CN111945069A - High-alloy corrosion-resistant oil sleeve material and preparation method thereof - Google Patents

High-alloy corrosion-resistant oil sleeve material and preparation method thereof Download PDF

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CN111945069A
CN111945069A CN202010832250.7A CN202010832250A CN111945069A CN 111945069 A CN111945069 A CN 111945069A CN 202010832250 A CN202010832250 A CN 202010832250A CN 111945069 A CN111945069 A CN 111945069A
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resistant oil
alloy corrosion
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CN111945069B (en
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邓叙燕
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Dalipal Pipe Co
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C37/00—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape
    • B21C37/06—Manufacture of metal sheets, bars, wire, tubes 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 by deformation combined with, or followed by, heat treatment
    • C21D8/10—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of tubular bodies
    • C21D8/105—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of tubular bodies of ferrous 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
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
    • 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
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/24—Ferrous alloys, e.g. steel alloys containing chromium with vanadium

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Treatment Of Steel In Its Molten State (AREA)

Abstract

The invention discloses a high-alloy corrosion-resistant oil casing material and a preparation method thereof, wherein the oil casing material comprises the following components in percentage by weight: c is more than or equal to 0.18 percent and less than or equal to 0.22 percent, Si is more than or equal to 0.40 percent and less than or equal to 0.4 percent and less than or equal to 0.6 percent, Cr is more than or equal to 12.2 percent and less than or equal to 13.2 percent, V is more than or equal to 0.12 percent and less than or equal to 0.06 percent, N is more than or equal to 0.03 percent and less than or equal to 0.05 percent, H is more than or equal to 0.0002 percent, T.O is more than or equal to 0.003 percent. The high-alloy corrosion-resistant oil casing material obtained by the method has good CO resistance through economic chemical component design and control of key preparation process parameters2Corrosion and sulfide stress corrosion resistance,and greatly simplifies the process flow of the traditional preparation of the high-alloy corrosion-resistant oil sleeve material and greatly reduces the manufacturing cost.

Description

High-alloy corrosion-resistant oil sleeve material and preparation method thereof
Technical Field
The invention relates to the technical field of oil casing material manufacturing, in particular to a high-alloy corrosion-resistant oil casing material and a preparation method thereof.
Background
According to the prediction of international authorities, the worldwide oil demand is increased by 1.6 percent in 2030 years, and 57.69 hundred million tons in 2030 years are reached; the demand of natural gas increases by 2.4% every year, and 42.03 hundred million tons of oil equivalent is reached in 2030. With the rapid increase of the demand of petroleum and natural gas, the drilling and production of oil and gas fields in China are being correctedThe oil and gas in many oil fields are highly corrosive oil and gas containing carbon dioxide and hydrogen sulfide corrosive medium, such as H in oil and gas fields in the east of Chuandong2S content up to 15% -18%, CO2The content is as high as 10 percent. The corrosion problem is a main obstacle for restricting safe, stable and efficient production, storage and transportation of the petroleum industry in China at present. The loss of petroleum and petrochemical industry in China due to corrosion accounts for about 6% of the output value of the petroleum industry, and the failure rate of oil-gas pipes due to corrosion can reach 70%. The leakage of crude oil and natural gas caused by corrosion in the processes of oil and gas exploitation, storage and transportation can also cause environmental pollution, and the large-scale leakage can also cause very serious catastrophic results.
API-13Cr martensitic stainless steel (API 5CT L80-13Cr) pipe is listed as a representative oil well pipe suitable for being used in a wet carbon dioxide environment by the American Petroleum institute, and has relatively excellent carbon dioxide corrosion resistance. However, API-13Cr stainless steel pipes are more than 100 ℃ or CO at temperatures2When the content is relatively high, the corrosion resistance is drastically reduced and sulfide stress corrosion resistance is not exhibited. The super 13Cr martensitic stainless steel is an improved 13Cr stainless steel developed by greatly reducing the C content and adding alloy elements such as Ni, Mo, Cu and the like on the basis of the traditional API-13Cr stainless steel. Compared with the traditional API-13Cr stainless steel, the super 13Cr stainless steel has lower carbon content and higher content of alloy elements, and is added with a proper amount of Ni, Mo and other elements, thereby resisting CO2、H2S and Cl-The corrosion performance of the oil well is better, and the oil well can be applied to a more severe oil well environment. However, the alloy content of the super 13Cr stainless steel is high, the cost is high, and the preparation difficulty is large. Therefore, the research and development of the CO-resistant material with simple manufacturing process, low production cost and CO resistance2The high-alloy corrosion-resistant oil casing material with excellent corrosion performance and better sulfide stress corrosion resistance has very important significance for the development of oil and gas fields containing corrosive gas.
Disclosure of Invention
Aiming at the problems of the existing products, the invention provides an economical high-alloy corrosion-resistant oil sleeve material and an economical high-alloy corrosion-resistant oil sleeve materialA method for preparing the same and simultaneously has excellent CO resistance2Corrosion and sulfide stress corrosion resistance.
In order to solve the technical problem, the embodiment of the invention provides the following technical scheme:
a high-alloy corrosion-resistant oil casing material comprises the following components in percentage by weight: c is more than or equal to 0.18 percent and less than or equal to 0.22 percent, Si is more than or equal to 0.40 percent and less than or equal to 0.4 percent and less than or equal to 0.6 percent, Cr is more than or equal to 12.2 percent and less than or equal to 13.2 percent, V is more than or equal to 0.12 percent and less than or equal to 0.06 percent, N is more than or equal to 0.03 percent and less than or equal to 0.05 percent, H is more than or equal to 0.0002 percent, T.O is more than or equal to 0.003 percent.
Compared with the prior art, the alloying cost is obviously reduced on the premise that the toughness, the strength and the corrosion resistance comprehensive performance of the high-alloy corrosion-resistant oil sleeve material are good by selectively adding V and N for alloying and accurately controlling the precipitation of VN to refine grains and strengthen tissues on the basis of the chemical components of the traditional 2Cr13 martensitic stainless steel. The mechanical property of the high-alloy corrosion-resistant oil casing material meets the requirement of API Spec 5CT standard on 110KSI steel grade products, the yield strength is 762-832MPa, the tensile strength is 932-997MPa, the elongation after fracture is 15.6-17.2 percent, the transverse full-size Charpy impact energy at 0 ℃ is 62-83J, the temperature can be 100 ℃, the total pressure is 30MPa, and CO can be used for treating the corrosion-resistant oil casing material at the temperature of 100 ℃, the total pressure is 30MPa2Partial pressure 1MPa, Cl-Concentration: 17495mg/L, Na++K+Concentration: 11350mg/L, HCO3 -1312mg/L、SO4 2-1663mg/L is used in a severe corrosive environment, can meet the oil field requirements of the severe corrosive environment, and has wide market prospect.
The invention also provides a high-alloy corrosion-resistant oil casing material which comprises the following components in percentage by weight: c is more than or equal to 0.18 percent and less than or equal to 0.22 percent, Si is more than or equal to 0.40 percent and less than or equal to 0.4 percent and less than or equal to 0.6 percent, Cr is more than or equal to 12.2 percent and less than or equal to 13.2 percent, V is more than or equal to 0.12 percent and less than or equal to 0.06 percent, N is more than or equal to 0.03 percent and less than or equal to 0.05 percent, Ce is more than or equal to 0.01 percent and less than or equal to 0.05 percent, H is less than or equal to 0.0002 percent, T.O.
Compared with the high-alloy corrosion-resistant oil casing material without the Ce element, after the Ce element is added, the structure is more uniform and fine, the crystal boundary is purified and strengthened, the toughness and the corrosion resistance of the prepared high-alloy corrosion-resistant oil casing material are further improved, and the high-alloy corrosion-resistant oil casing material with excellent mechanical properties is suitable for being prepared.
In the above composition of the present invention, t.o represents the total oxygen content in the material.
The chemical components are mainly designed based on the following ideas:
c can promote the precipitation of matrix carbide, and the content of martensite in the stainless steel can be increased by high carbon content, so that the strength is improved; however, when the C content of the martensitic stainless steel is too high, CO is contained therein2Etc. the corrosion resistance of stainless steel will deteriorate significantly in corrosive environments. Therefore, the C content is selected to be 0.18% to 0.22%.
Si is an effective deoxidizer, but if added in too large an amount, it will lower the hot workability and toughness of the steel, so the Si content is selected to be 0.25% to 0.40%.
Mn can effectively improve the strength and toughness of steel, but the Mn content is too high, so the Mn-Mn alloy is easy to be subjected to affinity with S in steel, forms MnS inclusions, and is unfavorable for the strength, the toughness and the sulfide stress corrosion cracking resistance. The influence of Mn on the strength and the corrosion resistance of steel is comprehensively considered, and the content of Mn is designed to be 0.40-0.60%.
Cr is capable of forming an oxide film on the surface of a steel pipe and is ensured to contain CO2、Cl-And the like, but the content of ferrite increases, hot workability deteriorates rapidly, and the strength decreases, so the Cr content is selected to be 12.2% to 13.2%.
N can form carbonitride with V and C, refines the crystalline grain through the pinning effect that the carbonitride precipitates, and then improves intensity and corrosion resistance, but, too high N content can reduce toughness and corrosion resistance, and V, N content is controlled to this application to through adding Ce purification grain boundary, not only reduced the influence of N to steel toughness, still further improved steel toughness and corrosion resistance. Therefore, the content of V is selected to be 0.06% -0.12%, the content of N is controlled to be 0.03% -0.05%, and the content of Ce is controlled to be 0.01% -0.05%.
The invention also provides a preparation method of the high-alloy corrosion-resistant oil casing material, which comprises the following steps:
step one, smelting a steel-making raw material in an electric arc furnace, refining a steel ladle, degassing in vacuum, and continuously casting to obtain a continuous casting round billet; after annealing treatment is carried out on the continuous casting round billet, turning treatment is carried out, and then a through hole is drilled in the center of the continuous casting round billet to obtain a pipe billet; the chemical components of the continuous casting round billet are the same as those of the high-alloy corrosion-resistant oil sleeve material;
step two, heating the tube blank by an annular furnace, perforating to prepare a tubular billet, rolling the tubular billet to obtain a pierced billet, and cooling the pierced billet by a micro-tension reducing and stepping cooling bed to obtain a rolled steel tube;
and step three, carrying out heat treatment on the rolled steel pipe to obtain the high-alloy corrosion-resistant oil casing material.
In the prior art, the 13Cr stainless steel oil casing pipe is manufactured by adopting a 'two-fire forming process', namely, molten steel is manufactured into a continuous casting billet or a die cast ingot, then is manufactured into a round bar by rolling or forging, and then the round bar is heated and rolled by a ring furnace to obtain a rolled steel pipe, so that the manufacturing process is complex and the production cost is high. According to the invention, the tube blank with the through hole drilled in the center is directly heated and rolled to obtain the rolled steel tube, so that one-shot forming is realized, the production process is simplified, the production cost is reduced, the problem of poor surface quality of the steel tube is solved, and the yield is improved.
According to the invention, the high-alloy corrosion-resistant oil casing material with excellent comprehensive performance and low cost is successfully prepared by strictly controlling the content of each chemical component in the material and the process parameters of the preparation process.
Optionally, the steelmaking raw materials comprise alloy and scrap steel, wherein the scrap steel accounts for 85-89 wt% of the total steelmaking raw materials.
Preferably, in the heat treatment step, the rolled steel pipe is heated to 980-.
The rolled steel pipe is heated to the temperature of 980-1020 ℃ in a high-temperature heating furnace, so that the quantity of martensite nucleation can be increased, and the residual austenite structure is reduced, thereby improving the toughness and the corrosion resistance of the steel. The mechanical property and the corrosion resistance of the steel are not improved when the heating temperature is too low or too high.
Heat treatment at 650-720 ℃ is beneficial to improving the toughness and the corrosion resistance of the steel pipe.
Preferably, in the heat treatment process, the heat preservation time in the high-temperature heating furnace is 10-20min, and the heat preservation time in the low-temperature heating furnace is 30-60 min.
The invention selects a heat treatment mode of heat preservation for 10-20min at the temperature of 980-.
Preferably, in the heat treatment step, the openings at both ends of the rolled steel pipe are plugged by plugs, and then the rolled steel pipe is heated in a high-temperature heating furnace.
The preferable high-temperature heat treatment mode of the steel pipe is beneficial to reducing the oxidation of the inner surface of the steel pipe and improving the surface quality of the steel pipe.
Preferably, in the smelting process of the electric arc furnace, the end point carbon content of the electric arc furnace is controlled to be 0.07-0.12%, and the tapping temperature is controlled to be more than or equal to 1640 ℃.
By controlling the carbon content in the molten steel and the temperature of the molten steel, the molten steel can be prevented from being over-oxidized, the metal yield in the production process is improved, and the inclusion in the molten steel is effectively reduced.
Preferably, in the ladle refining process, 80-100kg/t of micro-carbon ferrochrome is added into a ladle in advance, an oxygen burning gun is used for heating the micro-carbon ferrochrome to 900-.
The step of preheating the alloy is added before the molten steel in the electric arc furnace is transferred to a refining ladle, so that the burden of heating and raising the temperature of a large amount of alloy added in a refining process is relieved, the time for refining and removing impurities can be prolonged, and the cleanliness of the molten steel is improved; secondly, the water in the alloy can be removed, which is beneficial to reducing the hydrogen content in the molten steel, thereby improving the corrosion resistance of the material; thirdly, the production rhythm can be improved, thereby reducing the gas suction and oxidation of the molten steel in the refining process to a certain extent.
Preferably, in the annealing process, when the temperature of the continuous casting round billet is more than or equal to 500 ℃, the cooling speed is controlled to be 20-40 ℃/h.
When the temperature of the continuous casting round billet is more than or equal to 500 ℃, the cooling speed is controlled to be 20-40 ℃/h, and the round billet can be effectively prevented from cracking.
Preferably, in the heating procedure of the annular furnace, the heating temperature of the tube blank is controlled to 1180-1260 ℃, and the heating time of the tube blank in the annular furnace is controlled to 120-180 min.
The optimal heating temperature is beneficial to smooth proceeding of a subsequent perforation process, is also beneficial to reducing precipitation of ferrite, and is beneficial to improving the corrosion resistance and the impact toughness of the material.
Preferably, in the piercing step, the bite speed is controlled to be 0.45-0.55m/s, and the rolling line speed is controlled to be 0.55-0.65 m/s.
Preferably, the plug material used in the piercing step has chemical composition weight ratios of C less than or equal to 0.3%, Mn less than or equal to 1%, Cr less than or equal to 1%, Ni less than or equal to 0.9% and less than or equal to 1.1%, Mo less than or equal to 1.3% and less than or equal to 1.7%, Mo less than or equal to 2.8% and less than or equal to 3.2%, and Co less than or equal to 0.9% and less than or equal to 1.1%.
The optimized steel biting speed and rolling line speed are favorable for reducing the axial resistance of the top head, and the problems of sticking, internal folding and layering of the capillary can be effectively avoided by matching the optimized top head, so that the surface quality and the yield of the steel pipe are greatly improved.
Preferably, in the first step, the diameter of the through hole is 47-53 mm.
According to the invention, the through hole with the diameter of 47-53mm is drilled in the center of the continuous casting round billet, so that the influence of the center crack and center porosity of the continuous casting round billet on the quality of the inner surface of the steel pipe can be eliminated, and the yield and the surface quality of the steel pipe are improved.
Preferably, the time interval between the second step and the third step is 0-20 h.
The preferable interval time between the second step and the third step can effectively avoid the generation of steel pipe cracks, and improve the surface quality and the yield of the steel pipe.
Adopt the produced beneficial effect of above-mentioned technical scheme to lie in:
(1) the manufacturing of the pipe blank adopts a 'one-shot forming' process, the influence of central cracks and central looseness of the continuous casting round blank on the quality of the inner surface of the steel pipe is eliminated by drilling the through hole in the center of the continuous casting round blank, the manufacturing process is simplified, and the production cost is reduced.
(2) The method adopts unique chemical composition design and a smelting process, so that the purity of the molten steel is high, the T.O is less than or equal to 0.003 percent, and the H is less than or equal to 0.0002 percent, and the corrosion resistance of the material is obviously improved.
(3) The surface quality and the yield of the steel pipe are greatly improved by controlling the rolling temperature and the rolling speed in the rolling process.
(4) The steel pipe has good surface quality and corrosion resistance by adopting a unique heat treatment process.
Drawings
FIG. 1 is a metallographic structure diagram of a high alloy corrosion-resistant oil jacket material prepared in example 1 of the present invention;
FIG. 2 is a metallographic structure diagram of a high-alloy corrosion-resistant oil casing material prepared in example 2 of the present invention;
FIG. 3 is a metallographic structure diagram of a high alloy corrosion-resistant oil casing material prepared in example 3 of the present invention;
fig. 4 is a metallographic structure diagram of a high alloy corrosion-resistant oil jacket material prepared in example 4 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In order to better illustrate the invention, the following examples are given by way of further illustration.
Example 1
The embodiment of the invention provides a high-alloy corrosion-resistant oil casing material which comprises the following chemical components:
0.2% of C, 0.3% of Si, 0.5% of Mn, 13% of Cr, 0.09% of V, 0.04% of N, 0.0002% of H, 0.0025% of T.O, and the balance of Fe and inevitable impurities.
The preparation steps of the high-alloy corrosion-resistant oil casing material are as follows:
(1) using scrap steel as a main raw material, and preparing a continuous casting round billet with the diameter of phi 180mm, which has the same chemical components as the high-alloy corrosion-resistant oil sleeve material, through 80t electric arc furnace smelting, ladle refining, VD vacuum degassing and continuous casting processes; after annealing treatment, turning the surface of the continuous casting round billet, and then drilling a through hole with the diameter of 47-53mm in the center of the continuous casting round billet to obtain a pipe blank;
wherein, the end point carbon content in the smelting procedure of the electric arc furnace is controlled to be 0.07 percent, and the tapping temperature is 1650 ℃;
in the ladle refining process, before the ladle is connected with the molten steel of the electric arc furnace, 90kg/t of micro-carbon ferrochrome is added into the ladle, an oxygen burning gun is used for heating the micro-carbon ferrochrome to 900 ℃, and then the molten steel in the electric arc furnace is added into the ladle and is uniformly mixed for refining;
in the annealing treatment process, when the temperature of the continuous casting round billet is above 550 ℃, the cooling speed is controlled to be 20 ℃/h;
(2) heating and perforating the tube blank by using an annular furnace to prepare a capillary tube with the outer diameter of 208-;
in the heating procedure of the annular furnace, the heating temperature of the tube blank is controlled to be 1240 ℃, and the heating time of the tube blank in the annular furnace is controlled to be 150 min;
in the punching process, the biting steel speed is controlled to be 0.45m/s, the rolling line speed is controlled to be 0.55m/s, and the adopted plug material comprises the following chemical components in percentage by weight: less than or equal to 0.3 percent of C, less than or equal to 1 percent of Mn, less than or equal to 1 percent of Cr, less than or equal to 1.1 percent of Ni, less than or equal to 1.7 percent of Mo, less than or equal to 3.2 percent of Mo, more than or equal to 2.8 percent of Mo, less than or equal to 1.1 percent of Co, more than or equal to 0.9 percent of Co;
(3) heating the rolled steel pipe to 980 ℃ in a high-temperature heating furnace, preserving heat for 20min, then carrying out air cooling, heating the steel pipe to 650 ℃ in a low-temperature heating furnace, preserving heat for 60min, and then carrying out air cooling to obtain a high-alloy corrosion-resistant oil sleeve material;
before heating in a high-temperature heating furnace, plugging two end openings of the rolled steel pipe by using heat-insulating cotton plugs, and then putting the steel pipe into the high-temperature heating furnace for heating;
the time interval between the step (2) and the step (3) is less than 20 hours.
The metallographic structure of the high-alloy corrosion-resistant oil casing material prepared in this example is a uniform tempered sorbite, as shown in fig. 1.
The yield strength, tensile strength, elongation and transverse impact energy of the high alloy corrosion-resistant oil jacket material prepared in example 1 were arbitrarily sampled and analyzed according to the standard requirements of API 5CT version 10, and the statistical analysis results are shown in table 1. The number of samples in the figure is the number of the taken high-alloy corrosion-resistant oil casing materials, and a random sampling mode is adopted.
TABLE 1 statistical table of mechanical properties of the samples of example 1
Inspection item Number of samples Minimum value Maximum value Mean value of Standard deviation of
Yield strength/MPa 48 762 832 797 15.2
Tensile strength/MPa 48 932 997 965 13.2
Elongation/percent 48 15.6 17.2 16.2 1.5
Charpy impact work/J 48 62 83 72.1 5.2
As can be seen from the table above, the yield strength of the high-alloy corrosion-resistant oil casing material prepared by the method is 762-832MPa, the tensile strength is 932-997MPa, the elongation is 15.6-17.2%, and the transverse full-size Charpy impact energy at 0 ℃ is 62-83J. Wherein the average value of the yield strength is 797MPa, and the standard deviation is 15.2 MPa; the average value of the tensile strength is 965MPa, and the standard deviation is 13.2 MPa; the average elongation value is 16.2 percent, and the standard deviation is 1.5 percent; the average value of the transverse full-size Charpy impact energy at 0 ℃ is 72.1J, and the standard deviation is 5.2J.
The oil jacket material prepared in this example was placed in an autoclave for corrosion test, and the composition of the corrosion solutionThe method comprises the following steps: na (Na)++K+11350mg/L、Cl-17495mg/L、HCO3 -1312mg/L、SO4 2-1663mg/L, flow rate of 1.5m/s, test temperature of 100 deg.C, test time of 168h, total gas pressure of 30MPa, CO2The partial pressure of (A) was 1MPa, and the measured corrosion rate was 0.0482 mm/a. The oil jacket material obtained in example 1 was subjected to a sulfide stress cracking performance evaluation test in accordance with NACE TM0177-2005 standard, and a stress corrosion test was carried out by method A (Standard tensile method) at a test solution pH of 3.5 and H2The partial pressure of S was 3kPa, the stress was 606.4MPa, and after 720 hours, the tensile surface of the sample was observed with a microscope having a magnification of X10, and no crack was observed.
Example 2
The embodiment of the invention provides a high-alloy corrosion-resistant oil casing material which comprises the following chemical components:
0.18% of C, 0.35% of Si, 0.6% of Mn, 12.2% of Cr, 0.06% of V, 0.03% of N, 0.05% of Ce, 0.0002% of H, 0.0025% of T.O, and the balance of Fe and inevitable impurities.
The preparation steps of the high-alloy corrosion-resistant oil casing material are as follows:
(1) using scrap steel as a main raw material, and preparing a continuous casting round billet with the diameter of phi 180mm, which has the same chemical components as the high-alloy corrosion-resistant oil sleeve material, through 80t electric arc furnace smelting, ladle refining, VD vacuum degassing and continuous casting processes; after annealing treatment, turning the surface of the continuous casting round billet, and then drilling a through hole with the diameter of 47-53mm in the center of the continuous casting round billet to obtain a pipe blank;
wherein, the end point carbon content in the smelting process of the electric arc furnace is controlled to be 0.12 percent, and the tapping temperature is 1645 ℃;
in the ladle refining procedure, before the ladle is connected with the molten steel of the electric arc furnace, 95kg/t of micro-carbon ferrochrome is added into the ladle, an oxygen burning gun is used for heating the micro-carbon ferrochrome to 950 ℃, and then the molten steel in the electric arc furnace is added into the ladle and is uniformly mixed for refining;
in the annealing treatment process, when the temperature of the continuous casting round billet is above 550 ℃, the cooling speed is controlled to be 35 ℃/h;
(2) heating and perforating the tube blank by using an annular furnace to prepare a capillary tube with the outer diameter of 208-;
in the heating process of the annular furnace, the heating temperature of the tube blank is controlled to be 1200 ℃, and the heating time of the tube blank in the annular furnace is controlled to be 140 min;
in the punching process, the biting steel speed is controlled to be 0.5m/s, the rolling linear speed is controlled to be 0.6m/s, and the adopted plug material comprises the following chemical components in percentage by weight: less than or equal to 0.3 percent of C, less than or equal to 1 percent of Mn, less than or equal to 1 percent of Cr, less than or equal to 1.1 percent of Ni, less than or equal to 1.7 percent of Mo, less than or equal to 3.2 percent of Mo, more than or equal to 2.8 percent of Mo, less than or equal to 1.1 percent of Co, more than or equal to 0.9 percent of Co;
(3) heating the rolled steel pipe to 1000 ℃ in a high-temperature heating furnace, preserving heat for 15min, then carrying out air cooling, heating the steel pipe to 680 ℃ in a low-temperature heating furnace, preserving heat for 50min, and then carrying out air cooling to obtain a high-alloy corrosion-resistant oil sleeve material;
before heating in a high-temperature heating furnace, plugging two end openings of the rolled steel pipe by using heat-insulating cotton plugs, and then putting the steel pipe into the high-temperature heating furnace for heating;
the time interval between the step (2) and the step (3) is less than 20 hours.
The metallographic structure of the high-alloy corrosion-resistant oil casing material prepared in this example is a uniform tempered sorbite, as shown in fig. 2.
The yield strength, tensile strength, elongation and transverse impact energy of the high alloy corrosion-resistant oil jacket material prepared in example 2 were arbitrarily sampled and analyzed according to the standard requirements of API 5CT version 10, and the statistical analysis results are shown in table 2. The number of samples in the figure is the number of the taken high-alloy corrosion-resistant oil casing materials, and a random sampling mode is adopted.
Table 2 statistical table of mechanical properties of samples of example 2
Inspection item Number of samples Minimum value Maximum value Mean value of Standard deviation of
Yield strength/MPa 35 580 630 605.2 13.2
Tensile strength/MPa 35 760 815 795.2 11.3
Elongation/percent 35 16.3 18.3 17.2 1.2
Charpy impact work/J 35 98 115 106.2 4.1
As can be seen from the table above, the yield strength of the high-alloy corrosion-resistant oil casing material prepared by the method is 580-630MPa, the tensile strength is 760-815MPa, the elongation is 16.3-18.3%, and the transverse full-size Charpy impact energy at 0 ℃ is 98-115J. Wherein the average value of the yield strength is 605.2MPa, and the standard deviation is 13.2 MPa; the average value of the tensile strength is 795.2MPa, and the standard deviation is 11.3 MPa; the average elongation is 17.2%, and the standard deviation is 1.2%; the average value of transverse full-scale Charpy impact energy at 0 ℃ is 106.2J, and the standard deviation is 4.1J.
The oil casing material prepared in this example was placed in an autoclave for corrosion testing, and the corrosion solution had the following composition: na (Na)++K+11350mg/L、Cl-17495mg/L、HCO3 -1312mg/L、SO4 2-1663mg/L, flow rate of 1.5m/s, test temperature of 100 deg.C, test time of 168h, total gas pressure of 30MPa, CO2The partial pressure of (A) was 1MPa, and the measured corrosion rate was 0.0386 mm/a. The oil jacket material obtained in example 2 was subjected to a sulfide stress cracking performance evaluation test in accordance with NACE TM0177-2005 standard, and a stress corrosion test was carried out by method A (Standard tensile method) at a test solution pH of 3.5 and H2The partial pressure of S was 10kPa, the stress was 441.6MPa, and after 720 hours, the tensile surface of the sample was observed with a microscope having a magnification of X10, and no crack was observed.
Example 3
The embodiment of the invention provides a high-alloy corrosion-resistant oil casing material which comprises the following chemical components:
0.20% of C, 0.25% of Si, 0.4% of Mn, 13% of Cr, 0.12% of V, 0.05% of N, 0.03% of Ce, 0.0002% of H, 0.002% of T.O, and the balance of Fe and inevitable impurities.
The preparation steps of the high-alloy corrosion-resistant oil casing material are as follows:
(1) using scrap steel as a main raw material, and preparing a continuous casting round billet with the diameter of phi 180mm, which has the same chemical components as the high-alloy corrosion-resistant oil sleeve material, through 80t electric arc furnace smelting, ladle refining, VD vacuum degassing and continuous casting processes; after annealing treatment, turning the surface of the continuous casting round billet, and then drilling a through hole with the diameter of 47-53mm in the center of the continuous casting round billet to obtain a pipe blank;
wherein, the end point carbon content in the smelting process of the electric arc furnace is controlled to be 0.08 percent, and the tapping temperature is 1645 ℃;
in the ladle refining process, 80kg/t of micro-carbon ferrochrome is added into a ladle before the ladle is connected with molten steel of an electric arc furnace, an oxygen burning gun is used for heating the micro-carbon ferrochrome to 950 ℃, and then the molten steel in the electric arc furnace is added into the ladle and mixed uniformly for refining;
in the annealing treatment process, when the temperature of the continuous casting round billet is above 550 ℃, the cooling speed is controlled to be 30 ℃/h;
(2) heating and perforating the tube blank by using an annular furnace to prepare a capillary tube with the outer diameter of 208-;
in the heating procedure of the annular furnace, the heating temperature of the tube blank is controlled to be 1260 ℃, and the heating time of the tube blank in the annular furnace is controlled to be 120 min;
in the punching process, the biting steel speed is controlled to be 0.5m/s, the rolling line speed is controlled to be 0.65m/s, and the adopted plug material comprises the following chemical components in percentage by weight: less than or equal to 0.3 percent of C, less than or equal to 1 percent of Mn, less than or equal to 1 percent of Cr, less than or equal to 1.1 percent of Ni, less than or equal to 1.7 percent of Mo, less than or equal to 3.2 percent of Mo, more than or equal to 2.8 percent of Mo, less than or equal to 1.1 percent of Co, more than or equal to 0.9 percent of Co;
(3) heating the rolled steel pipe to 1020 ℃ in a high-temperature heating furnace, preserving heat for 10min, then carrying out air cooling, heating the steel pipe to 720 ℃ in a low-temperature heating furnace, preserving heat for 30min, and then carrying out air cooling to obtain a high-alloy corrosion-resistant oil sleeve material;
before heating in a high-temperature heating furnace, plugging two end openings of the rolled steel pipe by using heat-insulating cotton plugs, and then putting the steel pipe into the high-temperature heating furnace for heating;
the time interval between the step (2) and the step (3) is less than 20 hours.
The metallographic structure of the high-alloy corrosion-resistant oil casing material prepared in this example is a uniform tempered sorbite, as shown in fig. 3.
The yield strength, tensile strength, elongation, and transverse impact energy of the high alloy corrosion-resistant oil jacket material prepared in example 3 were arbitrarily sampled and analyzed according to the standard requirements of API 5CT version 10, and the statistical analysis results are shown in table 3. The number of samples in the figure is the number of the taken high-alloy corrosion-resistant oil casing materials, and a random sampling mode is adopted.
Table 3 statistical table of mechanical properties of samples of example 3
Figure BDA0002638407690000131
Figure BDA0002638407690000141
As can be seen from the above table, the yield strength of the high-alloy corrosion-resistant oil casing material prepared by the method is 770-820MPa, the tensile strength is 945-990MPa, the elongation is 16.3-18.4%, and the transverse full-size Charpy impact energy at 0 ℃ is 80-100J. Wherein the average value of the yield strength is 795.2MPa, and the standard deviation is 13.5 MPa; the average value of the tensile strength is 967.2MPa, and the standard deviation is 9.5 MPa; the average elongation value is 17.5 percent, and the standard deviation is 1.3 percent; the average value of the transverse full-size Charpy impact energy at 0 ℃ is 90.2J, and the standard deviation is 4.7J.
The oil casing material prepared in this example was placed in an autoclave for corrosion testing, and the corrosion solution had the following composition: na (Na)++K+11350mg/L、Cl-17495mg/L、HCO3 -1312mg/L、SO4 2-1663mg/L, flow rate of 1.5m/s, test temperature of 100 deg.C, test time of 168h, total gas pressure of 30MPa, CO2The partial pressure of (A) was 1MPa, and the measured corrosion rate was 0.0358 mm/a. EXAMPLES according to NACE TM0177-2005 Standard3, performing a sulfide stress cracking performance evaluation test on the prepared oil sleeve material, performing a stress corrosion test by adopting a method A (standard stretching method), wherein the pH value of a test solution is 3.5, and H is2The partial pressure of S was 10kPa, the stress was 606.4MPa, and after 720 hours, the tensile surface of the sample was observed with a microscope having a magnification of X10, and no crack was observed.
Example 4
The embodiment of the invention provides a high-alloy corrosion-resistant oil casing material which comprises the following chemical components:
0.22% of C, 0.40% of Si, 0.5% of Mn, 13.2% of Cr, 0.08% of V, 0.04% of N, 0.01% of Ce, 0.0002% of H, 0.002% of T.O, and the balance of Fe and inevitable impurities.
The preparation steps of the high-alloy corrosion-resistant oil casing material are as follows:
(1) using scrap steel as a main raw material, and preparing a continuous casting round billet with the diameter of phi 180mm, which has the same chemical components as the high-alloy corrosion-resistant oil sleeve material, through 80t electric arc furnace smelting, ladle refining, VD vacuum degassing and continuous casting processes; after annealing treatment, turning the surface of the continuous casting round billet, and then drilling a through hole with the diameter of 47-53mm in the center of the continuous casting round billet to obtain a pipe blank;
wherein, the end point carbon content in the smelting process of the electric arc furnace is controlled to be 0.09 percent, and the tapping temperature is 1650 ℃;
in the ladle refining process, before the ladle is connected with the molten steel of the electric arc furnace, 100kg/t of micro-carbon ferrochrome is added into the ladle, an oxygen burning gun is used for heating the micro-carbon ferrochrome to 1000 ℃, and then the molten steel in the electric arc furnace is added into the ladle and is uniformly mixed for refining;
in the annealing treatment process, when the temperature of the continuous casting round billet is above 550 ℃, the cooling speed is controlled to be 40 ℃/h;
(2) heating and perforating the tube blank by using an annular furnace to prepare a capillary tube with the outer diameter of 208-;
in the heating procedure of the annular furnace, the heating temperature of the tube blank is controlled to be 1180 ℃, and the heating time of the tube blank in the annular furnace is controlled to be 180 min;
in the punching process, the biting steel speed is controlled to be 0.55m/s, the rolling linear speed is controlled to be 0.6m/s, and the adopted plug material comprises the following chemical components in percentage by weight: less than or equal to 0.3 percent of C, less than or equal to 1 percent of Mn, less than or equal to 1 percent of Cr, less than or equal to 1.1 percent of Ni, less than or equal to 1.7 percent of Mo, less than or equal to 3.2 percent of Mo, more than or equal to 2.8 percent of Mo, less than or equal to 1.1 percent of Co, more than or equal to 0.9 percent of Co;
(3) heating the rolled steel pipe to 1000 ℃ in a high-temperature heating furnace, preserving heat for 15min, then carrying out air cooling, heating the steel pipe to 700 ℃ in a low-temperature heating furnace, preserving heat for 40min, and then carrying out air cooling to obtain a high-alloy corrosion-resistant oil sleeve material;
before heating in a high-temperature heating furnace, plugging two end openings of the rolled steel pipe by using heat-insulating cotton plugs, and then putting the steel pipe into the high-temperature heating furnace for heating;
the time interval between the step (2) and the step (3) is less than 20 hours.
The metallographic structure of the high-alloy corrosion-resistant oil casing material prepared in this example was a uniform tempered sorbite, as shown in fig. 4.
The yield strength, tensile strength, elongation, and transverse impact energy of the high alloy corrosion-resistant oil jacket material prepared in example 4 were arbitrarily sampled and analyzed according to the standard requirements of API 5CT version 10, and the statistical analysis results are shown in table 4. The number of samples in the figure is the number of the taken high-alloy corrosion-resistant oil casing materials, and a random sampling mode is adopted.
Table 4 statistical table of mechanical properties of samples of example 4
Inspection item Number of samples Minimum value Maximum value Mean value of Standard deviation of
Yield strength/MPa 51 685 735 710.3 14.2
Tensile strength/MPa 51 850 892 871.2 10.3
Elongation/percent 51 16.5 18.9 17.7 1.4
Charpy impact work/J 51 80 100 88.1 4.8
As can be seen from the above table, the yield strength of the high-alloy corrosion-resistant oil casing material prepared by the method is 685-minus 735MPa, the tensile strength is 850-minus 892MPa, the elongation is 16.5-18.9%, and the transverse full-size Charpy impact energy at 0 ℃ is 80-100J. Wherein the average value of the yield strength is 710.3MPa, and the standard deviation is 14.2 MPa; the average value of the tensile strength is 871.2MPa, and the standard deviation is 10.3 MPa; the average elongation value is 17.1 percent, and the standard deviation is 1.4 percent; the average value of transverse full-size Charpy impact energy at 0 ℃ is 88.1J, and the standard deviation is 5.4J.
The oil casing material prepared in this example was placed in an autoclave for corrosion testing, and the corrosion solution had the following composition: na (Na)++K+11350mg/L、Cl-17495mg/L、HCO3 -1312mg/L、SO4 2-1663mg/L, flow rate of 1.5m/s, test temperature of 100 deg.C, test time of 168h, total gas pressure of 30MPa, CO2The partial pressure of (A) was 1MPa, and the measured corrosion rate was 0.0372 mm/a.
The oil jacket material obtained in example 4 was subjected to a sulfide stress cracking performance evaluation test in accordance with NACE TM0177-2005 standard, and a stress corrosion test was carried out by method A (Standard tensile method) at a test solution pH of 3.5 and H2The partial pressure of S was 10kPa and the load stress was 524MPa, and after 720 hours, the tensile surface of the sample was observed with a microscope having a magnification of X10, and no crack was observed.
Random sampling is carried out on the oil casings prepared in the examples 1-4, and flaw detection is carried out according to the GB/T4162 standard, and the results show that the quality grades of the oil casings prepared in the examples 1-4 can reach the B grade.
The steelmaking materials of examples 1-4 above include alloys and scrap steel, wherein the scrap steel comprises 85-89 wt% of the total steelmaking material
Therefore, the high-alloy corrosion-resistant oil casing material prepared by the method has the advantages of uniform chemical components, low content of harmful elements, fine microstructure, reliable mechanical property and excellent corrosion resistance, can be widely used for exploiting corrosive oil and gas fields, and has wide market prospect.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (10)

1. The high-alloy corrosion-resistant oil casing material is characterized by comprising the following components in percentage by weight: c is more than or equal to 0.18 percent and less than or equal to 0.22 percent, Si is more than or equal to 0.40 percent and less than or equal to 0.4 percent and less than or equal to 0.6 percent, Cr is more than or equal to 12.2 percent and less than or equal to 13.2 percent, V is more than or equal to 0.12 percent and less than or equal to 0.06 percent, N is more than or equal to 0.03 percent and less than or equal to 0.05 percent, H is more than or equal to 0.0002 percent, T.O is more than or equal to 0.003 percent.
2. The high-alloy corrosion-resistant oil casing material is characterized by comprising the following components in percentage by weight: c is more than or equal to 0.18 percent and less than or equal to 0.22 percent, Si is more than or equal to 0.40 percent and less than or equal to 0.4 percent and less than or equal to 0.6 percent, Cr is more than or equal to 12.2 percent and less than or equal to 13.2 percent, V is more than or equal to 0.12 percent and less than or equal to 0.06 percent, N is more than 0.03 percent and less than or equal to 0.05 percent, Ce is more than or equal to 0.01 percent and less than or equal to 0.05 percent, H is less than or equal to 0.0002 percent, T.O is less.
3. A method for preparing the high alloy corrosion resistant oil jacket material according to claim 1 or 2, comprising the steps of:
step one, smelting a steel-making raw material in an electric arc furnace, refining a steel ladle, degassing in vacuum, and continuously casting to obtain a continuous casting round billet; after annealing treatment is carried out on the continuous casting round billet, turning treatment is carried out, and then a through hole is drilled in the center of the continuous casting round billet to obtain a pipe billet;
step two, heating the tube blank by an annular furnace, perforating to prepare a tubular billet, rolling the tubular billet to obtain a pierced billet, and cooling the pierced billet by a micro-tension reducing and stepping cooling bed to obtain a rolled steel tube;
and step three, carrying out heat treatment on the rolled steel pipe to obtain the high-alloy corrosion-resistant oil casing material.
4. The method for preparing the high alloy corrosion-resistant oil casing material according to claim 3, wherein in the heat treatment step, the rolled steel pipe is heated to 980-1020 ℃ in a high temperature heating furnace and then is heat-preserved, and then is air-cooled, and then the steel pipe is heated to 650-720 ℃ in a low temperature heating furnace and then is heat-preserved, and then is air-cooled.
5. The method for preparing a high alloy corrosion resistant oil jacket material according to claim 4, wherein in the heat treatment process, the holding time in the high temperature heating furnace is 10-20min, and the holding time in the low temperature heating furnace is 30-60 min.
6. The method for preparing a high alloy corrosion resistant oil jacket material according to claim 4, wherein in the heat treatment step, the openings at both ends of the rolled steel pipe are plugged by plugs and then heated in a high temperature heating furnace.
7. The method for preparing the high-alloy corrosion-resistant oil casing material according to claim 3, wherein in the smelting process of the electric arc furnace, the end-point carbon content of the electric arc furnace is controlled to be 0.07-0.12%, and the tapping temperature is controlled to be more than or equal to 1640 ℃; and/or
In the ladle refining process, 80-100kg/t of micro-carbon ferrochrome is added into a ladle in advance, an oxygen burning gun is used for heating the micro-carbon ferrochrome to 900-1000 ℃, and then molten steel in an electric arc furnace is added into the ladle to be uniformly mixed for refining.
8. The method for preparing the high-alloy corrosion-resistant oil bushing material according to claim 3, wherein in the annealing process, when the temperature of the continuous casting round billet is more than or equal to 500 ℃, the cooling speed is controlled to be 20-40 ℃/h; and/or
In the heating procedure of the annular furnace, the heating temperature of the tube blank is controlled to be 1180-.
9. The method for preparing a high alloy corrosion resistant oil jacket material according to claim 3, wherein in the piercing process, the bite speed is controlled to 0.45 to 0.55m/s, and the rolling line speed is controlled to 0.55 to 0.65 m/s; and/or
In the first step, the diameter of the through hole is 47-53 mm.
10. The method for preparing a high alloy corrosion resistant oil jacket material according to claim 3, wherein the time interval between the second step and the third step is 0-20 h.
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Publication number Priority date Publication date Assignee Title
CN1861832A (en) * 2005-05-09 2006-11-15 住友金属工业株式会社 Martensitic stainless steel for oil well and its producing method
EP2447386A1 (en) * 2009-06-24 2012-05-02 JFE Steel Corporation High-strength seamless steel tube for use in oil wells, which has excellent resistance to sulfide stress cracking and production method for same
CN105925899A (en) * 2016-07-13 2016-09-07 达力普石油专用管有限公司 Quenched and tempered X52 hydrogen sulfide corrosion resisting seamless line pipe and preparation method thereof
CN110408862A (en) * 2019-08-19 2019-11-05 衡阳华菱钢管有限公司 Seamless steel pipe, manufacturing method and its application

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1861832A (en) * 2005-05-09 2006-11-15 住友金属工业株式会社 Martensitic stainless steel for oil well and its producing method
EP2447386A1 (en) * 2009-06-24 2012-05-02 JFE Steel Corporation High-strength seamless steel tube for use in oil wells, which has excellent resistance to sulfide stress cracking and production method for same
CN105925899A (en) * 2016-07-13 2016-09-07 达力普石油专用管有限公司 Quenched and tempered X52 hydrogen sulfide corrosion resisting seamless line pipe and preparation method thereof
CN110408862A (en) * 2019-08-19 2019-11-05 衡阳华菱钢管有限公司 Seamless steel pipe, manufacturing method and its application

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