CN109234615B - Stainless steel for microbial corrosion resistant oil well pipe and manufacturing method thereof - Google Patents
Stainless steel for microbial corrosion resistant oil well pipe and manufacturing method thereof Download PDFInfo
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- 238000005260 corrosion Methods 0.000 title claims abstract description 49
- 230000007797 corrosion Effects 0.000 title claims abstract description 48
- 230000000813 microbial effect Effects 0.000 title claims abstract description 30
- 239000003129 oil well Substances 0.000 title claims abstract description 26
- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 22
- 239000010935 stainless steel Substances 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 42
- 239000010959 steel Substances 0.000 claims abstract description 42
- 239000000126 substance Substances 0.000 claims abstract description 8
- 239000012535 impurity Substances 0.000 claims abstract description 3
- 238000005242 forging Methods 0.000 claims description 25
- 238000005096 rolling process Methods 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- 238000004321 preservation Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 238000003723 Smelting Methods 0.000 claims description 7
- 229910001566 austenite Inorganic materials 0.000 claims description 6
- 238000005098 hot rolling Methods 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- 238000007670 refining Methods 0.000 claims description 4
- 230000000930 thermomechanical effect Effects 0.000 claims description 4
- 230000006698 induction Effects 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910001208 Crucible steel Inorganic materials 0.000 claims 4
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 10
- 229910052802 copper Inorganic materials 0.000 abstract description 9
- 229910052733 gallium Inorganic materials 0.000 abstract description 9
- 238000005336 cracking Methods 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 abstract description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 abstract description 4
- 229910001105 martensitic stainless steel Inorganic materials 0.000 abstract description 4
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 239000010949 copper Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
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- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 150000002910 rare earth metals Chemical class 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 3
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 230000000844 anti-bacterial effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910000734 martensite Inorganic materials 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
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- 238000002347 injection Methods 0.000 description 2
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- 150000004767 nitrides Chemical class 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- RMLPZKRPSQVRAB-UHFFFAOYSA-N tris(3-methylphenyl) phosphate Chemical compound CC1=CC=CC(OP(=O)(OC=2C=C(C)C=CC=2)OC=2C=C(C)C=CC=2)=C1 RMLPZKRPSQVRAB-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000295146 Gallionellaceae Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
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- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
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- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
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- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 201000008827 tuberculosis Diseases 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/005—Modifying the physical properties by deformation combined with, or followed by, heat treatment of ferrous alloys
-
- 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
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
- C21D8/0226—Hot rolling
-
- 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
- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
-
- 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
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- 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
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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
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
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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
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
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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
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
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- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
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- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/54—Ferrous alloys, e.g. steel alloys containing chromium with nickel with boron
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- 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
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/008—Martensite
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Abstract
The invention aims to provide stainless steel for an oil well pipe with microbial corrosion resistance and a manufacturing method thereof, so as to reduce the risk of microbial corrosion from the perspective of materials. The steel comprises the following chemical components in percentage by weight: c: less than or equal to 0.03; si: 0.1-0.3%; mn: less than or equal to 0.5 percent; cr: 12.0-14.0%; ni: 4.0 to 6.0; mo: 1.5-2.5%; cu: 1.0-2.0%; ga: 0.1 to 0.8 percent; ce: 0.1 to 0.2 percent; s is less than or equal to 0.02; p is less than or equal to 0.03 percent; the balance being Fe and unavoidable impurities. According to the invention, a proper amount of Cu, Ga and rare earth element Ce are added on the basis of the components of the traditional super martensitic stainless steel for the oil well pipe, and under the synergistic action of the Cu, Ga and rare earth element Ce, the steel can obtain better toughness and excellent hydrogen sulfide stress corrosion cracking resistance, and meanwhile, the steel also has excellent microbial corrosion resistance, and can be applied to the production of steel for the oil well pipe.
Description
Technical Field
The present invention relates to stainless steel for oil well pipes and a method for manufacturing the same, and more particularly, to stainless steel for oil well pipes having microbial corrosion resistance and a method for manufacturing the same.
Background
Microorganisms are an important factor in initiating and accelerating metal corrosion, and the loss due to microbial corrosion accounts for about 20% of the total metal corrosion. It has been reported that 75% of the corrosion in oil well 13Cr super martensitic stainless steels and 50% of the failures in buried pipeline steels above the X65 grade are due to microbial corrosion. In oilfield flooding systems, the growth, metabolism, and reproduction of Sulfate Reducing Bacteria (SRB), iron bacteria, saprophytic bacteria, and other microorganisms can cause severe damage to drilling equipment, water injection pipelines, and other metallic materialsCorrosion, and pipe blockage, damage to the oil reservoir, resulting in reduced water injection, oil production, and oil and gas quality, and also causing severe difficulties in crude oil processing. At present, the microbial corrosion protection of oil well pipes in China has not yet attracted attention, and most of the microbial corrosion protection is concentrated on CO2Corrosion, H2Stress corrosion and Cl caused by S-The research on the local corrosion protection is caused. The stainless steel for the oil well pipe which is already in service or is available in the prior art does not consider the microbial corrosion resistance of the material in terms of chemical composition or production process. Therefore, the research and development of new materials for inhibiting or slowing down the microbial corrosion of the stainless steel for the oil well pipe undoubtedly have important scientific significance and application value.
Disclosure of Invention
According to the invention, on the basis of the components of the traditional martensitic stainless steel for the oil well pipe, a proper amount of Cu, Ga and rare earth element Ce are added in a compounding manner, and the microbial corrosion resistance is endowed on the premise of meeting other performances of the martensitic stainless steel for the oil well pipe.
The technical scheme of the invention is as follows:
a stainless steel for an oil well pipe, which is resistant to microbial corrosion, is characterized in that: the steel comprises the following chemical components in percentage by weight:
c: less than or equal to 0.03; si: 0.1-0.3%; mn: less than or equal to 0.5 percent; cr: 12.0-14.0%; ni: 4.0 to 6.0; mo: 1.5-2.5%; cu: 1.0-2.0%; ga: 0.1 to 0.8 percent; ce: 0.1 to 0.2 percent; s is less than or equal to 0.02; p is less than or equal to 0.03 percent; the balance being Fe and unavoidable impurities.
The chemical composition of the steel also satisfies the following conditions:
Cu+Ga+Ce≥2％ (1)
wherein, each element symbol in the formula (1) is substituted into the corresponding element content (weight%)
The constraint condition of the formula (1) enables the steel to obtain better microbial corrosion resistance.
The chemical components of the stainless steel for the microbial corrosion resistant oil well pipe also comprise one or more of Nb, V, Ti, Al and B, and the weight percentage of each is less than or equal to 0.1 percent.
In the component design of the stainless steel for the microbial corrosion resistant oil well pipe, copper (Cu), gallium (Ga) and cerium (Ce) are the most important alloying elements in the steel, and the composite addition of the copper (Cu), the gallium (Ga) and the cerium (Ce) can play the roles of raising the advantages and avoiding the disadvantages.
Cu is an austenite forming element, the solid solubility of Cu in martensite is extremely low, and nano copper-rich phase particles can be precipitated in a martensite matrix by adding a proper amount of Cu and aging in a certain temperature range, and can play roles in strengthening, antibacterial property and hydrogen trap benefiting, so that the strength, microbial corrosion resistance and stress corrosion cracking resistance of the steel can be greatly improved. However, excessive Cu causes deterioration of hot workability of the steel, so that the steel is easily cracked during hot working. Therefore, the Cu content in the present invention is 1.0 to 2.0%.
Ga is a ferrite-forming element, and trace amounts of Ga are generally present in substitutional solid solutions in ferrite in low carbon steel. It is similar to Cu, does not exist in inclusions such as oxides, nitrides and sulfides, and does not form carbon and nitrides. Meanwhile, the trace Ga has a strengthening effect on the low-carbon steel, and can refine the steel structure to a certain extent and prevent phosphorus (P) from deviating to grain boundaries, so that the low-temperature impact toughness of the steel is obviously improved. In addition, Ga can also increase point defects in steel and play a role of hydrogen trap, so that the hydrogen-induced brittleness sensitivity of the low-carbon steel is reduced. Ga atoms can be enriched in a grain boundary area, so that harmful elements such as arsenic, antimony, bismuth, tin and the like with larger atomic radius than Ga are reduced from falling in the grain boundary area, the function of purifying the grain boundary is achieved, and the effect of improving the toughness of steel is achieved. In summary, gallium is a beneficial element in steel. In the present invention, Ga inhibits the normal proliferation activity of bacteria. The Ga content added in the invention is 0.1-0.8%.
The rare earth Ce can improve the corrosion resistance of the steel, purify molten steel, optimize grain boundaries, reduce corrosion sources, play a role in metamorphism, promote nucleation and refine grains, and thus improve the toughness of the steel. Meanwhile, the rare earth Ce is added into the steel to play a role in capturing hydrogen, so that the hydrogen embrittlement of the steel is inhibited. Rare earth Ce is a low toxic substance, has antibacterial property, is also an ideal antibacterial agent, and is used for preventing and treating tuberculosis in early stage. According to the invention, rare earth Ce and antibacterial elements Cu and Ga are added to generate a synergistic effect, so that more excellent microbial corrosion resistance can be obtained. The content of rare earth Ce in the invention is 0.1-0.2%.
The invention also provides a manufacturing method of the stainless steel with microbial corrosion resistance for the oil well pipe, the stainless steel can be obtained by smelting in a vacuum induction furnace, can also be obtained by adopting an electric furnace and external refining mode, and can also be obtained by adopting a blast furnace, the electric furnace and external refining mode; no matter which mode is adopted for smelting, Ga element needs to be added in the later stage of smelting, and the steel is poured and tapped immediately after being uniformly stirred.
The steel ingot poured by the invention is heated and forged in an austenite single-phase region, the initial forging temperature range is 1100-1200 ℃, and the final forging temperature is not lower than 900 ℃;
the 1 st forging deformation of the steel ingot is less than 10 percent, and the total forging ratio is more than 6;
after forging, air cooling to 400-600 ℃, putting the mixture into a heat treatment furnace for heat preservation, and preserving the heat for 20-120 minutes at 400-600 ℃;
or the steel ingot poured by the invention is homogenized for 4 hours in a heat treatment furnace at 1200 +/-50 ℃, and then thermo-mechanical controlled rolling (TMCP) is carried out, wherein the initial rolling temperature is 1100-1200 ℃, and the final rolling temperature is more than or equal to 800 ℃;
the deformation of the first rolling is less than 10%, the accumulated rolling reduction of hot rolling reaches more than 90%, and air cooling is carried out after rolling; and (4) stopping cooling at the temperature of 400-600 ℃, and then putting the plate into a heat treatment furnace at the temperature of 400-600 ℃ for heat preservation for 20-120 minutes.
Preferably:
the steel ingot poured by the invention is heated and forged in an austenite single-phase region, the initial forging temperature range is 1100-1150 ℃, and the final forging temperature is not lower than 900 ℃;
the 1 st forging deformation of the steel ingot is less than 10 percent, and the total forging ratio is more than 6;
after forging, air cooling to 550 ℃, putting the mixture into a heat treatment furnace for heat preservation, and preserving the heat for 60 minutes at 550 ℃;
or the steel ingot poured by the invention is subjected to homogenization treatment in a 1200 heat treatment furnace for 4 hours, and then thermo-mechanical controlled rolling (TMCP) is carried out, wherein the initial rolling temperature is 1100-1150 ℃, and the final rolling temperature is more than or equal to 800 ℃;
the deformation of the first rolling is less than 10%, the accumulated rolling reduction of hot rolling reaches more than 90%, and air cooling is carried out after rolling;
the final cooling temperature is 550 ℃, and then the plate is put into a 550 ℃ heat treatment furnace for heat preservation for 60 minutes.
The stainless steel for the oil well pipe obtained by the components and the manufacturing method has excellent toughness, stress corrosion cracking resistance and microbial corrosion resistance, and can be applied to the production of steel for the oil well pipe.
The invention has the beneficial effects that:
according to the invention, a proper amount of Cu, Ga and rare earth element Ce are added on the basis of the components of the traditional super martensitic stainless steel for the oil well pipe, and under the synergistic action of the Cu, Ga and rare earth element Ce, the steel can obtain better toughness and excellent stress corrosion cracking resistance, and meanwhile, the steel also has excellent microbial corrosion resistance.
Detailed Description
The invention will now be described by comparison of various examples and comparative examples, which are for illustrative purposes only and the invention is not limited to these examples.
Table 1 shows the chemical compositions of various steels in examples and comparative examples.
The preparation method comprises the following specific steps:
in each embodiment and the comparative example, a 25kg vacuum induction furnace is adopted for smelting, steel ingots are heated and forged in an austenite single-phase region, the initial forging temperature range is 1100-1150 ℃, and the final forging temperature is not lower than 900 ℃; the steel ingots of the examples had a 1 st forging strain of < 10% and a total forging ratio of > 6.
After forging, the steels of various examples and comparative examples are air-cooled to 550 ℃, and then placed into a 550 ℃ heat treatment furnace for heat preservation for 60 minutes.
Table 1 examples and comparative examples steel composition table (weight percentage,%)
Table 2 lists the mechanical properties of the example and comparative steels.
TABLE 2 mechanical properties of the examples and comparative examples
The impact specimen is full size: 10 mm. times.10 mm. times.55 mm, and the test temperature was room temperature.
Hydrogen sulfide stress corrosion test the resistance to hydrogen sulfide induced stress corrosion cracking of the examples and comparative examples was evaluated by the constant load method, referring to method a in NACE TM 0177 standard. The stress corrosion cracking resistance of the examples and comparative examples is shown in Table 3.
TABLE 3 Hydrogen induced cracking resistance parameters
The pitting corrosion performance of the stainless steels of examples and comparative examples after being co-cultured for 14 days with Sulfate Reducing Bacteria (SRB) inoculated bacteria isolated from petroleum produced water in a simulated fluid was evaluated. The pitting caused by microbial corrosion is the most recognized harm of the microbial corrosion to materials in the world at present, and the pitting depth is regarded as an important index for quantitatively evaluating the microbial corrosion resistance of the materials, so that the maximum pitting depth caused by sulfate reducing bacteria corrosion on the surface of a sample after corrosion is detected by a laser confocal microscope, and the test result is shown in table 4.
Table 4 maximum pitting depth test results of examples and comparative examples
As can be seen from the data in tables 2-4, compared with the comparative example, the stainless steel for the oil well pipe has excellent toughness, hydrogen sulfide stress corrosion cracking resistance and microbial corrosion resistance.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (5)
1. The stainless steel for the oil well pipe is characterized by comprising the following chemical components in percentage by weight:
c: less than or equal to 0.03; si: 0.1-0.3%; mn: less than or equal to 0.5 percent; cr: 12.0-14.0%; ni: 4.0 to 6.0; mo: 1.5-2.5%; cu: 1.0-2.0%; ga: 0.1 to 0.8 percent; ce: 0.1 to 0.2 percent; s is less than or equal to 0.02; p is less than or equal to 0.03 percent; the balance of Fe and inevitable impurities; according to weight percentage, the chemical components of the steel meet the following requirements:
Cu+Ga+Ce≥2％ (1)
wherein, each element symbol in the formula (1) is substituted into the corresponding element content.
2. The microbial corrosion resistant stainless steel for oil well pipes according to claim 1, further comprising one or more of Nb, V, Ti, Al, B, each in an amount of 0.1% by weight or less.
3. A method for producing the stainless steel for an oil well pipe resistant to microbial corrosion according to claim 1, characterized by comprising: the stainless steel is obtained by smelting in a vacuum induction furnace, or by adopting an electric furnace and external refining mode, or by adopting a blast furnace, an electric furnace and external refining mode; no matter which mode is adopted for smelting, Ga element needs to be added in the later stage of smelting, and the steel is poured and tapped immediately after being uniformly stirred.
4. The method of manufacturing a stainless steel for an oil well pipe resistant to microbial corrosion according to claim 3, wherein:
(1) the cast steel ingot is heated and forged in an austenite single-phase region, the initial forging temperature range is 1100-1200 ℃, and the final forging temperature is not lower than 900 ℃; the 1 st forging deformation of the steel ingot is less than 10 percent, and the total forging ratio is more than 6; after forging, air cooling to 400-600 ℃, putting the mixture into a heat treatment furnace for heat preservation, and preserving the heat for 20-120 minutes at 400-600 ℃;
or (2) homogenizing the cast steel ingot in a heat treatment furnace at 1200 +/-50 ℃ for 4 hours, and then performing thermo-mechanical controlled rolling at the initial rolling temperature of 1100-1200 ℃ and the final rolling temperature of more than or equal to 800 ℃; the deformation of the first rolling is less than 10%, the accumulated rolling reduction of hot rolling reaches more than 90%, and air cooling is carried out after rolling; and (4) stopping cooling at the temperature of 400-600 ℃, and then putting the plate into a heat treatment furnace at the temperature of 400-600 ℃ for heat preservation for 20-120 minutes.
5. The method for producing a stainless steel for an oil well pipe resistant to microbial corrosion according to claim 4, wherein:
(1) the cast steel ingot is heated and forged in an austenite single-phase region, the initial forging temperature range is 1100-1150 ℃, and the final forging temperature is not lower than 900 ℃; the 1 st forging deformation of the steel ingot is less than 10 percent, and the total forging ratio is more than 6; after forging, air cooling to 550 ℃, putting the mixture into a 550 ℃ heat treatment furnace for heat preservation for 60 minutes;
or (2) homogenizing the cast steel ingot in a 1200 heat treatment furnace for 4 hours, and then performing thermo-mechanical controlled rolling, wherein the initial rolling temperature is 1100-1150 ℃, and the final rolling temperature is more than or equal to 800 ℃; the deformation of the first rolling is less than 10%, the accumulated rolling reduction of hot rolling reaches more than 90%, and air cooling is carried out after rolling; the final cooling temperature is 550 ℃, and then the plate is put into a 550 ℃ heat treatment furnace for heat preservation for 60 minutes.
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| CN115558856B (en) * | 2022-09-30 | 2023-11-03 | 马鞍山钢铁股份有限公司 | Pipeline steel resistant to corrosion of microorganisms and carbon dioxide and preparation method thereof |
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