WO2025031448A1 - Tubage et gainage à haute résistance et résistants à la corrosion au dioxyde de carbone et procédé de fabrication associé - Google Patents

Tubage et gainage à haute résistance et résistants à la corrosion au dioxyde de carbone et procédé de fabrication associé Download PDF

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Publication number
WO2025031448A1
WO2025031448A1 PCT/CN2024/110665 CN2024110665W WO2025031448A1 WO 2025031448 A1 WO2025031448 A1 WO 2025031448A1 CN 2024110665 W CN2024110665 W CN 2024110665W WO 2025031448 A1 WO2025031448 A1 WO 2025031448A1
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Prior art keywords
oil casing
carbon dioxide
dioxide corrosion
corrosion
strength
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PCT/CN2024/110665
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English (en)
Chinese (zh)
Inventor
袁凯捷
董晓明
高展
卢小庆
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Baoshan Iron and Steel Co Ltd
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Baoshan Iron and Steel Co Ltd
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Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES, PROFILES OR LIKE SEMI-MANUFACTURED PRODUCTS OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C37/00—Manufacture of metal sheets, rods, wire, tubes, profiles or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape
    • B21C37/06—Manufacture of metal sheets, rods, wire, tubes, profiles or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape of tubes or metal hoses; Combined procedures for making tubes, e.g. for making multi-wall tubes
    • 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
    • C21D8/00—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
    • C21D8/10—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of tubular bodies
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/04—Making ferrous alloys by melting
    • 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
    • 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
    • C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
    • 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
    • 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
    • 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
    • C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium

Definitions

  • the invention relates to a steel material and a manufacturing method thereof, in particular to an oil casing and a manufacturing method thereof.
  • the Chinese patent document with publication number CN101899621A, publication date December 1, 2010, and title “3Cr seamless steel pipe and manufacturing method thereof” has a chemical composition of C: 0.1-0.2%, Si: 0.1-0.5%, Mn: 0.3-0.8%, Cr: 2-4%, Mo: 0.3-0.6%, Ti: 0.0024-0.024%, Al: 0.01-0.04%, P ⁇ 0.03%, S ⁇ 0.03%, and the remainder is Fe and unavoidable impurities.
  • the yield strength is ⁇ 552MPa, i.e. 80ksi, achieved by tempering heat treatment process.
  • the Chinese patent document with publication number CN103602903A, publication date February 26, 2014, and titled “High-strength carbon dioxide corrosion-resistant oil well pipe and manufacturing method thereof” has a chemical composition of C: 0.30-0.42%, Si: 0.10-1.0%, Mn: 0.80-1.5%, Cr: 0.5-1.5%, V: 0.21-0.4%, Al: 0.01-0.10%, N: 0.031-0.05%, P ⁇ 0.015%, S ⁇ 0.005%, the remainder is Fe and unavoidable impurities, the V/N ratio is controlled at 6-11, the normalizing process is adopted, and the mechanical properties reach above 95ksi steel grade.
  • One of the purposes of the present invention is to provide a high-strength carbon dioxide corrosion-resistant oil casing.
  • Reasonable chemical element composition design can produce oil casing with both ultra-high strength and excellent resistance to carbon dioxide corrosion.
  • the present invention provides a high-strength carbon dioxide corrosion-resistant oil casing, which contains Fe and inevitable impurities, and also contains the following chemical elements in the following mass percentages:
  • the present invention also provides a high-strength carbon dioxide corrosion-resistant oil casing, the mass percentage of each element of which is:
  • the present invention adopts a low- carbon component design to reduce the carbide content of Cr to promote the formation of corrosion film Cr enrichment, improve the stability of the corrosion film, and thus improve the corrosion resistance.
  • Ce and La elements are added.
  • rare earth have a strong affinity with elements such as O and S, and can be deeply deoxidized to form rare earth compounds for easy smelting and impurity removal, thereby reducing the content of coarse inclusions and preventing pitting pits from forming at the location of larger inclusions.
  • rare earth reduces the crystallization supercooling, resulting in a refined structure during the solidification process.
  • Rare earth modification forms uniformly dispersed fine rare earth inclusion particles, which can be used as the second phase nucleation core and can also produce a grain boundary pinning effect, which is conducive to grain refinement and promotes the improvement of comprehensive performance.
  • the V, Ni, Nb multi-element microalloying composition design enables the present invention to achieve a high yield strength of 140 ksi, thereby improving the anti-corrosion performance and the anti-collapse performance of the casing, thereby significantly increasing the service life of the casing.
  • C In the high-strength carbon dioxide corrosion-resistant oil casing described in the present invention, C is the main solid solution strengthening element and can improve the strength of steel. However, too high a content will worsen segregation, reduce toughness, and form carbides that will damage corrosion resistance. Therefore, the present invention controls the C content to 0.10-0.20%.
  • Si In the high-strength carbon dioxide corrosion-resistant oil casing described in the present invention, Si is a deoxidizer and has a strong solid solution strengthening effect on ferrite, improving hardenability, tempering resistance, and yield strength. However, too high a content will deteriorate the toughness and processing performance of the steel. Therefore, the present invention controls the Si content to 0.10-0.80%.
  • Mn In the high-strength carbon dioxide corrosion-resistant oil casing described in the present invention, Mn is one of the important alloying elements, which strongly improves the hardenability of steel and promotes the formation of martensite to ensure strength. However, too high a content has an unfavorable tendency to promote grain coarsening and structural segregation. Therefore, the present invention controls the Mn content to 0.10-1.50%.
  • Cr In the high-strength carbon dioxide corrosion-resistant oil casing of the present invention, Cr is the main alloying element for improving corrosion resistance and can increase the hardenability of steel, so the Cr content is controlled to be 3-5% in the present invention.
  • Mo has a strong ability to inhibit the transformation of austenite to pearlite, can inhibit temper brittleness, form dispersed special carbides at a higher tempering temperature, and improve strength. Based on this, the present invention controls the Mo content to 0.10-0.70%.
  • Al In the high-strength carbon dioxide corrosion-resistant oil casing of the present invention, Al is mainly used for deoxidation and grain refinement, and has a great solid solution strengthening effect. Based on this, the present invention controls the Al content to be 0.01-0.10%.
  • V In the high-strength carbon dioxide corrosion-resistant oil casing described in the present invention, V is a strong carbide and nitride forming element, which improves the tempering resistance of steel and has a strong secondary hardening effect. It is solid-dissolved in ferrite and has a very strong solid-solution strengthening effect. However, if the V content is too high, coarse V (C, N) is easily formed, which damages the toughness. Therefore, the V content is controlled to 0.10-0.20% in the present invention.
  • Ni has a certain solid solution strengthening effect and can improve the corrosion resistance.
  • Ni is used in combination with Cr and Mo to improve the thermal strength and corrosion resistance of steel. Based on this, the present invention controls the Ni content to 0.1-1.0%.
  • Ce, La In the high-strength carbon dioxide corrosion-resistant oil casing described in the present invention, trace amounts of Ce and La are added to refine grains and improve toughness, but excessive content thereof is prone to form coarse oxides or sulfur oxides. Therefore, the present invention controls the contents of Ce and La to 0.002-0.01%.
  • the mass percentage of each chemical element may further satisfy at least one of the following items:
  • the high-strength carbon dioxide corrosion-resistant oil casing of the present invention also contains 0 ⁇ Nb ⁇ 0.15wt%.
  • Nb has a strong solid solution strengthening effect and can refine grains. Trace addition can improve the strength of steel without affecting plasticity and toughness. Based on this, in some embodiments of the present invention, its content is controlled to 0 ⁇ Nb ⁇ 0.15wt%, for example, 0.01wt% ⁇ Nb ⁇ 0.15wt%.
  • P is controlled to be ⁇ 0.012%, S ⁇ 0.005%, and N ⁇ 0.006%.
  • P, S and N are all harmful impurity elements, among which P and S are severely segregated in steel, which is unfavorable to plasticity and toughness.
  • N has no significant strengthening effect, forms nitrides that damage the strengthening effect of micro-alloying elements, and easily causes aging hardening of low-carbon steel, reducing plasticity and toughness. Therefore, in order to obtain steel with better performance and better quality, the content of P, S and N should be reduced as much as possible under the condition that technology allows.
  • microstructure matrix of the high-strength carbon dioxide corrosion-resistant oil casing of the present invention is tempered troostite.
  • the grain size of the high-strength carbon dioxide corrosion-resistant oil casing of the present invention is above level 10. In some embodiments, the grain size of the high-strength carbon dioxide corrosion-resistant oil casing of the present invention is level 10-11.
  • the percentage of large-sized inclusions with an average diameter greater than 5 ⁇ m to the total inclusions is less than 6%. In some embodiments, 3% ⁇ the percentage of large-sized inclusions with an average diameter greater than 5 ⁇ m to the total inclusions is less than 6%.
  • the Cr content in the corrosion product film of the high-strength carbon dioxide corrosion-resistant oil casing of the present invention is higher than 13wt%.
  • the corrosion product film is generated under the corrosive environment conditions of temperature 60°C, CO2 partial pressure 1MPa, and NaCl concentration 20g/L.
  • the performance of the high-strength carbon dioxide corrosion-resistant oil casing of the present invention meets the following requirements: yield strength is 965-1173MPa, tensile strength is ⁇ 1034MPa, and 0°C transverse Charpy impact energy is ⁇ 80J.
  • the tensile strength of the high-strength carbon dioxide corrosion-resistant oil casing of the present invention is 1034-1300 MPa.
  • the high-strength carbon dioxide corrosion-resistant oil casing of the present invention has a 0°C transverse Charpy impact energy of 80 to 200 J.
  • the high-strength carbon dioxide corrosion-resistant oil casing of the present invention has an elongation after fracture of 18-25%.
  • the high-strength carbon dioxide corrosion-resistant oil casing of the present invention has a uniform corrosion rate of ⁇ 2.5 mm/a, for example, 0.5 to 2.5 mm/a, under the corrosive environment conditions of a temperature of 60°C, a CO2 partial pressure of 1 MPa, and a NaCl concentration of 20 g/L.
  • another object of the present invention is to provide a method for manufacturing the above-mentioned high-strength carbon dioxide corrosion-resistant oil casing, which has a simple process and low production cost.
  • the present invention proposes a method for manufacturing the above-mentioned high-strength carbon dioxide corrosion-resistant oil casing, which comprises the following steps:
  • the quenching temperature is 880-920°C, and the temperature is kept for 30-60 minutes before water quenching;
  • tempering temperature is 550-650°C and the holding time is 45-75min.
  • step (1) of the manufacturing method described in the present invention the superheat of the molten steel during the casting process is controlled to ⁇ 30°C, for example, 15-30°C, and the continuous casting speed is controlled to be below 2.0 m/min, for example, 1.8-2.0 m/min.
  • step (2) of the manufacturing method of the present invention the mixture is heated to an equalizing temperature of 1200 to 1250° C. and kept warm for 100 to 300 minutes.
  • step (2) of the manufacturing method described in the present invention the perforation temperature is controlled to be 1150-1250°C.
  • step (2) of the manufacturing method of the present invention the final rolling temperature is controlled to be 900-1000°C.
  • step (2) of the manufacturing method of the present invention the sizing temperature is controlled to be 850-950°C.
  • step (4) of the manufacturing method of the present invention air cooling is performed after the heat preservation is completed.
  • the high-strength carbon dioxide corrosion-resistant oil casing of the present invention is designed with low carbon components, and is added with appropriate Cr elements, as well as Ni, Mo, V, Ce, and La elements, so that the produced oil casing has high strength and excellent corrosion resistance.
  • the high-strength carbon dioxide corrosion-resistant oil casing of the present invention has a yield strength of 965-1173 MPa, reaching 140 ksi, a tensile strength ⁇ 1034 MPa, and a 0°C transverse Charpy impact energy ⁇ 80 J, and has excellent mechanical properties.
  • the high-strength carbon dioxide corrosion-resistant oil casing described in the present invention has a uniform corrosion rate of ⁇ 2.5mm/a under the corrosive environment conditions of temperature 60°C, CO2 partial pressure 1MPa, and NaCl concentration 20g/L, and thus has excellent carbon dioxide corrosion resistance.
  • FIG. 1 is a microstructure photograph of the oil casing of Example 1 of the present invention under an optical microscope.
  • FIG. 2 is a microstructure photograph of the oil casing of Example 1 of the present invention under a scanning electron microscope.
  • FIG3 is a microstructure photograph of the oil casing of Comparative Example 1 under a scanning electron microscope.
  • the high-strength carbon dioxide corrosion-resistant oil casings of Examples 1-18 are all prepared by the following steps:
  • the smelting is carried out by primary refining, refining outside the furnace and vacuum degassing.
  • the tapping temperature can be 1600-1700°C.
  • Tempering The tempering temperature is 550-650°C, the holding time is 45-75min, and then air cooling.
  • Comparative Examples 1-5 are prepared by referring to the steps of Example 1-18, but the chemical element content and/or process parameters in the manufacturing process of Comparative Examples 1-5 are not in line with the design of the present invention.
  • Table 1 lists the mass percentages of the chemical elements in the high-strength carbon dioxide corrosion-resistant oil casing of Examples 1-18 and the comparative oil casing of Comparative Examples 1-5.
  • Table 2 lists the specific process parameters of the high-strength carbon dioxide corrosion-resistant oil casing of Examples 1-18 and the comparative oil casing of Comparative Examples 1-5 in the above process steps.
  • the high-strength carbon dioxide corrosion-resistant oil casing of Examples 1-18 and the comparative pipes of Comparative Examples 1-5 were sampled respectively, and the statistics of large-sized inclusion particles with an average diameter of >5 ⁇ m and the grain size were measured.
  • the test results are listed in Table 3.
  • the inclusion statistics refer to the standard T/CSTM 00346-2021 "Automatic classification and statistics of inclusions in steel scanning electron microscope energy spectrum method", and the inclusion analysis is performed by scanning electron microscope energy spectrum method to count the size and number of inclusions.
  • the grain size statistics refer to the standard GB/T 6394-2017 "Method for determination of average grain size of metals", and the intercept method is used for measurement to calculate and determine the grain size grade number G.
  • the grain sizes of the embodiments of the present invention are all above level 10, and the percentage of large-sized inclusions with an average diameter greater than 5 ⁇ m accounts for less than 6% of the total inclusions.
  • the grain sizes of comparative examples 4 and 5 are lower than level 10, and the percentage of large-sized inclusions is also much higher than that of the embodiments of the present invention.
  • Figure 1 shows a microstructure photograph of the oil casing of Example 1 of the present invention under an optical microscope.
  • the microstructure of Example 1 at room temperature is a tempered troostite structure.
  • the microstructures of the oil casing of Examples 2-18 are also tempered troostite.
  • Figure 2 shows a microstructure photograph of the oil casing of Example 1 of the present invention under a scanning electron microscope. As can be seen from Figure 2, a small amount of fine dispersed carbides are distributed in the microstructure of Example 1. Through scanning electron microscope observation, a small amount of fine dispersed carbides are also distributed in the microstructure of the oil casing of Examples 2-18.
  • Figure 3 shows a microstructure photograph of the oil casing of Comparative Example 1 under a scanning electron microscope. As can be seen from Figure 3, the microstructure of Comparative Example 1 contains a lot of coarse carbides, which is not conducive to corrosion resistance.
  • V-shaped impact specimens were processed and tested at 0°C according to the standard GB/T 229-2020 "Charpy Pendulum Impact Test Method for Metallic Materials", and the impact energy at 0°C was measured.
  • the corrosion pieces were sampled and processed, and the test was carried out in a high-temperature autoclave under the corrosive environment conditions of temperature 60°C, CO2 partial pressure 1MPa, NaCl concentration 20g/L, rotation speed 1m/s, and test period 168h to measure the uniform corrosion.
  • the corrosion rate was determined by SEM+EDS analysis on the cross section of the corrosion film and the Cr content of the corrosion product film was measured.
  • Table 4 lists the test results of the high-strength carbon dioxide corrosion-resistant oil casing of Examples 1-18 and the comparative oil casing of Comparative Examples 1-5.
  • the yield strength of the high-strength carbon dioxide corrosion-resistant oil casing of Examples 1-18 of the present invention is higher than 965MPa, the tensile strength is higher than 1034MPa, and the 0°C transverse Charpy impact energy is greater than 80J.
  • the corrosion product film of each embodiment of the present invention The Cr content is higher than 13wt%, and the uniform corrosion rate is lower than 2.5mm/a.

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  • Mechanical Engineering (AREA)
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  • Manufacturing & Machinery (AREA)
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Abstract

La présente invention divulgue un tubage et un gainage à haute résistance et résistants à la corrosion au dioxyde de carbone, comprenant du Fe et des impuretés inévitables, et comprenant en outre les éléments chimiques suivants : C : 0,10 - 0,20 %, Si : 0,10 - 0,80 %, Mn : 0,10 - 1,50 %, Cr : 3 - 5 %, Mo : 0,10 - 0,70 %, Al : 0,01 - 0,10 %, V : 0,10 - 0,20 %, Ni : 0,1 à 1,0 %, Ce : 0,002 - 0,01 %, et La : 0,002 - 0,01 %. De manière correspondante, la présente invention divulgue en outre un procédé de fabrication des tubage et gainage à haute résistance et résistants à la corrosion au dioxyde de carbone. Selon la présente invention, au moyen d'une conception rationnelle de composant d'éléments chimiques, le tubage et le gainage ayant à la fois une ultra-haute résistance et une excellente résistance à la corrosion au dioxyde de carbone peuvent être obtenus.
PCT/CN2024/110665 2023-08-09 2024-08-08 Tubage et gainage à haute résistance et résistants à la corrosion au dioxyde de carbone et procédé de fabrication associé Pending WO2025031448A1 (fr)

Applications Claiming Priority (2)

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CN202310997786.8 2023-08-09
CN202310997786.8A CN119464921B (zh) 2023-08-09 2023-08-09 一种高强度抗二氧化碳腐蚀的油套管及其制造方法

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CN115369316A (zh) * 2021-05-21 2022-11-22 宝山钢铁股份有限公司 一种抗二氧化碳腐蚀性能优良的高强度无缝钢管及其制造方法
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