WO2023165614A1 - 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 - Google Patents

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 Download PDF

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WO2023165614A1
WO2023165614A1 PCT/CN2023/079637 CN2023079637W WO2023165614A1 WO 2023165614 A1 WO2023165614 A1 WO 2023165614A1 CN 2023079637 W CN2023079637 W CN 2023079637W WO 2023165614 A1 WO2023165614 A1 WO 2023165614A1
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valve body
strength
corrosion
steel
long
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PCT/CN2023/079637
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French (fr)
Chinese (zh)
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杨志强
汪开忠
胡芳忠
王自敏
陈世杰
吴林
杨少朋
金国忠
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马鞍山钢铁股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/18—Hardening; Quenching with or without subsequent tempering
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten

Definitions

  • the invention belongs to the technical field of alloy steel, and relates to a long-life, high-strength, high-strength, corrosion-resistant subsea tree valve body steel, a heat treatment method and a production method thereof.
  • my country is the second largest country in oil consumption and the third largest in natural gas consumption.
  • the country vigorously develops domestic oil and gas drilling and production, especially intensifying the development of deep sea oil and gas resources.
  • my country's current land oil and gas drilling depth has exceeded 7300 meters, and offshore oil and gas drilling depth is close to 3000 meters.
  • the Christmas tree is an essential device for oil and gas exploitation.
  • the Christmas trees used in my country are all imported, which seriously affects the safety of oil and gas in my country.
  • the Christmas tree is composed of multiple modules (valve bodies), which have high requirements on the strength and toughness of materials. In particular, subsea trees have higher requirements for low temperature toughness and corrosion resistance.
  • the valve body of the Christmas tree is usually made of 4130 steel, but with the deterioration of the oil and gas production environment, 4130 cannot meet the requirements of the underwater Christmas tree.
  • Patent CN 102839331 A discloses a high-toughness corrosion-resistant steel and its manufacturing method, which are used to manufacture the Christmas tree body.
  • the Cr content is as high as 12-14%
  • the yield strength of the material is ⁇ 517MPa
  • the impact energy at -46°C is ⁇ 27J.
  • This patent has high Cr content, high cost, although the yield strength is increased to 517MPa, it is still low, and the low temperature toughness is poor, and the toughness will be insufficient in a stricter low temperature environment.
  • Patent CN 112281069 A discloses a production method of 8630 super-long forgings for deep-sea oil tree equipment. Using the forging process of this patent, the yield strength of the obtained material is ⁇ 580MPa, and the impact energy at -29°C is ⁇ 30J. The low-temperature toughness of the material is relatively high. Low.
  • the object of the present invention is to provide a long-life, high-strength, high - strength, corrosion-resistant steel for underwater Christmas tree valve body and its heat treatment method and production method.
  • 230J the corrosion rate in seawater environment is ⁇ 0.07mm/a
  • its fatigue strength after 2 ⁇ 107 cycles of corrosion in seawater environment is ⁇ 350MPa, which can meet the use requirements of Christmas trees in more severe seawater environments, and is suitable for manufacturing underwater Christmas tree valve body.
  • a long-life, high-strength, high-strength, corrosion-resistant steel for underwater Christmas tree valve bodies including the following chemical components in weight percentages: C 0.22%-0.28%, Si 0.15%-0.35%, Mn 1.1%-1.4%, Cr 1.3%- 1.5%, Mo 0.5% ⁇ 0.6%, Ni 0.30% ⁇ 0.40%, Cu 0.30% ⁇ 0.50%, Al 0.015% ⁇ 0.035%, P ⁇ 0.015%, S ⁇ 0.015%, N ⁇ 0.0080%, O ⁇ 0.004% , and the rest are Fe and other unavoidable impurities;
  • A 457 ⁇ (C-0.077 ⁇ Cr)+45 ⁇ Cr+80 ⁇ Si+50 ⁇ Mn+10 ⁇ Mo+96 ⁇ Cu, 230% ⁇ A ⁇ 275%;
  • D 30 ⁇ Ni+20 ⁇ Mo+16 ⁇ Cu+22 ⁇ Mn-12 ⁇ Si ⁇ Mn+28 ⁇ C-10 ⁇ C ⁇ Mn, D ⁇ 52.5%, preferably D is 53-65%;
  • X 26 ⁇ Cu+4 ⁇ Ni+1.2 ⁇ Cr-1.5 ⁇ Si-7 ⁇ Cu ⁇ Ni-5 ⁇ Mn, X ⁇ 5.4%, preferably X is 5.5-7.5%.
  • the present invention performs the following controls:
  • C is the cheapest strengthening element in steel. For every increase of 0.1% solid solution C, the strength can be increased by about 450MPa. C and the alloying elements in the steel form precipitated phases to play a role in precipitation strengthening. C can significantly improve the hardenability, and make the core of the valve body of the large-scale Christmas tree obtain a martensitic structure. However, as its content increases, the plasticity and toughness decrease, and high C content is harmful to corrosion performance, so the C content is controlled at 0.22% to 0.28%.
  • Si is an effective solid-solution strengthening element in steel, which improves the strength and hardness of steel. Si can play a role in deoxidation during steelmaking and is a commonly used deoxidizer. However, Si is easy to segregate to austenite grain boundaries, which reduces the bonding force of grain boundaries and causes brittleness. In addition, Si is easy to cause element segregation in steel. Therefore, the Si content is controlled at 0.15% to 0.35%.
  • Mn can play a role in solid solution strengthening, and its solid solution strengthening ability is weaker than that of Si.
  • Mn is an austenite stabilizing element that can significantly improve the hardenability of steel and reduce decarburization of steel.
  • the combination of Mn and S can prevent Hot brittleness caused by S. But excessive Mn will reduce the plasticity of steel. Therefore, the Mn content is controlled at 1.1% to 1.4%.
  • Cr is a carbide forming element. Cr can improve the hardenability and strength of steel, but it is easy to cause temper brittleness. Cr can improve the oxidation resistance and corrosion resistance of steel, but when the Cr content is too high, it will increase the crack sensitivity. Cr content should be controlled at 1.3% to 1.5%.
  • Mo is mainly to improve the hardenability and heat resistance of steel. Mo solidly dissolved in the matrix can maintain a high stability of the steel structure during tempering, and can effectively reduce impurities such as P, S and As. The elements segregate at the grain boundaries, thereby improving the toughness of the steel and reducing temper brittleness. Mo reduces the stability of M 7 C 3 , and when the Mo content is high, acicular Mo 2 C will be formed, which will lead to a decrease in the Mo content of the matrix. Mo can improve the strength of steel through the joint action of solid solution strengthening and precipitation strengthening, and can also change the toughness of steel by changing the precipitation of carbides. Therefore, Mo is controlled at 0.5% to 0.6%.
  • Ni can form an infinitely soluble solid solution with Fe. It is an austenite stabilizing element. It has the effect of expanding the phase area, increasing the stability of supercooled austenite, shifting the C curve to the right, and improving the hardenability of steel. Ni can refine the width of the martensite lath and improve the strength. Ni can significantly reduce the ductile-brittle transition temperature of steel and improve low-temperature toughness. The Ni content is controlled at 0.30% to 0.40%.
  • Cu expands the austenite phase region.
  • Cu simple substance can be used as the second phase to significantly improve the strength, and can improve the tempering stability and strength of the structure. But if Cu is too high, it will cause Cu to be brittle. Therefore, the Cu content is controlled at 0.30% to 0.50%.
  • Al is the main deoxidizer in steelmaking. Al combines with N to form fine and dispersed AlN, and maintains a coherent relationship with the matrix, which can strengthen and refine the structure, and can increase the fatigue crack initiation and propagation resistance. , thereby increasing the durability of the steel. Al content is controlled at 0.015% to 0.035%.
  • T.O forms oxide inclusions in steel, control T.O ⁇ 0.0040%; N can form fine precipitated phase refinement structure with nitride forming elements in steel, so N is controlled within 0.0080%.
  • the main precipitated phase is the precipitated phase of Cr.
  • Cr consumes C to form carbides, and on the other hand, Cr can be dissolved into the matrix to improve the strength. This is related to the content of Cr and C in the steel type.
  • the C consumed by the formation of precipitates in the steel is 0.077 ⁇ Cr.
  • the solid solution C content should be C-0.077 ⁇ Cr.
  • the contribution coefficients of these five elements to the strength are 45, 80, 50, 10, and 96, respectively.
  • Ni is an element that can improve toughness at present, and Mo is beneficial to improve tempering stability, thereby improving the toughness of steel.
  • Cu can precipitate fine nano-copper precipitates in steel, thereby improving the toughness of steel. Therefore, the contribution coefficients of the above three elements to toughness are 30, 20, and 16, respectively.
  • Mn can promote the selection of steel in the phase transformation, so that the microstructure is finer and the toughness is improved, but the segregation of Si and Mn leads to the decrease of toughness, so the contribution of Mn to toughness has its own contribution, and there is an interaction with Si and Mn , so the coefficients are 22 and -12 respectively.
  • C content on toughness also has two sides. On the one hand, it promotes phase transformation refinement and improves toughness. On the one hand, it interacts with Mn to promote the hardening of steel, resulting in lower toughness. Therefore, C contributes independently to toughness, and there is an interaction with C and Mn, so the coefficients are 28 and -10, respectively. Because P and S in the steel are also harmful to the toughness of the steel, but because the present invention has set the maximum content limit for the content of P and S, the harm of P and S to the toughness is not considered. Toughness Determination Factor of Steel
  • the ratio of Si, Mn, Cu, Ni, and Cr needs to be limited, and the coefficient is 26 because Cu can improve the strength and significantly improve the corrosion resistance.
  • Si and Mn will aggravate segregation, cause microstructure inhomogeneity and reduce erosion performance, so the coefficients are -1.5 and -5, respectively.
  • Ni can improve stacking faults, significantly improve low-temperature toughness, and can passivate metals to improve erosion performance, so the coefficient of Ni is 4.
  • Cr can strengthen the passivation film on the steel surface, so the coefficients are 1.2 respectively.
  • the metallographic structure of the long-life, high-strength, toughness and corrosion-resistant subsea oil tree valve body steel is tempered sorbite, and the grain size is 20-25 ⁇ m.
  • the tensile strength at the 1/4 thickness of the steel valve body is 860-920MPa, the yield strength is 690-740MPa, -46°C KV 2 is 230-260J, A is 20-24%, Z is 70-75%; in seawater environment
  • the fatigue strength after medium corrosion 2 ⁇ 10 7 cycles is 350 ⁇ 375MPa.
  • the heat treatment method of the long-life, high-strength, toughness and corrosion-resistant underwater Christmas tree valve body steel provided by the present invention comprises the following steps:
  • Ladder quenching Heat the valve body of the Christmas tree to 900-940°C, keep it warm, and then water-cool it; then heat it to 840-880°C, keep it warm, and then water-cool it; the wall of the underwater Christmas tree valve body is thicker, and quench it through steps It can ensure that the material has a fine martensitic structure, which is conducive to strength and toughness.
  • the grain size and martensite of the steel are refined; during the second quenching, due to the refinement of the structure before heating, it is beneficial to the nucleation of the grains and the grain refinement; the temperature during the second quenching is lower than The first quenching temperature can ensure that the austenite grains are not coarsened, and after quenching, the grains and martensite variants will increase, and the microstructure will be refined, which is conducive to improving the strength, toughness and corrosion fatigue life;
  • the heating rate is 50-110° C./h
  • S is the valve body wall thickness in mm
  • the unit of t1 is min.
  • the above-mentioned heating rate can ensure that the temperature at different positions of the valve body is close; if the heating rate is too fast, the temperature gradient at different positions of the valve body will increase, which will increase the internal stress and increase the risk of cracks; Risk of tempering reactions, resulting in uncontrolled precipitated phase types and contents.
  • the holding time is the key to controlling the content and size of the precipitated phase. If the holding time is too short, the precipitated phase will be less and the beneficial effect will be reduced. If the holding time is too long, the precipitated phase will increase, but the size of the precipitated phase will increase, which will reduce the dispersed distribution of the precipitated phase. effect. Excessively large precipitates also increase the risk of internal microcracks.
  • the water cooling is all cooled to below 100°C.
  • the tempering parameters directly determine the mechanical properties and corrosion fatigue properties of the final product. If the tempering parameter is too large, the softening effect of the material will be large, resulting in a large decrease in the strength of the material and the strength cannot be guaranteed. It will also cause the size of the precipitate to be too large, weaken the precipitation strengthening effect, and increase the risk of microcracks in the steel and reduce the toughness. If the tempering parameter is small, the strength of the material will be insufficiently softened, the structural stress and internal stress will be large, and the toughness and corrosion fatigue performance will be reduced.
  • the production method of the long-life, high-strength, toughness and corrosion-resistant underwater Christmas tree valve body steel comprises the following steps: electric arc furnace or converter smelting ⁇ LF furnace refining ⁇ RH or VD vacuum degassing ⁇ round billet continuous casting ⁇ Round billet heating ⁇ forging into a valve body ⁇ heat treatment ⁇ machining ⁇ packaging and storage, wherein the heat treatment is carried out by the above heat treatment method.
  • the diameter of the round billet is ⁇ 380mm ⁇ 700mm.
  • the machining steps specifically include: rough turning of the valve body ⁇ flaw detection ⁇ finish turning of the valve body ⁇ grinding ⁇ flaw detection.
  • the present invention has the following beneficial effects:
  • the long-life, high-strength, corrosion-resistant steel for the valve body of the underwater Christmas tree provided by the present invention, by controlling the composition and dosage of the chemical components in the steel, makes its performance meet the requirements of the underwater Christmas tree in harsh environments;
  • Ni, Mo, Cu, Mn, Si and C in the long-life, high-strength, corrosion-resistant, corrosion-resistant subsea oil tree valve body steel satisfies 30 ⁇ Ni+20 ⁇ Mo+16 ⁇ Cu+ 22 ⁇ Mn-12 ⁇ Si ⁇ Mn+28 ⁇ C-10 ⁇ C ⁇ Mn ⁇ 74.5% to ensure the low temperature toughness of the subsea tree valve body;
  • the heat treatment of the long-life, high-strength, corrosion-resistant, corrosion-resistant underwater tree valve body steel provided by the present invention adopts a step quenching+tempering process for heat treatment, and controls the heating temperature and holding time during the tempering treatment to ensure water quality.
  • the overall performance of the steel used for the valve body of the lower Christmas tree can meet the needs of the underwater Christmas tree in harsh environments.
  • Fig. 1 is the metallographic structure diagram of the steel for subsea tree valve body in embodiment 3;
  • FIG. 2 is a metallographic structure diagram of the steel used for the subsea tree valve body in Comparative Example 2.
  • FIG. 2 is a metallographic structure diagram of the steel used for the subsea tree valve body in Comparative Example 2.
  • the invention provides a long-life, high-strength, high-strength, corrosion-resistant steel for underwater Christmas tree valve body, which includes the following chemical components in weight percentage: C 0.22%-0.28%, Si 0.15%-0.35%, Mn 1.1%-1.4%, Cr 1.3% ⁇ 1.5%, Mo 0.5% ⁇ 0.6%, Ni 0.30% ⁇ 0.40%, Cu 0.30% ⁇ 0.50%, Al 0.015% ⁇ 0.035%, P ⁇ 0.015%, S ⁇ 0.015%, N ⁇ 0.0080%, O ⁇ 0.004%, the rest is Fe and other unavoidable impurities;
  • A 457 ⁇ (C-0.077 ⁇ Cr)+45 ⁇ Cr+80 ⁇ Si+50 ⁇ Mn+10 ⁇ Mo+96 ⁇ Cu, 230% ⁇ A ⁇ 275%;
  • the production method of the long-life, high-strength, high-strength, corrosion-resistant, and corrosion-resistant underwater Christmas tree valve body steel comprises the following steps: electric arc furnace or converter smelting ⁇ LF furnace refining ⁇ RH or VD vacuum degassing ⁇ round billet continuous casting ⁇ round billet heating ⁇ Forging into valve body ⁇ heat treatment ⁇ machining ⁇ packaging and storage.
  • Oxygen is fixed before tapping, and steel is left in the tapping process to avoid slag;
  • Vacuum degassing pure degassing time ⁇ 15 minutes, to ensure [H] content ⁇ 1.5ppm after vacuum treatment, to avoid white spots in the steel, causing hydrogen embrittlement;
  • the target temperature of the molten steel in the tundish is controlled at 10-40°C above the liquidus temperature, and the round billet of ⁇ 380mm ⁇ 700mm is continuously cast.
  • Forging route round billet heating ⁇ forging ⁇ slow cooling.
  • Valve body heat treatment trolley furnace heating ⁇ heat preservation ⁇ quenching ⁇ trolley furnace heating ⁇ heat preservation ⁇ quenching ⁇ tempering ⁇ heat preservation ⁇ water cooling.
  • Machining route rough turning of valve body ⁇ flaw detection ⁇ fine turning of valve body ⁇ grinding ⁇ flaw detection.
  • Heat treatment is carried out according to the following steps:
  • the performance testing method of the long-life, high-strength, corrosion-resistant subsea tree valve body steel prepared by the above process is as follows:
  • Table 2 shows the heat treatment process parameters of the long-life, high-strength, corrosion-resistant subsea tree valve body steel in each embodiment and comparative example.
  • Table 3 shows the test results of the mechanical properties of the long-life, high-strength, corrosion-resistant steel for subsea tree valve bodies in each of the examples and comparative examples.

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Abstract

Long-service-life high-toughness corrosion-resistant steel for a subsea Christmas tree valve and a heat treatment method and production method for the long-service-life high-toughness corrosion-resistant steel for the subsea Christmas tree valve. The steel for the subsea Christmas tree valve mainly comprises the following components: C, Si, Mn, Cr, Mo, Ni, Cu, and Al. The compositions of the chemical components of the steel and the relationships and contents of the components are controlled, such that the tensile strength at the 1/4 thickness of the steel valve for the subsea Christmas tree valve is greater than or equal to 860 MPa, the yield strength is greater than or equal to 690 MPa, KV2 at -46°C is greater than or equal to 230 J, A is greater than or equal to 20%, and Z is greater than or equal to 70%; the corrosion rate in a seawater environment is less than or equal to 0.07 mm/a; the fatigue strength is greater than or equal to 350 MPa after 2*107 weeks of corrosion in a seawater environment; and the performance of the steel can meet the requirements of a subsea Christmas tree in a severe environment.

Description

一种长寿命高强韧耐腐蚀水下采油树阀体用钢及其热处理方法和生产方法A long-life, high-strength, toughness, corrosion-resistant subsea tree valve body steel, heat treatment method and production method thereof 技术领域technical field
本发明属于合金钢技术领域，涉及一种长寿命高强韧耐腐蚀水下采油树阀体用钢及其热处理方法和生产方法。The invention belongs to the technical field of alloy steel, and relates to a long-life, high-strength, high-strength, corrosion-resistant subsea tree valve body steel, a heat treatment method and a production method thereof.
背景技术Background technique
我国是石油消耗第二大国，天然气消耗第三大国，为了提高能源自给率及能源安全，国家大力发展国内油气钻采，尤其加大了深海油气资源的开发。据报道我国目前的陆地油气钻采深度已超过7300米，海洋油气钻采深度已接近3000米。采油树是油气开采的必备装置，我国采用的采油树均为进口，严重影响我国油气安全。采油树有多个模块(阀体)组成，对材料的强韧性等要求较高。尤其是水下采油树，对低温韧性、耐蚀性要求更高。采油树阀体通常采用4130钢制造，但是随着油气开采环境的恶化，4130不能满足水下采油树要求。my country is the second largest country in oil consumption and the third largest in natural gas consumption. In order to improve energy self-sufficiency and energy security, the country vigorously develops domestic oil and gas drilling and production, especially intensifying the development of deep sea oil and gas resources. According to reports, my country's current land oil and gas drilling depth has exceeded 7300 meters, and offshore oil and gas drilling depth is close to 3000 meters. The Christmas tree is an essential device for oil and gas exploitation. The Christmas trees used in my country are all imported, which seriously affects the safety of oil and gas in my country. The Christmas tree is composed of multiple modules (valve bodies), which have high requirements on the strength and toughness of materials. In particular, subsea trees have higher requirements for low temperature toughness and corrosion resistance. The valve body of the Christmas tree is usually made of 4130 steel, but with the deterioration of the oil and gas production environment, 4130 cannot meet the requirements of the underwater Christmas tree.
专利CN 102839331 A公开了一种高韧性耐腐蚀钢及其制造方法，用于制造采油树本体。该专利中Cr含量高达12-14％，材料的屈服强度≥517MPa，-46℃冲击功≥27J。该专利Cr含量较高，成本高，屈服强度虽然提高到517MPa但仍然较低，并且低温韧性较差，在更加严格的低温环境下，韧性会不足。Patent CN 102839331 A discloses a high-toughness corrosion-resistant steel and its manufacturing method, which are used to manufacture the Christmas tree body. In this patent, the Cr content is as high as 12-14%, the yield strength of the material is ≥517MPa, and the impact energy at -46°C is ≥27J. This patent has high Cr content, high cost, although the yield strength is increased to 517MPa, it is still low, and the low temperature toughness is poor, and the toughness will be insufficient in a stricter low temperature environment.
专利CN 112281069 A公开了一种深海采油树装备用8630超长锻件的生产方法，采用该专利的锻造工艺，所得到的材料屈服强度≥580MPa，-29℃冲击功≥30J，材料的低温韧性较低。Patent CN 112281069 A discloses a production method of 8630 super-long forgings for deep-sea oil tree equipment. Using the forging process of this patent, the yield strength of the obtained material is ≥580MPa, and the impact energy at -29°C is ≥30J. The low-temperature toughness of the material is relatively high. Low.
上述专利公开的采油树钢的性能均不能满足低温下的使用要求，并且并未对使用寿命进行考察。The properties of the christmas tree steels disclosed in the above patents cannot meet the requirements of use at low temperatures, and the service life has not been investigated.
发明内容Contents of the invention
本发明的目的在于提供了一种长寿命高强韧耐腐蚀水下采油树阀体用钢及其热处理方法和生产方法，本发明可实现采油树阀体屈服强度≥690MPa、-46℃KV2≥230J、在海水环境腐蚀速率≤0.07mm/a，其在海水环境中腐蚀2×107周次后的疲劳强度≥350MPa，能够满足更严苛海水环境采油树的使用要求，适用于制造水下采油树阀体。The object of the present invention is to provide a long-life, high-strength, high - strength, corrosion-resistant steel for underwater Christmas tree valve body and its heat treatment method and production method. 230J, the corrosion rate in seawater environment is ≤0.07mm/a, and its fatigue strength after 2× 107 cycles of corrosion in seawater environment is ≥350MPa, which can meet the use requirements of Christmas trees in more severe seawater environments, and is suitable for manufacturing underwater Christmas tree valve body.
为实现上述目的，本发明采取的技术方案如下：In order to achieve the above object, the technical scheme that the present invention takes is as follows:
一种长寿命高强韧耐腐蚀水下采油树阀体用钢，包括如下重量百分比的化学成分：C 0.22％～0.28％、Si 0.15％～0.35％、Mn 1.1％～1.4％、Cr 1.3％～1.5％、Mo 0.5％～0.6％、Ni 0.30％～0.40％、Cu 0.30％～0.50％、Al 0.015％～0.035％、P≤0.015％、S≤0.015％、N≤0.0080％、O≤0.004％，其余为Fe和其它不可避免的杂质；A long-life, high-strength, high-strength, corrosion-resistant steel for underwater Christmas tree valve bodies, including the following chemical components in weight percentages: C 0.22%-0.28%, Si 0.15%-0.35%, Mn 1.1%-1.4%, Cr 1.3%- 1.5%, Mo 0.5%~0.6%, Ni 0.30%~0.40%, Cu 0.30%~0.50%, Al 0.015%~0.035%, P≤0.015%, S≤0.015%, N≤0.0080%, O≤0.004% , and the rest are Fe and other unavoidable impurities;
其中，A＝457×(C-0.077×Cr)+45×Cr+80×Si+50×Mn+10×Mo+96×Cu，230％≤A≤275％；Among them, A=457×(C-0.077×Cr)+45×Cr+80×Si+50×Mn+10×Mo+96×Cu, 230%≤A≤275%;
D＝30×Ni+20×Mo+16×Cu+22×Mn-12×Si×Mn+28×C-10×C×Mn，D≥52.5％，优选D为53～65％；D=30×Ni+20×Mo+16×Cu+22×Mn-12×Si×Mn+28×C-10×C×Mn, D≥52.5%, preferably D is 53-65%;
X＝26×Cu+4×Ni+1.2×Cr-1.5×Si-7×Cu×Ni-5×Mn，X≥5.4％，优选X为5.5～7.5％。X=26×Cu+4×Ni+1.2×Cr-1.5×Si-7×Cu×Ni-5×Mn, X≥5.4%, preferably X is 5.5-7.5%.
为了生产得到具有优秀的强韧性、耐腐蚀及疲劳性能，能够满足更严苛的水下环境使用要求的高强韧耐蚀水下采油树阀体，本发明进行了如下控制：In order to produce a high-strength, toughness, corrosion-resistant subsea tree valve body with excellent strength, toughness, corrosion resistance and fatigue performance, which can meet the requirements of more severe underwater environments, the present invention performs the following controls:
C：C是钢中最低廉的强化元素，每提高0.1％的固溶C，可使强度提高约450MPa，C与钢中的合金元素形成析出相，起到析出强化作用。C能够显著提高淬透性，使大尺寸采油树阀体心部获得马氏体组织。但随着其含量增大，塑性和韧性降低，并且C含量高对腐蚀性能有危害，故C含量控制在0.22％～0.28％。C: C is the cheapest strengthening element in steel. For every increase of 0.1% solid solution C, the strength can be increased by about 450MPa. C and the alloying elements in the steel form precipitated phases to play a role in precipitation strengthening. C can significantly improve the hardenability, and make the core of the valve body of the large-scale Christmas tree obtain a martensitic structure. However, as its content increases, the plasticity and toughness decrease, and high C content is harmful to corrosion performance, so the C content is controlled at 0.22% to 0.28%.
Si：Si是钢中有效的固溶强化元素，提高钢的强硬度，Si在炼钢时能够起到脱氧作用，是常用的脱氧剂。但Si易偏聚有奥氏体晶界，降低晶界结合力，引发脆性。另外Si易引起钢中元素偏析。因此，Si含量控制在0.15％～0.35％。Si: Si is an effective solid-solution strengthening element in steel, which improves the strength and hardness of steel. Si can play a role in deoxidation during steelmaking and is a commonly used deoxidizer. However, Si is easy to segregate to austenite grain boundaries, which reduces the bonding force of grain boundaries and causes brittleness. In addition, Si is easy to cause element segregation in steel. Therefore, the Si content is controlled at 0.15% to 0.35%.
Mn：Mn能够起到固溶强化作用，固溶强化能力弱于Si，Mn是奥氏体稳定化元素能显著提高钢的淬透性，还能够减少钢的脱碳，Mn与S结合能够防止S引起的热脆性。但过量的Mn会降低钢的塑性。所以，Mn含量控制在1.1％～1.4％。Mn: Mn can play a role in solid solution strengthening, and its solid solution strengthening ability is weaker than that of Si. Mn is an austenite stabilizing element that can significantly improve the hardenability of steel and reduce decarburization of steel. The combination of Mn and S can prevent Hot brittleness caused by S. But excessive Mn will reduce the plasticity of steel. Therefore, the Mn content is controlled at 1.1% to 1.4%.
Cr：Cr是碳化物形成元素，Cr能够使钢的淬透性和强度均提高，却易引起回火脆性。Cr能够提高钢的抗氧化性能，增加耐蚀性，但Cr含量过高时将增加裂纹敏感性。应将Cr含量控制在1.3％～1.5％。Cr: Cr is a carbide forming element. Cr can improve the hardenability and strength of steel, but it is easy to cause temper brittleness. Cr can improve the oxidation resistance and corrosion resistance of steel, but when the Cr content is too high, it will increase the crack sensitivity. Cr content should be controlled at 1.3% to 1.5%.
Mo：Mo主要是提高钢的淬透性和耐热性，固溶于基体的Mo能够使钢的组织在回火过程中保持较高的稳定性，且能有效降低P、S和As等杂质元素在晶界处偏聚，从而提高钢的韧性，降低回火脆性。Mo降低M7C3的稳定性，当Mo含量较高时将形成针状Mo2C，将导致基体Mo含量减少。Mo能够通过固溶强化和沉淀强化的共同作用提高钢的强度，也能通过改变碳化物的析出来改变钢的韧性。故Mo控制在0.5％～0.6％。Mo: Mo is mainly to improve the hardenability and heat resistance of steel. Mo solidly dissolved in the matrix can maintain a high stability of the steel structure during tempering, and can effectively reduce impurities such as P, S and As. The elements segregate at the grain boundaries, thereby improving the toughness of the steel and reducing temper brittleness. Mo reduces the stability of M 7 C 3 , and when the Mo content is high, acicular Mo 2 C will be formed, which will lead to a decrease in the Mo content of the matrix. Mo can improve the strength of steel through the joint action of solid solution strengthening and precipitation strengthening, and can also change the toughness of steel by changing the precipitation of carbides. Therefore, Mo is controlled at 0.5% to 0.6%.
Ni：Ni能与Fe生成无限互溶的固溶体，是奥氏体稳定化元素，具有扩大相区的作用，增加过冷奥氏体的稳定性，使C曲线右移，提高钢的淬透性。Ni能够细化马氏体板条宽度，提高强度。Ni是显著降低钢的韧脆转变温度，提高低温韧性。将Ni含量控制在0.30％～0.40％。Ni: Ni can form an infinitely soluble solid solution with Fe. It is an austenite stabilizing element. It has the effect of expanding the phase area, increasing the stability of supercooled austenite, shifting the C curve to the right, and improving the hardenability of steel. Ni can refine the width of the martensite lath and improve the strength. Ni can significantly reduce the ductile-brittle transition temperature of steel and improve low-temperature toughness. The Ni content is controlled at 0.30% to 0.40%.
Cu：Cu是扩大奥氏体相区，Cu单质可以作为第二相显著提升强度，能提升组织回火稳定性和强度。但Cu过高将导致Cu脆。因此Cu含量控制在0.30％～0.50％。Cu: Cu expands the austenite phase region. Cu simple substance can be used as the second phase to significantly improve the strength, and can improve the tempering stability and strength of the structure. But if Cu is too high, it will cause Cu to be brittle. Therefore, the Cu content is controlled at 0.30% to 0.50%.
Al：Al是炼钢的主要脱氧剂，Al与N结合形成细小弥散分布的AlN，且与基体保持共格关系，能够起到强化和细化组织的作用，能够使疲劳裂纹萌生和扩展抗力增加，从而提高钢的持久强度。Al含量控制在0.015％～0.035％。Al: Al is the main deoxidizer in steelmaking. Al combines with N to form fine and dispersed AlN, and maintains a coherent relationship with the matrix, which can strengthen and refine the structure, and can increase the fatigue crack initiation and propagation resistance. , thereby increasing the durability of the steel. Al content is controlled at 0.015% to 0.035%.
O和N：T.O在钢中形成氧化物夹杂，控制T.O≤0.0040％；N在钢中能与氮化物形成元素形成细小析出相细化组织，因此将N控制在0.0080％以内。O and N: T.O forms oxide inclusions in steel, control T.O ≤ 0.0040%; N can form fine precipitated phase refinement structure with nitride forming elements in steel, so N is controlled within 0.0080%.
本发明中主要析出相为Cr的析出相，Cr一方面消耗C形成碳化物，另一方面Cr能够固溶到基体中提高强度。这与钢种Cr和C的含量有关，钢中形成析出相消耗的C为0.077×Cr，为保证强度需要充足的C进行固溶，固溶C含量应为C-0.077×Cr。为保证强度还需要强化元素Cr、Si、Mn、Mo、Cu的复合作用，这5种元素对强度贡献系数分别为45、80、50、10、96。故钢的综合强度判定因子为A＝457×(C-0.077×Cr)+45×Cr+80×Si+50×Mn+10×Mo+96×Cu。为保证强度与塑性230％≤A≤275％。In the present invention, the main precipitated phase is the precipitated phase of Cr. On the one hand, Cr consumes C to form carbides, and on the other hand, Cr can be dissolved into the matrix to improve the strength. This is related to the content of Cr and C in the steel type. The C consumed by the formation of precipitates in the steel is 0.077×Cr. In order to ensure the strength, sufficient C is needed for solid solution, and the solid solution C content should be C-0.077×Cr. In order to ensure the strength, it is necessary to strengthen the composite effect of elements Cr, Si, Mn, Mo, and Cu. The contribution coefficients of these five elements to the strength are 45, 80, 50, 10, and 96, respectively. Therefore, the comprehensive strength determination factor of steel is A=457×(C-0.077×Cr)+45×Cr+80×Si+50×Mn+10×Mo+96×Cu. In order to ensure the strength and plasticity 230%≤A≤275%.
为保证钢的低温韧性需对韧化元素进行限定，Ni是现在能够提高韧性的元素，Mo有利于提高回火稳定性，从而提高钢的韧性。Cu在钢中能够析出细小的纳米铜析出相，从而提高钢的韧性，因此以上三种元素对韧性的贡献系数分别为30、20、16。Mn能够促进钢在相变是变体选择，从而使微观组织细小提高韧性，但Si和Mn存在偏析作用导致韧性下降，故Mn对韧性的贡献存在独自贡献，有存在与Si和Mn的交互作用，因此系数分别为22、-12。C含量对韧性的影响也存在两面性，一方面促进相变细化，提高韧性。一方面与Mn交互促进钢的硬化，导致韧性较低，故C对韧性的贡献存在独自贡献，有存在与C和Mn的交互作用，因此系数分别为28、-10。由于钢中P、S也对钢的韧性有害，但是由于本发明对P和S含量已经做出最高含量限制，因此不考虑P和S对韧性的危害。故钢的韧性判定因子In order to ensure the low-temperature toughness of steel, toughening elements need to be limited. Ni is an element that can improve toughness at present, and Mo is beneficial to improve tempering stability, thereby improving the toughness of steel. Cu can precipitate fine nano-copper precipitates in steel, thereby improving the toughness of steel. Therefore, the contribution coefficients of the above three elements to toughness are 30, 20, and 16, respectively. Mn can promote the selection of steel in the phase transformation, so that the microstructure is finer and the toughness is improved, but the segregation of Si and Mn leads to the decrease of toughness, so the contribution of Mn to toughness has its own contribution, and there is an interaction with Si and Mn , so the coefficients are 22 and -12 respectively. The effect of C content on toughness also has two sides. On the one hand, it promotes phase transformation refinement and improves toughness. On the one hand, it interacts with Mn to promote the hardening of steel, resulting in lower toughness. Therefore, C contributes independently to toughness, and there is an interaction with C and Mn, so the coefficients are 28 and -10, respectively. Because P and S in the steel are also harmful to the toughness of the steel, but because the present invention has set the maximum content limit for the content of P and S, the harm of P and S to the toughness is not considered. Toughness Determination Factor of Steel
D＝30×Ni+20×Mo+16×Cu+22×Mn-12×Si×Mn+28×C-10×C×Mn≥52.5％。D=30×Ni+20×Mo+16×Cu+22×Mn-12×Si×Mn+28×C-10×C×Mn≥52.5%.
为了保证钢较好的抗海上腐蚀性能，需对Si、Mn、Cu、Ni、Cr的配比进行限定，由于Cu能够提高强度并且显著提高耐蚀性因此系数为26。Si和Mn会加剧偏聚，造成微观组织不均匀从而导致冲蚀性能降低，因此系数分别为-1.5和-5。Ni能够提高层错能显著提高低温韧性，并且能够钝化金属提高冲蚀性能，故Ni的系数为4。Cr能够增强钢表面的钝化膜，故系数分别为1.2。由于Cu、Ni之间存在交互作用会抵消元素单独的耐蚀性，故系数分别为-7；即X＝26×Cu+4×Ni+1.2×Cr-1.5×Si-7×Cu×Ni-5×Mn≥5.4％。In order to ensure better corrosion resistance at sea, the ratio of Si, Mn, Cu, Ni, and Cr needs to be limited, and the coefficient is 26 because Cu can improve the strength and significantly improve the corrosion resistance. Si and Mn will aggravate segregation, cause microstructure inhomogeneity and reduce erosion performance, so the coefficients are -1.5 and -5, respectively. Ni can improve stacking faults, significantly improve low-temperature toughness, and can passivate metals to improve erosion performance, so the coefficient of Ni is 4. Cr can strengthen the passivation film on the steel surface, so the coefficients are 1.2 respectively. Since the interaction between Cu and Ni will offset the corrosion resistance of the elements alone, the coefficients are -7 respectively; that is, X=26×Cu+4×Ni+1.2×Cr-1.5×Si-7×Cu×Ni- 5 x Mn ≥ 5.4%.
所述长寿命高强韧耐腐蚀水下采油树阀体用钢的金相组织为回火索氏体，晶粒尺寸为20～25μm。The metallographic structure of the long-life, high-strength, toughness and corrosion-resistant subsea oil tree valve body steel is tempered sorbite, and the grain size is 20-25 μm.
所述长寿命高强韧耐腐蚀水下采油树阀体用钢阀体1/4厚度处抗拉强度≥860MPa、屈服强度≥690MPa、-46℃KV2≥230J、A≥20％、Z≥70％；在海水环境中的腐蚀速率≤0.07mm/a；在海水环境中腐蚀2×107周次后的疲劳强度≥350MPa；具体为所述长寿命高强韧耐腐蚀水下采油树阀体用钢阀体1/4厚度处抗拉强度为860～920MPa、屈服强度为690～740MPa、-46℃KV2为230～260J、A为20～24％、Z为70～75％；在海水环境中腐蚀2×107周次后的疲劳强度350～375MPa。The tensile strength ≥ 860MPa, yield strength ≥ 690MPa, KV 2 ≥ 230J at -46°C, A ≥ 20%, Z ≥ 70 %; corrosion rate in seawater environment ≤ 0.07mm/a; fatigue strength ≥ 350MPa after 2×10 7 cycles of corrosion in seawater environment; specifically for the long-life, high-strength, corrosion-resistant underwater Christmas tree valve body The tensile strength at the 1/4 thickness of the steel valve body is 860-920MPa, the yield strength is 690-740MPa, -46°C KV 2 is 230-260J, A is 20-24%, Z is 70-75%; in seawater environment The fatigue strength after medium corrosion 2×10 7 cycles is 350~375MPa.
本发明提供的所述长寿命高强韧耐腐蚀水下采油树阀体用钢的热处理方法，包括以下步骤：The heat treatment method of the long-life, high-strength, toughness and corrosion-resistant underwater Christmas tree valve body steel provided by the present invention comprises the following steps:
(1)阶梯淬火：将采油树阀体加热至900～940℃，保温，而后水冷；再加热至840～880℃，保温，而后水冷；水下采油树阀体的壁较厚，通过阶梯淬火能保证材料具有细小的马氏体组织，利于强韧性。通过第一次淬火后钢的晶粒度和马氏体均细化；二次淬火时由于加热前组织细化，有利于晶粒形核，晶粒细化；二次淬火时的温度低于第一次淬火温度能够保证奥氏体后晶粒不粗化，且在经历淬火后使晶粒、马氏体变体增多，微观组织细化，有利于提高强韧性及腐蚀疲劳寿命；(1) Ladder quenching: Heat the valve body of the Christmas tree to 900-940°C, keep it warm, and then water-cool it; then heat it to 840-880°C, keep it warm, and then water-cool it; the wall of the underwater Christmas tree valve body is thicker, and quench it through steps It can ensure that the material has a fine martensitic structure, which is conducive to strength and toughness. After the first quenching, the grain size and martensite of the steel are refined; during the second quenching, due to the refinement of the structure before heating, it is beneficial to the nucleation of the grains and the grain refinement; the temperature during the second quenching is lower than The first quenching temperature can ensure that the austenite grains are not coarsened, and after quenching, the grains and martensite variants will increase, and the microstructure will be refined, which is conducive to improving the strength, toughness and corrosion fatigue life;
(2)回火：将采油树阀体加热至T＝580～680℃，保温，而后水冷。(2) Tempering: Heat the valve body of the Christmas tree to T=580-680°C, keep it warm, and then water-cool it.
所述步骤(1)中，两次加热的升温速度均为50～110℃/h，保温时间均为t＝0.4～1.0×S，S为阀体壁厚，单位为mm，t单位为min。In the step (1), the heating rate of the two heatings is 50～110°C/h, and the holding time is t=0.4～1.0×S, S is the valve body wall thickness, the unit is mm, and the unit of t is min .
所述步骤(2)中，加热的升温速度为50～110℃/h，保温时间为t1＝0.8～2.0×S，S为阀体壁厚，单位为mm，t1单位为min。In the step (2), the heating rate is 50-110° C./h, the holding time is t1=0.8-2.0×S, S is the valve body wall thickness in mm, and the unit of t1 is min.
上述这样的升温速率下可保证阀体不同位置的温度接近；如果升温速度过快则阀体不同位置的温度梯度较大会增加内应力、增加裂纹风险；如果升温速度过慢，在升温阶段有产生回火反应的风险，导致析出相的种类和含量不受控制。保温时间是控制析出相的含量和尺寸的关键，保温时间过短则析出相少，有益作用降低，保温时间过长虽然析出相会增多但是析出相尺寸会增大，会降低析出相的弥散分布作用。析出相过大还会增加内部微裂纹风险。The above-mentioned heating rate can ensure that the temperature at different positions of the valve body is close; if the heating rate is too fast, the temperature gradient at different positions of the valve body will increase, which will increase the internal stress and increase the risk of cracks; Risk of tempering reactions, resulting in uncontrolled precipitated phase types and contents. The holding time is the key to controlling the content and size of the precipitated phase. If the holding time is too short, the precipitated phase will be less and the beneficial effect will be reduced. If the holding time is too long, the precipitated phase will increase, but the size of the precipitated phase will increase, which will reduce the dispersed distribution of the precipitated phase. effect. Excessively large precipitates also increase the risk of internal microcracks.
所述步骤(1)和(2)中，水冷时均冷却至100℃以下。In the steps (1) and (2), the water cooling is all cooled to below 100°C.
回火工艺参数应符合Y＝T×(S/10+lgt1)/1000，24.75≤Y≤28.95。回火参数直接决定最终产品的力学性能和腐蚀疲劳性能。如果回火参数过大，材料的软化作用大，导致材料的强度下降大而不能保证强度，还会导致析出相的尺寸过大，削弱析出强化作用，并且增大钢内微裂纹风险降低韧性。如果回火参数小，材料的强度会软化不足，组织应力、内应力大，韧性和腐蚀疲劳性能都会降低。The tempering process parameters should meet Y=T×(S/10+lgt1)/1000, 24.75≤Y≤28.95. The tempering parameters directly determine the mechanical properties and corrosion fatigue properties of the final product. If the tempering parameter is too large, the softening effect of the material will be large, resulting in a large decrease in the strength of the material and the strength cannot be guaranteed. It will also cause the size of the precipitate to be too large, weaken the precipitation strengthening effect, and increase the risk of microcracks in the steel and reduce the toughness. If the tempering parameter is small, the strength of the material will be insufficiently softened, the structural stress and internal stress will be large, and the toughness and corrosion fatigue performance will be reduced.
本发明提供的所述长寿命高强韧耐腐蚀水下采油树阀体用钢的生产方法，包括以下步骤：电弧炉或转炉冶炼→LF炉精炼→RH或VD真空脱气→圆坯连铸→圆坯加热→锻造成阀体→热处理→机加工→包装入库，其中所述热处理采用上述热处理方法进行。The production method of the long-life, high-strength, toughness and corrosion-resistant underwater Christmas tree valve body steel provided by the present invention comprises the following steps: electric arc furnace or converter smelting→LF furnace refining→RH or VD vacuum degassing→round billet continuous casting→ Round billet heating → forging into a valve body → heat treatment → machining → packaging and storage, wherein the heat treatment is carried out by the above heat treatment method.
所述圆坯直径为Φ380mm～Φ700mm。The diameter of the round billet is Φ380mm˜Φ700mm.
所述机加工步骤具体包括：阀体粗车→探伤→阀体精车→修磨→探伤。The machining steps specifically include: rough turning of the valve body→flaw detection→finish turning of the valve body→grinding→flaw detection.
与现有技术相比，本发明具有以下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
1.本发明提供的长寿命高强韧耐腐蚀水下采油树阀体用钢，通过控制钢中化学成分的组成及用量，使得其性能满足严苛环境下水下采油树的需求；1. The long-life, high-strength, corrosion-resistant steel for the valve body of the underwater Christmas tree provided by the present invention, by controlling the composition and dosage of the chemical components in the steel, makes its performance meet the requirements of the underwater Christmas tree in harsh environments;
2.本发明提供的长寿命高强韧耐腐蚀水下采油树阀体用钢中的C、Cr、Si、Mn、Mo和Cu之间的关系满足A＝457×(C-0.077×Cr)+45×Cr+80×Si+50×Mn+10×Mo+96×Cu，230％≤A≤275％，以保证水下采油树阀体具有较高的强度；2. The relationship between C, Cr, Si, Mn, Mo and Cu in the long-life, high-strength, corrosion-resistant subsea oil tree valve body steel provided by the present invention satisfies A=457×(C-0.077×Cr)+ 45×Cr+80×Si+50×Mn+10×Mo+96×Cu, 230%≤A≤275%, to ensure the high strength of the subsea tree valve body;
3.本发明提供的长寿命高强韧耐腐蚀水下采油树阀体用钢中的Ni、Mo、Cu、Mn、Si和C之间的关系满足30×Ni+20×Mo+16×Cu+22×Mn-12×Si×Mn+28×C-10×C×Mn≥74.5％，以保证水下采油树阀体的低温韧性；3. The relationship between Ni, Mo, Cu, Mn, Si and C in the long-life, high-strength, corrosion-resistant, corrosion-resistant subsea oil tree valve body steel provided by the present invention satisfies 30×Ni+20×Mo+16×Cu+ 22×Mn-12×Si×Mn+28×C-10×C×Mn≥74.5% to ensure the low temperature toughness of the subsea tree valve body;
4本发明提供的长寿命高强韧耐腐蚀水下采油树阀体用钢中的Cu、Ni、Cr、Si和Mn之间的关系满足26×Cu+4×Ni+1.2×Cr-1.5×Si-7×Cu×Ni-5×Mn≥1.8％，保证水下采油树阀体具有较好的抗海上腐蚀性能；4 The relationship between Cu, Ni, Cr, Si and Mn in the long-life, high-strength, corrosion-resistant subsea oil tree valve body steel provided by the present invention satisfies 26×Cu+4×Ni+1.2×Cr-1.5×Si -7×Cu×Ni-5×Mn≥1.8%, to ensure that the subsea tree valve body has good corrosion resistance at sea;
5.本发明提供的长寿命高强韧耐腐蚀水下采油树阀体用钢的热处理采用阶梯淬火+回火工艺进行热处理，并对回火处理时的加热温度及保温时间进行控制，以保证水下采油树阀体用钢的整体性能能够满足严苛环境下水下采油树的需求。5. The heat treatment of the long-life, high-strength, corrosion-resistant, corrosion-resistant underwater tree valve body steel provided by the present invention adopts a step quenching+tempering process for heat treatment, and controls the heating temperature and holding time during the tempering treatment to ensure water quality. The overall performance of the steel used for the valve body of the lower Christmas tree can meet the needs of the underwater Christmas tree in harsh environments.
附图说明Description of drawings
图1为实施例3中的水下采油树阀体用钢的金相组织图；Fig. 1 is the metallographic structure diagram of the steel for subsea tree valve body in embodiment 3;
图2为对比例2中的水下采油树阀体用钢的金相组织图。FIG. 2 is a metallographic structure diagram of the steel used for the subsea tree valve body in Comparative Example 2. FIG.
具体实施方式Detailed ways
本发明提供的一种长寿命高强韧耐腐蚀水下采油树阀体用钢，包括如下重量百分比的化学成分：C 0.22％～0.28％、Si 0.15％～0.35％、Mn 1.1％～1.4％、Cr 1.3％～1.5％、Mo 0.5％～0.6％、Ni 0.30％～0.40％、Cu 0.30％～0.50％、Al 0.015％～0.035％、P≤0.015％、S≤0.015％、N≤0.0080％、O≤0.004％，其余为Fe和其它不可避免的杂质；The invention provides a long-life, high-strength, high-strength, corrosion-resistant steel for underwater Christmas tree valve body, which includes the following chemical components in weight percentage: C 0.22%-0.28%, Si 0.15%-0.35%, Mn 1.1%-1.4%, Cr 1.3%～1.5%, Mo 0.5%～0.6%, Ni 0.30%～0.40%, Cu 0.30%～0.50%, Al 0.015%～0.035%, P≤0.015%, S≤0.015%, N≤0.0080%, O≤0.004%, the rest is Fe and other unavoidable impurities;
其中，A＝457×(C-0.077×Cr)+45×Cr+80×Si+50×Mn+10×Mo+96×Cu，230％≤A≤275％；Among them, A=457×(C-0.077×Cr)+45×Cr+80×Si+50×Mn+10×Mo+96×Cu, 230%≤A≤275%;
D＝30×Ni+20×Mo+16×Cu+22×Mn-12×Si×Mn+28×C-10×C×Mn，D≥52.5％；D=30×Ni+20×Mo+16×Cu+22×Mn-12×Si×Mn+28×C-10×C×Mn, D≥52.5%;
X＝26×Cu+4×Ni+1.2×Cr-1.5×Si-7×Cu×Ni-5×Mn，X≥5.4％。X=26×Cu+4×Ni+1.2×Cr-1.5×Si-7×Cu×Ni-5×Mn, X≥5.4%.
所述长寿命高强韧耐腐蚀水下采油树阀体用钢的生产方法，包括以下步骤：电弧炉或转炉冶炼→LF炉精炼→RH或VD真空脱气→圆坯连铸→圆坯加热→锻造成阀体→热处理→机加工→包装入库。The production method of the long-life, high-strength, high-strength, corrosion-resistant, and corrosion-resistant underwater Christmas tree valve body steel comprises the following steps: electric arc furnace or converter smelting → LF furnace refining → RH or VD vacuum degassing → round billet continuous casting → round billet heating → Forging into valve body → heat treatment → machining → packaging and storage.
其中，电炉冶炼：出钢前定氧，出钢过程采用留钢操作，避免下渣；Among them, electric furnace smelting: Oxygen is fixed before tapping, and steel is left in the tapping process to avoid slag;
LF炉：C、Si、Mn、Cr、Ni、Mo、Cu、等元素调至目标值；LF furnace: C, Si, Mn, Cr, Ni, Mo, Cu, and other elements are adjusted to the target value;
真空脱气：纯脱气时间≥15分钟，保证真空处理后[H]含量≤1.5ppm，避免钢中出现白点，引起氢脆现象；Vacuum degassing: pure degassing time ≥ 15 minutes, to ensure [H] content ≤ 1.5ppm after vacuum treatment, to avoid white spots in the steel, causing hydrogen embrittlement;
连铸：中包钢水目标温度控制在液相线温度以上10～40℃，连铸φ380mm～φ700mm圆坯。Continuous casting: The target temperature of the molten steel in the tundish is controlled at 10-40°C above the liquidus temperature, and the round billet of φ380mm～φ700mm is continuously cast.
锻造路线：圆坯加热→锻造→缓冷。Forging route: round billet heating → forging → slow cooling.
阀体热处理：台车炉加热→保温→淬火→台车炉加热→保温→淬火→回火→保温→水冷。Valve body heat treatment: trolley furnace heating → heat preservation → quenching → trolley furnace heating → heat preservation → quenching → tempering → heat preservation → water cooling.
机加工路线：阀体粗车→探伤→阀体精车→修磨→探伤。Machining route: rough turning of valve body → flaw detection → fine turning of valve body → grinding → flaw detection.
热处理具体按照下述步骤进行：Heat treatment is carried out according to the following steps:
(1)阶梯淬火：将采油树阀体加热至900～940℃，保温，而后水冷至100℃以下；再加热至840～880℃，保温，而后水冷至100℃以下；两次加热的升温速度均为50～110℃/h，保温时间均为t＝0.4～1.0×S，S为阀体壁厚，单位为mm，t单位为min；(1) Step quenching: heat the christmas tree valve body to 900-940°C, keep it warm, and then water-cool it to below 100°C; then heat it to 840-880°C, keep it warm, and then water-cool it to below 100°C; the heating rate of the two heatings Both are 50～110℃/h, and the holding time is t=0.4～1.0×S, S is the wall thickness of the valve body, the unit is mm, and the unit of t is min;
(2)回火：将采油树阀体加热至T＝580～680℃，保温，而后水冷至100℃以下；加热的升温速度为50～110℃/h，保温时间为t1＝0.8～2.0×S，S为阀体壁厚，单位为mm，t1单位为min；回火工艺参数应符合Y＝T×(S/10+lgt1)/1000，24.75≤Y≤28.95。(2) Tempering: Heat the Christmas tree valve body to T=580-680°C, keep it warm, and then water-cool it to below 100°C; the heating rate is 50-110°C/h, and the holding time is t1=0.8-2.0× S, S is the wall thickness of the valve body in mm, and the unit of t1 is min; the tempering process parameters should meet Y=T×(S/10+lgt1)/1000, 24.75≤Y≤28.95.
由上述工艺制备的长寿命高强韧耐腐蚀水下采油树阀体用钢的性能检测方法如下：The performance testing method of the long-life, high-strength, corrosion-resistant subsea tree valve body steel prepared by the above process is as follows:
组织：在阀体延长体上取样，在延长体1/4厚度(厚度为400mm)位置内取样进行金相、晶粒尺寸分析。Organization: Sampling on the extension of the valve body, sampling within 1/4 of the thickness of the extension (400mm in thickness) for metallographic and grain size analysis.
性能：在阀体延长体上取样，在延长体1/4厚度(厚度为400mm)位置内取拉伸、冲击、腐蚀、疲劳试样，参照GB/T228、GB/T229、GB/T 5776、GB/T7733进行性能试验。Performance: Sampling on the extension body of the valve body, taking tensile, impact, corrosion and fatigue samples within 1/4 of the thickness of the extension body (thickness is 400mm), referring to GB/T228, GB/T229, GB/T 5776, GB/T7733 conducts performance tests.
下面结合实施例对本发明进行详细说明。The present invention will be described in detail below in conjunction with examples.
各实施例和对比例中的长寿命高强韧耐腐蚀水下采油树阀体用钢的化学成分及重量百分比如表1所示，余量为铁及不可避免的杂质。The chemical composition and weight percentage of the long-life, high-strength, corrosion-resistant subsea tree valve body steel in each embodiment and comparative example are shown in Table 1, and the balance is iron and unavoidable impurities.
[根据细则26改正 14.04.2023]
表1 [Correction 14.04.2023 under Rule 26]
Table 1
[根据细则26改正 14.04.2023]
各实施例和对比例中的长寿命高强韧耐腐蚀水下采油树阀体用钢的热处理工艺参数如表2所示。[Correction 14.04.2023 under Rule 26]
Table 2 shows the heat treatment process parameters of the long-life, high-strength, corrosion-resistant subsea tree valve body steel in each embodiment and comparative example.
[根据细则26改正 14.04.2023]
表2 [Correction 14.04.2023 under Rule 26]
Table 2
[根据细则26改正 14.04.2023]
各实施例和对比例中的长寿命高强韧耐腐蚀水下采油树阀体用钢的力学性能检测结果如表3所示。[Correction 14.04.2023 under Rule 26]
Table 3 shows the test results of the mechanical properties of the long-life, high-strength, corrosion-resistant steel for subsea tree valve bodies in each of the examples and comparative examples.
[根据细则26改正 14.04.2023]
表3本发明实施例及对比例的力学性能检测情况列表 [Correction 14.04.2023 under Rule 26]
Table 3 The mechanical performance detection situation list of the embodiment of the present invention and comparative examples
[根据细则26改正 14.04.2023]
从上述数据可以看出，按照本发明进行控制的实施例1～3中的钢的强度、塑性、韧性及耐腐蚀性能均较好。而对比例1中虽然各化学成分的含量及热处理工艺按照本发明设置的范围进行了控制，但是由于A值、D值及X值的控制不当导致材料强度过低，塑韧性、耐腐蚀及疲劳性能不足；对比例2中虽然成分设计合理，但是热处理工艺不当，导致材料的晶粒粗大使强度、韧性不足，且腐蚀及疲劳性能不足；对比例3中由于部分化学成分的含量及A值、X值控制不当，导致材料强度过低，韧性不足，且腐蚀及疲劳性能不足。[Correction 14.04.2023 under Rule 26]
It can be seen from the above data that the strength, plasticity, toughness and corrosion resistance of the steels in Examples 1-3 controlled according to the present invention are all better. In comparative example 1, though the content of each chemical composition and the heat treatment process are controlled according to the scope of the present invention, the improper control of A value, D value and X value leads to low material strength, plastic toughness, corrosion resistance and fatigue Insufficient performance; although the composition design is reasonable in comparative example 2, the heat treatment process is improper, resulting in coarse grains of the material, insufficient strength, toughness, and insufficient corrosion and fatigue performance; in comparative example 3, due to the content of some chemical components and the A value, Improper control of the X value leads to low material strength, insufficient toughness, and insufficient corrosion and fatigue properties.
[根据细则26改正 14.04.2023]
上述参照实施例对一种长寿命高强韧耐腐蚀水下采油树阀体用钢及其热处理和生产方法进行的详细描述，是说明性的而不是限定性的，可按照所限定范围列举出若干个实施例，因此在不脱离本发明总体构思下的变化和修改，应属本发明的保护范围之内。[Correction 14.04.2023 under Rule 26]
The detailed description of a long-life, high-strength, corrosion-resistant, corrosion-resistant subsea tree valve body steel and its heat treatment and production methods described above with reference to the embodiments is illustrative rather than restrictive, and several examples can be listed according to the limited scope Therefore, changes and modifications without departing from the general concept of the present invention shall fall within the protection scope of the present invention.

Claims (9)

  1. 一种长寿命高强韧耐腐蚀水下采油树阀体用钢，其特征在于，包括如下重量百分比的化学成分：C 0.22％～0.28％、Si 0.15％～0.35％、Mn 1.1％～1.4％、Cr 1.3％～1.5％、Mo 0.5％～0.6％、Ni 0.30％～0.40％、Cu 0.30％～0.50％、Al 0.015％～0.035％、P≤0.015％、S≤0.015％、N≤0.0080％、O≤0.004％，其余为Fe和其它不可避免的杂质；A long-life, high-strength, high-strength, corrosion-resistant steel for underwater Christmas tree valve bodies is characterized in that it includes the following chemical components in weight percentages: C 0.22% to 0.28%, Si 0.15% to 0.35%, Mn 1.1% to 1.4%, Cr 1.3%～1.5%, Mo 0.5%～0.6%, Ni 0.30%～0.40%, Cu 0.30%～0.50%, Al 0.015%～0.035%, P≤0.015%, S≤0.015%, N≤0.0080%, O≤0.004%, the rest is Fe and other unavoidable impurities;
    其中，A＝457×(C-0.077×Cr)+45×Cr+80×Si+50×Mn+10×Mo+96×Cu，230％≤A≤275％；
    D＝30×Ni+20×Mo+16×Cu+22×Mn-12×Si×Mn+28×C-10×C×Mn，D≥52.5％；
    X＝26×Cu+4×Ni+1.2×Cr-1.5×Si-7×Cu×Ni-5×Mn，X≥5.4％；    Among them, A=457×(C-0.077×Cr)+45×Cr+80×Si+50×Mn+10×Mo+96×Cu, 230%≤A≤275%;
    D=30×Ni+20×Mo+16×Cu+22×Mn-12×Si×Mn+28×C-10×C×Mn, D≥52.5%;
    X=26×Cu+4×Ni+1.2×Cr-1.5×Si-7×Cu×Ni-5×Mn, X≥5.4%;
    所述长寿命高强韧耐腐蚀水下采油树阀体用钢的金相组织为回火索氏体，晶粒尺寸为20～25μm。The metallographic structure of the long-life, high-strength, toughness and corrosion-resistant subsea oil tree valve body steel is tempered sorbite, and the grain size is 20-25 μm.
  2. 根据权利要求1所述的长寿命高强韧耐腐蚀水下采油树阀体用钢，其特征在于，所述长寿命高强韧耐腐蚀水下采油树阀体用钢阀体1/4厚度处抗拉强度≥860MPa、屈服强度≥690MPa、-46℃KV2≥230J、A≥20％、Z≥70％；在海水环境中的腐蚀速率≤0.07mm/a；在海水环境中腐蚀2×107周次后的疲劳强度≥350MPa。According to claim 1, the long-life, high-strength, toughness, and corrosion-resistant steel for underwater Christmas tree valve bodies is characterized in that the valve body of the long-life, high-strength, toughness, and corrosion-resistant underwater Christmas tree valve body is resistant to 1/4 of the thickness of the steel valve body. Tensile strength ≥ 860MPa, yield strength ≥ 690MPa, -46°C KV 2 ≥ 230J, A ≥ 20%, Z ≥ 70%; corrosion rate in seawater environment ≤ 0.07mm/a; corrosion in seawater environment 2×10 7 The fatigue strength after the cycle is ≥350MPa.
  3. 如权利要求1或2所述的长寿命高强韧耐腐蚀水下采油树阀体用钢的热处理方法，其特征在于，所述热处理方法包括以下步骤：The heat treatment method of the long-life, high-strength, corrosion-resistant underwater tree valve body steel according to claim 1 or 2, wherein the heat treatment method comprises the following steps:
    (1)阶梯淬火：将采油树阀体加热至900～940℃，保温，而后水冷；再加热至840～880℃，保温，而后水冷；(1) Ladder quenching: heat the valve body of the Christmas tree to 900-940°C, keep it warm, and then water-cool it; then heat it to 840-880°C, keep it warm, and then water-cool it;
    (2)回火：将采油树阀体加热至T＝580～680℃，保温，而后水冷。(2) Tempering: Heat the valve body of the Christmas tree to T=580-680°C, keep it warm, and then water-cool it.
  4. 根据权利要求3所述的热处理方法，其特征在于，所述步骤(1)中，两次加 热的升温速度均为50～110℃/h，保温时间均为t＝0.4～1.0×S，S为阀体壁厚，单位为mm，t单位为min。The heat treatment method according to claim 3, characterized in that, in the step (1), adding twice The heating rate of heat is 50-110°C/h, and the holding time is t=0.4-1.0×S, S is the wall thickness of the valve body, the unit is mm, and the unit of t is min.
  5. 根据权利要求3所述的热处理方法，其特征在于，所述步骤(2)中，加热的升温速度为50～110℃/h，保温时间为t1＝0.8～2.0×S，S为阀体壁厚，单位为mm，t1单位为min。The heat treatment method according to claim 3, characterized in that, in the step (2), the heating rate is 50-110° C./h, the holding time is t1=0.8-2.0×S, and S is the valve body wall Thickness, in mm, t1 in min.
  6. 根据权利要求5所述的热处理方法，其特征在于，回火工艺参数应符合Y＝T×(S/10+lgt1)/1000，24.75≤Y≤28.95。The heat treatment method according to claim 5, characterized in that the tempering process parameters should meet Y=T×(S/10+lgt1)/1000, 24.75≤Y≤28.95.
  7. 如权利要求1或2所述的长寿命高强韧耐腐蚀水下采油树阀体用钢的生产方法，其特征在于，所述生产方法包括以下步骤：电弧炉或转炉冶炼→LF炉精炼→RH或VD真空脱气→圆坯连铸→圆坯加热→锻造成阀体→热处理→机加工→包装入库，其中所述热处理采用权利要求3-6任意一项所述的热处理方法进行。The production method of long-life, high-strength, toughness and corrosion-resistant subsea tree valve body steel according to claim 1 or 2, characterized in that the production method comprises the following steps: electric arc furnace or converter smelting → LF furnace refining → RH Or VD vacuum degassing → round billet continuous casting → round billet heating → forging into a valve body → heat treatment → machining → packaging and storage, wherein the heat treatment is carried out by the heat treatment method described in any one of claims 3-6.
  8. 根据权利要求7所述的生产方法，其特征在于，所述圆坯直径为Φ380mm～Φ700mm。The production method according to claim 7, characterized in that, the diameter of the round billet is Φ380mm˜Φ700mm.
  9. 根据权利要求7所述的生产方法，其特征在于，所述机加工步骤具体包括：阀体粗车→探伤→阀体精车→修磨→探伤。 The production method according to claim 7, wherein the machining step specifically comprises: rough turning of the valve body→flaw detection→finish turning of the valve body→regrinding→flaw detection.
PCT/CN2023/079637 2022-03-04 2023-03-03 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 WO2023165614A1 (en)

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CN202210209972.6 2022-03-04
CN202210209972.6A CN114561593B (en) 2022-03-04 2022-03-04 Steel for long-life high-strength-toughness corrosion-resistant underwater Christmas tree valve body, heat treatment method and production method thereof

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CN117778889A (en) * 2024-01-06 2024-03-29 五洲阀门股份有限公司 Alloy material for valve and valve body production process

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