CN114921727A - Production method of acid-resistant pipeline steel X65MS - Google Patents

Production method of acid-resistant pipeline steel X65MS Download PDF

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CN114921727A
CN114921727A CN202210699006.7A CN202210699006A CN114921727A CN 114921727 A CN114921727 A CN 114921727A CN 202210699006 A CN202210699006 A CN 202210699006A CN 114921727 A CN114921727 A CN 114921727A
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molten steel
carbon
steel
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周文浩
陈奇明
罗登
史术华
熊祥江
李中平
周凯
范明
彭宁琦
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Hunan Valin Xiangtan Iron and Steel Co Ltd
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Hunan Valin Xiangtan Iron and Steel Co Ltd
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    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
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Abstract

The production method of the acid-resistant pipeline steel X65MS comprises the following chemical components, by mass, 0.03-0.04% of carbon, 0.10-0.20% of silicon, 1.20-1.25% of manganese, 0.012 or less of phosphorus, 0.0010 or less of sulfur, 0.038-0.044% of niobium, 0.012-0.018% of titanium, 0.015 or less of aluminum, 0.10-0.13% of nickel, 0.15-0.18% of chromium, 0.08-0.10% of molybdenum, 0.15-0.18% of copper, 0.03-0.04% of V, and the balance Fe and inevitable impurities. The produced steel has the advantages of high strength, good toughness, excellent low-temperature toughness, excellent HIC (hydrogen induced cracking) and SSCC (sulfide stress cracking) resistance, excellent processability and welding performance, the yield strength of the steel is 450-550 Mpa, the tensile strength is 550-650 Mpa, the yield ratio is less than or equal to 0.86, the plate thickness low-temperature impact toughness is-40 ℃, Akv is more than or equal to 230J, the crack arrest drop hammer temperature is-30 ℃, the toughness area is more than or equal to 88%, the HIC resistance CLR is less than or equal to 5%, the CTR is less than or equal to 1%, and the CSR is less than or equal to 1%. The 90% yield strength load SSCC is qualified.

Description

Production method of acid-resistant pipeline steel X65MS
Technical Field
The invention belongs to the technical field of metallurgy, and relates to a production method of steel X65MS for an acid-resistant pipeline of petroleum and natural gas.
Background
With the change of energy structures and the increase of energy demand, the exploitation of energy is gradually extended from inland to ocean and polar regions, which greatly promotes the development of long-distance transmission pipelines, and with the further reduction of exploitation resources, H is rich ２ Ｓ／ＣＯ ２ The exploitation of natural gas resources in corrosive medium is increasing day by day, while H ２ S is one of harmful media with the most corrosive effect in oil gas, H atoms generated in a corrosive environment continuously permeate and accumulate to the defect positions in the pipeline steel, the steel is corroded and cracked even under low gas transmission pressure, and in order to ensure the safety of oil gas transmission, the oil gas pipeline steel is required to have good HIC (hydrogen induced cracking) resistance, so that the requirement of the acid environment service steel is met. The acid-resistant pipeline steel has high yield strength and tensile strength, good extensibility, cold bending property, welding property, low-temperature crack arrest property and HIC (hydrogen induced cracking) resistance, is mainly applied to the natural gas and petroleum transportation industry to adapt to the transportation service environment of an acid medium and effectively resist H 2 And corrosion damage of S reduces carbon emission, increases engineering safety factor and saves resources.
Disclosure of Invention
The invention aims to provide a production method of high-strength and good-low-temperature-toughness steel X65MS for an acid-resistant petroleum and natural gas pipeline, which has the advantages of high strength, good toughness, excellent low-temperature toughness, excellent HIC (hydrogen induced cracking) resistance and SSCC (single stranded chain copper) resistance, excellent processability and welding performance, yield strength of the steel is 450-550 Mpa, tensile strength of 550-650 Mpa, yield ratio of the steel is less than or equal to 0.86, plate thickness low-temperature impact toughness of-40 ℃, Akv of more than or equal to 230J, crack arrest drop hammer temperature of-30 ℃, toughness area of more than or equal to 88%, HIC resistance CLR of less than or equal to 5%, CTR of less than or equal to 1%, and CSR of less than or equal to 1%. The 90% yield strength load SSCC is qualified.
The invention is realized by the following technical scheme:
a production method of acid-resistant pipeline steel X65MS comprises the steps of converter smelting, refining, continuous casting, heating rolling, cooling, inspection and warehousing, wherein the steel comprises the following chemical components, by mass, 0.03-0.04% of carbon, 0.10-0.20% of silicon, 1.20-1.25% of manganese, 0.012 or less of phosphorus, 0.0010 or less of sulfur, 0.038-0.044% of niobium, 0.012-0.018% of titanium, 0.015 or less of aluminum, 0.10-0.13% of nickel, 0.15-0.18% of chromium, 0.08-0.10% of molybdenum, 0.15-0.18% of copper, 0.03-0.04% of V, and the balance of Fe and inevitable impurities; the key process steps comprise:
(1) converter: controlling oxygen content of the converter to be more than or equal to 450ppm and carbon-oxygen product to be 0.0023 percent, stopping slag and tapping by adopting a sliding plate device, adding lime and a modifier after the converter is used for slag treatment, and performing aluminum-free deoxidation; feeding no Al wire and alloying operation after the furnace;
(2) refining: and LF starts large-flow Ar blowing stirring, an electrode heats molten steel, oxygen in the molten steel of the converter and carbon are utilized to further carry out carbon-oxygen reaction, the oxygen content of the molten steel is reduced, after the carbon-oxygen reaction is finished, the measured value of the carbon is less than or equal to 0.025 percent, after decarburization reaction, alloy is added, and the oxygen content of the molten steel is controlled to be less than or equal to 30 ppm. Adding lime into molten steel, deoxidizing and desulfurizing refining slag, and adding CaO/SiO into the refining slag 2 Not more than 4.2 to 5.5, controlling the aluminum content in the molten steel in the whole process, and reducing Al 2 O 3 Generating inclusions; controlling inclusions in the molten steel, and keeping the vacuum for more than 18min under the condition of the working vacuum degree of 0.5 tor; performing denitrification, hydrogen and oxygen treatment on the molten steel, wherein the oxygen content is less than or equal to 15 ppm;
(3) continuous casting: the casting process is protected by low superheat degree in the whole process, the superheat degree is controlled to be 8-12 ℃, a method of dynamically proportioning water is adopted for secondary cooling, the center segregation and the looseness of the casting blank are reduced by a dynamic soft reduction technology, the casting blank is quenched to be less than or equal to 600 ℃ by a casting blank quenching device after being discharged from a secondary cooling flame and cut, and the casting blank is inserted into a heat preservation device to be slowly cooled to be less than or equal to 350 ℃ and then is charged and rolled;
(4) rolling: heating temperature is 1150-1180 ℃, heating time is 280-320 min, when the thickness of the warm blank is more than 3h, rolling temperature is 840-930 ℃, final rolling temperature is 770-810 ℃, water cooling is adopted, cooling temperature is 780-820 ℃, final cooling temperature is 480-570 ℃, and cooling rate is 10-20 ℃/s.
The principle of the invention is as follows:
in the step (1), a molten pool is stirred by a large oxygen jet flow to produce high-alkalinity slag, so that the oxygen content of the discharged steel is more than or equal to 450ppm, the carbon-oxygen product is 0.0023 percent, and the P is less than or equal to 0.010 percent.
And (2) after LF, starting the flow of large argon for stirring, heating the molten steel by an electrode, and raising the temperature to further generate carbon-oxygen reaction to generate CO 2 Discharging to further reduce the carbon content of the molten steel, reduce the precipitation of carbide, eliminate the generation of abnormal structures, stably control the carbon content to be less than or equal to 0.025 percent, reduce the inclusion Al by adopting non-aluminum deoxidation alloying 2 O 3 After the deoxidation reaction, alloy is added for deoxidation alloying, lime and refining slag are adopted for deoxidation and sulphur to produce high-alkalinity fluidity slag, and the alkalinity of the refining slag is CaO/SiO 2 : 4.2-5.5, controlling the aluminum content in the molten steel in the whole process, and reducing Al 2 O 3 The generation of inclusions is convenient for CaO-Al 2 O 3 CaO-Al with low melting point 2 O 3 The conversion of MgO composite inclusions is beneficial to the floating and the removal of the inclusions, and the A-type thickness/fineness system is stably controlled to be less than or equal to 0.5 grade; class B coarse/fine is less than or equal to 1.0 grade; class C coarse/fine is less than or equal to 0.5 grade; class D coarse/fine is less than or equal to 1.0 grade.
Regarding the step (3), continuous casting adopts low superheat degree protective casting, the generation of secondary oxides can be effectively reduced through the whole protective casting, the superheat degree is controlled to be 8-12 ℃, a continuous casting secondary cooling dynamic water distribution technology, a solidification end three-section dynamic soft reduction technology are adopted, the reduction amount is 7-9 mm, the formation of a central bridge chain is reduced, the central segregation and the porosity are reduced, and the central segregation is less than or equal to 0.5 grade; after flame cutting, the casting blank is quenched to be less than or equal to 600 ℃ by a casting blank quenching device, the casting blank structure is uniform, cooling is carried out on the lower wire protection cover to be less than or equal to 350 ℃, furnace rolling is carried out, the casting blank state structure is further stabilized, and the fine isometric crystal structure is obtained.
And (5) performing low-temperature heating at 1150-1180 ℃, wherein initial austenite is fine, further crushing grains by matching with high-pressure rolling, and obtaining a mixed structure of a large amount of acicular ferrite intermediate bainite on the surface at a high cooling speed. Ferrite tissues are mutually wound, so that the extension of fracture is prevented, the crack arrest performance of the material is improved, and the acid resistance performance is improved.
The invention has the advantages that: simple production process, low alloy cost, and effective reduction of Al by controlling the micro-aluminum component 2 O 3 The production of inclusions reduces the amount of large inclusions in the steel and improves the performance of the steel. The unique LF decarburization technology utilizing the residual oxygen in the molten steel saves the traditional RH vacuum decarburization link, reduces the production procedures, saves the energy and reduces the CO 2 Discharging, reducing the production cost, reducing the blowing pressure of the converter, protecting the converter lining, prolonging the service life of the converter, and stably controlling 0.03-0.04% of carbon element by further generation of argon carbon-oxygen blowing reaction through LF temperature rise. The quenching and chilling of the continuous casting blank and the heat preservation technology of the heat preservation cover ensure that the casting blank obtains as much fine isometric crystal structure as possible. Ferrite and bainite winding structures, and excellent HIC resistance and SSCC resistance are obtained. The acid-resistant pipeline steel X65MS produced by the method has the casting blank segregation C of not more than 0.5, uniform and stable steel plate performance, excellent HIC and SSCC resistance, yield strength of 450-550 Mpa, tensile strength of 550-650 Mpa, yield ratio of not more than 0.86, impact of 260-450J at-40 ℃, and shear area of-30 drop hammer of not less than 88%; the inclusions A class coarse system/fine system is less than or equal to 0.5 grade, B class coarse system/fine system is less than or equal to 1.0 grade, C class coarse system/fine system is less than or equal to 0.5 grade, D class coarse system/fine system is less than or equal to 1.0 grade, HIC resistance CLR is less than or equal to 5 percent, CTR is less than or equal to 1 percent, and CSR is less than or equal to 1 percent. The SSCC with 90 percent strength is qualified.
Drawings
FIG. 1 is a metallographic structure drawing of a steel plate according to an example.
Detailed Description
The invention is further illustrated by the following examples:
example 1: production of 9.5mmX65MS pipeline steel
The chemical composition weight percentage of the alloy elements is carbon =0.035, silicon =0.18, manganese =1.23, phosphorus = 0.011, sulfur = 0.0008, niobium =0.042, titanium =0.01, aluminum =0.012, nickel =0.13, chromium =0.16, molybdenum =0.09, copper =0.16, V =0.037, and the balance of iron and inevitable impurities, the key process steps are as follows:
(1) smelting in a converter: the oxygen content of converter tapping is 480ppm, the carbon content is 0.049%, argon stirring is controlled after the converter tapping, 600kg of lime and 300kg of modifier are added;
（2）refining in an LF furnace: starting large argon flow for stirring at the early stage, wherein the argon flow is 600-1000L/H, and the refining temperature is 1500-1650 ℃; feeding electricity for 30min, fully reacting carbon and oxygen, reducing the carbon content C =0.022%, adding argon into alloy for deoxidation and alloying treatment, deoxidizing and decarburizing refining treatment, controlling the aluminum content in molten steel in the whole process, and reducing Al 2 O 3 The generation of inclusions is convenient for CaO-Al 2 O 3 CaO-Al with low melting point 2 O 3 -MgO composite inclusion transformation is beneficial to inclusion floating and removal, and A-type thickness/fineness system is 0 grade; class B coarse/fine 0.5 grade; class C coarse/fine 0; class D coarse/fine is 0.5 grade, and the vacuum is kept for 18min under the vacuum of 0.5 tor; the molten steel is subjected to denitrification, hydrogen and oxygen treatment, the oxygen content is 12ppm, and the purity of the molten steel is greatly improved;
(3) continuous casting: controlling the superheat degree to be 10 ℃, controlling the water ratio of continuous casting secondary cooling water distribution to be 0.18L/kg, and adopting a three-section dynamic soft reduction technology at the solidification end, wherein the reduction is 7mm, so that the formation of a center bridge chain is reduced, the center segregation and the porosity are reduced, and the center segregation is 0.5 grade; after flame cutting, a casting blank quenching device quenches 580 ℃, a lower line protective cover is cooled to 330 ℃ and then is subjected to furnace rolling, and the casting blank state structure is further stabilized to obtain a fine isometric crystal structure;
(4) rolling: heating temperature is 1150-1180 ℃, heating time is 290min, the thickness of a blank to be heated is 68mm, the initial rolling temperature is 930 ℃, the final rolling temperature is 770-810 ℃, online quenching is adopted, the initial cooling temperature is 825 ℃, the final cooling temperature is 240-320 ℃, and the cooling rate is 15.6 ℃/s.
The results of the property measurements of the steels are shown in Table 1.
TABLE 19.5 mm acid-resistant pipeline steel X65MS Performance Table
Figure 584586DEST_PATH_IMAGE001
SSC adopts ASTM G39 to carry out 4-point bending test in NACE TM0177-2016 standard A solution, the loading stress is 90 percent of the actual yield strength of the steel plate, no crack appears on the surface, HIC is tested according to NACE TM0284 standard A solution, and CLR, CTR and CSR all meet the standard requirements.
Example 2: production of 25.4mmX65MS pipeline steel
The alloy comprises the following chemical components of, by weight, carbon =0.035, silicon =0.18, manganese =1.23, phosphorus = 0.011, sulfur = 0.0008, niobium =0.042, titanium =0.01, aluminum =0.012, nickel =0.13, chromium =0.16, molybdenum =0.09, copper =0.16, and V = 0.037. The key process steps are as follows:
(1) smelting in a converter: smelting in a converter: the oxygen content of converter tapping is 480ppm, the carbon content is 0.049%, argon stirring is controlled after the converter tapping, 600kg of lime and 300kg of modifier are added;
(2) refining in an LF furnace: starting large argon flow for stirring at the early stage, wherein the argon flow is 600-1000L/H, and the refining temperature is 1500-1650 ℃; transmitting electricity for 30min, fully reacting carbon and oxygen, reducing the carbon content C =0.022%, adding argon into alloy for deoxidation and alloying treatment, deoxidizing and decarburizing refining treatment, controlling the aluminum content in molten steel in the whole process, and reducing Al 2 O 3 The generation of inclusions is facilitated for CaO-Al 2 O 3 CaO-Al with low melting point 2 O 3 -MgO composite inclusion transformation is beneficial to inclusion floating and removal, and A-type thickness/fineness system is 0 grade; class B coarse/fine 0.5 grade; class C coarse/fine 0; class D coarse/fine is 0.5 grade, and the vacuum is kept for 18min under the vacuum of 0.5 tor; the molten steel is subjected to denitrification, hydrogen and oxygen treatment, the oxygen content is 12ppm, and the purity of the molten steel is greatly improved;
(3) continuous casting: controlling the superheat degree to be 10 ℃, controlling the water ratio of continuous casting secondary cooling water distribution to be 0.18L/kg, and adopting a three-section dynamic soft reduction technology at the solidification end, wherein the reduction is 7mm, so that the formation of a center bridge chain is reduced, the center segregation and the porosity are reduced, and the center segregation is 0.5 grade; after flame cutting, a casting blank quenching device quenches 580 ℃, a lower line protective cover is cooled to 330 ℃ and then is subjected to furnace rolling, and the casting blank state structure is further stabilized to obtain a fine isometric crystal structure;
(4) rolling: the heating temperature is 1150-1180 ℃, the heating time is 290min, the thickness of the blank to be heated is 90mm, the initial rolling temperature is 840 ℃, the final rolling temperature is 770-810 ℃, online quenching is adopted, the initial cooling temperature is 805 ℃, the final cooling temperature is 240-320 ℃, and the cooling speed is 18.2 ℃/s.
The results of the property measurements of the steels are shown in Table 2.
TABLE 225.4 mm acid-fast pipeline Steel X65MS Performance Table
Figure 46791DEST_PATH_IMAGE002
SSC adopts ASTM G39 to carry out 4-point bending test in NACE TM0177-2016 standard A solution, the loading stress is 90 percent of the actual yield strength of the steel plate, no crack appears on the surface, HIC is tested according to NACE TM0284 standard A solution, and CLR, CTR and CSR all meet the standard requirements.

Claims (1)

1. A production method of acid-resistant pipeline steel X65MS comprises the steps of converter smelting, refining, continuous casting, heating rolling, cooling, inspection and warehousing, wherein the steel comprises the following chemical components, by mass, 0.03-0.04% of carbon, 0.10-0.20% of silicon, 1.20-1.25% of manganese, 0.012 or less of phosphorus, 0.0010 or less of sulfur, 0.038-0.044% of niobium, 0.012-0.018% of titanium, 0.015 or less of aluminum, 0.10-0.13% of nickel, 0.15-0.18% of chromium, 0.08-0.10% of molybdenum, 0.15-0.18% of copper, 0.03-0.04% of V, and the balance of Fe and inevitable impurities; the key process steps comprise:
(1) converter: controlling oxygen content of the converter to be more than or equal to 450ppm and carbon-oxygen product to be 0.0023 percent, stopping slag and tapping by adopting a sliding plate device, adding lime and a modifier after the converter is used for slag treatment, and performing aluminum-free deoxidation; feeding no Al wire and alloying after the furnace;
(2) refining: LF opens large flow Ar stirring, the electrode heats the molten steel, oxygen in the molten steel of the converter and carbon are utilized to further generate carbon-oxygen reaction, the oxygen content of the molten steel is reduced, after the carbon-oxygen reaction end point, the measured value of the carbon is less than or equal to 0.025 percent, after decarburization reaction, alloy is added, the oxygen content of the molten steel is controlled to be less than or equal to 30ppm, lime and refining slag are added into the molten steel for deoxidation and sulfur, and the alkalinity of the refining slag is CaO/SiO 2 Not more than 4.2 to 5.5, controlling the aluminum content in the molten steel in the whole process, and reducing Al 2 O 3 Generating inclusions; controlling inclusions in the molten steel, and keeping the vacuum for more than 18min under the condition of the working vacuum degree of 0.5 tor; performing denitrification, hydrogen and oxygen treatment on the molten steel, wherein the oxygen content is less than or equal to 15 ppm;
(3) continuous casting: the casting is protected by low superheat degree in the whole process, the superheat degree is controlled to be 8-12 ℃, a method of dynamically proportioning water is adopted for secondary cooling, the center segregation and the looseness of the casting blank are reduced by a dynamic soft reduction technology, the casting blank is quenched to be less than or equal to 600 ℃ by a casting blank quenching device after being discharged from a secondary cooling flame for cutting, and the casting blank is discharged from a heat preservation device and slowly cooled to be less than or equal to 350 ℃ for charging and rolling;
(4) rolling: the heating temperature is 1150-1180 ℃, the heating time is 280-320 min, the thickness of the blank to be heated is more than 3h, the initial rolling temperature is 840-930 ℃, the final rolling temperature is 770-810 ℃, water cooling is adopted, the initial cooling temperature is 780-820 ℃, the final cooling temperature is 480-570 ℃, and the cooling rate is 10-20 ℃/s.
CN202210699006.7A 2022-06-21 2022-06-21 Production method of acid-resistant pipeline steel X65MS Pending CN114921727A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116970865A (en) * 2023-07-22 2023-10-31 湖南华菱湘潭钢铁有限公司 Production method of aluminum-free pipe fitting steel Q555PF
CN117026065A (en) * 2023-09-23 2023-11-10 湖南华菱湘潭钢铁有限公司 Production method of quenched and tempered acid-resistant pipeline steel
CN117248163A (en) * 2023-11-09 2023-12-19 湖南华菱湘潭钢铁有限公司 Production method of high-strength low-temperature toughness pipe fitting steel

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US20030180174A1 (en) * 2001-07-13 2003-09-25 Jfe Steel Corporation High-strength steel pipe of API X65 grade or higher and manufacturing method therefor
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116970865A (en) * 2023-07-22 2023-10-31 湖南华菱湘潭钢铁有限公司 Production method of aluminum-free pipe fitting steel Q555PF
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