CN111304454B - Low-fluorine slag system for electroslag remelting B-containing 9Cr rotor steel ingot and use method thereof - Google Patents
Low-fluorine slag system for electroslag remelting B-containing 9Cr rotor steel ingot and use method thereof Download PDFInfo
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Abstract
The invention relates to a low-fluorine slag system for electroslag remelting B-containing 9Cr rotor steel ingot and a using method thereof, belongs to the technical field of electroslag special metallurgy, and solves the problem that the existing electroslag remelting method has the defects of high efficiency, low cost and low costIn the technology, the low-fluorine slag system for electroslag remelting of the B-containing 9Cr high-pressure rotor steel ingot has high fluorine content and great environmental pollution. A low-fluorine slag system for electroslag remelting of a B-containing 9Cr rotor steel ingot comprises the following components in percentage by mass: CaF2；5％～30％，CaO；25％～35％，Al2O3：40％～50％，MgO：2％～5％，B2O3: 0.1-3 percent of the total weight of the composition, and the balance of impurities; SiO in impurities2Is less than 0.5 percent. The low-fluorine slag system for electroslag remelting of the B-containing 9Cr rotor steel ingot has the advantages of obvious energy-saving and emission-reduction effects, high electric efficiency and small environmental pollution.
Description
Technical Field
The invention relates to the technical field of electroslag special metallurgy, in particular to a low-fluorine slag system for electroslag remelting of a B-containing 9Cr rotor steel ingot and a using method thereof.
Background
China is the first world-wide country of large electric power production and consumption, and the proportion of thermal power generation in China is 70-80%. However, most thermal power generating units are generally low in efficiency, which not only causes energy waste, but also brings serious environmental pollution. Therefore, China is urgently required to develop a high-efficiency power generation technology from both an economic perspective and an environmental protection perspective. The method for improving the generating efficiency of the power station comprises a reasonable management technology and a method for improving the unit efficiency, wherein the effective method for improving the unit efficiency is to improve the steam parameter level and develop the (supercritical) thermal power unit. At present, the heat-resistant steel rotor with 9-12% of Cr has good application performance, wherein European COST-FB2 is a typical leading edge steel type of 9Cr heat-resistant steel, the B content is about 0.01%, and the melting temperature range is 1329-1504 ℃.
The development of the supercritical rotor material and the key manufacturing technology thereof in China still needs to start from the aspects of smelting, heat treatment and the like. The smelting process is mainly used for improving the uniformity and purity of components and structures of cast ingots, and electroslag remelting is an important special smelting means. For example, FB2 steel of a generator set in China basically depends on import, and the important point is that some difficulties exist in electroslag smelting, such as control of narrow element components of a special slag system for FB2 steel and large-diameter electroslag ingots.
For a slag system for B-containing steel electroslag smelting, taking FB2 steel as an example, the conventional smelting slag system includes: (1) ternary slag system CaF2，Al2O3CaO and the balance of impurities, and is used for smelting COST-FB2 steel or CB2 steel and the like; (2) slag system CaF of five elements2，CaO，Al2O3，MgO，B2O3The slag system of (2). However, the design choice of the two slag systems is to determine the main component by the common ternary slag and properly supplement MgO and B2O3And finishing slag system design by a method of equal components. The two slag system common components have the problems of high fluorine content, great pollution and insufficient structural stability of the slag system components in the long-time electroslag smelting process. For the heat-resistant steel for the B-containing 9Cr high-pressure rotor and the special slag system for electroslag smelting of other stainless steel containing B less than or equal to 0.015 percent, further design is still needed from the aspects of energy conservation, consumption reduction, smelting stability and environmental protection.
Disclosure of Invention
In view of the above analysis, the embodiments of the present invention are directed to provide a low-fluorine slag system for electroslag remelting B-containing 9Cr rotor steel ingot and a use method thereof, so as to solve the problems of high energy consumption, unstable melting and environmental pollution of the existing B-containing electroslag melting slag system.
A low-fluorine slag system for electroslag remelting of a B-containing 9Cr rotor steel ingot comprises the following components in percentage by mass: CaF2；5％～30％，CaO；25％～35％，Al2O3：40％～50％，MgO：2％～5％，B2O3: 0.1-3 percent of the total weight of the composition, and the balance of impurities; SiO in impurities2＜0.5％。
Further, the slag system comprises the following components in percentage by mass: CaF2：5％～18％，CaO：25％～30％，Al2O3：45％～50％，MgO：2％～3％，B2O3: 0.1 to 1 percent, and the balance of impurities; SiO in impurities2＜0.5％。
Further, the melting point range is 1320-1420 ℃; the density is 2.80-3.0 g/cm at 800 DEG C3Viscosity less than or equal to 0.025 Pa.s and electric conductivityThe range is 0.9 to 1.5S/cm.
Further, the low-fluorine slag system is used for producing 9Cr rotor steel ingots with the B content of less than 0.015%.
A use method of a low-fluorine slag system for electroslag remelting of a B-containing 9Cr rotor steel ingot comprises the following steps:
step 1: using industrial pure CaF2、CaO、Al2O3、MgO、B2O3Slag is prepared according to the mass percentage of each component in the slag system and is preheated;
step 2: adding the preheated thermal-state slag into an electroslag furnace crystallizer;
and step 3: and (4) smelting in an electroslag furnace.
Further, in the step 1, the preheating temperature is higher than 600 ℃, and the preheating time is 3-5 hours.
Further, in step 2, firstly, adding hot slag before an electrode is filled into a crystallizer of the electroslag furnace, and uniformly spreading part of the hot slag to the bottom of the crystallizer; and uniformly adding the residual thermal slag into the crystallizer by using a feeder, and finishing the addition within 1-4 h.
Further, in the smelting process in the step 3, the thickness of a slag layer is designed to be 200-400 mm, the power input in an arc striking stage is 400-3500 kW, and the power input in a steady state stage is 390-3000 kW.
Further, the electrode melting speed in the melting process is 4-35 kg/min.
Further, after the smelting is finished, the thickness of the slag crust on the surface of the steel ingot is less than or equal to 1.8 mm.
Compared with the prior art, the invention can realize at least one of the following beneficial effects:
1. the invention is realized by adding B2O3，B2O3The steel slag melting furnace has the advantages that B elements which are easy to burn and lose among steel slag can be balanced, the burning loss of B is reduced, the content of the B elements in the steel slag is ensured, the energy-saving effect is achieved, and the technical requirements of difficult electroslag melting of 9Cr rotor steel are met.
2. Compared with high-fluorine slag system, the invention reduces CaF2The addition amount of the additive reduces environmental pollution and harm to human.
3. When the slag system electroslag is in steady state smelting, compared with a high-fluorine slag system, the power consumption can be reduced by more than 25%, the highest temperature of a slag pool can reach 1800-2000 ℃, the heat transfer quantity from the slag pool to a crystallizer accounts for 30-45% of the total energy input, the heat transfer quantity from the slag pool to a molten pool accounts for 4-9% of the total energy input, and the thickness of a slag crust is less than 2mm when the energy input is reasonable, so that the slag system electroslag has a good energy-saving advantage.
In the invention, the technical schemes can be combined with each other to realize more preferable combination schemes. Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description.
Detailed Description
The following detailed description of the preferred embodiments of the invention is provided to illustrate the principles of the invention and not to limit the scope of the invention.
The invention aims to provide a low-fluorine slag system for electroslag remelting of a B-containing 9Cr rotor steel ingot and a using method thereof. Based on a thermodynamic phase diagram, the contents of all components in the slag system are calculated according to the designed temperature range of the slag system, the obtained slag system has stable component structure, can balance B elements which are easy to burn between steel slag, has the advantages of energy-saving effect and the like, meets the technical requirements of difficult electroslag smelting of B-containing 9Cr high-pressure rotor steel and the like, and provides technical support for the electroslag smelting of new materials.
On one hand, the invention provides a low-fluorine slag system for electroslag remelting B-containing 9Cr rotor steel ingot, and the slag system comprises the following components in percentage by mass: CaF2：5％～30％，CaO：25％～35％，Al2O3：45％～60％，MgO：2％～5％，B2O3: 0.1-3 percent of the total content of the components and the balance of impurities, wherein the sum of all the components is 100 percent, and SiO in the impurities2The content should be less than 0.5%.
In a possible slag system design, the slag system comprises the following components in percentage by mass: CaF2；5％～18％，CaO；25％～30％，Al2O3：45％～50％，MgO：2％～3％，B2O3: 0.1 to 1 percent, and the balance of impurities; SiO in impurities2＜0.5％。
CaF2The melting point, viscosity and surface tension of the slag can be reduced in the slag system. However, CaF is comparable to other components2The conductivity of (2) is higher; the effect of CaO in the slag system increases the alkalinity of the slag, improves the desulfurization efficiency and reduces the slag conductivity; al (Al)2O3The conductivity of the slag can be obviously reduced in a slag system, the power consumption is reduced, and the productivity is improved.
The MgO has two functions in a slag system, firstly, because the rotor steel has strict requirements on the mass fraction of H in a steel ingot, a certain amount of MgO needs to be added into the slag system in the design of the slag system to reduce the permeability of H and also has the function of reducing oxygen and nitrogen in a molten pool; and MgO can form a layer of semi-solidified film on the surface of the slag pool, so that the radiation heat loss of the slag surface to the atmosphere is reduced.
B2O3The function in the slag system is to balance the B element which is easy to burn and lose in the slag system.
Different from the existing high-fluorine slag system, the low-fluorine slag is adopted in the application, and CaF in the slag system2Reduced content of CaO and Al2O3The content is increased. In the research, CaF is found2MgO is related to the viscosity of the slag system. CaF2The addition amount of (A) is in negative correlation with the viscosity of the slag system, and CaF2The addition amount of (b) increases, and the viscosity of the slag system decreases. The slag system has low melting point and viscosity and good fluidity, and is beneficial to the smooth operation of the electroslag remelting process. Thus, the CaF of the present application2And the addition amount of MgO is 5-30% and 2-5%, respectively, the viscosity of the slag system at 1800 ℃ is less than or equal to 0.025 Pa.s, and the surface of the slag crust is uniform at the viscosity.
At high temperatures, both the density and surface tension of the slag system decrease with increasing temperature, and with CaF2The content and MgO content increase and decrease gradually. The slag system has low fluorine content, small environmental pollution, good fluidity, low viscosity, small surface tension, good refining effect and good surface quality of the electroslag ingot obtained by refining.
Through detection, the basic of the slag of the inventionThe physical properties are as follows: the melting point is 1320-1420 ℃, and the density is 2.80-3.0 g/cm at 1800 DEG C3Viscosity is less than or equal to 0.025 Pa.s at 1800 ℃, conductivity is 0.9-1.5S/cm at 1800 ℃, and surface tension is 350-500 m N/m.
In the process of electroslag remelting for producing a B-containing 9Cr rotor steel ingot, the physicochemical property of a slag system influences the production quality of the steel ingot.
(1) Melting point: the melting point of the slag affects the conductivity, viscosity and heat productivity of the slag system. The over-high or over-low melting point is not beneficial to the physicochemical reactions of dephosphorization and desulfurization and the like, and is easy to cause the problems of internal and surface quality of steel ingot products and metallurgical defects of cavities, air holes, inclusions and the like. The design melting point range is 1320-1420 ℃, and the uniform surface quality of the steel ingot is ensured, and no air holes are generated on the surface.
(2) Viscosity: the viscosity of the slag influences the circulating flow speed of the slag, and the low-viscosity slag has a strong stirring effect due to the action of electromagnetic stirring force, so that the fluidity of the slag can be enhanced, heat transfer is facilitated, and meanwhile, the diffusion of a reaction interface can be enhanced. The viscosity of the steel slag is less than or equal to 0.025 Pa.s at 1800 ℃, so that the steel slag in smelting has good fluidity, the heat and mass transfer efficiency in a smelting furnace is improved, and the energy loss is reduced.
(3) Density: the density of the slag system mainly determines the slag consumption in the electroslag remelting process, the rate of a melting point penetrating through a slag layer in the electroslag remelting process, the residence time and the like, so that the purification and purification effects in the electroslag remelting process are determined, the difficulty degree of slag-metal separation in the electroslag remelting process is determined, and the like, so that the selection of the proper density of the slag system has certain influence on the metallurgical quality in the electroslag remelting process. The density of the invention is 2.80-3.0 g/cm at 1800 DEG C3The method ensures the uniform quality of the steel ingot and less impurity content, and simultaneously ensures the better separation of the steel ingot and the electroslag surface.
(4) Surface tension: the surface tension of the molten metal can make the liquid drop shrink into a sphere with the smallest specific surface area, and the larger the interface tension of the slag metal is, the larger the size of the metal small molten drop is. The larger the interfacial tension, the poorer the wettability of the slag to steel, and the more favorable the separation of the slag. The surface tension of the steel ingot is 350-500 mN/m, so that the steel ingot is separated from electroslag, and the surface of slag crust is smooth.
(5) Conductivity: the slag bath can be regarded as a resistor in the loop of the whole electroslag remelting process, and provides required resistance heat for remelting. When the current and the voltage passing through the slag bath and the effective area of the slag bath are fixed, the distance between the consumable electrode and the metal molten bath is in direct proportion to the conductivity of the slag. The too small conductivity can shorten the inter-polar distance (the distance between the consumable electrode and the metal molten pool), the too short inter-polar distance can easily cause the instability of the electroslag remelting process, and simultaneously, the reaction time of the steel slag in the falling process of the small metal molten drops is influenced, and the removal of impurities is not facilitated. The electric conductivity is 0.9-1.5S/cm at 1800 ℃, so that enough heat transmission is provided for the electroslag smelting process, and the smooth operation of the electroslag smelting process is ensured.
It is worth mentioning that the addition of B increases the quench heating temperature of this type of steel and thus contributes significantly to the creep strength of high Cr ferritic hot-strength steels. Excessive addition of B causes hot forging brittleness and decreases weldability, and as the B mass fraction increases, toughness decreases, while creep rupture strength does not increase. B is an easily-oxidized element and is easily burnt during the electroslag remelting process. The main strengthening effect of B in the high-temperature rotor steel can obviously improve the high-temperature creep property of the steel, and the rotor steel has strict requirements on components and a narrow control range, so that the qualified B-containing rotor steel is difficult to smelt. Through the discovery of deep research, the method ensures that the composition of the electroslag is stable in the long-time smelting process, the surface of the slag crust is uniform, and B2O3The content of the elements should be controlled between 0.1 percent and 5 percent.
The element B can react in the smelting process as follows:
3[Si]+2(Al2O3)＝3(SiO2)+4[Al](formula 1)
4[Nb]+5(SiO2)＝2(Nb2O5)+5[Si](formula 2)
2[Mn]+(SiO2)＝2(MnO)+[Si](formula 3)
4[B]+3(SiO2)＝2(B2O3)+3[Si](formula 4)
In order to accurately control the mass fraction of main alloy elements in steel and prevent easy-to-oxidize elements in molten steel from being burnt, SiO in a slag system2The mass fraction must be small. And SiO is used for controlling the mass fraction of the main strengthening element B in the steel to be stable2The content of (A) should be controlled below 0.5%.
On the other hand, the invention provides a use method of a low-fluorine slag system, which comprises the following steps:
step 1: using industrial pure CaF2、CaO、Al2O3、MgO、B2O3The slag system is prepared according to the mass percentage. The addition amounts of the components in the slag system are shown in table 1. Baking the slag system for 3-5 hours at the temperature higher than 600 ℃ so as to remove water.
Step 2: adding the preheated slag system into an electroslag furnace crystallizer by adopting a vacuum smelting furnace;
illustratively, when pilot-scale production is carried out in a 5t electroslag furnace, about 100-120 Kg of slag is taken before, and the slag is baked for 3-5 hours at the temperature higher than 600 ℃ for the purpose of removing water. Adding 5-20 kg of slag to the bottom of the crystallizer before the electroslag crystallizer is filled with the electrode, wherein the slag is uniformly spread and is not accumulated. The residual thermal state slag is uniformly added into the crystallizer by a feeder, and the addition is preferably finished within 1-4 hours, so that the slag is slowly added after a metal molten pool and a slag pool are formed in the electroslag crystallizer, and the phenomenon of difficult slag melting caused by excessive slag inclusion in a short time is avoided. Meanwhile, low-speed slag charging is selected, the slag charging time is properly prolonged, and B after the slag charging can be delayed to a certain extent2O3Decomposition of (3).
And step 3: smelting in an electroslag furnace;
1.5-2.2 t of smelting electrode bar is filled into an electroslag furnace crystallizer. The electrode composition is in accordance with FB2The steel is subjected to component requirements, the surface is polished and peeled, and the surface gloss is represented without an oxide layer for later use. And (5) detecting and testing systems such as water, electricity and gas of the atmosphere protection electroslag furnace equipment at 5t, and preparing for standby.
At present, electroslag remelting is mostly smelted under atmospheric conditions, and unstable slag systems can be caused by various oxygen transfer waysThe mass fraction of the fixed oxide increases, resulting in the burning loss of the easily oxidizable element B in the steel. Different from the prior art, in order to control the mass fraction of B in the steel to be stable, the invention removes the B added in the steel2O3And smelting by adopting a vacuum smelting furnace, and strictly controlling the mass fraction of unstable oxides in the slag system, thereby realizing the stability of the mass fraction of B in the steel.
The low-fluorine slag system CaF provided by the invention2Low content of CaF25-30%, preferably CaF29-18% of common high-fluorine slag (containing CaF)2Electroslag slag system of not less than 45%) phase ratio of CaF2The dosage of the low-fluorine slag system is reduced by more than 30 percent, and in industrial operation, when the low-fluorine slag system is melted, the addition amount of an arc striking agent is 30-50 kg in an arc striking melting pool, and the high-fluorine slag (containing CaF)2Electroslag slag system of not less than 45 percent) is increased, but the ingot with uniform distribution of ingot slag crust and no difference in surface quality can be obtained.
The invention realizes the normal smelting of the electroslag by designing the diameter of the electrode, namely the filling ratio, overcomes the problem of electroslag smelting caused by low conductivity of a low-fluorine slag system, and ensures the electrical safety for the operation of the electroslag furnace. The diameter of the electrode used in the invention is 375-395 mm, the filling ratio of the electrode processing area is 0.74-0.83, compared with the high fluorine slag system, the filling ratio of the electrode is improved by about 10% to carry out electroslag smelting, and the safe production of electroslag smelting can be realized.
Table 1: slag system component
TABLE 2 physicochemical Properties and smelting parameters of the slag Components
Pilot-scale production is carried out in a 5t electroslag furnace, and the key point conditions of the process are as follows: the electrode diameter is 375mm, the crystallizer diameter is 435mm, the slag layer is designed to be about 220mm, the arc striking dosage is improved by 50%, the power input in the arc striking stage is about 450kW, the power input in the steady state stage is 390-420 kW, and the average melting speed is about 4.7 kg/min. The smelting effect is as follows: the height of the ingot after smelting is 1.73m, and the actual ingot weighs about 2 tons. The surface quality is good, the thickness distribution of the slag crust is uniform, and the thickness of the slag crust at the middle section of the steel ingot is less than or equal to 1.8 mm.
When the slag system is used for electroslag steady-state smelting, compared with high-fluorine slag such as ANF-6 slag, the highest temperature of a slag pool can reach 1800-2000 ℃, the heat transfer quantity from the slag pool to a crystallizer accounts for 30-45% of the total energy input, the heat transfer quantity from the slag pool to a molten pool accounts for 4-9% of the total energy input, the thickness of a slag skin is below 2mm when the energy input is reasonable, and the power consumption can be reduced by more than 25%.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Claims (8)
1. The use method of the low-fluorine slag system for electroslag remelting of the B-containing 9Cr rotor steel ingot is characterized in that the low-fluorine slag system comprises the following components in percentage by mass: CaF2：5%~30%，CaO：27.3%~35%，Al2O3：40%~50%，MgO：2%~5%，B2O3: 0.1% -3% of the total weight of the composition, and the balance of impurities; SiO in impurities2Less than 0.5 percent; at 1800 ℃, the viscosity is less than or equal to 0.025 Pa.s, and the conductivity range is 0.9-1.5S/cm; the melting point is 1320-1420 ℃, and the density is 2.80-3.0 g/cm at 1800 DEG C3The surface tension is 350-500 m N/m;
the use method of the low-fluorine slag system comprises the following steps:
step 1: using industrial pure CaF2、CaO、Al2O3、MgO、B2O3Slag is prepared according to the mass percentage of each component in the slag system and is preheated;
step 2: adding the preheated thermal-state slag into an electroslag furnace crystallizer;
and step 3: smelting in an electroslag furnace;
in the step 2, firstly, adding the thermal-state slag before the electrode is filled into the crystallizer of the electroslag furnace, and uniformly spreading part of the thermal-state slag to the bottom of the crystallizer; uniformly adding the residual thermal slag into the crystallizer by using a feeder, and finishing the addition within 1-4 h; after a metal molten pool and a slag pool are formed in the electroslag crystallizer, slag is slowly added, so that the phenomenon that the slag is difficult to melt due to excessive slag addition in a short time is avoided;
in the smelting process in the step 3, the thickness of a slag layer is designed to be 200 mm-400 mm, the power input in an arc striking stage is 400 kW-3500 kW, and the power input in a steady state stage is 390-3000 kW; the electrode melting speed in the melting process is 4-35 kg/min;
the diameter of the electrode is 375-395 mm, and the electrode processing area filling ratio is 0.74-0.83.
2. The use method of the low-fluorine slag system for electroslag remelting B-containing 9Cr rotor steel ingot according to claim 1, wherein the low-fluorine slag system comprises the following components in percentage by mass: CaF2：5%~18%，CaO：27.3%~30%，Al2O3：45%~50%，MgO：2%~3%，B2O3: 0.1% -1% and the balance of impurities; SiO in impurities2＜0.5%。
3. The use method of the low-fluorine slag system for electroslag remelting B-containing 9Cr rotor steel ingot according to claim 1, wherein the melting point range is 1320-1405 ℃; the density is 2.80-2.97 g/cm at 1800 DEG C3。
4. Use of a low-fluorine slag system for electroslag remelting 9Cr rotor ingot containing B according to claim 1, characterized in that the low-fluorine slag system is used for producing a 9Cr rotor ingot containing B less than 0.015%.
5. The use method of the low-fluorine slag system for electroslag remelting B-containing 9Cr rotor steel ingot according to claim 1, wherein the preheating temperature in the step 1 is higher than 600 ℃, and the preheating time is 3-5 h.
6. The use method of the low-fluorine slag system for electroslag remelting B-containing 9Cr rotor steel ingot according to claim 1, wherein in the smelting process in the step 3, the thickness of a slag layer is designed to be 220 mm-400 mm, the power input in an arc starting stage is 400 kW-450 kW, and the power input in a steady state stage is 390-420 kW.
7. The use method of the low-fluorine slag system for electroslag remelting B-containing 9Cr rotor steel ingot according to claim 1, wherein the melting speed of an electrode in a melting process is 4.7-35 kg/min.
8. The use method of the low-fluorine slag system for electroslag remelting B-containing 9Cr rotor steel ingot according to any one of claims 1 to 7, wherein the thickness of slag skin on the surface of the steel ingot is less than or equal to 1.8mm after smelting.
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| CN1616700A (en) * | 2003-08-28 | 2005-05-18 | 河南中原特殊钢厂 | Steel for processing movement limiting core stick of continuous tube grimper and its producing process |
| CN101654743A (en) * | 2009-09-18 | 2010-02-24 | 沈阳东大兴科冶金技术有限公司 | Device and method for directionally solidifying steel ingot with oversized cross section by electric slag furnace |
| CN108411162A (en) * | 2018-03-30 | 2018-08-17 | 四川六合锻造股份有限公司 | A kind of High-temperature resistant alloy material of strong mechanical performance and low impurity content |
| CN110453085A (en) * | 2019-09-09 | 2019-11-15 | 东北大学 | The electroslag remelting heat resisting steel of 9Cr containing Type B slag system, preparation method and application method |
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