CN101929313A - High-strength hydrogen-sulfide environmental corrosion-resistant seamless petroleum casing pipe and manufacturing method thereof - Google Patents
High-strength hydrogen-sulfide environmental corrosion-resistant seamless petroleum casing pipe and manufacturing method thereof Download PDFInfo
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Abstract
The invention discloses a high-strength hydrogen-sulfide environmental corrosion-resistant seamless petroleum casing pipe which conforms to a 125ksi steel grade and comprises the following components in mass percentage: 0.25-0.35 percent of C, 0.1-0.5 percent of Si, 0.4-1.0 percent of Mn, 0.1-2.0 percent of Cr, 0.2-2.0 percent of Mo, 0.03-0.3 percent of V, 0.01-0.3 percent of Nb, less than 0.015 percent of P, less than 0.010 percent of S and the balance of Fe and inevitable impurities. The seamless petroleum casing pipe can be widely applied to sulfur-contained deep-well and ultradeep-well drilling and mining operations and has quite broad application prospect. The invention also discloses a manufacturing method of the seamless petroleum casing pipe.
Description
Technical field
The present invention relates to a kind of seamless tubing and casing and manufacture method thereof of hydrogen-sulfide environmental corrosion-resistant of the 125ksi of meeting grade of steel.
Background technology
In the existing oil gas field in the world about 1/3 all contains hydrogen sulfide gas, these acid stink damps are known from experience makes ferrous materials generation sulfide-stress cracking (Sulfide Stress Cracking), and it is particularly outstanding that this problem shows in Aldecor (High Strength Low Alloy Steel).Because the hydrogen sulfide corrosion resistance of oil well pipe can be directly connected to oil field equipment and personnel's safety, so the sulfur resistance of HSLA steel becomes the problem that each oil well pipe manufacturing enterprise and oil field user pay close attention to.The oil company when steel pipe is purchased except that requiring product to satisfy the API standard; also often have the requirement of hydrogen sulfide corrosion resistance energy; promptly require steel pipe to meet the standard of NACE MR0175, and carry out SSCC (Sulfide Stress Corrosion Cracking) by NACE TM0177 standard and test with material.
In the past few decades, the production technology of the anti-sulphur pipe of high strength has obtained the development of advancing by leaps and bounds, and its minimum nominal yield strength (Specified Minimum Yield Strength) is brought up to 110ksi (758MPa) from 80ksi (552MPa), 90ksi (621MPa), 95ksi (655MPa) always.API with 90 and the anti-sulphur pipe of 95ksi grade of steel take in the API 5CT/ISO11960 standard and called after C90 and T95 respectively.100 and the anti-sulphur pipe of 110ksi grade of steel revenue standard not also, be commonly referred to as C100 and C110.As for the anti-sulphur sleeve pipe of 125ksi (862MPa) grade of steel, though there are some reports, still there is suitable difficulty in its commercialization.For example the flat 6-322478 of Japanese Patent Application Laid-Open, spy open the big at the scene production of technologies such as eddy-current heating among flat 8-311551 and the Te Kai 2006-265657 and direct quenching and have bigger difficulty in implementing; 2000-178682 communique, spy are opened 2000-256783, the spy opens 2000-297344 and Te Kai 2000-119798 has adopted the B element to improve quenching degree and the flat 11-335731 of Japanese Patent Application Laid-Open, spy open, but must add Ti to prevent to produce fragility BN after adding B, the control difficulty of smelting and the fluctuation of material property have been increased, in addition, resistance to tempering and the enhancing precipitating reinforcing effect of alloying elements such as W, Zr to improve material also adopted in these patent applications, improved cost of alloy greatly.
Summary of the invention
The object of the present invention is to provide a kind of seamless petroleum casing pipe, it meets the requirement of 125ksi grade of steel and has good hydrogen sulfide corrosion resistance energy.
Another object of the present invention is to provide a kind of preparation method of described petroleum casing pipe.
Petroleum casing pipe provided by the present invention has following composition quality percentage (wt%):
C： 0.25～0.35％，
Si： 0.1～0.5％，
Mn： 0.4～1.0％，
Cr： 0.1～2.0％，
Mo： 0.2～2.0％，
V： 0.03～0.3％，
Nb： 0.01～0.3％，
P： ＜0.015％，
S： ＜0.010％，
Surplus is Fe and unavoidable impurities.
The method of the above-mentioned seamless petroleum casing pipe of manufacturing provided by the present invention, comprise steel-making, double refining, continuous casting, hot-puncturing process, air cooling, conditioning treatment and final heat treatment, the heating-up temperature of described conditioning treatment is 900～930 ℃, temperature retention time is no more than 30min, described final heat treatment is modulation heat treatment, its quenching temperature is 930～1000 ℃, and temperature retention time is more than 45min, and its temperature is more than 650 ℃.
Preferably, described conditioning treatment is normalizing or modulation heat treatment.
Preferably, described method also comprises thermal straightening.
Preferably, the temperature of described thermal straightening is more than 480 ℃.
To further specify the present invention below.
The high steel grade sulfur resistant sleeve pipe not only requires material to have higher intensity, also require to have certain hydrogen sulfide corrosion resistant ability simultaneously, yet a pair of often contradiction of intensity and sulfur resistance, higher intensity generally can cause the reduction of sulfur resistance, and, must sacrifice the certain intensity index usually in order to obtain higher sulfur resistance.In the present invention, the applicant finds near separate out the crystal boundary of high-strength Cr-Mo alloy steel thick carbide such as M
23C
6, M
3Meetings such as C become the weak spot that cracking takes place in loading process, cause the generation of intercrystalline corrosion cracking, directly influence the sulfur resistance of material.The applicant also finds can suppress thick carbide and separate out by adding trace alloying element, and makes tiny carbide be disperse evenly to distribute, thereby effectively improves the anti intercrystalline corrosion cracking ability of Cr-Mo steel, improves its sulfur resistance.Trace alloying element in the steel is not to play a role separately, and the applicant adopts the mode of compound interpolation, obtains best strengthening effect with less alloy adding, reaches cost-benefit maximization.Below the design of alloying component of the present invention is described:
C:C is a carbide former, can improve the intensity of steel, and it is too low that carbon content is lower than 0.25% o'clock strength of materials, surpasses at 0.35% o'clock and can reduce the toughness of steel greatly, and form thick carbide, reduces the hydrogen sulfide corrosion resistance energy of material;
Si:Si act as solution strengthening, helps deoxidation, improves the intensity and the quenching degree of steel, and content is not obvious less than effect in 0.1% o'clock, and content was greater than 0.5% o'clock, and the microstructure segregation tendency increases the weight of;
Mn:Mn is an austenite former, can improve the quenching degree of steel, and content is not obvious less than effect in 0.4% o'clock, and content was greater than 1.0% o'clock, and the microstructure segregation tendency increases the weight of, and influences the uniformity of hot rolling microstructure;
Cr:Cr is a carbide former, can improve the intensity and the quenching degree of steel, is lower than 0.1% o'clock DeGrain, is higher than the toughness that can reduce steel at 2.0% o'clock greatly;
Mo:Mo mainly by forming the intensity that carbide improves steel, is lower than 0.2% o'clock DeGrain, is higher than the toughness that can reduce steel at 2.0% o'clock;
V:V can crystal grain thinning, forms carbide, improves the intensity and the toughness of steel, is lower than 0.03% o'clock DeGrain, is higher than the toughness that can reduce steel at 0.3% o'clock;
Nb:Nb can crystal grain thinning, forms carbide, improves the intensity and the toughness of steel, is lower than 0.01% o'clock DeGrain, is higher than 0.3% back strengthening effect and does not further improve;
P:P easily forms abnormal structure's segregation, reduces sulfur resistance, and the present invention controls P＜0.015%;
S:S easily forms sulphide inculsion, has a strong impact on sulfur resistance, and the present invention controls S＜0.010%.
In the present invention, the applicant finds to adopt conditioning treatment+final heat-treating methods, can produce the tubing and casing that meets the good hydrogen sulfide corrosion resistance energy of having of 125ksi grade of steel.
Before carrying out final heat treatment, carry out a conditioning treatment earlier, can adjust the microscopic structure of material, make to organize tinyly evenly to keep a part of undissolved carbide with crystal grain thinning, for final heat treatment ready.The carbide of Nb, V is even and tiny, mainly with M
3The form of C and MC exists, the applicant finds that the heating-up temperature of conditioning treatment should be between 900～930 ℃, temperature retention time should be no more than 30min, if it is insufficient to be lower than 900 ℃ of austenitizings, there is hot rolling microstructure to exist, influence sulfur resistance and mechanical property, be higher than 930 ℃ or temperature retention time surpass 30min then carbide fully dissolve, can not in final heat treatment process subsequently, play the effect that hinders grain growth.Conditioning treatment can be modes such as normalizing or modulation heat treatment.
Final heat treated hardening heat should be more than 930 ℃, to reach the complete austenitizing temperature, thereby in quench cooled subsequently, finish austenite to martensitic transition process, but quenching temperature surpasses 1000 ℃ can make crystal grain thick, reduce the toughness of steel, the heat tracing time before quenching should fully dissolve in the austenite alloying element in the steel more than 45min, obtains single-phase martensite tissue as much as possible to guarantee the quenching back.The quenched martensite of steel is organized many more, and the microscopic structure after the tempering is even more, and its hydrogen sulfide corrosion resistance can be good more.Temperature should be higher than 650 ℃, to guarantee that quenched martensite can fully decompose, obtains the good tempered sorbite tissue of comprehensive mechanical property.
As carrying out thermal straightening, should carry out more than 480 ℃ after the final heat treatment,, help improving the sulfur resistance of material to reduce the residual stress that produces because of aligning.
Steel grade of the present invention can reach following performance after tube rolling and heat treatment:
Yield strength Rt0.65=862～1035MPa
Tensile strength Rm 〉=932MPa
Elongation per unit length A50.8 〉=18%
Impact toughness vertically＞100J
Hydrogen sulfide corrosion resistance energy: press the A method of NACE TM0177 standard, in the B solution that feeds saturated hydrogen sulfide, apply 125ksi * 80% load immersion 720h and do not ftracture.
The present invention is by being to add microalloy elements such as Nb, V on the basis of alloy system at Cr-Mo, and carries out rational conditioning treatment+final heat treatment, can produce meet the good hydrogen sulfide corrosion resistance of having of 125ksi grade of steel can tubing and casing.
The advantage that the present invention compared with prior art has is:
(1) the compound interpolation of the present invention by microalloy element greatly reduces the cost of alloy of material, has great economic benefit, and given full play to alloying element improve quenching degree, increase resistance to tempering and precipitation strength effect;
(2) the production method operation of electric resistance welding petroleum sleeve pipe provided by the invention is simple, implements easily.
The specific embodiment
Embodiment and Comparative Examples chemical composition see Table 1, and its mechanical property and sulfur resistance contrast see Table 2, and wherein Comparative Examples 1 and 2 is respectively the anti-sulphur sleeve pipe of API Q125 steel and 110ksi.Make seamless steel pipe through steps such as steel-making, continuous casting, hot-puncturing process, air cooling, conditioning treatment and final heat treatments, begin about 1650 ℃ of tapping temperature when wherein making steel, continuous casting begins about 1550 ℃ of temperature, about 1200 ℃ of beginning drilling/rollings, temperature was about 900 ℃ behind the final stretch reducing when continuous casting billet carried out hot rolling.The type of conditioning treatment is modified heat treatment, and the austenitizing heating-up temperature is 920 ℃, and temperature is 670 ℃, insulation 60min.Final heat treatment is modified heat treatment, and the austenitizing heating-up temperature is 950 ℃, insulation 90min; Its temperature is 700 ℃, insulation 120min.
The chemical composition wt% of table 1 steel of the present invention and existing alloy steel
Annotate: surplus is Fe and unavoidable impurities element.
The performance comparison of table 2 steel of the present invention and existing alloy steel
By table 1 and 2 as seen, though the intensity of API Q125 steel has reached the 125ksi grade of steel, sulfur resistance is bad; Though the anti-sulphur pipe of 110ksi grade of steel has sulfur resistance preferably, intensity rank is far below the 125ksi grade of steel; And on being the basis of alloy system, Cr-Mo only adds microalloy elements such as Nb, V according to the present invention, and carry out reasonably final heat treatment, can produce yield strength more than the 125ksi grade of steel and have good hydrogen sulfide corrosion resistance can petroleum casing pipe, this petroleum casing pipe can be widely used in deep-well, the ultradeep well probing mining operations of sulfur-bearing, has very wide application prospect.
Claims (5)
1. seamless petroleum casing pipe, its composition quality percentage is:
C： 0.25～0.35％，
Si： 0.1～0.5％，
Mn： 0.4～1.0％，
Cr： 0.1～2.0％，
Mo： 0.2～2.0％，
V： 0.03～0.3％，
Nb： 0.01～0.3％，
P： ＜0.015％，
S： ＜0.010％，
Surplus is Fe and unavoidable impurities.
2. make the method for seamless petroleum casing pipe as claimed in claim 1, comprise steel-making, double refining, continuous casting, hot-puncturing process, air cooling, conditioning treatment and final heat treatment, it is characterized in that, the heating-up temperature of described conditioning treatment is 900～930 ℃, temperature retention time is no more than 30min, and described final heat treatment is modulation heat treatment, and its quenching temperature is 930～1000 ℃, temperature retention time is more than 45min, and its temperature is more than 650 ℃.
3. method as claimed in claim 2 is characterized in that, described conditioning treatment is normalizing or modulation heat treatment.
4. as claim 2 or 3 described methods, it is characterized in that described method also comprises thermal straightening.
5. method as claimed in claim 4 is characterized in that, the temperature of described thermal straightening is more than 480 ℃.
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Cited By (10)
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| CN102251180A (en) * | 2011-07-07 | 2011-11-23 | 内蒙古包钢钢联股份有限公司 | Rare-earth-containing ultrahigh strength collapse-resistant petroleum casing and production method thereof |
| CN102251079A (en) * | 2011-07-11 | 2011-11-23 | 温州市开诚机械有限公司 | Water-quenching-and-tempering heat treatment process for high-temperature high-pressure low-alloy steel casting for turbine |
| CN104388825A (en) * | 2014-11-25 | 2015-03-04 | 江苏常宝钢管股份有限公司 | Preparation process of anti-CO2-corrosion oil well pipe with steel grade of less than 150ksi produced by CPE unit |
| CN104480278A (en) * | 2014-12-24 | 2015-04-01 | 江苏隆盛钻采机械制造有限公司 | Thermal processing process for oil casing pup joint |
| CN105002425A (en) * | 2015-06-18 | 2015-10-28 | 宝山钢铁股份有限公司 | Steel for super-high-strength and super-high-toughness petroleum casing, petroleum casing and manufacturing method of petroleum casing |
| CN105177434A (en) * | 2015-09-25 | 2015-12-23 | 天津钢管集团股份有限公司 | Manufacturing method of 125ksi steel grade hydrogen-sulfide-stress-corrosion-resistant oil well pipe |
| CN105648339A (en) * | 2016-02-04 | 2016-06-08 | 攀钢集团成都钢钒有限公司 | 125 ksi steel grade casing steel and manufacturing method thereof |
| JPWO2015190377A1 (en) * | 2014-06-09 | 2017-04-20 | 新日鐵住金株式会社 | Low alloy oil well steel pipe |
| CN108866443A (en) * | 2018-07-19 | 2018-11-23 | 张家港宏昌钢板有限公司 | Normalizing type low yield strength ratio high-strength steel sheet and preparation method |
| CN116640989A (en) * | 2023-05-26 | 2023-08-25 | 鞍钢股份有限公司 | High-strength corrosion-resistant seamless steel pipe for oil well and production process thereof |
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| CN102251180A (en) * | 2011-07-07 | 2011-11-23 | 内蒙古包钢钢联股份有限公司 | Rare-earth-containing ultrahigh strength collapse-resistant petroleum casing and production method thereof |
| CN102251079A (en) * | 2011-07-11 | 2011-11-23 | 温州市开诚机械有限公司 | Water-quenching-and-tempering heat treatment process for high-temperature high-pressure low-alloy steel casting for turbine |
| JPWO2015190377A1 (en) * | 2014-06-09 | 2017-04-20 | 新日鐵住金株式会社 | Low alloy oil well steel pipe |
| CN104388825B (en) * | 2014-11-25 | 2016-08-17 | 江苏常宝钢管股份有限公司 | The anti-CO of below 150ksi grade of steel that CPE unit produces2the preparation technology of corrosion oil well pipe |
| CN104388825A (en) * | 2014-11-25 | 2015-03-04 | 江苏常宝钢管股份有限公司 | Preparation process of anti-CO2-corrosion oil well pipe with steel grade of less than 150ksi produced by CPE unit |
| CN104480278A (en) * | 2014-12-24 | 2015-04-01 | 江苏隆盛钻采机械制造有限公司 | Thermal processing process for oil casing pup joint |
| CN105002425A (en) * | 2015-06-18 | 2015-10-28 | 宝山钢铁股份有限公司 | Steel for super-high-strength and super-high-toughness petroleum casing, petroleum casing and manufacturing method of petroleum casing |
| CN105177434B (en) * | 2015-09-25 | 2017-06-20 | 天津钢管集团股份有限公司 | The manufacture method of 125ksi grade of steel sulfurated hydrogen stress etching-resisting oil well pipes |
| CN105177434A (en) * | 2015-09-25 | 2015-12-23 | 天津钢管集团股份有限公司 | Manufacturing method of 125ksi steel grade hydrogen-sulfide-stress-corrosion-resistant oil well pipe |
| CN105648339A (en) * | 2016-02-04 | 2016-06-08 | 攀钢集团成都钢钒有限公司 | 125 ksi steel grade casing steel and manufacturing method thereof |
| CN105648339B (en) * | 2016-02-04 | 2018-05-08 | 攀钢集团成都钢钒有限公司 | 125ksi steel-grade bushing steel and preparation method thereof |
| CN108866443A (en) * | 2018-07-19 | 2018-11-23 | 张家港宏昌钢板有限公司 | Normalizing type low yield strength ratio high-strength steel sheet and preparation method |
| CN116640989A (en) * | 2023-05-26 | 2023-08-25 | 鞍钢股份有限公司 | High-strength corrosion-resistant seamless steel pipe for oil well and production process thereof |
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Application publication date: 20101229 |