CN101397637A - 13Cr high anti-carbon dioxide and trace hydrogen sulfide corrosion tubing and casing steel and method for producing the same - Google Patents
13Cr high anti-carbon dioxide and trace hydrogen sulfide corrosion tubing and casing steel and method for producing the same Download PDFInfo
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- CN101397637A CN101397637A CNA2007100466213A CN200710046621A CN101397637A CN 101397637 A CN101397637 A CN 101397637A CN A2007100466213 A CNA2007100466213 A CN A2007100466213A CN 200710046621 A CN200710046621 A CN 200710046621A CN 101397637 A CN101397637 A CN 101397637A
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Abstract
The invention discloses a 13Cr oil bushing steel which has high resistance to carbondioxide and trace hydrogen sulfide corrosion and a manufacturing method thereof, wherein, the chemical constituents ratio according to weight percentage is as follows: C: 0.01 to 0.05 percent, Si: is less than or equal to 0.5 percent, Mn: 0.20 to 1.00 percent, Cr: 12 to 14 percent, Mo: 1.0 to 3.0 percent, Ni: 4.0 to 6.0 percent, Cu: 1.0 to 2.0 percent, Nb: 0.02 to 0.10 percent, and Fe and inevitable impurity as the rest, and the total amount of the impurity is lower than 0.05 percent. Non-API corrosion-resistant oil bushing can be obtained after electric furnace steelmaking, ingot casting, calcining, cogging, rolling, pipe-manufacturing and reasonable heat treatment. The resistance to hydrogen sulfide corrosion of the materials is obviously improved by copper-niobium alloying.
Description
Technical field
The present invention relates to a kind of super 13Cr stainless steel oil annular tube steel and manufacture method thereof, particularly contain the chemical ingredients of the oil gas well oil annular tube steel under the combination of acidic corrosion working conditions such as high-humidity carbonic acid gas, chlorion, trace hydrogen sulfide.
Background technology
13Cr stainless steel tubing and casing steel grade has only one of 2Cr13 in the existing API 5CT standard, and the product grade of steel is up to 95ksi, and the highest service temperature is 120 ℃.In addition, this product anti-H 2 S stress corrosion cracking performance is poor, is not suitable for the hydrogen sulfide corrosion environment.Along with the oil and gas exploitation condition constantly worsens, well depth surpasses 5000m, corrosive environment is rich in CO simultaneously
2The oil gas well that surpasses API standard 13Cr steel pipe service condition with hydrogen sulfide and intensity constantly increases, be badly in need of anti-higher service temperature (〉=150 ℃), corrosion resisting property better (carbonic acid gas and trace hydrogen sulfide), tubing and casing that intensity is higher, as 110 steel grade oil sleeve pipes.For satisfying high strength and high anti-corrosion requirement, external each big steel pipe factory develops the nonstandard 110-13Cr stainless steel tubing and casing of high temperature resistant high carbon dioxide and trace hydrogen sulfide corrosion one after another, as the KO-HP2-13Cr110 of Kawasaki, the low-carbon (LC) SM13CRM-110 of Sumitomo etc., its chemical ingredients is as shown in table 1.
The chemical ingredients of the super 13Cr tubing and casing in table 1 Kawasaki and Sumitomo
Japanese patent laid-open 4-224656 is applicable to 100-150 ℃, requirement of strength 90-100 grade of steel, and 0.007Mpa hydrogen sulfide does not ftracture; Grade of steel is the highest in clear 61-207550, the flat 4-88152 patent can only arrive 100Ksi, and in addition, carbon content is higher, H
2The S poor-performing; And the spy opens the compound elements such as Al, N, Ti that added in the flat 11-140594 patent, and smelting process forms AlN, TiN etc. easily to H
2The influential brittle inclusion of S stress corrosion crack.Above-mentioned patent is primarily aimed at and requires anti-CO
2With micro-H
2Tubing and casing is used in the S corrosion, and its chemical ingredients is as shown in table 2.
The chemical ingredients of oil annular tube steel (wt%) in table 2 Japanese Patent
| The patent No. (grade of steel) | C | Si | Mn | Cr | Ni | Mo | Cu | Al | N | B(Ti) | Nb | Fe |
| Clear 61-207550 (100Ksi) | 0.03 /0.20 | ≤1.0 | ≤ 1.0 | 12 /14 | 0.5 /6.0 | 0.5 /4.0 | ≤ 0.006 | Balance | ||||
| Te Kaiping 4-224656 (90-100Ksi) | 0.02 /0.05 | ≤0.3 | 0.30/ 1.2 | 12 /14 | 3.0 /5.0 | 0.5 /1.5 | 0.01 /0.05 | 0.03 /0.08 | Balance | |||
| Te Kaiping 11-140594 (nothing) | ≤0.05 | ≤0.5 | ≤ 1.5 | 10 /14 | 4.0 /7.0 | 1.0 /3.0 | 1 /2 | 0.06 /0.3 | ≤ 0.08 | 0.005 / 0.05Ti | Balance | |
| Flat 4-88152 (≤100Ksi) | 0.08 /0.25 | ≤1.0 | ≤ 2.0 | 14 /16 | 0.5 /3.0 | 0.1 /1.0 | 0.03 /0.10 | 0.05 /0.30 | Balance |
Summary of the invention
The object of the present invention is to provide a kind of 13Cr high anti-carbon dioxide and trace hydrogen sulfide corrosion tubing and casing steel and manufacture method thereof.
The present invention is achieved in that a kind of 13Cr high anti-carbon dioxide and trace hydrogen sulfide corrosion tubing and casing steel, and by weight percentage, its chemical ingredients proportioning is:
C：0.01～0.05％， Si：≤0.5％，
Mn：0.20～1.00％， Cr：12～14％，
Mo：1.0～3.0％， Ni：4.0～6.0％，
Cu：1.0～2.0％， Nb：0.02～0.10％，
All the other are Fe and unavoidable impurities element, and the impurity element total amount is lower than 0.05%.
The characteristics of oil annular tube steel of the present invention are by a small amount of Cu of compound adding and micro-Nb element, not only composition is simple relatively, and guaranteed that intensity rank reaches 110 grade of steels, under 150-180 ℃, guaranteed the corrosive natures such as resistant to carbon dioxide, hydrogen sulfide and chlorion of steel simultaneously.
The selection reason of oil annular tube steel chemical composition design of the present invention is as follows:
C: be the bioelement that guarantees steel strength performance and corrosive nature.Be to guarantee necessary strength, carbon content can not be low excessively, and carbon content is lower than 0.01% o'clock hardening capacity and undercapacity; Carbon content surpasses 0.05%, reduces crystal boundary chromium content because of carbon and chromium form carbide in the tissue, the reduction corrosion resistance.
Cr: be the main alloy element that improves solidity to corrosion and intensity.Cr content is less than 12% o'clock, the solidity to corrosion deficiency, and Cr content was greater than 14% o'clock, and the intensity and the hardness of material are too high, reduce the toughness of material.The too high plain body of high temperature iron that also easily causes of chromium forms, and reduces hot workability.
Ni: improve corrosive nature and toughness, useful to reducing Cold Brittleness Transition Temperature simultaneously.The Ni add-on is less than 4%, the sulfur resistance DeGrain, and add-on surpasses 6%, and cost increases too high.
Mo: be anti-spot corrosion and the necessary element of anti-sulphide stress corrosion performance.Be lower than 1.0% DeGrain, surpass the increase of 3% cost and very easily cause the high temperature delta ferrite to form the high temperature deformation mis-behave.
Nb: can improve the steel temper resistance as micro alloying element, be lower than 0.02% o'clock DeGrain, surpass 0.1% o'clock poor processability.
Cu: at CO
2Form protective membrane in the medium, improve corrosion resisting property.Less than 1%, it is not obvious that the copper amount is crossed low effect, surpasses 2%, is prone to crystal boundary and separates out, and worsens processing characteristics.
Si: add and play deoxidation in the steel and improve corrosion proof effect, but be higher than 0.5%, processing and toughness worsen.
Mn: improve the element of the obdurability of steel, not obvious less than effect in 0.2% o'clock, greater than 1%, will reduce corrosive nature.
The manufacture method of a kind of 13Cr high anti-carbon dioxide and trace hydrogen sulfide corrosion tubing and casing steel comprises the steps:
1) oil annular tube steel chemical composition proportioning is by weight percentage: C:0.01～0.05%, Si :≤0.5%, Mn:0.20～1.00%, Cr:12～14%, Mo:1.0～3.0%, Ni:4.0～6.0%, Cu:1.0～2.0%, Nb:0.02～0.10%, all the other are Fe and unavoidable impurities element, the impurity element total amount is lower than 0.05%;
2) oil annular tube steel with the mentioned component proportioning becomes ingot casting by the electrosmelting steel casting, adopts warm ingot to go into stove before forging, and goes into stove surface of steel ingot temperature less than 600 ℃;
3) forge the circle base and anneal after forging, annealing temperature is controlled between 650～800 ℃, annealed tube blank 1150 ℃～1250 ℃ heat tracings 1.5～2 hours after perforation, be rolled into hollow forging;
4) hot finished steel pipe carries out double tempering at 600～700 ℃ and 550～600 ℃ respectively after carrying out water quenching under 900～1000 ℃ of temperature, and tempering time all is controlled within an hour.
The principal feature of manufacture method of the present invention is that hot-rolled tube through obviously having improved the tissue of steel behind the double tempering, has greatly improved the corrosion resistance of product.
Embodiment
Table 3 is depicted as the chemical ingredients of oil annular tube steel of the present invention and existing oil annular tube steel, and by weight percentage, wherein 1-7 is a steel grade of the present invention, and 8-10 is the contrast steel grade of the stainless steel oil annular tube steel that generally uses of present oil field.
The chemical ingredients of table 3 oil annular tube steel of the present invention and existing oil annular tube steel, wt%
By the chemical ingredients shown in the table 3 steel grade of grade of steel 1-7 is become ingot casting by the electrosmelting steel casting, adopt warm ingot to go into stove before forging, go into stove surface of steel ingot temperature less than 600 ℃; Forge the circle base and anneal after forging, annealing temperature is controlled between 650～800 ℃, annealed tube blank 1150 ℃～1250 ℃ heat tracings 1.5～2 hours after perforation, be rolled into hollow forging; Hot finished steel pipe carries out double tempering at 600～700 ℃ and 550～600 ℃ respectively after carrying out water quenching under 900～1000 ℃ of temperature, tempering time all is controlled within an hour, obtains 110 steel grade oil sleeve pipe products thus.
The mechanical property of the contrast steel of the steel of the present invention of grade of steel 1～7 and grade of steel 8～10 and resistant to carbon dioxide, trace hydrogen sulfide (less than 0.01MPa) and chloride ion corrosion performance compare in the embodiment of the invention, referring to table 4.Wherein, corrosive nature is with 180 ℃ of condition carbon dioxide dividing potential drop 2.5MPa and add 3.5%NaCl, and velocity of medium is set at 2m/S, and experimental period is 168 hours, measures corrosion weight loss and converts erosion rate to, the mm/a of unit.The anti-H 2 S experiment utilizes existing high anti-sulphur constant load experimental technique (20 ℃ of room temperatures, hydrogen sulfide sectional pressure 0.01Mpa), accelerated tests as trace hydrogen sulfide, relatively whether steel of the present invention is suitable with the oil annular tube steel generation rupture time of the anti-carbonic acid gas of 110 grade of steels, trace hydrogen sulfide (less than 0.01MPa) and the chloride ion corrosion of the use of existing oil field, according to its corrosion resistance in the trace hydrogen sulfide corrosion environment.
The mechanical property of table 4 steel of the present invention and contrast steel and resistant to carbon dioxide, chlorion, hydrogen sulfide corrosion performance
| Numbering | Rt0.6 (MPa) | Rm (MPa) | A50.8(％) | 180℃，(2.5Mpa CO 2+ 3.5% NaCl), speed mm/a | Constant load hydrogen sulfide corrosion in 720 hours experiment |
| 1 | 810 | 920 | 25.0 | 0.04 | Do not ftracture |
| 2 | 800 | 924 | 25.0 | 0.03 | Do not ftracture |
| 3 | 805 | 923 | 26.0 | 0.02 | Do not ftracture |
| 4 | 803 | 916 | 28.5 | 0.05 | Do not ftracture |
| 5 | 789 | 918 | 27.5 | 0.03 | Do not ftracture |
| 6 | 778 | 910 | 22.5 | 0.02 | Do not ftracture |
| 7 | 795 | 901 | 23.0 | 0.05 | Do not ftracture |
| 8 | 800 | 890 | 22 | 0.06 | Cracking |
| 9 | 820 | 910 | 23 | 0.02 | Cracking |
| 10 | 815 | 921 | 23.5 | 0.21 | Cracking |
From the result of table 4 as can be seen, the intensity and the corrosion resistance nature of the chromium of the low-carbon (LC) that uses of oil annular tube steel high temperature resistant of the present invention, carbonic acid gas, hydrogen sulfide and chloride ion corrosion performance and existing oil field, molybdenum high-alloy stainless steel oil annular tube steel are suitable.The present invention through after Electric furnace steel making, die casting, hammer cogging, rolling tubulation and the rational heat treatment technology, can obtain the anti-corrosion tubing and casing of non-API that mechanical property satisfies 110 grade of steels with steel.By copper, niobium alloy, can obviously improve the anti-H 2 S stress corrosion cracking performance of material.
Claims (2)
1, a kind of 13Cr high anti-carbon dioxide and trace hydrogen sulfide corrosion tubing and casing steel is characterized in that: by weight percentage, its chemical ingredients proportioning is:
C：0.01～0.05％， Si：≤0.5％，
Mn：0.20～1.00％， Cr：12～14％，
Mo：1.0～3.0％， Ni：4.0～6.0％，
Cu：1.0～2.0％， Nb：0.02～0.10％，
All the other are Fe and unavoidable impurities element, and the impurity element total amount is lower than 0.05%.
2, the manufacture method of a kind of 13Cr high anti-carbon dioxide and trace hydrogen sulfide corrosion tubing and casing steel is characterized in that: comprise the steps:
1) oil annular tube steel chemical composition proportioning is by weight percentage: C:0.01～0.05%, Si :≤0.5%, Mn:0.20～1.00%, Cr:12～14%, Mo:1.0～3.0%, Ni:4.0～6.0%, Cu:1.0～2.0%, Nb:0.02～0.10%, all the other are Fe and unavoidable impurities element, the impurity element total amount is lower than 0.05%;
2) oil annular tube steel with the mentioned component proportioning becomes ingot casting by the electrosmelting steel casting, adopts warm ingot to go into stove before forging, and goes into stove surface of steel ingot temperature less than 600 ℃;
3) forge the circle base and anneal after forging, annealing temperature is controlled between 650～800 ℃, annealed tube blank 1150 ℃～1250 ℃ heat tracings 1.5～2 hours after perforation, be rolled into hollow forging;
4) hot finished steel pipe carries out double tempering at 600～700 ℃ and 550～600 ℃ respectively after carrying out water quenching under 900～1000 ℃ of temperature, and tempering time all is controlled within an hour.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2007100466213A CN101397637B (en) | 2007-09-29 | 2007-09-29 | 13Cr high anti-carbon dioxide and trace hydrogen sulfide corrosion tubing and casing steel and method for producing the same |
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|---|---|---|---|
| CN2007100466213A CN101397637B (en) | 2007-09-29 | 2007-09-29 | 13Cr high anti-carbon dioxide and trace hydrogen sulfide corrosion tubing and casing steel and method for producing the same |
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| CN101397637A true CN101397637A (en) | 2009-04-01 |
| CN101397637B CN101397637B (en) | 2010-11-24 |
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| CN102296245A (en) * | 2010-06-23 | 2011-12-28 | 宝山钢铁股份有限公司 | High-strength high-corrosion-resistance wear-resisting sleeve steel and manufacturing method |
| CN104108003A (en) * | 2013-04-19 | 2014-10-22 | 宝山钢铁股份有限公司 | Manufacturing method for super 13Cr tool joint |
| WO2019037544A1 (en) | 2017-08-25 | 2019-02-28 | 宝山钢铁股份有限公司 | Smelting method for ultra-low carbon 13cr stainless steel |
| CN113913708A (en) * | 2021-09-08 | 2022-01-11 | 邯郸新兴特种管材有限公司 | 95-steel-grade super 13Cr seamless steel pipe and production method thereof |
| CN114318123A (en) * | 2020-09-29 | 2022-04-12 | 宝山钢铁股份有限公司 | High-strength low-hardness low-cost 13Cr oil casing steel, oil casing and manufacturing method thereof |
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| CN104108003A (en) * | 2013-04-19 | 2014-10-22 | 宝山钢铁股份有限公司 | Manufacturing method for super 13Cr tool joint |
| WO2014169593A1 (en) * | 2013-04-19 | 2014-10-23 | 宝山钢铁股份有限公司 | Method for manufacturing super 13cr tool coupler |
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| US11162150B2 (en) * | 2013-04-19 | 2021-11-02 | Baoshan Iron & Steel Co., Ltd. | Method for manufacturing superior 13Cr tool coupler |
| WO2019037544A1 (en) | 2017-08-25 | 2019-02-28 | 宝山钢铁股份有限公司 | Smelting method for ultra-low carbon 13cr stainless steel |
| JP2020531691A (en) * | 2017-08-25 | 2020-11-05 | 宝山鋼鉄股▲分▼有限公司 | Refining method of ultra-low carbon 13Cr stainless steel |
| CN114318123A (en) * | 2020-09-29 | 2022-04-12 | 宝山钢铁股份有限公司 | High-strength low-hardness low-cost 13Cr oil casing steel, oil casing and manufacturing method thereof |
| CN113913708A (en) * | 2021-09-08 | 2022-01-11 | 邯郸新兴特种管材有限公司 | 95-steel-grade super 13Cr seamless steel pipe and production method thereof |
| CN114921723A (en) * | 2022-05-20 | 2022-08-19 | 无锡双马钻探工具有限公司 | Corrosion-resistant steel for trenchless drill rod and preparation method and application thereof |
| CN116288064A (en) * | 2022-12-14 | 2023-06-23 | 鞍钢股份有限公司 | Ultrahigh-strength corrosion-resistant low Wen Haigong steel plate and manufacturing method thereof |
| CN116288064B (en) * | 2022-12-14 | 2024-05-14 | 鞍钢股份有限公司 | Ultra-high-strength corrosion-resistant low Wen Haigong steel plate and manufacturing method thereof |
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