CN112226676A - Low-cost L320MS/X46MS hot-rolled steel strip for hydrogen sulfide corrosion resistant welded pipe and manufacturing method thereof - Google Patents
Low-cost L320MS/X46MS hot-rolled steel strip for hydrogen sulfide corrosion resistant welded pipe and manufacturing method thereof Download PDFInfo
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
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Abstract
The invention discloses a low-cost L320MS/X46MS hot rolled steel strip for hydrogen sulfide corrosion resistant welded pipe and a manufacturing method thereof, wherein the steel comprises the following chemical components in percentage by mass: less than or equal to 0.08 percent of C, less than or equal to 0.10 to 0.20 percent of Si, 1.05 to 1.20 percent of Mn, 0.010 to 0.025 percent of Ti, 0.10 to 0.25 percent of Cr0.020 to 0.035 percent of Alt, less than or equal to 0.015 percent of P, less than or equal to 0.0015 percent of S, less than or equal to 0.0002 percent of H, less than or equal to 0.0030 percent of O, less than or equal to 0.0050 percent of N, and the balance of Fe and inevitable impurities. Its preparing process is also disclosed. The L390MS/X46MS hot rolled steel strip manufactured by the invention has excellent comprehensive mechanical property, and has outstanding economic benefit and good social benefit.
Description
Technical Field
The invention relates to the technical field of high-purity low-alloy high-strength steel products, mainly relates to pipeline steel for oil and gas transmission and a manufacturing method of a hot rolled steel strip of the pipeline steel, and particularly relates to an L320MS/X46MS pipeline steel hot rolled steel strip with excellent low-cost Hydrogen Induced Cracking (HIC) resistance, hydrogen Sulfide Stress Corrosion Cracking (SSCC) resistance and low-temperature toughness and a manufacturing method of the hot rolled steel strip.
Background
The L320MS/X46MS H2S corrosion resistant hot rolled steel strip for the welded pipe is used for the project construction of the natural gas pipeline of the Burma petroleum gas company. Due to the influence of geological environment, the product is required to have dual performances of hydrogen sulfide corrosion resistance and stress corrosion cracking resistance.
The document CN101418419 discloses a production process for a seamless oil jacket steel pipe, which needs heat treatment state delivery, and the patent is applicable to the production of L320MS/X46MS acid-resistant pipeline steel hot rolled steel strip for welded pipes, can be used for the production of oil, gas and water conveying pipes, and has different manufacturing processes and product purposes, the manufacturing process of the seamless steel pipe is complex, the cost is higher than that of the welded pipes, so that the development of the pipeline steel hot rolled steel strip with the function of hydrogen sulfide corrosion resistance has wider applicability and stronger practicability.
The document CN101451214 discloses the production of a large-thickness hydrogen sulfide resistant steel plate, which has great difference from the patent in component design and production process, and the patent is suitable for the production of a small-thickness hot rolled steel strip, and the yield strength range is 320-400 MPa. The low-carbon microalloy component design is adopted, the alloy cost is low, the ultralow-sulfur control capability of the low-carbon microalloy component design reaches the international advanced level, and higher guarantee is provided for the low-power quality and the hydrogen resistance of a casting blank.
The document CN109457179 discloses a hot rolled steel strip for an L290M/X42MS grade hydrogen sulfide corrosion-resistant welding pipe and a manufacturing method thereof, the patent is suitable for the manufacturing method of the hot rolled steel strip for the L320M/X46MS grade hydrogen sulfide corrosion-resistant welding pipe, the addition of precious metals in the product is avoided, and the product manufacturing cost is greatly reduced by adopting the design of low carbon + Ti + Cr alloy components and the equipment advantage of a 2250mm hot continuous rolling production line.
Disclosure of Invention
The invention aims to provide a low-cost L320MS/X46MS hot rolled steel strip for hydrogen sulfide corrosion resistant welded pipe and a manufacturing method thereof, and the mechanical properties of the produced hot rolled steel strip meet the following requirements: the yield strength is 365-.
In order to solve the technical problems, the invention adopts the following technical scheme:
a low-cost L320MS/X46MS hot-rolled steel strip for hydrogen sulfide corrosion resistant welded pipes comprises the following components in percentage by mass: less than or equal to 0.07 percent of C, 0.10 to 0.20 percent of Si, 1.05 to 1.20 percent of Mn, 0.015 to 0.025 percent of Ti, 0.10 to 0.20 percent of Cr, less than or equal to 0.020 to 0.035 percent of Alt, less than or equal to 0.015 percent of P, less than or equal to 0.0015 percent of S, less than or equal to 0.0002 percent of H, less than or equal to 0.0030 percent of O, less than or equal to 0.0050 percent of N, and the balance of Fe and inevitable impurities.
Further, the composition comprises the following components in percentage by mass: 0.06% of C, 0.15% of Si, 1.12% of Mn, 0.020% of Ti, 0.13% of Cr, 0.031% of Alt, 0.011% of P, 0.001% of S, 0.0002% of H, 0.001% of O, 0.0035% of N, and the balance of Fe and inevitable impurities.
Further, the composition comprises the following components in percentage by mass: 0.06% of C, 0.16% of Si, 1.12% of Mn, 0.020% of Ti, 0.14% of Cr, 0.032% of Alt, 0.012% of P, 0.001% of S, 0.0001% of H, 0.001% of O, 0.0041% of N, and the balance of Fe and inevitable impurities.
Further, the composition comprises the following components in percentage by mass: 0.06% of C, 0.14% of Si, 1.13% of Mn, 0.022% of Ti, 0.15% of Cr, 0.026% of Alt, 0.013% of P, 0.001% of S, 0.0001% of H, 0.001% of O, 0.0023% of N, and the balance of Fe and inevitable impurities.
A method for manufacturing a low-cost L320MS/X46MS hot-rolled steel strip for hydrogen sulfide corrosion-resistant welded pipes comprises the following steps: KR molten iron desulfurization pretreatment, converter top and bottom blowing, LF refining, RH refining, slab continuous casting, reheating, rough rolling and finishing mill set controlled rolling, cooling, coiling, tray transportation system sampling and inspection; wherein the controlled rolling process of the rough rolling and finishing mill group comprises rough rolling high-pressure water descaling, a fixed width press, an E1R1 roughing mill, an E2R2 roughing mill, a heat preservation cover, a flying shear, finish rolling high-pressure water descaling, and an F1-F7 finishing mill; cooling is carried out by adopting dense laminar cooling, and P in a continuous casting billet formed after the continuous casting treatment of the plate blank is less than or equal to 0.015 percent; s is less than or equal to 0.0015 percent; the content of [ N ] is less than or equal to 0.005, the content of [ O ] is less than or equal to 0.003, and the content of [ H ] is less than or equal to 0.0002; the vacuum degree requirement of the RH refining process is less than or equal to 2.6mbar, and the vacuum maintaining time is more than or equal to 10 min. Ensuring that the circulating pure degassing time is more than or equal to 7min during the RH vacuum treatment period; after RH vacuum treatment is finished, calcium wires are fed for calcium treatment, and soft blowing time is ensured to be more than 8min after wire feeding; and adopting a continuous casting billet soft reduction technology to control center segregation.
Further, 2250mm hot continuous rolling is adopted, the thickness of the continuous casting slab is 230mm, the continuous casting slab is heated to 1170-1190 ℃ through a stepping heating furnace and discharged, then two-stage controlled rolling is carried out through a rough rolling unit and a finishing rolling unit, the rolling pass is 6-8, the thickness of the intermediate slab is 38-55mm, the finish rolling temperature is 930-865 ℃, the finish rolling temperature is 825-865 ℃, then a front concentrated laminar cooling mode, namely the uniform cooling at the speed of 15-25 ℃/s, is adopted, and the coiling is carried out at 480-580 ℃.
Compared with the prior art, the invention has the beneficial technical effects that:
(1) by means of the advantages of 2250mm rolling mill equipment, the product design is flexible and reasonable, the cost is low, the method is suitable for the requirements of hydrogen sulfide corrosion resistant L320MS/X46MS hot rolled products at home and abroad, the C-Mn steel is taken as the main material, only trace Cr and Ti alloy elements are added, and the cost reduction and the efficiency improvement of enterprises are facilitated.
(2) The product has good plasticity and low-temperature toughness, can be applied to extremely cold regions, has the double characteristics of hydrogen induced cracking resistance and hydrogen sulfide stress corrosion cracking resistance, and completely meets the requirements of national standards and international standards.
(3) The L320MS/X46MS hot-rolled coil plate has excellent product performance and economic and reasonable component design, is rolled into a coil plate by combining a pure steel smelting continuous casting technology and a controlled rolling and controlled cooling process, has excellent quality, can be widely applied to the construction of oil and gas transmission pipelines, meets the requirements of API SPEC 5L specifications and general technical conditions for petrochemical in petroleum in all indexes, and has outstanding economic benefit and good social benefit.
Drawings
The invention is further illustrated in the following description with reference to the drawings.
FIG. 1 is a metallographic structure of an L320MS/X46MS hot rolled steel strip obtained in example 1 of the present invention.
Detailed Description
The invention provides a method for manufacturing L390M/X46MS hot rolled steel strip for a petroleum gas welding pipe with hydrogen sulfide corrosion resistance aiming at China-Burma energy project engineering.
Wherein:
c: the C content in the steel increases, the yield strength and the tensile strength increase, but the ductility and the toughness decrease. For pipeline steel, if the carbon content is too high, the toughness of the steel can be reduced rapidly, the weldability is deteriorated, meanwhile, C is an easily-segregated element which can aggravate the center segregation of a casting blank, a pearlite banded structure is easily formed after rolling, and the hydrogen-induced cracking resistance of the steel can be seriously influenced, so that the design idea of adopting low-carbon components is a premise for designing H2S-resistant pipeline products, and the strength loss of the steel is compensated by the action of alloy elements. Therefore, the carbon content is controlled to be less than or equal to 0.07 percent.
Si: deoxidizing element, which is solid-dissolved in ferrite to improve the strength of steel, but loses plasticity and toughness, the Si content is controlled to be 0.10-0.20%.
Mn: manganese can be infinitely replaced and dissolved with iron, and is a good solid solution strengthening element, but for the hydrogen sulfide resistance, the content of manganese which is less than 1.2 percent is generally required to be added into steel in the industry, because manganese is easily enriched in the center of a casting blank to form a hard phase segregation zone like carbon and phosphorus elements in the steel, and pearlite zonal structure is generated after rolling to cause the HIC performance of the steel to be reduced. Therefore, the manganese content is reduced to 1.05-1.20% as much as possible.
Ti: titanium has strong affinity with carbon and nitrogen in the heating and solidification processes, forms very stable TiC and TiN particles which are enriched at a crystal boundary, forms insoluble second phase particles to block the migration and dislocation motion of the crystal boundary, has the function of strongly preventing the growth of the crystal particles, and has obvious effect of improving the fracture toughness of a heat affected zone during steel welding. Therefore, the invention controls the Ti content to be 0.015-0.025%.
Cr: cr is extremely beneficial to slowing down the corrosion rate in the environment of CO 2-H2S-Cl-; on the other hand, the dispersed carbide of the steel is also a strong trap of hydrogen, so that the content of Cr is enough under the condition of permission, and the hardenability of Cr can be improved, so that the steel has better comprehensive mechanical properties after quenching. However, the cost of Cr alloy is high, so the addition amount is selected according to the thickness of the product and the requirements of users, and the content of Cr is generally controlled to be 0.10-0.20%.
And (3) Alt: the deoxidation element is added with a proper amount of aluminum to form fine and dispersed AlN particles, which is beneficial to refining crystal grains and improving the toughness of steel, and the content of Alt is controlled to be 0.020-0.035%.
S: is an extremely harmful element in acid-resistant pipeline steel, and the HIC and SSCC sensitivity is improved sharply. MnS inclusions formed by S and Mn are the most easily nucleated positions of HIC, and MnS can become scattered spheroids through calcium treatment, so that the formation of HIC can be inhibited, and the crack sensitivity is obviously reduced. There are studies showing that: only when the sulfur content is below 0.002% HIC and SSC sensitivity is significantly reduced, even negligible. Therefore, the content of S is controlled to be less than or equal to 0.0020 percent.
P: is an inevitable impurity element in steel, is an easily segregated element, causes nonuniformity of components and tissues, and increases crack sensitivity. Therefore, the content of P is controlled to be less than or equal to 0.015 percent.
H: the solubility of H in solid steel is very low, the H is dissolved in molten steel at high temperature, and the H cannot escape in time during cooling and is gathered in a structure to form high-pressure fine pores, so that the cracking of the HIC and SSCC of steel products is aggravated, and the content of H is controlled to be below 0.0002% through vacuum degassing.
O: the O exists in the steel mainly in the form of inclusions, and the excessive oxygen can form complex oxide inclusions with Ca and Al in a massive or linear distribution mode, so that the phenomenon that the HIC and SSCC sensitivity is reduced due to a crack source caused by stress concentration at the tip of the complex oxide inclusions is avoided.
N: is an inevitable impurity element in steel. In the invention, the content of N is controlled to be less than or equal to 0.0050 percent.
The invention adopts TMCP thermomechanical rolling technology to manufacture the L320MS/X46MS pipeline steel hot-rolled coil. The production process flow relates to: KR desulfurization, converter, LF furnace, RH, slab continuous casting, reheating furnace, rough rolling high-pressure water descaling, fixed width press, E1R1 rough rolling machine, E2R2 rough rolling machine, heat preservation cover, flying shear, finish rolling high-pressure water descaling, F1-F7 finishing rolling machine, dense laminar cooling, coiling, tray transportation system, sampling and inspection.
Smelting raw materials are sequentially subjected to KR molten iron desulphurization pretreatment, converter top and bottom blowing, LF refining, RH refining and continuous casting process treatment to form a high-purity continuous casting billet, wherein P is less than or equal to 0.015%; s is less than or equal to 0.0015 percent; the content of [ N ] is less than or equal to 0.005, the content of [ O ] is less than or equal to 0.003, and the content of [ H ] is less than or equal to 0.0002; the vacuum degree requirement of the RH refining process is less than or equal to 2.6mbar, and the vacuum maintaining time is more than or equal to 10 min. Ensuring that the circulating pure degassing time is more than or equal to 7min during the RH vacuum treatment period; after RH vacuum treatment is finished, calcium wires are fed for calcium treatment, and soft blowing time is ensured to be more than 8min after wire feeding; and adopting a continuous casting billet soft reduction technology to control center segregation.
The method comprises the steps of adopting 2250mm hot continuous rolling for rolling, wherein the thickness of the continuous casting blank is 230mm, heating the continuous casting blank to 1170-1190 ℃ through a stepping heating furnace, discharging, then carrying out two-stage controlled rolling through a rough rolling unit and a finishing rolling unit, wherein the rolling pass is 6-8 pass mode, the thickness of an intermediate blank is 38-55mm, the finish rolling start temperature is 930-1000 ℃, the finish rolling finish temperature is 825-865 ℃, then adopting a front concentrated laminar cooling mode, namely uniformly cooling at the speed of 15-25 ℃/s, and coiling at 480-580 ℃.
The present invention will be described in detail by examples, and it should be understood by those skilled in the art that the examples are only for the purpose of facilitating understanding of the present invention, and do not limit the present invention.
The weight percentages of the components used in the experimental steels of examples 1-4 are shown in table 1 below, table 2 shows the specific process regime for each example, and table 3 shows the mechanical properties of the steels of each example. Wherein, figure 1 shows the metallographic structure of the steel strip obtained in example 1, and the metallographic structure is ferrite + bainite, the crystal grains are fine and uniform, no strip structure exists, and the size of the crystal grains is more than 10 grades.
Table 1: chemical composition of the examples (wt%)
Examples | C | Si | Mn | P | S | Alt | Ti | Cr | H | O | N |
202101708 | 0.06 | 0.15 | 1.12 | 0.011 | 0.001 | 0.031 | 0.020 | 0.13 | 0.0002 | 0.001 | 0.0035 |
203111999 | 0.06 | 0.16 | 1.12 | 0.012 | 0.001 | 0.032 | 0.020 | 0.14 | 0.0001 | 0.001 | 0.0041 |
204100951 | 0.06 | 0.14 | 1.13 | 0.013 | 0.001 | 0.026 | 0.022 | 0.15 | 0.0001 | 0.001 | 0.0023 |
Table 2: process system of each example
Examples | Thickness of casting blank/mm | Tapping temperature/. degree C | The rolling start temperature/DEG C of finish rolling | Finish rolling temperature/DEG C | Coiling temperature/. degree.C |
1 | 230 | 1169 | 966 | 820 | 495 |
2 | 230 | 1170 | 977 | 831 | 500 |
3 | 230 | 1185 | 988 | 826 | 496 |
Table 3: mechanical properties of the steels of the examples
TABLE 4 HIC resistance of the steels of the examples
Note: no hydrogen bubbles were present on the surface of the samples.
As can be seen from the examples, the steel provided by the embodiment of the invention has excellent low-temperature impact toughness, yield strength of 365-.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (6)
1. A low-cost L320MS/X46MS hot-rolled steel strip for hydrogen sulfide corrosion resistant welded pipes is characterized by comprising the following components in percentage by mass: less than or equal to 0.07 percent of C, 0.10 to 0.20 percent of Si, 1.05 to 1.20 percent of Mn, 0.015 to 0.025 percent of Ti, 0.10 to 0.20 percent of Cr, less than or equal to 0.020 to 0.035 percent of Alt, less than or equal to 0.015 percent of P, less than or equal to 0.0015 percent of S, less than or equal to 0.0002 percent of H, less than or equal to 0.0030 percent of O, less than or equal to 0.0050 percent of N, and the balance of Fe and inevitable impurities.
2. The hot-rolled steel strip for low-cost L320MS/X46MS hydrogen sulfide corrosion-resistant welded pipes according to claim 1, comprising the following components in percentage by mass: 0.06% of C, 0.15% of Si, 1.12% of Mn, 0.020% of Ti, 0.13% of Cr, 0.031% of Alt, 0.011% of P, 0.001% of S, 0.0002% of H, 0.001% of O, 0.0035% of N, and the balance of Fe and inevitable impurities.
3. The hot-rolled steel strip for low-cost L320MS/X46MS hydrogen sulfide corrosion-resistant welded pipes according to claim 1, comprising the following components in percentage by mass: 0.06% of C, 0.16% of Si, 1.12% of Mn, 0.020% of Ti, 0.14% of Cr, 0.032% of Alt, 0.012% of P, 0.001% of S, 0.0001% of H, 0.001% of O, 0.0041% of N, and the balance of Fe and inevitable impurities.
4. The hot-rolled steel strip for low-cost L320MS/X46MS hydrogen sulfide corrosion-resistant welded pipes according to claim 1, comprising the following components in percentage by mass: 0.06% of C, 0.14% of Si, 1.13% of Mn, 0.022% of Ti, 0.15% of Cr, 0.026% of Alt, 0.013% of P, 0.001% of S, 0.0001% of H, 0.001% of O, 0.0023% of N, and the balance of Fe and inevitable impurities.
5. The method for producing a hot-rolled steel strip for low-cost L320MS/X46MS hydrogen sulfide corrosion-resistant welded pipe according to any one of claims 1 to 4, comprising the steps of: KR molten iron desulfurization pretreatment, converter top and bottom blowing, LF refining, RH refining, slab continuous casting, reheating, rough rolling and finishing mill set controlled rolling, cooling, coiling, tray transportation system sampling and inspection; wherein the controlled rolling process of the rough rolling and finishing mill group comprises rough rolling high-pressure water descaling, a fixed width press, an E1R1 roughing mill, an E2R2 roughing mill, a heat preservation cover, a flying shear, finish rolling high-pressure water descaling, and an F1-F7 finishing mill; the cooling adopts the encryption type laminar flow cooling, and is characterized in that: in the continuous casting billet formed after the continuous casting treatment of the plate blank, P is less than or equal to 0.015 percent; s is less than or equal to 0.0015 percent; the content of [ N ] is less than or equal to 0.005, the content of [ O ] is less than or equal to 0.003, and the content of [ H ] is less than or equal to 0.0002; the vacuum degree requirement of the RH refining process is less than or equal to 2.6mbar, and the vacuum maintaining time is more than or equal to 10 min; ensuring that the circulating pure degassing time is more than or equal to 7min during the RH vacuum treatment period; after RH vacuum treatment is finished, calcium wires are fed for calcium treatment, and soft blowing time is ensured to be more than 8min after wire feeding; and adopting a continuous casting billet soft reduction technology to control center segregation.
6. The manufacturing method as claimed in claim 1, wherein 2250mm hot continuous rolling is adopted, the thickness of the continuous casting slab is 230mm, the continuous casting slab is heated to 1170-1190 ℃ through a step-type heating furnace and discharged, then two-stage controlled rolling is carried out through a rough rolling unit and a finish rolling unit, the rolling pass is in a 6-8 pass mode, the thickness of the intermediate billet is 38-55mm, the finish rolling start temperature is 930-1000 ℃, the finish rolling finish temperature is 825-865 ℃, then uniform cooling is carried out in a front concentrated laminar cooling mode at the speed of 15-25 ℃/s, and coiling is carried out at 480-580 ℃.
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CN113943892A (en) * | 2021-09-16 | 2022-01-18 | 包头钢铁(集团)有限责任公司 | Preparation method of low-cost Ti microalloyed thin 700 MPa-grade steel belt for automobile crossbeam |
CN114959468A (en) * | 2022-05-18 | 2022-08-30 | 包头钢铁(集团)有限责任公司 | Thick-specification extremely cold-resistant nickel-free L360MSX52MS H-resistant material 2 S-corrosion hot-rolled coil and preparation method thereof |
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CN109457179A (en) * | 2018-11-19 | 2019-03-12 | 包头钢铁(集团)有限责任公司 | A kind of hydrogen sulfide corrosion resistant welded tube hot rolled strip and its manufacturing method |
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CN109457179A (en) * | 2018-11-19 | 2019-03-12 | 包头钢铁(集团)有限责任公司 | A kind of hydrogen sulfide corrosion resistant welded tube hot rolled strip and its manufacturing method |
Cited By (4)
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CN113943892A (en) * | 2021-09-16 | 2022-01-18 | 包头钢铁(集团)有限责任公司 | Preparation method of low-cost Ti microalloyed thin 700 MPa-grade steel belt for automobile crossbeam |
CN114959468A (en) * | 2022-05-18 | 2022-08-30 | 包头钢铁(集团)有限责任公司 | Thick-specification extremely cold-resistant nickel-free L360MSX52MS H-resistant material 2 S-corrosion hot-rolled coil and preparation method thereof |
WO2024066987A1 (en) * | 2022-09-26 | 2024-04-04 | 武汉钢铁有限公司 | Economical hydrogen gas conveying pipeline steel, and production method |
CN117187686A (en) * | 2023-08-01 | 2023-12-08 | 包头钢铁(集团)有限责任公司 | Spiral submerged arc welded pipe hot rolled steel strip for hydrogen-doped conveying pipeline and production method thereof |
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