olivine structure, low melting temperature slag 1290℃), inhibiting binder formation. Simultaneously, the low-melting-point slag covers the surface of the molten steel, providing insulation. During the process of inhibiting or melting the binders in the ladle, steel entrained in the binders is introduced into the molten steel.

[0094] Example 8 (Method A slagging agent, bb)

[0095] A FeO-Al2O3-SiO2 mixture (composition, olivine structure, (FeO) / SiO2 (molar ratio) = 2:1, with Al2O3 mass percentage of 3%) is added to a ladle (molten steel temperature 1490℃, empty ladle temperature 750℃) at a rate of 2.3 kg / ton of molten steel. The binders, CaO, and SiO2 in the molten steel react to form a low-melting-point slag system (ferroolivine structure, low melting temperature slag 1320℃), inhibiting binder formation. Simultaneously, the low-melting-point slag covers the surface of the molten steel, providing insulation. During the process of inhibiting or melting the binders in the ladle, steel entrained in the binders is introduced into the molten steel.

[0096] Example 9 (Method A slag-forming agent, bb)

[0097] A MnO-SiO2 mixture (composition based on manganese olivine structure, (MnO) / SiO2 (molar ratio) = 2:1) is added to a ladle (molten steel temperature 1490℃, empty ladle temperature 750℃) at a rate of 1.3 kg / ton of molten steel. The binders in the molten steel, MnO, and SiO2 react to form a low-melting-point slag system (manganese olivine structure, low melting point slag temperature 1220℃), inhibiting binder formation. Simultaneously, the low-melting-point slag covers the surface of the molten steel, providing insulation. During the process of inhibiting or melting the binders in the ladle, steel entrained in the binders is introduced into the molten steel.

[0098] Comparative Example 8

[0099] Other conditions were the same as in Example 9, but MnO was not added, so a low melting temperature slag could not be formed, and the binder could not be melted.

[0100] Example 10 (Method A slag-forming agent, bb)

[0101] A FeO-MnO-SiO2 mixture (composition based on a manganese-iron olivine structure, with a molar ratio of (MnO+FeO) / SiO2 = 2:1), and a FeO mass percentage of 20%) is added to a ladle (the temperature of the molten steel in the ladle is 1490℃, and the temperature of the empty ladle is 750℃). The addition amount is 1.4 kg per ton of molten steel. The binders in the molten steel, FeO, MnO, and SiO2 react to form a low-melting-point slag system (manganese-iron olivine structure, with a low melting point of 1230℃), thus inhibiting the formation of binders. Simultaneously, the low-melting-point slag covers the surface of the molten steel, providing insulation. During the process of inhibiting or melting the binders in the ladle, steel entrained in the binders is introduced into the molten steel.

[0102] Example 11 (Method A slag-forming agent, bb)

[0103] A mixture of FeO-MnO-Al2O3-MgO-CaO-SiO2 (composition: basicity CaO / SiO2 = 1.1, MgO mass percentage 8%, Al2O3 mass percentage 9%, FeO mass percentage 6%, MnO mass percentage 4%, based on a manganese-iron olivine structure mixed with ordinary blast furnace slag) is added to a ladle (the ladle temperature is 750℃, and the empty ladle temperature is 1310℃). The addition amount is 1.8 kg per ton of molten steel. The binders in the molten steel, FeO, MnO, and SiO2 react to form a low-melting-point slag system (a manganese-iron olivine structure mixed with ordinary blast furnace slag, with a low-melting-point slag temperature of 1310℃), inhibiting the formation of binders. Simultaneously, the low-melting-point slag covers the surface of the molten steel, providing insulation. During the process of inhibiting or melting the binders in the ladle, steel entrained in the binders is introduced into the molten steel.

[0104] Comparative Example 9

[0105] Other conditions are the same as in Implementation 11, but without the addition of SiO2, it is impossible to form a low melting temperature slag (olivine structure or ordinary blast furnace slag structure), and the binder cannot be melted.

[0106] Example 12 (Method A slag-forming agent, cc)

[0107] Desulfurized molten ordinary blast furnace slag (CaO / SiO2 = 1.1%, Al2O3 = 7%, MgO = 6%, other components = 3%, TiO2 ≤ 3%) is added to molten steel in a ladle (temperature 1490℃ in the ladle, temperature 750℃ in the empty ladle). The sulfur content in the desulfurized blast furnace slag is 0.35%, and the addition rate is 2.3 kg / ton of molten steel. The adhering material in the molten steel reacts with the desulfurized, cooled blast furnace slag to form a low melting temperature slag (melting temperature 1330℃), thus inhibiting the formation of adhering material. Simultaneously, the low melting temperature slag covers the surface of the molten steel, providing insulation. During the process of inhibiting or melting the adhering material in the ladle, steel entrained in the adhering material is introduced into the molten steel.

[0108] Example 13 (Method A slagging agent, cc)

[0109] Desulfurized cold refining slag (dicalcium silicate slag, CaO 60%, SiO2 28%, Al2O3 8%, other components 4%) is added to molten steel in a ladle (molten steel temperature 1490℃, empty ladle temperature 750℃). The sulfur content of the desulfurized slag is 0.28%, and the addition rate is 5 kg / ton of molten steel. The adhering substances in the molten steel react and melt with the desulfurized cold refining slag, forming a low melting temperature slag (melting temperature 1400℃), thus inhibiting the formation of adhering substances. Simultaneously, the low melting temperature slag covers the surface of the molten steel, providing insulation. During the process of inhibiting or melting the adhering substances in the ladle, steel entrained in the adhering substances enters the molten steel.

[0110] Example 14 (Method A slagging agent, cc)

[0111] Molten refining slag (calcium aluminate slag, CaO 50%, SiO2 3%, Al2O3 45%, other components 2%) is added to a ladle (molten steel temperature 1490℃, empty ladle temperature 750℃). The sulfur content of the desulfurized slag is 0.28%, and the addition rate is 3 kg / ton of molten steel. The adhering substances in the molten steel react and melt with the cold refining slag after desulfurization, forming a low melting temperature slag (melting temperature 1390℃), thus inhibiting the formation of adhering substances. Simultaneously, the low melting temperature slag covers the surface of the molten steel, providing insulation. During the process of inhibiting or melting the adhering substances in the ladle, steel entrained in the adhering substances enters the molten steel.

[0112] Example 15 (Method A slagging agent, cc)

[0113] Molten steel (temperature in the ladle: 1490℃, empty ladle: 750℃) is mixed with desulfurized molten electric furnace smelting slag (CaO / SiO2: 1.0%, MgO: 8%, Al2O3: 10%, other components: 8%). The sulfur content of the desulfurized slag is 0.28%, and the addition rate is 3 kg per ton of molten steel. The adhering substances in the molten steel react and melt with the desulfurized cold refining slag, forming a low-melting-temperature slag (melting temperature: 1380℃), thus inhibiting the formation of adhering substances. Simultaneously, the low-melting-temperature slag covers the surface of the molten steel, providing insulation. During the process of inhibiting or melting the adhering substances in the ladle, steel entrained in the adhering substances enters the molten steel.

[0114] Example 16 (Method A slagging agent, cc)

[0115] A mixture of desulfurized heavy metal smelting slag (nickel smelting slag (FeO 36%, Fe3O4 15%, SiO2 40%, others 9%)) and tin smelting slag (FeO 39%, Fe3O4 12%, SiO2 38%, others 11%)) and tin smelting slag (FeO 39%, Fe3O4 12%, SiO2 38%, others 11%), with nickel smelting slag comprising 90%) was added to molten steel in a ladle (molten steel temperature 1490℃, empty ladle temperature 750℃). The sulfur content in the desulfurized slag was 0.12%, and the addition rate was 5.0 kg / ton of molten steel. The adhering substances in the molten steel reacted with the desulfurized mixed smelting slag (low melting temperature slag, fir olivine phase), dissolving to form a low melting temperature slag (melting temperature 1390℃), thus inhibiting the formation of adhering substances. Meanwhile, the low melting temperature slag covers the surface of the molten steel, which plays a role in heat preservation. During the process of inhibiting or melting the adhering material in the molten steel ladle, steel entrained in the adhering material enters the molten steel.

[0116] Comparative Example 10

[0117] Other conditions were the same as in Example 16, but the amount of inhibitor added was 5.1 kg, which resulted in an excessive amount of steel slag, affecting the quality of molten steel. The steel slag was also difficult to handle.

[0118] Example 17 (Method A slagging agent, cc)

[0119] First, a mixture of desulfurized heavy metal smelting slag (copper smelting slag (43% FeO, 15% Fe3O4, 31% SiO2, and 11% other components) and lead smelting slag (36% FeO, 15% Fe3O4, 38% SiO2, and 11% other components) with copper smelting slag comprising 90% was added to an empty ladle containing adhering material (the ladle temperature was 750℃). The sulfur content of the desulfurized slag was 0.12%, and the addition rate was 0.8 kg / ton of molten steel. Then, molten steel was added, and the ladle temperature was 1400℃. The adhering material in the molten steel reacted with the desulfurized nickel smelting slag (low melting temperature slag, fir olivine phase), melting and forming a low melting temperature slag (melting temperature 1220℃), gradually dissolving the adhering material. Meanwhile, the low melting temperature slag covers the surface of the molten steel, which plays a role in heat preservation. During the process of inhibiting or melting the adhering material in the molten steel ladle, steel entrained in the adhering material enters the molten steel.

[0120] Repeat the above process 28 times until the adhesive residue on the molten steel ladle disappears.

[0121] Comparative Example 11

[0122] Under the same conditions as in Example 17, the experiment was performed once, but the adhesive could not be eliminated.

[0123] Example 18 (Method A slagging agent, dd)

[0124] A mixture of desulfurized molten dicalcium silicate refining slag, SiO2, MgO, and Al2O3 (based on mass, dicalcium silicate refining slag is 100%, CaO is 60%, SiO2 is 28%, Al2O3 is 7%, and others are 5%), with SiO2 added at 34%, MgO at 12%, and Al2O3 at 10%). The sulfur content in the desulfurized slag is 0.30%, and the addition rate is 3 kg / ton of molten steel. The binders in the molten steel react and melt with the desulfurized cold refining slag mixture, forming a low melting temperature slag (ordinary blast furnace slag structure, melting temperature 1330℃), thus inhibiting the formation of binders. Meanwhile, the low melting temperature slag covers the surface of the molten steel, which plays a role in heat preservation. During the process of inhibiting or melting the adhering material in the molten steel ladle, steel entrained in the adhering material enters the molten steel.

[0125] Example 19 (Method A slag-forming agent, dd)

[0126] Add 2.2 kg / ton of molten steel to a ladle (molten steel temperature 1490℃, empty ladle temperature 750℃) of desulfurized cold-state electric arc furnace slag (sulfur content 0.25%), a mixture of SiO2 and Al2O3 (the mixture consists of 100% electric arc furnace slag (CaO / SiO2 1.0, MgO 8%, Al2O3 10%, others 8%), with SiO2 added at 5% and Al2O3 added at 2%), forming a common blast furnace slag structure. The binders in the molten steel, the desulfurized cold-state electric arc furnace slag (sulfur content 0.25%), SiO2, CaO, MgO, and Al2O3 react and dissolve, forming a low-melting-temperature slag (common blast furnace slag structure, melting temperature 1330℃), thus inhibiting the formation of binders. Meanwhile, the low melting temperature slag covers the surface of the molten steel, which plays a role in heat preservation. During the process of inhibiting or melting the adhering material in the molten steel ladle, steel entrained in the adhering material enters the molten steel.

[0127] Example 20 (Method A slag-forming agent, dd)

[0128] Add the following mixtures to the molten steel in the ladle (the temperature of the molten steel in the ladle is 1490℃, and the temperature of the empty ladle is 750℃): desulfurized cold-state calcium aluminate refining slag, ordinary blast furnace slag, electric furnace smelting slag, and SiO2 (by mass, the mixture consists of 100% mixed slag, 5% refining slag (CaO 50%, SiO2 3%, Al2O3 45%, others 2%), 70% ordinary blast furnace slag (CaO / SiO2 1.1, MgO 6%, Al2O3 7%, others 3%), 20% electric furnace smelting slag (CaO / SiO2 1.0, MgO 8%, Al2O3 10%, others 8%), and 5% SiO2 (ordinary blast furnace slag structure). The sulfur content in the desulfurized slag is 0.25%, and the addition amount is 3 kg per ton of molten steel. The binders in the molten steel react with the cold refining slag after desulfurization, melting and forming a low melting temperature slag (melting temperature 1370℃), thus inhibiting the formation of binders. At the same time, the low melting temperature slag covers the surface of the molten steel, playing a heat-insulating role. During the process of inhibiting or melting the binders in the molten steel ladle, steel entrained in the binders enters the molten steel.

[0129] Example 21 (Method A slag-forming agent, bb)

[0130] A mixture of FeO and SiO2 (molar ratio 2:1, based on an olivine structure) is sprayed onto the inner wall of an empty molten steel ladle (empty ladle temperature 780℃) at a rate of 5.0 kg / ton of molten steel. Molten steel is then added, bringing the ladle temperature to 1490℃. The binders in the molten steel, along with FeO and SiO2, react to form a low-melting-point slag system (olivine structure, low-melting-point slag temperature 1240℃), inhibiting binder formation. Simultaneously, the low-melting-point slag covers the surface of the molten steel, providing insulation. During the process of inhibiting or melting the binders in the ladle, steel entrained in the binders is introduced into the molten steel.

[0131] Example 22 (Method B)

[0132] Molten ordinary blast furnace slag (slag temperature 1420℃, TiO2 ≦ 3%) is poured into an empty steel ladle containing adhesive. A mixture of nitrogen and argon is introduced, and the adhesive in the steel ladle gradually melts and enters the blast furnace slag. The steel entrained in the adhesive settles to the bottom, and the settled steel and the settled metallic iron in the slag are sent to the converter for steelmaking.

[0133] Example 23 (Method B)

[0134] Molten ordinary blast furnace slag (TiO2≦3% in ordinary blast furnace slag), refined slag, electric furnace smelting slag and molten reducing slag mixed slag (the mixed slag contains 70% ordinary blast furnace slag, 10% refined slag, 10% electric furnace slag, 10% molten reducing slag, and the mixed slag temperature is 1280℃) is poured into an empty steel ladle containing adhesive material. Argon gas is introduced, and the adhesive material in the steel ladle gradually melts and enters the mixed slag. The steel entrained in the adhesive material settles to the bottom, and the settled steel and the settled metallic iron in the slag are sent to the converter for steelmaking.

[0135] Example 24 (Method B)

[0136] Molten ordinary blast furnace slag (TiO2≦3% in ordinary blast furnace slag), refined slag, electric furnace smelting slag and molten reducing slag mixed slag (the mixed slag contains 75% ordinary blast furnace slag, 10% refined slag, 5% electric furnace slag, and 10% molten reducing slag, and the mixed slag temperature is 1300℃) is poured into an empty steel ladle containing adhesive material. Nitrogen gas is introduced, and the adhesive material in the steel ladle gradually melts and enters the mixed slag. The steel entrained in the adhesive material settles to the bottom, and the settled steel and the settled metallic iron in the slag are sent to the converter for steelmaking.

[0137] Example 25 (Method B)

[0138] The molten titanium-containing blast furnace slag (slag temperature is 1390℃, TiO2 content in ordinary blast furnace slag is >3%), refined slag, electric furnace slag, and molten reducing slag are mixed and poured into an empty ladle containing adhesive. Oxygen is introduced, and the adhesive in the ladle gradually melts and enters the mixed slag. The steel entrained in the adhesive settles to the bottom, and the settled steel and the settled metallic iron in the slag are sent to the converter for steelmaking.

[0139] Comparative Example 12

[0140] Other conditions are the same as in Implementation 24, but no oxygen is introduced, and the low-valence titanium in the titanium-containing blast furnace slag is not oxidized, so a low melting temperature slag system cannot be formed.

[0141] Example 26 (Method B)

[0142] Cold ordinary blast furnace slag (TiO2≦3%) is poured into an empty molten steel ladle containing adhesive material. The ladle is heated to a molten state in an electric furnace (temperature 1420℃), and argon gas is introduced. The adhesive material in the molten steel ladle gradually melts and enters the blast furnace slag. The entrained metallic steel in the adhesive material settles to the bottom. The settled steel and the metallic iron settled in the slag are sent to the converter for steelmaking.

[0143] Example 27 (Method B)

[0144] Molten refining slag (slag temperature 1400℃) is poured into an empty steel ladle containing adhesive material. A mixture of argon and nitrogen (nitrogen accounts for 70%) is introduced. The adhesive material in the steel ladle gradually melts and enters the slag. The entrained metallic steel in the adhesive material settles to the bottom, and the settled steel is sent to the electric arc furnace for steelmaking.

[0145] Example 28 (Method B)

[0146] Cold heavy metal smelting slag (copper smelting slag) is poured into an empty steel ladle containing adhesive material. The electric furnace is heated to 1400°C, and nitrogen gas is introduced for stirring. The adhesive material in the steel ladle gradually melts and enters the molten slag. The entrained metal steel in the adhesive material settles to the bottom, and the settled steel is sent to the electric furnace for steelmaking.

[0147] Example 29 (Method B)

[0148] Molten ferroalloy smelting slag (molten nickel slag, slag temperature 1550℃) is poured into an empty steel ladle containing adhesive material. Nitrogen gas is introduced and stirred. The adhesive material in the steel ladle gradually melts and enters the slag. The entrained metallic steel in the adhesive material settles to the bottom, and the settled steel is sent to the electric arc furnace for steelmaking.

[0149] Example 30 (Method B)

[0150] Molten ordinary blast furnace slag (TiO2≦3% in ordinary blast furnace slag, slag temperature 1410℃) is poured into an empty steel ladle containing adhesive material. Argon gas is introduced, and the adhesive material in the steel ladle gradually melts and enters the blast furnace slag. The entrained metallic steel in the adhesive material settles to the bottom. The settled steel and the metallic iron settled in the slag are sent to the converter for steelmaking.

[0151] Repeat the above process three times until all the adhesive residue on the molten steel ladle disappears.

Claims

1. A method for inhibiting or eliminating adhesions in molten steel ladles, characterized in that, Includes either of the following two methods: Method A, which involves inhibiting the adhesion of substances to molten steel ladles, comprises the following steps: (A-1) Add an inhibitor of ladle adhesion to molten steel in a ladle and / or to an empty ladle; (A-2) The inhibitor reacts directly with the binder in the molten steel ladle, melts, and forms and / or enters the low melting temperature slag, which is distributed on the surface of the molten steel. (A-3) During the process of suppressing or melting the adhering material in the molten steel ladle, metallic steel is entrained in the adhering material and enters the molten steel. Method B, which removes adhering substances from molten steel ladles, comprises the following steps: (B-1) Mix one or more of the following: molten blast furnace slag, molten refining slag, electric furnace smelting slag, molten reduction slag, ferroalloy slag and heavy metal smelting slag, pour into an empty steel ladle with adhesive material, and introduce gas to agitate. (B-2) The binder in the molten steel ladle gradually dissolves and enters one or more of the following: molten blast furnace slag, molten refining slag, electric furnace smelting slag, molten reduction smelting slag, ferroalloy slag, and heavy metal smelting slag. The steel entrained in the binder settles to the bottom, forming bottom-settled molten steel.

2. The method for inhibiting or eliminating adhesions in a molten steel ladle according to claim 1, characterized in that, The inhibitor in step (A-1) of method A also has the effect of eliminating the adhesion of the molten steel ladle; the elimination of the adhesion of the molten steel ladle is achieved by repeating the process of steps (A-1) and (A-2) until the adhesion of the molten steel ladle disappears, with the number of cycles being 15-400; the inhibitor in step (A-1) of method A is added in the following ways: directly adding the inhibitor to the molten steel during the pouring process, and / or adding the inhibitor to the bottom of an empty molten steel ladle before pouring in the molten steel, and / or spraying it onto the refractory material surface of the inner wall of the empty molten steel ladle; the empty molten steel ladle is a molten steel ladle that has been baked or poured out of the molten steel, and the temperature of the empty molten steel ladle is ≥700℃; the temperature of the molten steel in the molten steel ladle is ≥1400℃.

3. The method for inhibiting or eliminating adhesions in a molten steel ladle according to claim 1, characterized in that, In step A (A-1) of the method, the inhibitor is a slag-forming agent, and the slag-forming agent is: (aa)FeO; or; (bb) One or more of FeO, MnO, CaO, Al2O3, and MgO are mixed and used with SiO2; or; (cc) One or more of the following: ordinary blast furnace slag, refining slag, electric furnace smelting slag, and heavy metal smelting slag; or; (dd)SiO2, CaO, Al2O3, FeO, MnO, MgO are mixed together and then mixed with one or more of ordinary blast furnace slag, refining slag, electric furnace smelting slag and heavy metal smelting slag.

4. The method for inhibiting or eliminating adhesions in a molten steel ladle according to claim 1, characterized in that, The ordinary blast furnace slag, refining slag, electric furnace smelting slag, and heavy metal smelting slag are in a molten or cold state; the melting temperature of the low melting temperature slag in step A (A-2) of the method is ≤1400℃.

5. The method for inhibiting or eliminating adhesions in a molten steel ladle according to claim 1, characterized in that, In step A (A-1) of the method, the ordinary blast furnace slag, refining slag, electric furnace smelting slag, and heavy metal smelting slag are desulfurized slags; the total sulfur content in the desulfurized slag is ≤0.35% by mass; and the TiO2 content in the ordinary blast furnace slag and electric furnace smelting slag is ≤3% by mass.

6. The method for inhibiting or eliminating adhesions in a molten steel ladle according to claim 1, characterized in that, In step A (A-1) of the method, the amount of inhibitor added is: 5 kg ≥ 0.6 kg per ton of molten steel.

7. The method for inhibiting or eliminating adhesions in a molten steel ladle according to claim 1, characterized in that, In step (A-2) of method A, the main crystalline phase in the low melting temperature slag is one or more of the following: olivine structure, ordinary blast furnace slag, FeO structure, and binary eutectic structure, excluding magnesium olivine structure; the melting temperature of the olivine is ≤1350℃; the melting temperature of the ordinary blast furnace slag structure is ≤1350℃.

8. The method for inhibiting or eliminating adhesions in a molten steel ladle according to claim 1, characterized in that, Steps (B-1) and (B-2) are repeated multiple times to remove the adhering material from the molten steel ladle, with the number of cycles being 2-5.

9. A method for inhibiting or eliminating adhesions in a molten steel ladle according to claim 1, characterized in that, The blast furnace slag in step B (B-1) of the method is one or both of ordinary blast furnace slag and titanium-containing blast furnace slag, with TiO2 > 3% in the titanium-containing blast furnace slag; TiO2 ≦ 3% in the ordinary blast furnace slag; the molten blast furnace slag, molten refining slag, electric furnace smelting slag, molten reduction slag, ferroalloy slag, and heavy metal smelting slag are either molten or cold; the temperature of one or more of the mixed slags among the molten blast furnace slag, molten refining slag, electric furnace smelting slag, molten reduction slag, ferroalloy slag, and heavy metal smelting slag is ≥ 1280℃, and when the slag temperature is < 1280℃, it is heated by an electric furnace; the molten blast furnace slag, molten refining slag, electric furnace smelting slag, molten reduction slag, ferroalloy slag, and heavy metal smelting slag directly comes from the blast furnace, electric furnace, molten reduction furnace, and heavy metal smelting process; the molten refining slag directly comes from the steel refining process.

10. A method for inhibiting or eliminating adhesions in a molten steel ladle according to claim 1, characterized in that, In step B (B-1) of method B, the gas is one or a mixture of two or more of oxygen, air, oxygen-enriched air, nitrogen, and argon; the gas introduced into the titanium-containing blast furnace slag is one or more of oxygen, air, and oxygen-enriched air; the iron impurities in the molten blast furnace slag, molten refining slag, electric furnace smelting slag, molten reduction smelting slag, ferroalloy slag, and heavy metal smelting slag settle to the bottom of the molten steel ladle; the molten steel settling at the bottom of the molten steel ladle and the molten iron settling in the slag are directly returned to the converter or electric furnace; the heavy metal smelting slag in methods A and B is copper, lead, nickel, tin, and zinc pyrometallurgical slag.