CN102839331A - High-toughness corrosion-resistant steel and manufacturing method thereof - Google Patents
High-toughness corrosion-resistant steel and manufacturing method thereof Download PDFInfo
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Abstract
The invention relates to high-toughness corrosion-resistant steel. The high-toughness corrosion-resistant steel comprises the following chemical components in percentage by weight: 0.03 to 0.10 percent of C, 0.2 to 0.6 percent of Si, 0.35 to 0.75 percent of Mn, 12 to 14 percent of Cr, 0.5 to 1.5 percent of Ni, 0.01 to 0.04 percent of Al, 0.1 to 0.3 percent of Mo, less than or equal to 0.015 percent of P, less than or equal to 0.006 percent of S and less than or equal to 0.01 percent of N, wherein the Al/N is greater than 2, and the balance is Fe and unavoidable impurities. The manufacturing method of the high-toughness corrosion-resistant steel comprises the following steps of: smelting the chemical components by refining in and out of an electric arc furnace and performing vacuum refining treatment, or refining in and out of an oxygen converter and performing vacuum refining treatment or adopting an electroslag remelting method, and casting into ingots; making hot ingots enter the furnace before forging, wherein the surface temperature of ingots entering the furnace is less than 600 DEG C, the forging heating temperature is 1,200 to 1,250 DEG C, the finish forging temperature is greater than 1,000 DEG C, the forging ratio is greater than 6, and the grain fineness number at 1/2 of the thickness of the wall of a forged piece is not less than level 6. The high-toughness corrosion-resistant steel obtained by the method has the yield strength of greater than 517 MPa, and the ballistic work at -46 DEG C is greater than 27 J; and the high-toughness corrosion-resistant steel is suitable for FF-grade 105 MPa production tree body in oil and gas industry.
Description
Technical field
The present invention relates to a kind of oil and gas industry low temperature and use the high tenacity corrosion resistant steel, particularly relate to HS, high tenacity corrosion resistant steel and method of manufacture thereof that a kind of use temperature reaches-46 ℃.
Background technology
X-tree is an oil gas well well head set-up, for the tubing string that produces oil provides access, is to be used for the valve of fluid control and the assembly of accessory.X-tree is hanging the tubing string in the lower going-into-well, and oil well production is controlled and regulated to sealing oil telescopic annular space, guarantees operation, construction, and admission is oily, the casing pressure data, daily production managements such as test and wax removal.
X-tree is divided special-purpose well head set-uies such as oil recovery (blowing, artificial lift), gas production (Sweet natural gas and various sour gas), water filling, thermal recovery, pressure break, acidifying again by different effects.And according to the different series that form of applying pressure grade.Because Sweet natural gas gas specific density is low, it is low that gas is annotated pressure, no matter gas production or gas input well mouth pressure are all high, flow velocity is high, and easy to leak has H in the Sweet natural gas sometimes simultaneously
2S, CO
2Deng corrosive medium, thereby the material of X-tree there is strict requirement.As at FF level 105MPa X-tree body, its minimum use temperature is-46 ℃, environment for use be partial pressure of carbon dioxide less than 200psi, hydrogen sulfide sectional pressure is less than 0.5psi.105MPa is the maximum intensity rank of X-tree, and this grade requirement ys is greater than 517MPa, and-46 ℃ of ballistic works are greater than 27J.Low-temperature impact toughness requirement simultaneously is also high owing to the intensity height, and the material of therefore present this rank X-tree generally adopts USS trade mark UNS41000 (UNIFIED NUMBERING SYSTEM), and (its chemical ingredients is C≤0.15%, Si≤1.00%; Mn≤1.00%; P≤0.04%, S≤0.03%, Cr:11.5-13.5%; Ni≤0.50%), is equivalent to Chinese steel code name 1Cr13.In production practice, there is certain problem in each manufacturer when using 1Cr13 to produce X-tree in quality control, promptly satisfying the high-intensity while;-46 ℃ of low temperature impact test results are extremely unstable; With the coupon of furnace treatment reason, the smelting heat (batch) number coupon that has is qualified, and what have is defective.Even same smelting heat (batch) number, different forging batch, the coupon that has is qualified, and what have is defective.Use UNS42400 (C≤0.06%, Si:0.3-0.6%, Mn:0.5-1.00%; P≤0.03%, S≤0.03%, Cr:12-14%; Ni:3.5-4.5%; Mo:0.3-0.7%) material can solve the impact problem of unstable preferably, but owing to added expensive alloying element such as more Ni, Mo in the material, cost of alloy is too high.
CN101096744A discloses a kind of high-grade highly carbon-dioxide resistant, chloride ion corrosion oil annular tube steel and method of manufacture, C:0.15-0.25%, Si:0.2-1.0%; Mn:0.2-1.0%, Cr:12/14%, Ni:0.5-1.5%; Mo:0.2-1.0%, Al:0.01-0.05%, this steel are the anticorrosive stainless steels of a kind of Cr13 type; But because its carbon content is high, when satisfying intensity ,-46 ℃ of low-temperature impact toughness can not satisfy the requirement of FF level 105MPa X-tree body greater than 27J.
Disclosed Martensite Stainless Steel of CN1816639A and UNS42400 Standard are similar, also have the too high problem of cost of alloy.
The all not mentioned method that how to obtain H.T. under the low temperature of above-mentioned patent.
Summary of the invention
The object of the present invention is to provide a kind of low temperature to use steel with high tenacity corrosion resistant.
High request in view of aspects such as FF level 105MPa X-tree body, intensity anticorrosive and low-temperature flexibilities to material; The present invention is based on the basis of existing 1Cr13 material; Strong, the moderate material that is suitable for FF level 105MPa X-tree body of a kind of manufacturability is proposed, to satisfy the Cr13 type HS that the oil and gas industry use temperature reaches-46 ℃, the requirement of high tenacity corrosion resistant steel.
To achieve these goals, low temperature of the present invention is used the high tenacity corrosion resistant steel, and its chemical ingredients per distribution ratio is: C:0.03-0.10%, Si:0.2-0.6%; Mn:0.35-0.75%, Cr:12-14%, Ni:0.5-1.5%, Al:0.01-0.04%; Mo:0.1-0.3%, P≤0.015%, S≤0.006%; N≤0.01%, Al/N＞2 wherein, surplus is Fe and unavoidable impurities.
Below be the present invention with the effect of each chemical ingredients of steel and specify:
C: austenite former, the intensity and the corrosive nature of raising steel.For guaranteeing necessary strength, carbon content can not be low excessively, and carbon content is lower than 0.03% o'clock steel-making difficulty and increases, and carbon content is higher than 0.10%, and the toughness of material degenerates, and therefore, should adopt carbon content in the steel of the present invention is 0.03-0.1%.
Cr: ferrite former, improve alloy corrosion resistance and intensity.Cr content was less than 12% o'clock, and solidity to corrosion is not enough, and Cr content was greater than 14% o'clock, and the intensity and the hardness of material are too high, caused the toughness of material to descend.Therefore, should adopt Cr content in the steel of the present invention is 12-14%.
Ni: austenite former, the low-temperature flexibility of raising material reduces Cold Brittleness Transition Temperature.The Ni add-on is low excessively, DeGrain, and the too high cost that then significantly increases of add-on, therefore, should adopt Ni content in the steel of the present invention is 0.5-1.5%.
Mo: ferrite former, effectively improved the temper resistance of material, improve the intensity and the anti-local corrosion performance of material.Be lower than 0.1% like add-on, DeGrain is crossed expensive increase, and therefore, should adopt Mo content in the steel of the present invention is 0.1-0.3%.
Si: ferrite former, in steel, play deoxidation and improve corrosion proof effect, be lower than 0.2%, DeGrain, greater than 0.6%, processing and toughness worsen, and therefore, should adopt Si content in the steel of the present invention is 0.2-0.6%.
Mn: austenite former, play the solution strengthening effect, improve the obdurability of steel, but be prone to segregation, not obvious less than effect in 0.35% o'clock, greater than 0.75%, segregation is serious, and therefore, should adopt Mn content in the steel of the present invention is 0.35-0.75%.
Al: ferrite former, played deoxidation, the effect of N, crystal grain thinning admittedly, when add-on is lower than 0.006% in steel; DeGrain, add-on surpasses 0.04%, the mechanical property variation; Therefore, should adopt Al content in the steel of the present invention is 0.01-0.04%.
P, S, N are residual element in the steel, and in order to improve low-temperature impact toughness, P content should not be greater than 0.015%, and S content should not be greater than 0.006%, and N content should not be greater than 0.01%, and Al/N >=2.
Another object of the present invention provides the method for manufacture of above-mentioned low temperature with high energy toughness corrosion-resistant steel.This method comprises:
The alloying element of mentioned component proportioning is adopted electric arc furnace to add external refining and handles or oxygen coverter adds external refining and handles or esr process is cast into ingot after smelting through vacuum refinement through vacuum refinement; Adopt warm ingot to go into stove before forging, go into stove surface of steel ingot temperature requirement less than 600 ℃.1200 ℃-1250 ℃ of Forge Heating temperature, final forging temperature are greater than 1000 ℃, and forging ratio is greater than 6, and forging wall thickness 1/2 place's grain fineness number is not less than 6 grades;
Forging requires carrying out shrend or oil quenching behind the austenitizing under the 940-980 ℃ of temperature after being processed into finished product; The exemplar wall thickness can quench in air less than 30mm; Cool time is 0.5-3 hour; Thereafter carry out double tempering and handle, promptly respectively 690-720 ℃ of tempering 0.5-3 hour with 650-680 ℃ tempering 0.5-3 hour, be cooled to room temperature then.The characteristics of this method of manufacture be through double tempering guaranteeing the impact property under the low temperature, and air cooling is to room temperature, forbids furnace cooling after the exemplar tempering.
Steel grade of the present invention is after using method of manufacture of the present invention to make; The mechanical property of exemplar and all can satisfy of the requirement of FF level 105MPa X-tree body to material-46 ℃ impelling strength, promptly ys is greater than 517MPa, and-46 ℃ of ballistic works are greater than 27J; And allowance is abundant, and manufacturability is strong.
Embodiment
Below through embodiment the present invention is carried out comparatively detailed explanation.
Table 1 is depicted as the chemical ingredients of experiment steel grade, and wherein 1-4 is a steel grade of the present invention; 5-7 is the contrast steel grade, the stainless steel oil annular tube steel that generally uses for present oil field.
The chemical ingredients of table 1 steel of the present invention and existing steel alloy, wt%
Test Example: mechanical property
According to GBT228-2002 tension specimen national standard method, measure the mechanical property of the embodiment of the invention and Comparative Examples, its result sees table 2.
The mechanical property of table 2 the present invention and compared steel
The alloying element of mentioned component proportioning is adopted electric arc furnace to add external refining and handles or oxygen coverter adds external refining and handles or esr process is cast into ingot after smelting through vacuum refinement through vacuum refinement; Adopt warm ingot to go into stove before forging, go into stove surface of steel ingot temperature requirement less than 600 ℃.1200 ℃-1250 ℃ of Forge Heating temperature, final forging temperature are greater than 1000 ℃, and forging ratio is greater than 6, and forging wall thickness 1/2 place's grain fineness number is not less than 6 grades.
Forging requires carrying out shrend or oil quenching behind the austenitizing under the 920-980 ℃ of temperature after being processed into finished product; The exemplar wall thickness can quench in air less than 30mm; Cool time is 0.5-3 hour; Thereafter carry out double tempering and handle, promptly, be cooled to room temperature then respectively 690-720 ℃ of tempering 0.5-3 hour and 650-680 ℃ tempering 0.5-3 hour.Behind the double tempering of method of manufacture of the present invention, the equal air cooling of exemplar is to room temperature.
Can find out from the result of table 2; Steel grade of the present invention is after using method of manufacture of the present invention to make; The mechanical property of exemplar and all can satisfy of the requirement of FF level 105MPa X-tree body to material-46 ℃ impelling strength, promptly ys is greater than 517MPa, and-46 ℃ of ballistic works are greater than 27J; And allowance is abundant, and manufacturability is strong.Comparative Examples 4 for steel grade 4 of the present invention only after a temper low-temperature impact work on the low side, can not meet the demands.Comparative Examples 5 is a Cr13 type stainless steel, owing to do not add alloying elements such as Ni, Mo, after twice thermal treatment, though impelling strength is qualified, undercapacity.Comparative Examples 6 is because carbon content is too high, and low-temperature impact toughness can not meet the demands.The Al/N of Comparative Examples 7＜2; Al in the steel (nucleidic mass 27) can not the completely consumed solid solution N (nucleidic mass 14); In the drawing process after 950 ℃ high temperature austeniteization,, the intensity of steel is improved because AlN, CrN second-phase dispersion such as separate out at the influence of factor; And low-temperature impact toughness significantly reduces, and can not satisfy the requirement of the high-end X-tree material of preparation FF level 105MPa.
Compared with prior art, steel grade of the present invention and working method have following substantive distinguishing features: on chemical ingredients 1) carbon content is low; 2) Ni, Mo microalloying; 3) Al/N >=2; On working method 4) forging ratio is greater than 6; 5) double tempering thermal treatment process.
Though abovely introduced the present invention through specific embodiment, be not limited only to these embodiment, conceive under the prerequisite not breaking away from the present invention, more changeableization or improved embodiment can also be arranged, these variations and improve the scope that all should belong to the claim protection.
Claims (6)
1. high tenacity corrosion resistant steel, its chemical component weight per-cent is: C:0.03-0.10%, Si:0.2-0.6%, Mn:0.35-0.75%; Cr:12-114%, Ni:0.5-1.5%, Al:0.01-0.04%; Mo:0.1-0.3%, P≤0.015%, S≤0.006%; N≤0.01%, Al/N＞2 wherein, surplus is Fe and unavoidable impurities.
2. high tenacity corrosion resistant steel as claimed in claim 1 is characterized in that, the ys of said steel is greater than 517MPa, and-46 ℃ of ballistic works are greater than 27J.
3. according to claim 1 or claim 2 the method for manufacture of high tenacity corrosion resistant steel comprises:
Adopt electric arc furnace to add external refining and handle, or oxygen coverter adds external refining and handle through vacuum refinement, or esr process is cast into ingot after smelting through vacuum refinement;
Adopt warm ingot to go into stove before forging, go into stove surface of steel ingot temperature less than 600 ℃;
1200-1250 ℃ of Forge Heating temperature, final forging temperature are greater than 1000 ℃, and forging ratio is greater than 6, and forging wall thickness 1/2 place's grain fineness number is not less than 6 grades.
4. method as claimed in claim 3; It is characterized in that; Forging is carrying out shrend or oil quenching behind the austenitizing under the 940-980 ℃ of temperature after being processed into finished product, then respectively 690-720 ℃ of tempering 0.5-3 hour with 650-680 ℃ tempering 0.5-3 hour, sky is cooled to room temperature then.
5. method as claimed in claim 3; It is characterized in that; Behind austenitizing under the 940-980 ℃ of temperature, when the exemplar wall thickness quenches in air during less than 30mm, the cool time is 0.5-3 hour to forging after being processed into finished product; Then respectively 690-720 ℃ of tempering 0.5-3 hour with 650-680 ℃ tempering 0.5-3 hour, sky is cooled to room temperature then.
6. the high tenacity corrosion resistant steel of making like the arbitrary described method of claim 3-5, its ys is greater than 517MPa, and-46 ℃ of ballistic works are greater than 27J.
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Cited By (10)
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| CN104263885A (en) * | 2014-09-22 | 2015-01-07 | 安徽应流集团霍山铸造有限公司 | Heat treatment process for improving low-temperature toughness of castings |
| CN106436112A (en) * | 2016-12-13 | 2017-02-22 | 苏州陈恒织造有限公司 | Wire guiding structure for corrosion-resistant and wear-resistant mercerizing machine |
| CN106756520A (en) * | 2017-03-04 | 2017-05-31 | 蒋培丽 | A kind of slit and corrosion resistant reinforcing bar high and preparation method thereof |
| CN111020401A (en) * | 2018-10-09 | 2020-04-17 | 中国电力科学研究院有限公司 | Stainless steel for power transmission and transformation engineering and production method thereof |
| CN111485085A (en) * | 2020-05-22 | 2020-08-04 | 无锡派克新材料科技股份有限公司 | Method for improving grain growth resistance of 18CrNiMo7-6 alloy at 930-950 DEG C |
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| WO2023165614A1 (en) | 2022-03-04 | 2023-09-07 | 马鞍山钢铁股份有限公司 | Long-service-life high-toughness corrosion-resistant steel for subsea christmas tree valve and heat treatment method and production method for long-service-life high-toughness corrosion-resistant steel for subsea christmas tree valve |
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| CN104263885A (en) * | 2014-09-22 | 2015-01-07 | 安徽应流集团霍山铸造有限公司 | Heat treatment process for improving low-temperature toughness of castings |
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| CN106756520A (en) * | 2017-03-04 | 2017-05-31 | 蒋培丽 | A kind of slit and corrosion resistant reinforcing bar high and preparation method thereof |
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| WO2023165617A1 (en) | 2022-03-04 | 2023-09-07 | 马鞍山钢铁股份有限公司 | High-strength and high-toughness steel with long service life and wall thickness of ≥ 600 mm for valve body of subsea christmas tree, and heat treatment method and production method therefor |
| WO2023165614A1 (en) | 2022-03-04 | 2023-09-07 | 马鞍山钢铁股份有限公司 | Long-service-life high-toughness corrosion-resistant steel for subsea christmas tree valve and heat treatment method and production method for long-service-life high-toughness corrosion-resistant steel for subsea christmas tree valve |
| CN115449706A (en) * | 2022-08-15 | 2022-12-09 | 建湖县鸿达阀门管件有限公司 | High-pressure-resistant alloy material and high-strength valve member |
| CN119040592A (en) * | 2024-09-11 | 2024-11-29 | 江苏常宝钢管股份有限公司 | Production method of hydrogen sulfide corrosion resistant oil casing and hydrogen sulfide corrosion resistant oil casing |
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