CN109082591B - 125ksi hydrogen sulfide stress corrosion resistant high-strength oil casing steel and preparation process thereof - Google Patents
125ksi hydrogen sulfide stress corrosion resistant high-strength oil casing steel and preparation process thereof Download PDFInfo
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Abstract
The invention provides 125ksi hydrogen sulfide stress corrosion resistant high-strength oil casing steel and a preparation process thereof. The steel for the invention comprises the following chemical components (mass percent): c: 0.08-0.27%, Si: 0.1-0.5%, Mn: 0.15-1.8%, Cr: 0.3-1.0%, Mo: 0.4-1.0%, V: 0.05 to 0.4%, Ti: 0.01-0.1%, Cu: 0.1-0.7%, Ni: 0.2-3.0%, B: 0.0001-0.002%, P: 0-0.015%, S: 0-0.010%, O: 0-0.06%, N: 0-0.05%, H: 0 to 0.05 percent, and the balance of Fe and inevitable impurities. Yield strength of the steel grade: 862-1034MPa, and meets the requirement of NACE-A test for resisting hydrogen sulfide stress corrosion of international standard.
Description
Technical Field
The invention relates to a 125ksi grade seamless oil casing steel resisting hydrogen sulfide stress corrosion and a preparation process thereof.
Background
Since the oil well pipe hydrogen sulfide stress corrosion cracking accidents occurred in the oil field of alberta flatcro gulf of canada in the early 50 s of the last century, the hydrogen sulfide stress corrosion cracking accidents occurred in the oil and gas fields of all over the world in succession, and the attention of the oil industry and the steel industry of all over the world was attracted. It has been found that about 1/3 in the world's oil and gas fields contains hydrogen sulfide gas. When the common casing is applied to a sulfur-containing oil and gas field, the common casing can be suddenly broken when the stress is far smaller than the yield strength of the common casing, a light person generates a casing string or a whole well to be scrapped, and a heavy person causes blowout, so that hydrogen sulfide is overflowed along with oil and gas, and the whole drilling machine and surrounding ecology are greatly damaged. With the increasing demand of energy resources, research and development of high-performance hydrogen sulfide stress corrosion resistant oil casings (hereinafter referred to as sulfur-resistant oil well pipes) have attracted high attention from countries in the world.
Oil casing manufacturers in japan and the united states, for example: the research and development work of the sulfur-resistant oil casing is firstly developed by Sumitomo corporation, JFE and V & M in Japan, and 80 ksi-grade, 95 ksi-grade and 110 ksi-grade sulfur-resistant oil casings are successively researched and developed and put into application. Enterprises in China, such as Bao steel, first steel, Tianjin steel pipe factories, south steel, saddle steel and the like, also develop and produce C90, 80SS, BGM65 and other sulfur-resistant oil casings of multiple grades from the last 90 th century, and the sulfur-resistant oil casings of T95 and C110ksi grades are in the stages of development and small-batch trial production at present.
In recent years, with the continuous exhaustion of shallow wells with low corrosivity, the development number of high-pressure deep wells with high corrosivity is increasing, for example, the volume fractions of hydrogen sulfide in south texas and mississippi gas reservoirs in north america are respectively as high as 98% and 78%; the volume fractions of hydrogen sulfide in the Zhaolanzhuang oil-gas reservoir and the Sichuan oil-gas reservoir in North China are respectively as high as 92% and 17%. In addition, with the increasing drilling depth, the partial pressure born by the sulfur-resistant oil casing pipe is higher and higher, and the severe environment factors such as the temperature in the well are considered, so that the research and development of the 125 ksi-level and even higher-level sulfur-resistant oil casing pipe steel becomes an inevitable trend.
The strength of steel and the hydrogen sulfide stress corrosion resistance of the steel are in a relationship of opposite relationship, namely the higher the strength is, the weaker the hydrogen sulfide stress corrosion resistance of the steel is, so that the development of high-strength hydrogen sulfide stress corrosion resistance steel becomes a technical difficulty of the world level. With the continuous and deep research, researchers around the world successively find that the quenched tempered martensite is an ideal hydrogen sulfide stress corrosion resistant structure. Another generally accepted view is that grain refinement, whether beneficial or not from the standpoint of increased strength or increased resistance to hydrogen sulfide stress cracking, is not detrimental. It is also commonly accepted that the morphology and distribution of the second phase in steel strongly affects the hydrogen sulfide stress corrosion resistance of the steel, where long-strip MnS inclusions are often the origin of cracks leading to hydrogen sulfide stress corrosion cracking; in addition, there are also large carbides M precipitated at grain/subgrain boundaries23C6It may be a starting point of a crack.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides 125ksi hydrogen sulfide stress corrosion resistant high-strength oil casing steel and a preparation process thereof, which improve the strength of an oil casing on the basis of meeting the requirement of hydrogen sulfide stress corrosion resistance, enable the strength to reach 125ksi-140ksi, and reduce the manufacturing cost of an oil well pipe.
The invention provides 125ksi hydrogen sulfide stress corrosion resistant high-strength oil casing steel which comprises the following chemical components in percentage by mass: c: 0.08-0.27%, Si: 0.1-0.5%, Mn: 0.15-1.8%, Cr: 0.3-1.0%, Mo: 0.4-1.0%, V: 0.05 to 0.4%, Ti: 0.01-0.1%, Cu: 0.1-0.7%, Ni: 0.2-3.0%, B: 0.0001-0.002%, P: 0-0.015%, S: 0-0.010%, O: 0-0.06%, N: 0-0.05%, H: 0 to 0.05 percent, and the balance of Fe and inevitable impurities.
According to the above technical solution, preferably, the steel for oil casing pipes further comprises the following chemical components in percentage by mass: al: 0-0.005%, Nb: 0-0.2%, Ca: 0-0.008%, Ce: 0-0.03%, Zr: 0.0005-0.01%, REM: 0.003-0.05%, Mg: 0.0005-0.02% of one or more of the above. Namely, Al: 0-0.005%, Nb: 0-0.2%, Ca: 0-0.008%, Ce: 0-0.03%, Zr: 0.0005-0.01%, REM: 0.003-0.05%, Mg: 0.0005-0.02%, one or more of which is substituted for a portion of said Fe.
The 125ksi hydrogen sulfide stress corrosion resistant high-strength oil casing steel is smelted according to the set chemical composition, and subjected to hot rolling and heat treatment, and the final mechanical property of the 125ksi hydrogen sulfide stress corrosion resistant high-strength oil casing steel meets the following requirements: yield strength: 862 and 1034MPa, tensile strength not less than 930MPa, and impact power not less than 100J at 0 ℃. The steel does not break when being soaked in NACE-A solution for 720h under the loading strength of 85% multiplied by 862MPa, and meets the requirements of NACE-A test on hydrogen sulfide stress corrosion resistance of international standard.
The invention also relates to the protection of an oil casing made of the 125ksi hydrogen sulfide stress corrosion resistant high-strength oil casing steel.
The invention also provides a preparation process of the 125ksi hydrogen sulfide stress corrosion resistant high-strength oil casing steel, which comprises the following steps:
(1) smelting the steel ingot into a steel ingot in a vacuum induction furnace or a vacuum intermediate frequency furnace by utilizing an oxide metallurgy process and a vacuum intermediate frequency furnace smelting technology according to the set chemical composition, and forging the steel ingot into a square billet;
(2) heating the square billet obtained in the step (1), then hot-rolling the square billet into a steel plate, and then cooling the steel plate to a temperature M at which the martensite transformation is finishedfBelow or at room temperature;
the cooling mode is air cooling, water cooling or TMCP cooling;
(3) carrying out heat treatment on the steel plate subjected to hot rolling and cooling in the step (2), wherein the heat treatment process comprises quenching and tempering; the method specifically comprises the following steps:
quenching the steel plate after the hot rolling and cooling in the step (2) to a temperature M for finishing the martensite phase transformationfTempering the quenched and cooled steel plate and then cooling to room temperature to finally prepare 125ksi hydrogen sulfide stress corrosion resistant high-strength oil casing steel (hydrogen sulfide corrosion resistant oil pipeline steel and low-carbon low-alloy corrosion resistant sulfur casing steel);
wherein the quenching temperature is controlled at 830 ℃ and 950 ℃, and the heat preservation time is 30-90 min; the tempering temperature is 500-;
the cooling mode after quenching is water quenching, oil quenching or spray water cooling;
and the cooling mode after tempering is slow cooling or air cooling.
According to the technical scheme, the side length of the square billet in the step (1) is preferably 80-120 mm.
According to the above technical scheme, preferably, the square billet in the step (2) is heated to 1150-.
According to the above technical solution, preferably, the thickness of the hot-rolled steel plate in the step (2) is 13-16 mm.
According to the above technical solution, preferably, the heat treatment in step (3) further comprises normalizing, and the partially hot-rolled and cooled steel plate is further subjected to normalizing and then cooled to room temperature before quenching and high-temperature tempering, wherein the normalizing temperature is controlled to Ac according to specific components of the steel3The normalizing and heat-preserving time is controlled within 10-40min according to the thickness of the hot rolled steel plate within 30-50 ℃, namely between 860 and 950 ℃.
The structure of the low-carbon low-alloy corrosion-resistant and sulfur-resistant casing steel is a tempered martensite structure, and part of the steel contains a small amount of lower bainite structure.
In addition, the present invention combines oxide metallurgy with an increase in tempering temperature to reduce dislocation density and pin dislocations by creating nanometer-sized fine secondary phase particles.
The invention has the beneficial effects that:
the hydrogen sulfide stress corrosion resistant high-strength oil casing steel has yield strength of more than 862MPa (125ksi), and the hydrogen sulfide stress corrosion resistant performance meets the NACE-A experiment of the international standard.
According to the stipulations and suggestions of chemical compositions of the high-strength sulfur-resistant oil casing in NACE and API standards, the chemical compositions of the steel for the high-strength oil casing resisting the hydrogen sulfide stress corrosion are set as follows by combining the action of each element in steel grades:
carbon (C): the mass percent is 0.08-0.27%
Carbon (C) is an essential element determining the properties of steel sheets, and the strength, hardness, toughness and plasticity of steel sheets vary depending on the carbon content, that is: increasing the carbon content can significantly improve the strength of the steel plate, but at the same time, reduces the toughness and plasticity of the steel, and significantly deteriorates the corrosion resistance of the steel plate. After considering the comprehensive high strength and hydrogen sulfide stress corrosion resistance, the C content of the steel for the high-strength sulfur-resistant oil casing is designed to be 0.08-0.27%.
Silicon (Si): the mass percent is 0.1-0.5%
Silicon (Si) plays a vital role in the steel making process, having reducing and deoxidizing effects. In addition, Si is one of effective elements for ensuring the strength of the steel sheet, and has important influence on the strength and toughness, because Si can improve the hardness and strength of solid solution in steel and increase the hardenability of steel; and because the thermal stability is good, the tempering resistance of the quenched steel is also increased, so that the steel can be tempered at higher temperature, and the toughness and the delayed fracture resistance of the steel are improved. However, too high Si content deteriorates the thermal conductivity of steel, and cracks or crack defects are liable to occur on the surface of steel ingots and billets. Therefore, the content of Si is set to 0.1-0.5%.
Manganese (Mn): the mass percent is 0.15-1.8%
Manganese (Mn) exists in steel as a solid solution strengthening element, can ensure steel sheet strength and is favorable for toughness, and a high Mn/C ratio is favorable for improving yield strength and impact toughness; measures of reducing C and increasing Mn are taken for low-alloy high-strength steel, so that the strength is improved, and good toughness can be obtained. However, manganese is an easily segregated element, so that harmful elements such as P, S, Sn and Sb are promoted to segregate to grain boundaries to form segregation zones, and the structure and hardness of steel are uneven; and P, Sn, Sb and the like positioned at the grain boundary after segregation are easy to interact with H, so that the bonding force of the grain boundary is greatly reduced, hydrogen-induced peritectic fracture is easy to cause, and the performance of resisting hydrogen sulfide is unfavorable, so that the content of manganese in the steel is limited. In addition, Mn has the function of reducing the martensitic transformation temperature of steel, and when the Mn and C contents in a segregation region reach a certain proportion, martensite and bainite structures which are extremely sensitive to SSC are easily generated in the cooling process after hot rolling. In order to ensure high strength and good toughness of the steel sheet and to limit hydrogen induced fracture, the range of Mn is determined to be between 0.15 and 1.8%.
Chromium (Cr): the mass percent is 0.3-1.0%
Chromium (Cr) can improve the strength and hardness of steel materials by increasing the hardenability of steel, and the effect is more remarkable when other alloying elements are added to the steel materials. Cr is a weak oxidation element, has certain deoxidation capability in the smelting process, and is beneficial to adjusting the oxygen content. In addition, Cr can reduce Ar3The effect of grain refinement can be further increased. The addition of a small amount of Cr remarkably enhances the effect on CO2Gas corrosion resistance, because Cr accumulates in the corrosion product film, making it more stable than the corrosion product film of normal carbon steel. In addition, an increase in the content of Cr element weakens the positive effect of relieving the average corrosion and the localized corrosion, but as the content of Cr in the steel increases, a temperature rise occurs at which the maximum corrosion rate is increased. Under high temperature conditions, Cr element tends to increase local corrosion. The appropriate amount of C in the steel is reduced, and the formation of Cr carbide generated by precipitation of Cr element in the matrix is inhibited, so that the SSC resistance of the steel matrix can be improved.
Molybdenum (Mo): the mass percent is 0.4-1.0%
The micro Mo element can improve the hardenability and the tempering stability of the steel, thereby improving the strength of the steel and improving the ductility and the toughness of the steel; mo may also reduce Ar3The effect of grain refinement can be further increased. Carbide Mo in high-dispersion distribution in steel after high-temperature tempering2C can fix diffusible hydrogen in the steel, so that the content of diffusible enriched hydrogen is greatly reduced, the hydrogen is prevented from being gathered to a fragile crystal boundary, and the carbides are beneficial strong traps and can effectively improve the strength, refine the crystal grains and strengthen the crystal boundary; mo may also hinder P segregation; when Mo reacts with S, the S content in the matrix can be reduced, and dispersed MoS is formed2It has the functions of refining crystal grains and raising the hydrogen sulfide stress corrosion resistance and local corrosion resistance of the material.
Vanadium (V): the mass percent is 0.05-0.4%
Because the dissolution temperature of vanadium (V) is low, the solubility is high, only moderate precipitation strengthening and weak grain refinement can be generated, and the effect of preventing recrystallization is weak. Vanadium only delays recrystallization below 900 ℃, and after austenite transformation, vanadium has almost completely dissolved, so that vanadium hardly forms precipitates in austenite. However, a large amount of precipitation can be generated during or after the γ/a conversion to produce precipitation strengthening, and the strength of the steel can be greatly improved. V is generally precipitated as C, N or its compound in steel, or forms high-density dislocation junctions, and plays a pinning role for dislocations, thereby improving SSC resistance. VN generated by combining V and N is small in size, but high in volume fraction, and can be attached to the surfaces of other types of inclusions, so that beneficial effects on refining intragranular tissues and improving toughness are achieved.
Titanium (Ti): the mass percent is 0.01-0.1%
Titanium (Ti) is one of the commonly used microalloying elements in low alloy, high strength steels. When the Ti content in the steel is more than 0.01 percent, a large amount of Ti oxides and nitrides which are finely dispersed can be obtained by a proper adding method during smelting or continuous casting. These fine Ti oxides and composite inclusions thereof are effective particles for suppressing the coarsening of γ grains and promoting the induction of inclusions to produce intragranular ferrite. However, when the Ti content exceeds 0.1%, the excessive oxide formed by titanium is easily coagulated and coarsened during the smelting or continuous casting process, and if it cannot float upward, it remains in the steel as a micro-crack source to adversely affect the strength and toughness of the steel, so that the upper limit content of Ti must be less than 0.1%.
Copper (Cu): the mass percent is 0.1-0.7%
Copper (Cu) is an austenite stabilizing element, and its solid solution strengthening action can improve the strength of the steel sheet without lowering toughness and increase the corrosion resistance of the steel sheet. However, if the control is not proper in the smelting or continuous casting process, the casting blank cracks are easily generated. A high strengthening effect cannot be obtained with Cu less than 0.1%; if the content is more than 0.7%, the-Cu phase is significantly precipitated, which causes deterioration in toughness and hot workability of the steel sheet, and defects such as hot cracks are likely to occur. The addition of Cu, although not very significant in terms of the effect on the resistance to sulphur, can to some extent alter the electrochemical behaviour of the steel in hydrogen sulphide solution. In addition, sulfide formed by Mo and Cu can promote the formation of a Cu oxide single-layer film close to a metal substrate, and the corrosion resistance of the steel in a hydrogen sulfide medium is improved.
Nickel (Ni): the mass percent is 0.2-3.0%
Nickel (Ni) also improves the strength and toughness of the steel sheet by solid solution strengthening, and can ensure the strength and toughness of the steel sheet. Too low Ni does not provide high strength, and too much Ni increases the cost. Therefore, the Ni content is preferably in the range of 0.2 to 3.0%.
Boron (B): the mass percent is 0.0001-0.002%
Boron (B) can increase hardenability and increase the strength of the steel. After the temperature is higher than 1300 ℃, B diffuses fast at high temperature and is easy to be segregated in austenite grain boundaries, and is firstly combined with N to form BN during cooling, so that the growth of grain boundary ferrite is inhibited, and the B becomes a nucleation point of intragranular ferrite during gamma → alpha phase transformation. B may also form Fe in steel23(CB)6It is beneficial to improve the toughness. However, the B-containing steel tends to cause a phenomenon in which the yield of the steel strength is unstable, and particularly has a great influence on the steel material requiring heat treatment. Therefore, the content of B is controlled to be in the range of 0.0001 to 0.002%, and if it exceeds 0.002%, the toughness of the steel is deteriorated.
Phosphorus (P): the mass percent is 0-0.015%
Phosphorus (P) is an inevitable element mixed as an impurity, and increases the strength of the steel sheet and deteriorates the toughness. If the content exceeds 0.015%, the elongation and toughness of the steel sheet are significantly reduced, and if the content is too low, the refining cost is significantly increased, so that the content should be reduced as much as possible within a range that can be tolerated by the smelting cost.
Sulfur (S): the mass percentage is 0 to 0.010 percent
Sulfur (S) is an inevitable element incorporated in steel as an impurity element, and when the content of S is appropriate, sulfides such as CuS and CaS having a high melting point are formed, and a part of MnS adheres to the periphery of the complex oxide or nitride and is distributed in a spherical form. When the S content is too high, coarse MnS and CaS inclusions can be generated, the sensitivity of stress corrosion cracking is obviously increased, and the steel plate is resistant to H2The corrosion capacity of S is significantly reduced. Therefore, the S content should be lower than0.01 percent, and the content of S should be reduced as much as possible within the range that the smelting cost can bear.
Oxygen (O): the mass percent is 0 to 0.06 percent
Oxygen (O) can ensure that oxides such as Ti, Mg, Ca, Zr, REM and the like with high melting points are formed in steel, various alloy elements have different influences on the oxygen concentration in the steel, and the operation process in the smelting and continuous casting process also has important influences on the oxygen content and the oxides in the steel. Controlling the oxygen content and oxides in steel is a central content of the "oxide metallurgy" technology. Generally, when the oxygen content in the cast slab is more than 60ppm, the formed oxides are coarse, and the toughness and stress corrosion cracking resistance of the steel are lowered. Therefore, the oxygen content is controlled to be below 0.006 percent.
Nitrogen (N): 0 to 0.005 percent by mass
Nitrogen (N) is an element which can not be completely removed in industrial steel, and a proper amount of N can be combined with Al and Ti in the steel to refine austenite grains, so that the comprehensive mechanical property of the steel is improved. In the range that the content of N determined by the invention is less than 0.005 percent, TiN, BN, VN and other particles formed in the steel can refine gamma grains and intragranular structures, and are beneficial to improving the toughness and H resistance of the steel2S corrosion performance.
Hydrogen (H): the mass percent is 0 to 0.05 percent
In the steel-making process and in the storage or use of the steel, H ions are present in the steel, which are the origin of H embrittlement, and have a decisive influence on the resistance to hydrogen sulfide stress corrosion, so that the lower the H content in the steel, the better.
Aluminum (Al): 0 to 0.005 percent by mass
Feeding aluminum wire in the steel-making process, and reacting with oxygen in the steel to form AI2O3The oxygen content in the steel is reduced, and in addition, a certain desulfurization effect and a certain grain refinement effect can be achieved.
Niobium (Nb): the mass percent is 0 to 0.2 percent
Nb is added into steel and forms highly dispersed carbide NbC after high-temperature tempering, the combination energy of NbC and hydrogen is high, the hydrogen diffusion in the steel is favorably fixed, the hydrogen is prevented from being gathered to a fragile crystal boundary, the carbide formed by Nb is a beneficial hydrogen trap, the strength can be effectively improved, crystal grains can be refined, the crystal boundary can be strengthened, and trace Nb reacts with carbon to form dispersed strong carbide particles and high-density dislocation junctions, so that the pinning effect on dislocations is achieved. These are all advantageous in improving the SSC resistance of the steel.
Calcium (Ca): the mass percent is 0-0.008%
Generally, a silicon-calcium wire, a calcium iron wire or a calcium wire is added at the end stage of the refining of industrial production, so that inclusions in steel are spheroidized, and the improvement of flaw detection qualification rate is facilitated. Ca can spheroidize the strip MnS inclusions, which is helpful for reducing the anisotropy of the steel plate and improving the Z-direction performance; meanwhile, CaO or CaS formed by Ca is compounded with other inclusions to be beneficial to toughness. However, since CaS precipitation temperature in molten steel is lower than CaO and the influence of both on the formation of ferrite by inclusion is different, the size and density distribution of CaO and CaS are adjusted by a process. If the Ca content in the steel exceeds 0.008%, coarse inclusions are formed, and the toughness is lowered.
Cerium (Ce): the mass percent is 0-0.03%
If Al is expected to form during the steelmaking process2O3When the content is too high and the hydrogen sulfide stress corrosion resistance of the steel is influenced, Ce needs to be added to promote the formation ratio of Al2O3More basic Ce2O3At the same time Ce2O3With Al2O3Combined formed xCe2O3·yAl2O3The compound can reduce Al2O3Activity.
Zirconium (Zr): the mass percent is 0.0005-0.01%
Zirconium (Zr) can react through an oxide metallurgical process to form high-melting-point composite inclusions in steel, effectively refine inclusion particles, spheroidize MnS in the steel, and is beneficial to improving toughness and obviously improving the hydrogen sulfide corrosion resistance of steel.
Rare earth element (REM): the mass percent is 0.003 to 0.05 percent
The rare earth element (REM) has high binding energy with impurities such as oxygen, sulfur and the like in the molten steel, and can be used as a strong deoxidizer and a desulfurizer of the molten steel; in addition, oxides, sulfides or oxysulfides generated by the reaction of the rare earth and oxygen and sulfur in the molten steel can partially remain in the molten steel to become inclusions in the steel, and the inclusions have high melting points and can be used as non-homogeneous nucleation centers during the solidification of the molten steel to play a role in refining the solidification structure of the steel; and because the inclusions are not easy to deform at the steel rolling temperature and still keep fine spherical or spindle shapes, the shapes of the inclusions in the steel are controlled, so that the anisotropy of the steel performance caused by the extension deformation of other types of inclusions (such as MnS) during the hot-pressing processing of the steel is avoided or overcome, and the longitudinal performance, the transverse performance and the thickness direction of the steel tend to be consistent. In addition, trace rare earth may be dissolved in steel, and particularly, high-carbon steel and some steel plates with high alloy content have high content of dissolved rare earth (parts per million), and some alloying effects may be generated. The alloying action is shown in that rare earth influences the phase change process of steel, changes the composition and structure of a phase change product, thereby improving the corrosion resistance of the steel and improving the microhardness of the steel.
Magnesium (Mg): the mass percent is 0.0005-0.02%
Magnesium (Mg) is a strong oxidizing element and has a strong binding force with oxygen. Mg and Al can form MgO & Al in molten steel2O3Spinel, which is a high-melting-point particle, is used as a core of other elements, usually aluminum magnesium spinel, so as to form composite inclusions, and the toughness is improved. However, Al2O3The inclusions often serve as starting and stopping sites for pitting corrosion or propagation paths for cracks, reducing the hydrogen sulfide stress corrosion resistance. In addition, since Mg has a high vapor pressure at the temperature of molten steel and is very active during steel making, the yield and the hit rate of components are difficult to control, and the mechanical properties of the steel sheet are easily unstable.
The 125ksi hydrogen sulfide stress corrosion resistant high-strength oil casing steel provided by the invention is based on reasonable chemical composition design and utilizes an oxide metallurgy process technology to control the micronization, spheroidization and composition structure diversification of inclusions in the steel (figure 1); the adopted quenching and tempering heat treatment process obtains a tempered martensite phase transformation structure with high strength and high toughness (figure 2); control principle of carbideIs that the formation of huge M at the grain boundary is reduced23C6The carbide can generate micro spherical carbide with the diameter of nanometer level in the crystal or the grain boundary (figure 3), thereby improving the hydrogen sulfide stress corrosion resistance of the steel matrix.
Drawings
FIG. 1 shows an inclusion structure of a steel for a hydrogen sulfide corrosion-resistant oil-resistant pipeline according to example 7 of the present invention;
a) the shape of the inclusions of the 125ksi hydrogen sulfide stress corrosion resistant high-strength steel is shown;
b) is a spectrum of this feature.
FIG. 2 is a microscopic metallographic structure of steel for a hydrogen sulfide corrosion-resistant oil-resistant pipeline according to example 7 of the present invention;
FIG. 3 shows the carbide precipitation morphology of the steel for hydrogen sulfide corrosion and oil pipe of example 7 of the present invention;
a) the shape and distribution state of carbide precipitation under low power;
b) the form of precipitates in the test steel sheet was high;
c) the spectrum of the precipitate is shown.
FIG. 4 shows martensite lath bundles and dislocation patterns of steel for hydrogen sulfide corrosion-resistant oil-resistant pipeline in example 7 of the present invention.
Detailed Description
The following non-limiting examples will allow one of ordinary skill in the art to more fully understand the present invention, but are not intended to limit the invention in any way.
The evaluation method of the hydrogen sulfide stress corrosion resistance sensitivity referred to in the following examples is as follows:
the evaluation of the hydrogen sulfide stress corrosion resistance sensitivity is verified by a constant load tensile test, and the test sample is soaked in saturated H according to the indoor experimental evaluation standard NACE TM 0177-2And in the S aqueous solution, the cracking resistance of the steel is tested under the condition of uniaxial load tensile stress, and the load stress is 85% of the actual yield strength. The experimental temperature is 24 +/-3 ℃, and the solution medium is NACE TM 0177-: by saturated H2An aqueous solution of S, consisting of 5.0% sodium chloride and 0.5% glacial acetic acid dissolved in distilled waterAnd (the volume fraction of glacial acetic acid is 99.5%). the experimental time is 720h (30d), and the test sample is not fractured after 720h, so that the hydrogen Sulfide Stress Corrosion (SSC) resistance of the sulfur-resistant casing steel is judged to be qualified.
Example 1
Table 1 shows the chemical composition of the steel for hydrogen sulfide stress corrosion resistant oil casing pipe of the present invention, and Table 2 shows the heat treatment method of the steel for hydrogen sulfide stress corrosion resistant oil casing pipe of the present invention (heat treatment of the hot rolled steel sheet, some parameters are shown in Table 2). The steel is smelted in a vacuum induction furnace according to the chemical composition set in table 1 by an oxide metallurgical process, then cast to form a steel ingot, and cooled to room temperature. And heating the steel ingot to 1050 ℃ for forging, and cooling to room temperature to form a square billet of 80X 80 mm. Then the square billet is subjected to heat preservation for 2 hours at the heating temperature of 1150 ℃ in a furnace and then is subjected to hot rolling, finally is rolled into a steel plate with the thickness of 13mm, and is cooled to the room temperature in the air. Normalizing the hot-rolled and cooled steel plate at 900 ℃, preserving heat for 10min, cooling in air to room temperature, quenching at 820 ℃, preserving heat for 30min, spraying water to cool to martensite phase transformation completion temperature MfAnd tempering at 540 ℃, keeping the temperature for 30min, and slowly cooling the steel plate in an asbestos cloth to room temperature to finally obtain the 125ksi hydrogen sulfide corrosion resistant steel plate, wherein the mechanical properties and the hydrogen sulfide resistance test results are shown in Table 3.
Example 2
Table 1 shows the chemical composition of the steel for hydrogen sulfide stress corrosion resistant oil casing pipe of the present invention, and Table 2 shows the heat treatment method of the steel for hydrogen sulfide stress corrosion resistant oil casing pipe of the present invention (heat treatment of the hot rolled steel sheet, some parameters are shown in Table 2). The chemical compositions set forth in table 1 were smelted in a vacuum induction furnace using an oxide metallurgy process, and then cast to form a steel ingot, and cooled to room temperature. And heating the steel ingot to 1100 ℃ for forging, and cooling to room temperature to obtain a square billet of 80X 80 mm. And then keeping the temperature of the steel plate at 1200 ℃ for 2h in a furnace, carrying out hot rolling, finally rolling the steel plate into a steel plate with the thickness of 15mm, and cooling the steel plate to room temperature in air. Normalizing the hot-rolled and cooled steel plate at 910 ℃, preserving heat for 15min, cooling in air to room temperature, quenching at 830 ℃, preserving heat for 30min, and quenching in oil to the martensite phase transformation completion temperature MfTempering at 570 deg.C for 40min, and processing steelThe plates were slowly cooled in an asbestos cloth to room temperature to finally obtain 125ksi hydrogen sulfide corrosion resistant steel plates, the mechanical properties and the hydrogen sulfide resistance test results of which are shown in Table 3.
Example 3
Table 1 shows the chemical composition of the steel for hydrogen sulfide stress corrosion resistant oil casing pipe of the present invention, and Table 2 shows the heat treatment method of the steel for hydrogen sulfide stress corrosion resistant oil casing pipe of the present invention (heat treatment of the hot rolled steel sheet, some parameters are shown in Table 2). The chemical compositions set forth in table 1 were smelted in a vacuum induction furnace using an oxide metallurgy process, and then cast to form a steel ingot, and cooled to room temperature. And heating the steel ingot to 1100 ℃ for forging, and cooling to room temperature to obtain a 100X 100 square billet. And then keeping the temperature of the steel plate at 1200 ℃ for 2h in a furnace, carrying out hot rolling, finally rolling the steel plate into a steel plate with the thickness of 15mm, and cooling the steel plate to room temperature in air. Normalizing the hot-rolled and cooled steel plate at 920 ℃, preserving heat for 20min, cooling in air to room temperature, quenching at 850 ℃, preserving heat for 30min, and quenching in oil to the martensite phase transformation completion temperature MfAnd finally tempering at 600 ℃, preserving the heat for 30min, and air-cooling to room temperature to finally obtain the 125ksi hydrogen sulfide corrosion resistant steel plate, wherein the mechanical properties and the hydrogen sulfide resistance experiment results are shown in Table 3.
Example 4
Table 1 shows the chemical composition of the steel for hydrogen sulfide stress corrosion resistant oil casing pipe of the present invention, and Table 2 shows the heat treatment method of the steel for hydrogen sulfide stress corrosion resistant oil casing pipe of the present invention (heat treatment of the hot rolled steel sheet, some parameters are shown in Table 2). The chemical compositions set forth in table 1 were smelted in a vacuum induction furnace using an oxide metallurgy process, and then cast to form a steel ingot, and cooled to room temperature. Then the steel ingot is heated to 1150 ℃ for forging and cooled to room temperature to form a square billet of 80X 80 mm. And then keeping the temperature of the steel plate at 1200 ℃ for 2h in a furnace, carrying out hot rolling, finally rolling the steel plate into a steel plate with the thickness of 16mm, and cooling the steel plate to room temperature in air. Normalizing the hot-rolled and cooled steel plate at 930 ℃, preserving heat for 25min, cooling in air to room temperature, quenching at 900 ℃, preserving heat for 30min, spraying water to cool to the martensite phase transformation completion temperature MfTempering at 630 ℃, keeping the temperature for 50min, and air-cooling to room temperature to finally obtain the 125ksi hydrogen sulfide corrosion resistant steel plate with the strength ofThe chemical properties and the results of the hydrogen sulfide resistance test are shown in Table 3.
Example 5
Table 1 shows the chemical composition of the steel for hydrogen sulfide stress corrosion resistant oil casing pipe of the present invention, and Table 2 shows the heat treatment method of the steel for hydrogen sulfide stress corrosion resistant oil casing pipe of the present invention (heat treatment of the hot rolled steel sheet, some parameters are shown in Table 2). Smelting the chemical components set in the table 1 in a vacuum induction furnace by using an oxide metallurgy process, forming a steel ingot by using an ingot casting method, and cooling the steel ingot to room temperature to obtain a round ingot. And heating the steel ingot to 1050 ℃ for forging, and cooling to room temperature to obtain a square billet of 120 x 120 mm. And then keeping the temperature of 1250 ℃ in a furnace for 2h, performing hot rolling, finally rolling into a steel plate with the thickness of 15mm, and cooling to room temperature in air. Quenching the hot-rolled and cooled steel plate at 850 ℃, preserving heat for 40min, and spraying water to cool to the martensite phase transformation completion temperature MfAnd tempering at 750 ℃, keeping the temperature for 70min, and slowly cooling the steel plate in an asbestos cloth to room temperature to finally obtain the 125ksi hydrogen sulfide corrosion resistant steel plate, wherein the mechanical properties and the hydrogen sulfide resistance test results are shown in Table 3.
Example 6
Table 1 shows the chemical composition of the steel for hydrogen sulfide stress corrosion resistant oil casing pipe of the present invention, and Table 2 shows the heat treatment method of the steel for hydrogen sulfide stress corrosion resistant oil casing pipe of the present invention (heat treatment of the hot rolled steel sheet, some parameters are shown in Table 2). The chemical compositions set forth in table 1 were smelted in a vacuum induction furnace using an oxide metallurgy process, and then cast to form a steel ingot, and cooled to room temperature. And heating the steel ingot to 1100 ℃ for forging, and cooling to room temperature to obtain a square billet of 80X 80 mm. And then keeping the temperature of 1250 ℃ in a furnace for 2h, performing hot rolling, finally rolling into a steel plate with the thickness of 14mm, and cooling to room temperature in air. Quenching the hot-rolled and cooled steel plate at 920 ℃, preserving heat for 30min, and spraying water to cool to the martensite phase transformation completion temperature MfAnd finally tempering at 720 ℃, preserving the heat for 60min, and air-cooling to room temperature to finally obtain the 125ksi hydrogen sulfide corrosion resistant steel plate, wherein the mechanical properties and the hydrogen sulfide resistance experiment results are shown in Table 3.
Example 7
Table 1 shows the chemical composition of the steel for hydrogen sulfide stress corrosion resistant oil casing pipe of the present invention, and Table 2 shows the heat treatment method of the steel for hydrogen sulfide stress corrosion resistant oil casing pipe of the present invention (heat treatment of the hot rolled steel sheet, some parameters are shown in Table 2). The chemical compositions set forth in table 1 were smelted in a vacuum induction furnace using an oxide metallurgy process, and then cast to form a steel ingot, and cooled to room temperature. Then the steel ingot is heated to 1150 ℃ for forging and cooled to room temperature to form a square billet of 80X 80 mm. And then keeping the temperature of the steel plate at 1200 ℃ for 2h in a furnace, carrying out hot rolling, finally rolling the steel plate into a steel plate with the thickness of 16mm, and cooling the steel plate to room temperature in air. Quenching the hot-rolled and cooled steel plate at 880 ℃, preserving heat for 30min, and performing oil quenching to the martensite phase transformation completion temperature MfAnd tempering at 760 ℃, keeping the temperature for 30min, and slowly cooling the steel plate in an asbestos cloth to room temperature to finally obtain the 125ksi hydrogen sulfide corrosion resistant steel plate, wherein the mechanical properties and the hydrogen sulfide resistance test results are shown in Table 3.
It is clear from FIG. 2 that the steel of the present invention has a tempered martensite structure, and further, it can be seen that inclusions are uniformly distributed in the inside of grains and on grain boundaries. The steel sheet has a structure in which EPMA test shows that the inclusions are spherical in a diameter of less than 2 μm in many cases and only polygonal inclusions having individual lengths of less than 3 μm are present. FIG. 1 shows a typical inclusion in the steel plate of the present invention under EPMA, the diameter of the inclusion is less than 1 μm, the inclusion is spherical, and the energy spectrum in FIG. 1b) shows that the inclusion in FIG. 1a) is MnS, and the small circular MnS changes the conventional strip structure, thereby greatly reducing the probability of pitting corrosion and further improving the hydrogen sulfide stress cracking resistance of the material.
FIG. 3 shows the precipitation of various carbides during the final part of the tempering heat treatment of the steel, including: m3Type C carbide, moderate in size and spheroidized, uniformly distributed in grain boundaries and in the crystal, as shown in FIG. 3 b); another nano-scale fine carbide is a nano-sized tetragonal MC (M ═ V, Mo) carbide formed by bonding of V, Mo and C, which have a strong carbide-forming ability, and as shown in fig. 3a), the MC carbide causes precipitation strengthening. In addition, M, which is coarse in the steel for the present invention23C6(M＝Fe，Cr，Mo) The inclusions are very few, and further the hydrogen sulfide stress corrosion sensitivity of the steel for the oil casing pipe is reduced.
As can be seen from fig. 4, the dislocation density of the steel used in the present invention is low, and the dislocations do not occur in one direction, but form a dislocation network through entanglement, and the dislocation entanglement is favorable for forming effective H traps, thereby increasing the hydrogen sulfide stress corrosion resistance.
Example 8
Table 1 shows the chemical composition of the steel for hydrogen sulfide stress corrosion resistant oil casing pipe of the present invention, and Table 2 shows the heat treatment method of the steel for hydrogen sulfide stress corrosion resistant oil casing pipe of the present invention (heat treatment of the hot rolled steel sheet, some parameters are shown in Table 2). The chemical compositions set forth in table 1 were smelted in a vacuum induction furnace using an oxide metallurgy process, and then cast to form a steel ingot, and cooled to room temperature. And heating the steel ingot to 1100 ℃ for forging, and cooling to room temperature to obtain a square billet of 80X 80 mm. And then keeping the temperature of 1250 ℃ in a furnace for 2h, performing hot rolling, finally rolling into a steel plate with the thickness of 16mm, and cooling in air to room temperature. Quenching the hot-rolled and cooled steel plate at 900 ℃, preserving heat for 90min, and performing water quenching to the martensite phase transformation completion temperature MfAnd finally, tempering at 630 ℃, preserving the heat for 150min, and cooling in air to room temperature to finally obtain the 125ksi hydrogen sulfide corrosion resistant steel plate, wherein the mechanical properties and the hydrogen sulfide resistance test results are shown in Table 3.
The steels of the above embodiments 1-8 of the present invention pass NACE TM0117A test, and become qualified 125 ksi-grade low-carbon low-alloy sulfur-resistant oil-resistant casing steel with hydrogen sulfide stress corrosion resistance.
The steel of the above-mentioned examples 2 to 8 of the present invention had a structure of tempered martensite, and the steel of example 1 had a structure of tempered martensite containing a small amount of lower bainite, and the content of the lower bainite was less than 15%.
TABLE 1 composition (m%) of steel for hydrogen sulfide stress corrosion resistant oil casing according to the present invention
| Numbering | C | Si | Mn | Cr | Mo | V | Ti | Cu | Ni | Nb | B | Mg | REM |
| Example 1 | 0.10 | 0.5 | 0.5 | 0.9 | 0.5 | 0.1 | 0.06 | 0.6 | - | - | - | - | - |
| Example 2 | 0.15 | 0.4 | 0.7 | 0.8 | 0.5 | 0.3 | 0.02 | 0.4 | - | - | - | - | - |
| Example 3 | 0.20 | 0.1 | 0.5 | 0.3 | 0.5 | 0.2 | 0.06 | 0.6 | - | - | - | - | - |
| Example 4 | 0.25 | 0.4 | 0.3 | 0.8 | 0.7 | 0.3 | 0.04 | 0.6 | - | - | - | - | - |
| Example 5 | 0.12 | 0.1 | 0.5 | 0.8 | 0.5 | 0.3 | 0.06 | 0.6 | - | 0.1 | - | - | - |
| Example 6 | 0.18 | 0.1 | 1.1 | 0.6 | 0.5 | 0.3 | 0.08 | 0.5 | 1.0 | 0.2 | 0.0015 | - | - |
| Example 7 | 0.27 | 0.4 | 0.5 | 0.3 | 0.8 | 0.3 | 0.06 | 0.6 | 1.0 | - | - | 0.02 | - |
| Example 8 | 0.10 | 0.4 | 1.8 | 0.8 | 1.0 | 0.4 | 0.10 | 0.6 | 1.0 | 0.2 | 0.0015 | - | 0.05 |
TABLE 2 Heat treatment method for hydrogen sulfide stress corrosion resistant oil casing steel of the present invention
TABLE 3 mechanical Properties and Hydrogen sulfide resistance test results of the steel for hydrogen sulfide stress corrosion resistant oil casing according to the present invention
| Numbering | Yield strength/MPa | Tensile strength/MPa | Impact power/0 ℃/J | NACE TM 0177-one 2005-A experiment |
| Example 1 | 913 | 965 | 107 | 720h |
| Example 2 | 896 | 932 | 164 | 720h |
| Example 3 | 887 | 946 | 132 | 720h |
| Example 4 | 924 | 1017 | 105 | 720h |
| Example 5 | 961 | 1043 | 169 | 720h |
| Example 6 | 895 | 947 | 182 | 720h |
| Example 7 | 989 | 1145 | 101 | 720h |
| Example 8 | 982 | 1095 | 116 | 720h |
It will be apparent to those skilled in the art from this disclosure that many changes and modifications can be made, or equivalents modified, in the embodiments of the invention without departing from the scope of the invention. Therefore, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention shall still fall within the protection scope of the technical solution of the present invention, unless the contents of the technical solution of the present invention are departed.
Claims (8)
1. The steel for the hydrogen sulfide stress corrosion resistant oil casing is characterized by comprising the following chemical components in percentage by mass:
C：0.08-0.27％，
Si：0.1-0.5％，
Mn：0.15-1.8％，
Cr：0.3-1.0％，
Mo：0.4-1.0％，
V：0.05-0.4％，
Ti：0.01-0.1％，
Cu：0.1-0.7％，
Ni：0.2-3.0％，
B：0.0001-0.002％，
P：0-0.015％，
S：0-0.010％，
O：0-0.06％，
N：0-0.05％，
H：0-0.05％，
Zr：0.0005-0.01％，
Ce：0-0.03％，
Mg：0.0005-0.02％,
Al：0-0.005％，
the balance of Fe and inevitable impurities;
the preparation process of the steel for the hydrogen sulfide stress corrosion resistant oil casing is characterized by comprising the following steps:
(1) smelting the steel ingot according to the set chemical components, and forging the steel ingot into a square billet;
(2) heating the square billet obtained in the step (1), hot rolling the square billet into a steel plate, and cooling the steel plate until the martensite phase transformation is finishedTemperature MfBelow or at room temperature;
(3) and (3) carrying out heat treatment on the steel plate subjected to hot rolling and cooling in the step (2), wherein the heat treatment comprises quenching and tempering, and specifically comprises the following steps:
quenching the steel plate after the hot rolling and cooling in the step (2) to a temperature M for finishing the martensite phase transformationfTempering the steel plate after quenching and cooling to room temperature below or at room temperature;
wherein the quenching temperature is 830-950 ℃, and the heat preservation time is 30-90 min; the tempering temperature is 500-790 ℃, and the heat preservation time is 30-150 min.
2. The steel for the hydrogen sulfide stress corrosion resistant oil casing according to claim 1, further comprising the following chemical components in percentage by mass: nb: 0-0.2%, Ca: 0-0.008%, REM: 0.003-0.05% of one or more of the following components.
3. The steel for hydrogen sulfide stress corrosion resistant oil casing pipes according to claim 1, characterized by having the following mechanical properties: yield strength: 862 and 1034MPa, tensile strength not less than 930MPa, and impact energy not less than 100J at 0 ℃.
4. The steel for hydrogen sulfide stress corrosion resistant oil casing pipes according to claim 1, characterized in that the hydrogen sulfide stress corrosion resistance satisfies the international standard NACE-a test.
5. The oil casing pipe made of the steel for hydrogen sulfide stress corrosion resistant oil casing pipe according to any one of claims 1 to 4.
6. The preparation process of the steel for the hydrogen sulfide stress corrosion resistant oil casing as claimed in claim 1, wherein the heat treatment in the step (3) further comprises normalizing, the normalizing is carried out before quenching and tempering the hot-rolled and cooled steel plate, the normalizing temperature is 860 and 950 ℃, and the heat preservation time is 10-40 min.
7. The preparation process of the steel for the hydrogen sulfide stress corrosion resistant oil casing according to claim 1, wherein the square billet is heated to 1150-1250 ℃ in the step (2) and is subjected to heat preservation for 1.5-5 h.
8. The process for preparing the steel for a hydrogen sulfide stress corrosion resistant oil casing according to claim 1, wherein the thickness of the hot-rolled steel plate in the step (2) is 13 to 16 mm.
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