CN110592494A - Nickel-containing ferrite stainless steel smelted from laterite-nickel ore and preparation method thereof - Google Patents
Nickel-containing ferrite stainless steel smelted from laterite-nickel ore and preparation method thereof Download PDFInfo
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Abstract
The invention provides nickel-containing ferrite stainless steel smelted from laterite-nickel ore and a preparation method thereof, belonging to the field of ferrous metallurgy. The basic components are as follows: 0.01 to 0.07wt percent of C, less than or equal to 0.8wt percent of Si, less than or equal to 0.8wt percent of Mn, 14 to 26wt percent of Cr, less than or equal to 1.6wt percent of Ni, less than or equal to 0.05wt percent of P, less than or equal to 0.030wt percent of S, 0.01 to 0.05wt percent of Al, less than or equal to 40ppm of total O, and the balance of Fe and inevitable impurities; the steel is based on the chromium-containing characteristic and the low-nickel characteristic of the laterite-nickel ore surface layer ore, and various nickel-containing ferrite stainless steels are created by utilizing the effective components of resources. The invention recycles and valuates the nearly discarded surface ores of the laterite-nickel ores, and the nickel-containing ferritic stainless steel carries out component adjustment and process selection according to the requirements of neutral salt spray corrosion resistance and pitting corrosion resistance so as to meet the functional requirements of various stainless steels, thereby being beneficial to industrial production and use.
Description
Technical Field
The invention relates to the field of ferrous metallurgy, in particular to nickel-containing ferrite stainless steel smelted from laterite-nickel ore and a preparation method thereof.
Background
The reserves of laterite-nickel ore resources on the earth are as high as hundreds of billions of tons, and the laterite-nickel ore resources are subjected to geological stratification according to nickel content in an ore layer with the depth of several meters to dozens of meters on the earth surface. The middle layer ore has high nickel content which can reach more than 1.0 percent, has the value of smelting nickel metal and can generally become the raw material of 300 series stainless steel.
The laterite-nickel ore is a natural alloy ore with high iron content and is a huge resource. Although the surface layer ores of the laterite-nickel ores have high iron content, including valuable alloys such as chromium, nickel, cobalt and the like, and the metal content can reach more than 55%, the laterite-nickel ores become wastes without utilization values due to low nickel content and high phosphorus content.
The conventional ferritic stainless steel has been widely used even in the construction field as structural steel due to its excellent corrosion resistance, good mechanical properties, good cold rolling properties, almost the same expansion coefficient as that of ordinary carbon steel, easy welding, and the like.
Nickel is a favourable element for the mechanical properties of the steel, in particular for the ductility of the steel; particularly for duplex stainless steel and austenitic stainless steel, nickel is the key element. Nickel has the effect of ensuring the non-magnetic properties of the steel for austenitic stainless steels, and nickel is also used in small portions of ferritic stainless steels. From the international nickel association point of view, the reduction of nickel usage in stainless steel is a process option from cost and price considerations, and no data is available showing the adverse effect of nickel on stainless steel structure and performance.
In the face of the resource amount of several billion tons and even trillion tons of the laterite-nickel ore, the surface layer resource with the nickel content lower than 1 percent at least accounts for more than 40 percent and also accounts for at least several billion tons. The smelting technology fully utilizing the iron, nickel and chromium elements of the ores can fill up the great technical blank in the aspect of development of stainless steel production resources.
In order to fully utilize the surface layer ore resources of the laterite-nickel ore, in particular to high-content iron, chromium and nickel elements in the ore, the invention provides stainless steel, namely nickel-containing ferrite stainless steel, which fully utilizes the resources. The invention provides an economic and effective industrial preparation method for preparing ferrite stainless steel containing nickel with the content of less than 1.6 wt% by using surface layer ore resources with the nickel content of less than 1% of laterite-nickel ore, which is an almost waste laterite-nickel ore surface layer ore.
Disclosure of Invention
The invention aims to solve the technical problem of how to prepare nickel-containing ferrite stainless steel by utilizing nearly discarded laterite-nickel ore surface layer ores, meet the use requirements of hot-rolled and cold-rolled sheet materials, be suitable for occasions without needing nonmagnetic property and being used as anti-seismic energy-absorbing steel, and also be capable of selecting the nickel-containing ferrite stainless steel with corresponding corrosion resistance according to the requirements of a corrosion-resistant scene.
The invention provides nickel-containing ferritic stainless steel smelted from laterite-nickel ore, which comprises the following basic components in percentage by mass: 0.01 to 0.07wt percent of C, less than or equal to 0.8wt percent of Si, less than or equal to 0.8wt percent of Mn, 14 to 26wt percent of Cr, less than or equal to 1.6wt percent of Ni, less than or equal to 0.05wt percent of P, less than or equal to 0.030wt percent of S, 0.01 to 0.05wt percent of Al, less than or equal to 40ppm of total O, and the balance of Fe and inevitable impurities.
Preferably, the metallographic structure of the nickel-containing ferritic stainless steel is: uniformly distributing a small amount of nano-scale carbide on a ferrite matrix, controlling the average size of the carbide to be below 400 nanometers, and controlling the average size of crystal grains to be less than 8 micrometers; yield strength sigma0.2350MPa or more, breaking strength 450MPa or more and elongation 20% or more.
Preferably, the nickel-containing ferritic stainless steel includes Cr17-26 wt%, Mo 0.6-0.8 wt% of a high chromium nickel-containing pitting corrosion resistant ferritic stainless steel in addition to a medium chromium nickel-containing ferritic stainless steel of Cr14-17 wt% and a high chromium nickel-containing ferritic stainless steel of Cr17-26 wt%.
Preferably, the medium chromium nickel-containing ferritic stainless steel has a neutral salt spray corrosion resistance equal to or better than that of austenitic stainless steel 304 stainless steel, and is close to that of ferritic stainless steel 430.
Preferably, the neutral salt spray corrosion resistance of the high-chromium nickel-containing ferritic stainless steel is equal to or better than that of 316 stainless steel.
Preferably, the neutral salt spray corrosion resistance of the high-chromium nickel-containing pitting corrosion resistant ferritic stainless steel is equal to or better than that of 2205 duplex stainless steel and 316 stainless steel, and meanwhile, the high-chromium nickel-containing pitting corrosion resistant ferritic stainless steel has certain pitting corrosion resistance.
The preparation method of the nickel-containing ferritic stainless steel specifically comprises the following steps:
s1, taking the raw material as the surface layer ore of the low-nickel laterite-nickel ore, smelting the raw material into molten iron through blast furnace smelting or ore smelting electric furnace smelting, and sending the molten iron to AOD for blowing; or molten iron obtained by smelting low-nickel iron blocks by an induction furnace and an electric arc furnace is sent to AOD for blowing; in the AOD converting process, according to the requirement of the Cr component of the nickel-containing ferritic stainless steel, the lower limit target of the Cr component is adjusted, and the lower limit target of the components of main alloy elements Ni, Mn and Si is adjusted;
s2, transferring the molten steel blown by the AOD in the S1 into an LF furnace, and enabling the content of C and the content of P in the molten steel entering the LF furnace to be below the lower limit of final components, so as to prevent C increase in the later period and reserve the allowance for C increase and P increase in the later operation;
s3, adding 200-300 mm-thick reduction refining slag into the LF, and carrying out reduction refining on the molten steel entering the LF so as to carry out deoxidation and desulfurization and carry out accurate component adjustment; reducing refining slag with CaO/SiO alkalinity2Controlling the content in the range of 2-3, wherein the components of the reduction refining slag are CaO: 50-60 wt% of high-quality CaCO3The content ratio of CaO in the total amount is more than 50 wt%; SiO 22：25-30wt％；CaF2: 10 wt%; the rest high-aluminum refractory brick block material; the lumpiness of the reduced refining slag is less than 20mm, powder materials cannot exist, and the reduced refining slag needs to be packaged in a sealed moisture-proof bag;
s4, blowing argon gas into the LF for stirring, wherein the argon gas blown into the LF is only required to be stirred to the extent that the slag surface is blown to be broken; then adding aluminum in a manner of adding 0.8-1.2kg of Al into each ton of steel, and in the subsequent process, adding no aluminum into molten steel for deoxidation; aluminum particles can be added to the surface of the LF slag when the formation of white slag is promoted, but aluminum powder cannot be used for replacing the aluminum particles, so that the aluminum powder is prevented from being violently combusted;
s5, blowing argon into the LF furnace, stirring for 10 minutes, then keeping white slag, adding limestone with high calcium proportion to adjust slag when the slag is too thin, so as to keep foamability of the slag, and smoothly refining and adjusting components of the LF furnace; the time consumed for keeping LF refined and adjusted is generally not more than 40 minutes;
s6, after refining, performing modification treatment on inclusions in molten steel through an alkali metal cored wire to enable the components of the molten steel to meet the basic components of the nickel-containing ferritic stainless steel;
the molten steel obtained after refining in S7 and S6 is sent to a continuous casting machine to be cast into a plate blank, a square blank or a rectangular blank;
and S8, cooling the plate blank or the square blank or the rectangular blank, then checking and grinding the plate blank or the square blank or the rectangular blank, and then performing controlled rolling and controlled cooling rolling process and heat treatment in a rolling mill to obtain the required steel.
Preferably, the rolling and heat treatment of the controlled rolling and controlled cooling in S8 of the medium chromium nickel-containing ferritic stainless steel or the high chromium nickel-containing ferritic stainless steel is: the initial rolling temperature of the steel billet is 1080-; and after finishing rolling, immediately spraying and cooling the steel to 670-.
Preferably, the content of chromium in the high-chromium nickel-containing pitting corrosion resistant ferritic stainless steel S1 needs to be controlled to be 17-26 wt%, Mo needs to be added in an amount of 0.6-0.8 wt% in S2, and the rolling and heat treatment of controlled rolling and controlled cooling in S8 are as follows: the initial rolling temperature of the steel billet is 1080-; after finishing rolling, sending the steel into a 1080-1120 ℃ solution furnace for isothermal treatment for 1.5-2.0 hours to achieve the purpose that the added Mo element is dissolved in the high-chromium nickel-containing pitting corrosion resistant ferritic stainless steel in a solid manner; immediately spraying and cooling the steel to 670-; the high-chromium nickel-containing pitting corrosion resistant ferritic stainless steel can be processed and used in a hot rolling state.
Preferably, when the nickel-containing ferritic stainless steel is required to produce cold rolled materials, the isothermal heat preservation treatment is required to be kept at 670-730 ℃ for 8-12 hours.
The technical scheme of the invention has the following beneficial effects:
according to the invention, the alloy design and the heat treatment process design of the system are carried out according to the iron and alloy values of the surface layer ore resources of the laterite-nickel ore. By reasonably proportioning ores in the smelting process, smelting in a blast furnace or a submerged arc furnace, a converter or an AOD furnace, and properly adding and adjusting a small amount of alloy in an LF refining furnace, a series of nickel-containing ferritic stainless steel, medium chromium nickel-containing ferritic stainless steel, high chromium nickel-containing ferritic stainless steel and high chromium nickel-containing pitting corrosion resistant ferritic stainless steel are produced. The invention recycles and valuates the nearly waste surface layer ores of the laterite-nickel ores and meets the functional requirements of stainless steel.
The nickel-containing ferritic stainless steel realizes grain refining through controlled rolling and controlled cooling, the average grain size is less than 8 microns, and the grain refining plays an important role in reducing intergranular corrosion and pitting corrosion. The addition of Mo element in the LF realizes the function of resisting pitting corrosion under the condition of less alloy elements.
In addition, the tensile strength of the nickel-containing ferrite stainless steel provided by the invention is more than or equal to 450MPa, the yield strength is more than or equal to 350MPa, and the elongation after fracture is more than or equal to 22%; the reduction of area is more than or equal to 40 percent, is suitable for sheet materials of hot rolling and cold rolling, is also suitable for occasions without needing nonmagnetic property, can be used as shock-resistant energy-absorbing steel, and can also select nickel-containing ferrite stainless steel with corresponding corrosion resistance according to the requirements of corrosion-resistant scenes.
Detailed Description
In order to make the technical problems, technical solutions and advantages to be solved by the present invention clearer, the following detailed description is given with reference to specific embodiments.
The invention aims to solve the technical problem of how to prepare nickel-containing ferrite stainless steel by utilizing nearly discarded laterite-nickel ore surface layer ores, meet the use requirements of hot-rolled and cold-rolled sheet materials, be suitable for occasions without needing nonmagnetic property and being used as anti-seismic energy-absorbing steel, and also be capable of selecting the nickel-containing ferrite stainless steel with corresponding corrosion resistance according to the requirements of a corrosion-resistant scene.
In order to solve the technical problems, the invention provides nickel-containing ferritic stainless steel smelted from laterite-nickel ore, which comprises the following basic components in percentage by mass: 0.01 to 0.07wt percent of C, less than or equal to 0.8wt percent of Si, less than or equal to 0.8wt percent of Mn, 14 to 26wt percent of Cr, less than or equal to 1.6wt percent of Ni, less than or equal to 0.05wt percent of P, less than or equal to 0.030wt percent of S, 0.01 to 0.05wt percent of Al, less than or equal to 40ppm of total O, and the balance of Fe and inevitable impurities.
Wherein the metallographic structure of the nickel-containing ferritic stainless steel is as follows: uniformly distributing a small amount of nano-scale carbide on a ferrite matrix, controlling the average size of the carbide to be below 400 nanometers, and controlling the average size of crystal grains to be less than 8 micrometers; yield strength sigma0.2350MPa or more, breaking strength 450MPa or more and elongation 20% or more.
Wherein the nickel-containing ferritic stainless steel comprises Cr17-26 wt% and Mo 0.6-0.8 wt% of high chromium nickel-containing pitting corrosion resistant ferritic stainless steel besides Cr14-17 wt% of medium chromium nickel-containing ferritic stainless steel and Cr17-26 wt% of high chromium nickel-containing ferritic stainless steel.
Wherein the neutral salt spray corrosion resistance of the medium chromium nickel-containing ferritic stainless steel is equal to or better than that of austenitic stainless steel 304 stainless steel, and is close to that of ferritic stainless steel 430.
Wherein the neutral salt spray corrosion resistance of the high-chromium nickel-containing ferritic stainless steel is equal to or better than that of 316 stainless steel.
The neutral salt spray corrosion resistance of the high-chromium nickel-containing pitting corrosion resistant ferritic stainless steel is equal to or superior to that of 2205 duplex stainless steel and 316 stainless steel, and the high-chromium nickel-containing pitting corrosion resistant ferritic stainless steel has certain pitting corrosion resistance.
The preparation method of the nickel-containing ferritic stainless steel specifically comprises the following steps:
s1, taking the raw material as the surface layer ore of the low-nickel laterite-nickel ore, smelting the raw material into molten iron through blast furnace smelting or ore smelting electric furnace smelting, and sending the molten iron to AOD for blowing; or molten iron obtained by smelting low-nickel iron blocks by an induction furnace and an electric arc furnace is sent to AOD for blowing; in the AOD converting process, according to the requirement of the Cr component of the nickel-containing ferritic stainless steel, the lower limit target of the Cr component is adjusted, and the lower limit target of the components of main alloy elements Ni, Mn and Si is adjusted;
s2, transferring the molten steel blown by the AOD in the S1 into an LF furnace, and enabling the content of C and the content of P in the molten steel entering the LF furnace to be below the lower limit of final components, so as to prevent C increase in the later period and reserve the allowance for C increase and P increase in the later operation;
s3, adding 200-300 mm-thick reduction refining slag into the LF, and carrying out reduction refining on the molten steel entering the LF so as to carry out deoxidation and desulfurization and carry out accurate component adjustment; reducing refining slag with CaO/SiO alkalinity2Controlling the content in the range of 2-3, wherein the components of the reduction refining slag are CaO: 50-60 wt% of high-quality CaCO3The content ratio of CaO in the total amount is more than 50 wt%; SiO 22：25-30wt％；CaF2: 10 wt%; the rest high-aluminum refractory brick block material; the lumpiness of the reduced refining slag is less than 20mm, powder materials cannot exist, and the reduced refining slag needs to be packaged in a sealed moisture-proof bag;
s4, blowing argon gas into the LF for stirring, wherein the argon gas blown into the LF is only required to be stirred to the extent that the slag surface is blown to be broken; then adding aluminum in a manner of adding 0.8-1.2kg of Al into each ton of steel, and in the subsequent process, adding no aluminum into molten steel for deoxidation; aluminum particles can be added to the surface of the LF slag when the formation of white slag is promoted, but aluminum powder cannot be used for replacing the aluminum particles, so that the aluminum powder is prevented from being violently combusted;
s5, blowing argon into the LF furnace, stirring for 10 minutes, then keeping white slag, adding limestone with high calcium proportion to adjust slag when the slag is too thin, so as to keep foamability of the slag, and smoothly refining and adjusting components of the LF furnace; the time consumed for keeping LF refined and adjusted is generally not more than 40 minutes;
s6, after refining, performing modification treatment on inclusions in molten steel through an alkali metal cored wire to enable the components of the molten steel to meet the basic components of the nickel-containing ferritic stainless steel;
the molten steel obtained after refining in S7 and S6 is sent to a continuous casting machine to be cast into a plate blank, a square blank or a rectangular blank;
and S8, cooling the plate blank or the square blank or the rectangular blank, then checking and grinding the plate blank or the square blank or the rectangular blank, and then performing controlled rolling and controlled cooling rolling process and heat treatment in a rolling mill to obtain the required steel.
Wherein the rolling and heat treatment of the S8 central controlled rolling and controlled cooling of the medium chromium nickel-containing ferritic stainless steel or the high chromium nickel-containing ferritic stainless steel is as follows: the initial rolling temperature of the steel billet is 1080-; and after finishing rolling, immediately spraying and cooling the steel to 670-.
Wherein, the S1 of the high-chromium nickel-containing pitting corrosion resistant ferritic stainless steel needs to control the chromium content to be 17-26 wt%, 0.6-0.8 wt% of Mo needs to be added in S2, and the rolling and heat treatment of controlled rolling and controlled cooling in S8 are as follows: the initial rolling temperature of the steel billet is 1080-; after finishing rolling, sending the steel into a 1080-1120 ℃ solution furnace for isothermal treatment for 1.5-2.0 hours to achieve the purpose that the added Mo element is dissolved in the high-chromium nickel-containing pitting corrosion resistant ferritic stainless steel in a solid manner; immediately spraying and cooling the steel to 670-; the high-chromium nickel-containing pitting corrosion resistant ferritic stainless steel can be processed and used in a hot rolling state.
Wherein, when the nickel-containing ferritic stainless steel needs to produce cold rolled materials, the isothermal heat preservation treatment needs to be kept at 670-730 ℃ for 8-12 hours.
Specific nickel-containing ferritic stainless steels and methods for making the same are described with reference to the following examples:
the first embodiment is as follows:
the basic components of the medium chromium nickel-containing ferritic stainless steel smelted from the laterite nickel ore in percentage by mass are as follows: 0.01 to 0.07 percent of C, less than or equal to 0.8 percent of Si, less than or equal to 0.8 percent of Mn, 16 percent of Cr, less than or equal to 1.6 percent of Ni, less than or equal to 0.05 percent of P, less than or equal to 0.030 percent of S, 0.01 to 0.05 percent of Al, less than or equal to 40ppm of total O, and the balance of Fe and inevitable impurities.
Wherein the metallographic structure of the medium chromium nickel-containing ferritic stainless steel is as follows: uniformly distributing a small amount of nano-scale carbide on a ferrite matrix, controlling the average size of the carbide to be below 400 nanometers, and controlling the average size of crystal grains to be less than 8 micrometers; yield strength sigma0.2350MPa or more, breaking strength 450MPa or more and elongation 20% or more.
Wherein the neutral salt spray corrosion resistance of the medium chromium nickel-containing ferritic stainless steel is equal to or better than that of austenitic stainless steel 304 stainless steel, and is close to that of ferritic stainless steel 430.
Wherein, the preparation method of the medium chromium nickel-containing ferritic stainless steel comprises the following steps:
s1, taking the raw material as the surface layer ore of the low-nickel laterite-nickel ore, smelting the raw material into molten iron through blast furnace smelting or ore smelting electric furnace smelting, and sending the molten iron to AOD for blowing; or molten iron obtained by smelting low-nickel iron blocks by an induction furnace and an electric arc furnace is sent to AOD for blowing; finishing the adjustment of the lower limit target of the components of the main alloy elements Cr, Ni, Mn and Si in the AOD converting process;
s2, transferring the molten steel blown by the AOD in the S1 into an LF furnace, and enabling the content of C and the content of P in the molten steel entering the LF furnace to be below the lower limit of final components, so as to prevent C increase in the later period and reserve the allowance for C increase and P increase in the later operation;
s3, adding 200-300 mm-thick reduction refining slag into the LF, and carrying out reduction refining on the molten steel entering the LF so as to carry out deoxidation and desulfurization and carry out accurate component adjustment; reducing refining slag with CaO/SiO alkalinity2Controlling the content in the range of 2-3, wherein the components of the reduction refining slag are CaO: 50-60% of high-quality CaCO3The content ratio of the total CaO in the mixture is more than 50 percent; SiO 22：25-30％；CaF2: 10 percent; the rest high-aluminum refractory brick block material; the lumpiness of the reduced refining slag is less than 20mm, powder materials cannot exist, and the reduced refining slag needs to be packaged in a sealed moisture-proof bag;
s4, blowing argon gas into the LF for stirring, wherein the argon gas blown into the LF is only required to be stirred to the extent that the slag surface is blown to be broken; then adding aluminum in a manner of adding 0.8-1.2kg of Al into each ton of steel, and in the subsequent process, adding no aluminum into molten steel for deoxidation; aluminum particles can be added to the surface of the LF slag when the formation of white slag is promoted, but aluminum powder cannot be used for replacing the aluminum particles, so that the aluminum powder is prevented from being violently combusted;
s5, blowing argon into the LF furnace, stirring for 10 minutes, then keeping white slag, adding limestone with high calcium proportion to adjust slag when the slag is too thin, so as to keep foamability of the slag, and smoothly refining and adjusting components of the LF furnace; the time consumed for keeping LF refined and adjusted is generally not more than 40 minutes;
s6, after refining, performing modification treatment on inclusions in molten steel through an alkali metal cored wire to enable the components of the molten steel to meet the basic components of the nickel-containing ferritic stainless steel;
the molten steel obtained after refining in S7 and S6 is sent to a continuous casting machine to be cast into a plate blank, a square blank or a rectangular blank;
and S8, cooling the plate blank or the square blank or the rectangular blank, then checking and grinding the plate blank or the square blank or the rectangular blank, and then performing controlled rolling and controlled cooling rolling process and heat treatment in a rolling mill to obtain the required steel.
Wherein the rolling and heat treatment of the S8 controlled rolling and controlled cooling of the medium chromium nickel-containing ferritic stainless steel are as follows: the initial rolling temperature of the steel billet is 1080-; and after finishing rolling, immediately spraying and cooling the steel to 670-.
Wherein, when the nickel-containing ferritic stainless steel needs to produce cold rolled materials, the isothermal heat preservation treatment needs to be kept at 670-730 ℃ for 8-12 hours.
Example two:
the basic components of the high-chromium nickel-containing ferritic stainless steel smelted from the laterite-nickel ore are as follows by mass percent: 0.01 to 0.07 percent of C, less than or equal to 0.8 percent of Si, less than or equal to 0.8 percent of Mn, 24 percent of Cr, less than or equal to 1.6 percent of Ni, less than or equal to 0.05 percent of P, less than or equal to 0.030 percent of S, 0.01 to 0.05 percent of Al, less than or equal to 40ppm of total O, and the balance of Fe and inevitable impurities.
Wherein the metallographic structure of the high-chromium nickel-containing ferritic stainless steelThe method comprises the following steps: uniformly distributing a small amount of nano-scale carbide on a ferrite matrix, controlling the average size of the carbide to be below 400 nanometers, and controlling the average size of crystal grains to be less than 8 micrometers; yield strength sigma0.2350MPa or more, breaking strength 450MPa or more and elongation 20% or more.
Wherein the neutral salt spray corrosion resistance of the high-chromium nickel-containing ferritic stainless steel is equal to or better than that of 316 stainless steel.
The preparation method of the high-chromium nickel-containing ferritic stainless steel comprises the following steps:
s1, taking the raw material as the surface layer ore of the low-nickel laterite-nickel ore, smelting the raw material into molten iron through blast furnace smelting or ore smelting electric furnace smelting, and sending the molten iron to AOD for blowing; or molten iron obtained by smelting low-nickel iron blocks by an induction furnace and an electric arc furnace is sent to AOD for blowing; finishing the adjustment of the lower limit target of the components of the main alloy elements Cr, Ni, Mn and Si in the AOD converting process;
s2, transferring the molten steel blown by the AOD in the S1 into an LF furnace, and enabling the carbon content and the phosphorus content of the molten steel entering the LF furnace to be below the final component lower limit, so as to prevent later-stage carburetion and leave the allowance for later-stage operation of C increase and P increase;
s3, adding 200-300 mm-thick reduction refining slag into the LF, and carrying out reduction refining on the molten steel entering the LF so as to carry out deoxidation and desulfurization and carry out accurate component adjustment; reducing refining slag with CaO/SiO alkalinity2Controlling the content in the range of 2-3, wherein the components of the reduction refining slag are CaO: 50-60% by weight of high quality CaCO3The content ratio of CaO in the total amount is more than 50 wt%; SiO 22：25-30wt％；CaF2: 10 wt%; the rest high-aluminum refractory brick block material; the lumpiness of the reduced refining slag is less than 20mm, powder materials cannot exist, and the reduced refining slag needs to be packaged in a sealed moisture-proof bag;
s4, blowing argon gas into the LF for stirring, wherein the argon gas blown into the LF is only required to be stirred to the extent that the slag surface is blown to be broken; then adding aluminum in a manner of adding 0.8-1.2kg of Al into each ton of steel, and in the subsequent process, adding no aluminum into molten steel for deoxidation; aluminum particles can be added to the surface of the LF slag when the formation of white slag is promoted, but aluminum powder cannot be used for replacing the aluminum particles, so that the aluminum powder is prevented from being violently combusted;
s5, blowing argon into the LF furnace, stirring for 10 minutes, then keeping white slag, adding limestone with high calcium proportion to adjust slag when the slag is too thin, so as to keep foamability of the slag, and smoothly refining and adjusting components of the LF furnace; the time consumed for keeping LF refined and adjusted is generally not more than 40 minutes;
s6, after refining, performing modification treatment on inclusions in molten steel through an alkali metal cored wire to enable the components of the molten steel to meet the basic components of the nickel-containing ferritic stainless steel;
the molten steel obtained after refining in S7 and S6 is sent to a continuous casting machine to be cast into a plate blank, a square blank or a rectangular blank;
and S8, cooling the plate blank or the square blank or the rectangular blank, then checking and grinding the plate blank or the square blank or the rectangular blank, and then performing controlled rolling and controlled cooling rolling process and heat treatment in a rolling mill to obtain the required steel.
The rolling and heat treatment process method of the high-chromium nickel-containing ferritic stainless steel with controlled rolling and controlled cooling comprises the following steps: the initial rolling temperature of the steel billet is 1080-; and after finishing rolling, immediately performing spray cooling to 670-.
Wherein the rolling and heat treatment of the S8 controlled rolling and controlled cooling of the high-chromium nickel-containing ferritic stainless steel are as follows: the initial rolling temperature of the steel billet is 1080-; and after finishing rolling, immediately spraying and cooling the steel to 670-.
Wherein, when the nickel-containing ferritic stainless steel needs to produce cold rolled materials, the isothermal heat preservation treatment needs to be kept at 670-730 ℃ for 8-12 hours.
Example three:
the basic components of the high-chromium nickel-containing pitting corrosion resistant ferritic stainless steel smelted from the laterite-nickel ore are as follows by mass percent: 0.01 to 0.07 percent of C, less than or equal to 0.8 percent of Si, less than or equal to 0.8 percent of Mn, 26 percent of Cr, less than or equal to 1.6 percent of Ni, less than or equal to 0.05 percent of P, less than or equal to 0.030 percent of S, 0.8 percent of Mo0.05 percent of Al, less than or equal to 40ppm of total O, and the balance of Fe and inevitable impurities.
Wherein the metallographic structure of the high-chromium nickel-containing pitting corrosion resistant ferritic stainless steel is as follows: uniformly distributing a small amount of nano-scale carbide on a ferrite matrix, controlling the average size of the carbide to be below 400 nanometers, and controlling the average size of crystal grains to be less than 8 micrometers; yield strength sigma0.2350MPa or more, breaking strength 450MPa or more and elongation 20% or more.
The neutral salt spray corrosion resistance of the high-chromium nickel-containing pitting corrosion resistant ferritic stainless steel is equal to or superior to that of 2205 duplex stainless steel and 316 stainless steel, and the high-chromium nickel-containing pitting corrosion resistant ferritic stainless steel has certain pitting corrosion resistance.
Wherein, the preparation method of the high-chromium nickel-containing pitting corrosion resistant ferritic stainless steel comprises the following steps:
s1, taking the raw material as the surface layer ore of the low-nickel laterite-nickel ore, smelting the raw material into molten iron through blast furnace smelting or ore smelting electric furnace smelting, and sending the molten iron to AOD for blowing; or molten iron obtained by smelting low-nickel iron blocks by an induction furnace and an electric arc furnace is sent to AOD for blowing; finishing the adjustment of the lower limit target of the components of the main alloy elements Cr, Ni, Mn and Si in the AOD converting process;
s2, transferring the molten steel blown by the AOD in the S1 into an LF furnace, and enabling the carbon content and the phosphorus content of the molten steel entering the LF furnace to be below the final component lower limit, so as to prevent later-stage carburetion and leave the allowance for later-stage operation of C increase and P increase;
s3, adding 200-300 mm-thick reduction refining slag into the LF, and carrying out reduction refining on the molten steel entering the LF so as to carry out deoxidation and desulfurization and carry out accurate component adjustment; reducing refining slag with CaO/SiO alkalinity2Controlling the content in the range of 2-3, wherein the components of the reduction refining slag are CaO: 50-60% of high-quality CaCO3The content ratio of the total CaO in the mixture is more than 50 percent; SiO 22：25-30％；CaF2: 10 percent; the rest high-aluminum refractory brick block material; the lumpiness of the reduced refining slag is less than 20mm, powder materials cannot exist, and the reduced refining slag needs to be packaged in a sealed moisture-proof bag;
s4, blowing argon gas into the LF for stirring, wherein the argon gas blown into the LF is only required to be stirred to the extent that the slag surface is blown to be broken; then adding aluminum in a manner of adding 0.8-1.2kg of Al into each ton of steel, and in the subsequent process, adding no aluminum into molten steel for deoxidation; aluminum particles can be added to the surface of the LF slag when the formation of white slag is promoted, but aluminum powder cannot be used for replacing the aluminum particles, so that the aluminum powder is prevented from being violently combusted;
s5, blowing argon into the LF furnace, stirring for 10 minutes, then keeping white slag, adding limestone with high calcium proportion to adjust slag when the slag is too thin, so as to keep foamability of the slag, and smoothly refining and adjusting components of the LF furnace; the time consumed for keeping LF refined and adjusted is generally not more than 40 minutes;
s6, after refining, performing modification treatment on inclusions in molten steel through an alkali metal cored wire to enable the components of the molten steel to meet the basic components of the nickel-containing ferritic stainless steel;
the molten steel obtained after refining in S7 and S6 is sent to a continuous casting machine to be cast into a plate blank, a square blank or a rectangular blank;
and S8, cooling the plate blank or the square blank or the rectangular blank, then checking and grinding the plate blank or the square blank or the rectangular blank, and then performing controlled rolling and controlled cooling rolling process and heat treatment in a rolling mill to obtain the required steel.
Wherein, the S1 of the high-chromium nickel-containing pitting corrosion resistant ferritic stainless steel needs to control the chromium content to be 17-26 wt%, 0.6-0.8 wt% of Mo needs to be added in S2, and the rolling and heat treatment of controlled rolling and controlled cooling in S8 are as follows: the initial rolling temperature of the steel billet is 1080-; after finishing rolling, sending the steel into a 1080-1120 ℃ solution furnace for isothermal treatment for 1.5-2.0 hours to achieve the purpose that the added Mo element is dissolved in the high-chromium nickel-containing pitting corrosion resistant ferritic stainless steel in a solid manner; immediately spraying and cooling the steel to 670-; the high-chromium nickel-containing pitting corrosion resistant ferritic stainless steel can be processed and used in a hot rolling state.
Wherein, when the nickel-containing ferritic stainless steel needs to produce cold rolled materials, the isothermal heat preservation treatment needs to be kept at 670-730 ℃ for 8-12 hours.
In conclusion, the invention carries out systematic alloy design and heat treatment process design according to the iron and alloy values of the laterite-nickel ore surface layer ore resources. By reasonably proportioning ores in the smelting process, smelting in a blast furnace or a submerged arc furnace, a converter or an AOD furnace, and properly adding and adjusting a small amount of alloy in an LF refining furnace, a series of nickel-containing ferritic stainless steel, medium chromium nickel-containing ferritic stainless steel, high chromium nickel-containing ferritic stainless steel and high chromium nickel-containing pitting corrosion resistant ferritic stainless steel are produced. The invention recycles and valuates the nearly waste surface layer ores of the laterite-nickel ores and meets the functional requirements of stainless steel.
The nickel-containing ferritic stainless steel realizes grain refining through controlled rolling and controlled cooling, the average grain size is less than 8 microns, and the grain refining plays an important role in reducing intergranular corrosion and pitting corrosion. The addition of Mo element in the LF realizes the function of resisting pitting corrosion under the condition of less alloy elements.
In addition, the tensile strength of the nickel-containing ferrite stainless steel provided by the invention is more than or equal to 450MPa, the yield strength is more than or equal to 350MPa, and the elongation after fracture is more than or equal to 22%; the reduction of area is more than or equal to 40 percent, is suitable for sheet materials of hot rolling and cold rolling, is also suitable for occasions without needing nonmagnetic property, can be used as shock-resistant energy-absorbing steel, and can also select nickel-containing ferrite stainless steel with corresponding corrosion resistance according to the requirements of corrosion-resistant scenes.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A nickel-containing ferritic stainless steel smelted from laterite-nickel ore is characterized by comprising the following basic components in percentage by mass: 0.01 to 0.07wt percent of C, less than or equal to 0.8wt percent of Si, less than or equal to 0.8wt percent of Mn, 14 to 26wt percent of Cr, less than or equal to 1.6wt percent of Ni, less than or equal to 0.05wt percent of P, less than or equal to 0.030wt percent of S, 0.01 to 0.05wt percent of Al, less than or equal to 40ppm of total O, and the balance of Fe and inevitable impurities.
2. The nickel-containing ferritic stainless steel of claim 1, characterized in that the nickel-containing ferritic stainless steelThe metallographic structure of the steel is as follows: uniformly distributing a small amount of nano-scale carbide on a ferrite matrix, controlling the average size of the carbide to be below 400 nanometers, and controlling the average size of crystal grains to be less than 8 micrometers; yield strength sigma0.2350MPa or more, breaking strength 450MPa or more and elongation 20% or more.
3. The nickel-containing ferritic stainless steel of claim 1, characterized in that the nickel-containing ferritic stainless steel includes Cr17-26 wt.%, Mo 0.6-0.8 wt.% high chromium nickel-containing pitting resistant ferritic stainless steel in addition to the medium chromium nickel-containing ferritic stainless steel of Cr14-17 wt.% and the high chromium nickel-containing ferritic stainless steel of Cr17-26 wt.%.
4. The nickel-containing ferritic stainless steel of claim 3, wherein the medium chromium nickel-containing ferritic stainless steel has a neutral salt spray corrosion resistance equal to or better than that of austenitic stainless steel 304 stainless steel, close to that of ferritic stainless steel 430.
5. The nickel-containing ferritic stainless steel of claim 3, wherein the high chromium nickel-containing ferritic stainless steel has equivalent or superior resistance to neutral salt spray corrosion as 316 stainless steel.
6. The nickel-containing ferritic stainless steel of claim 3, wherein the high chromium nickel-containing pitting resistant ferritic stainless steel has a neutral salt spray corrosion resistance equal to or better than 2205 duplex stainless steel and 316 stainless steel.
7. A method for producing a nickel-containing ferritic stainless steel according to any of claims 1 to 6, characterized in that the method comprises in particular the steps of:
s1, taking the raw material as the surface layer ore of the low-nickel laterite-nickel ore, smelting the raw material into molten iron through blast furnace smelting or ore smelting electric furnace smelting, and sending the molten iron to AOD for blowing; or molten iron obtained by smelting low-nickel iron blocks by an induction furnace and an electric arc furnace is sent to AOD for blowing; in the AOD converting process, according to the requirement of the Cr component of the nickel-containing ferritic stainless steel, the lower limit target of the Cr component is adjusted, and the lower limit target of the components of main alloy elements Ni, Mn and Si is adjusted;
s2, transferring the molten steel blown by the AOD in the S1 into an LF furnace, and enabling the content of C and the content of P in the molten steel entering the LF furnace to be below the lower limit of final components, so as to prevent C increase in the later period and reserve the allowance for C increase and P increase in the later operation;
s3, adding 200-300 mm-thick reduction refining slag into the LF, and carrying out reduction refining on the molten steel entering the LF so as to carry out deoxidation and desulfurization and carry out accurate component adjustment; reducing refining slag with CaO/SiO alkalinity2Controlling the content in the range of 2-3, wherein the components of the reduction refining slag are CaO: 50-60 wt% of high-quality CaCO3The content ratio of CaO in the total amount is more than 50 wt%; SiO 22：25-30wt％；CaF2: 10 wt%; the rest high-aluminum refractory brick block material; the lumpiness of the reduced refining slag is less than 20mm, powder materials cannot exist, and the reduced refining slag needs to be packaged in a sealed moisture-proof bag;
s4, blowing argon gas into the LF for stirring, wherein the argon gas blown into the LF is only required to be stirred to the extent that the slag surface is blown to be broken; then adding aluminum in a manner of adding 0.8-1.2kg of Al into each ton of steel, and in the subsequent process, adding no aluminum into molten steel for deoxidation; aluminum particles can be added to the surface of the LF slag when the formation of white slag is promoted, but aluminum powder cannot be used for replacing the aluminum particles, so that the aluminum powder is prevented from being violently combusted;
s5, blowing argon into the LF furnace, stirring for 10 minutes, then keeping white slag, adding limestone with high calcium proportion to adjust slag when the slag is too thin, so as to keep foamability of the slag, and smoothly refining and adjusting components of the LF furnace; the time consumed for keeping LF refined and adjusted is generally not more than 40 minutes;
s6, after refining, performing modification treatment on inclusions in molten steel through an alkali metal cored wire to enable the components of the molten steel to meet the basic components of the nickel-containing ferritic stainless steel;
the molten steel obtained after refining in S7 and S6 is sent to a continuous casting machine to be cast into a plate blank, a square blank or a rectangular blank;
and S8, cooling the plate blank or the square blank or the rectangular blank, then checking and grinding the plate blank or the square blank or the rectangular blank, and then performing controlled rolling and controlled cooling rolling process and heat treatment in a rolling mill to obtain the required steel.
8. The method of making a nickel-containing ferritic stainless steel of claim 7, wherein the S8 controlled rolling and controlled cooling rolling and heat treatment of the medium chromium nickel-containing ferritic stainless steel or the high chromium nickel-containing ferritic stainless steel is: the initial rolling temperature of the steel billet is 1080-; and after finishing rolling, immediately spraying and cooling the steel to 670-.
9. The method for preparing a nickel-containing ferritic stainless steel according to claim 7, wherein the high-chromium nickel-containing pitting resistant ferritic stainless steel is S1 with chromium content controlled to be 17-26 wt%, Mo is added in S2 with 0.6-0.8 wt%, and the rolling and heat treatment of controlled rolling and controlled cooling in S8 are as follows: the initial rolling temperature of the steel billet is 1080-; after finishing rolling, sending the steel into a 1080-1120 ℃ solution furnace for isothermal treatment for 1.5-2.0 hours to achieve the purpose that the added Mo element is dissolved in the high-chromium nickel-containing pitting corrosion resistant ferritic stainless steel in a solid manner; immediately spraying and cooling the steel to 670-.
10. The method for preparing a nickel-containing ferritic stainless steel as set forth in claim 7, wherein the isothermal heat-preservation treatment is performed at 670-730 ℃ for 8-12 hours when the nickel-containing ferritic stainless steel is to be produced as a cold rolled material.
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| PCT/CN2019/109535 WO2021056602A1 (en) | 2019-09-24 | 2019-09-30 | Nickel-containing ferritic stainless steel smelted from laterite nickel ore, and preparation method therefor |
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