CN102242321A - Sulfide stress cracking (SSC) corrosion-resistant C110 steel grade petroleum special pipe steel and preparation method thereof - Google Patents
Sulfide stress cracking (SSC) corrosion-resistant C110 steel grade petroleum special pipe steel and preparation method thereof Download PDFInfo
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Abstract
The invention provides sulfide stress cracking (SSC) corrosion-resistant C110 steel grade petroleum special pipe steel, which comprises the following components in percentage by mass: 0.15 to 0.30 percent of C, 0.15 to 0.35 percent of Si, 0.20 to 0.50 percent of Mn, less than or equal to 0.015 percent of P, less than or equal to 0.005 percent of S, 0.80 to 1.50 percent of Cr, 0.60 to 1.00 percent of Mo, 0.01 to 0.05 percent of Nb, 0 to 0.05 percent of V, less than or equal to 0.20 percent of Ni, more than or equal to 0.0015 percent of Ca and the balance of Fe and unavoidable impurities. Meanwhile, the invention provides a preparation method of the SSC corrosion-resistant C110 steel grade petroleum special pipe steel. The invention has the advantages that: trace alloy components are added on the basis of refining clean steel, so that the hardenability of the steel is improved, a tempered sorbite structure with uniformly distributed fine carbide particles is formed after the steel is subjected to heat treatment, the impact toughness of the material is improved, the hardness of the material is reduced, the structure stress of a steel pipe subjected to heat treatment is reduced, the problems that dislocation density is increased and the like caused by high-strength steel are solved, the speed of hydrogen atoms diffusing to the inside of the material is reduced, the sensitivity of SSC corrosion is reduced, and the steel has high SSC resistance.
Description
Technical field
The present invention relates to special-purpose pipe steel of a kind of corrosive of anti-sulfide stress cracking (SSC) C110 steel level oil and manufacture method thereof.
Background technology
Along with the swift and violent increase of the whole world to the petroleum and natural gas demand, the development of resources of shallow-layer high-quality oil gas is deficient day by day, and many oil companies change over to and carry out oil-gas exploration and exploitation in severe environment, and oil gas wells such as super dark sulfur compound are more and more.Oil pipes tool generation stress cracking corrosion accident is except that causing enormous economic loss, and the hydrogen sulfide of generation has hypertoxicity, understands serious threat personnel life security, and environment is done great damage, and causes serious social influence.Hydrogen sulfide is contained in a lot of oil fields, and content is very high, as Sichuan oilfield, long celebrating oil field, oil field, Tarim Basin etc., must use the oil pipes tool with resisting sulfide stress cracking performance.Therefore the oil pipes tool of developing the resisting sulfide stress cracking is significant.
Continuous increase along with oil, gas field drilling depth, the C90 of anti-sulfide stress cracking (SSC), the special-purpose pipe of T95 steel level oil can not satisfy the demand of oil-gas field development, and developing more, the special-purpose pipe of C110 steel level oil of high strength anti sulfide stress cracking (SSC) has become particularly urgent and important.
In recent years, the relevant patent documentation that constantly occurs the research corrosion material of anti-the sulfide stress cracking (SSC) both at home and abroad:
[patent documentation 1] open (bulletin) number: CN101146924
[patent documentation 2] open (bulletin) number: CN1837394
[patent documentation 3] open (bulletin) number: CN1914343
[patent documentation 4] open (bulletin) number: CN1969053
[patent documentation 5] open (bulletin) number: CN101542001
[patent documentation 6] open (bulletin) number: CN101542002
[patent documentation 7] open (bulletin) number: CN1361306
[patent documentation 8] open (bulletin) number: CN1837395
[patent documentation 9] open (bulletin) number: CN1888119
[patent documentation 10] open (bulletin) number: CN1924068
[patent documentation 11] open (bulletin) number: CN1948538
[patent documentation 12] open (bulletin) number: CN101413088
[patent documentation 13] open (bulletin) number: CN101418419
[patent documentation 14] open (bulletin) number: CN101418421
[patent documentation 15] open (bulletin) number: CN101440460
[patent documentation 16] open (bulletin) number: CN101724785A
Above the situation of these patent documentations report, some are by the scope of strictness restriction chemical ingredients or increase the purpose that too much alloying element reaches anti-sulfide stress cracking (SSC), the production cost height, the production difficulty is big, uneconomical, be unfavorable for saving the precious metal resource, go back the enlarged link environment pollution, do great damage to ecology.Some are the low pipe steel of tensile strength, and mechanical property does not reach the requirement of the special-purpose tubing of C110 steel level oil.Also have some tensile strengths to reach the requirement of the special-purpose pipe of C110 steel level oil, load the requirement of 85%*S.M.Y.S new edition API 5CT the oil pipes tool but anti-sulfide stress cracking (SSC) performance still can not satisfy the C110 grade of steel fully.
Summary of the invention
The objective of the invention is to be to provide special-purpose pipe steel of a kind of corrosive of anti-sulfide stress cracking (SSC) C110 steel level oil and manufacture method thereof, be beneficial to guarantee the mechanical property and the oil well use properties of oil pipes tool steel excellence, reduce cost, technology is simple to operation.
For realizing above-mentioned target, the technical solution used in the present invention provides the special-purpose pipe steel of a kind of corrosive of anti-sulfide stress cracking (SSC) C110 steel level oil, and its composition is C 0.15～0.30% by mass percentage, Si 0.15～0.35%, and Mn 0.20～0.50%, P≤0.015%, S≤0.005%, Cr 0.80～1.50%, and Mo 0.60～1.00%, and Nb 0.01～0.05%, V 0～0.05%, Ni≤0.20%, Ca 〉=0.0015%, all the other are Fe and unavoidable impurities.
The manufacture method of the special-purpose pipe steel of a kind of corrosive of anti-sulfide stress cracking (SSC) C110 steel level oil is provided simultaneously.
The characteristics that the present invention compared with prior art has:
1, alloy content is few, production cost is low, technology is simple to operation, the present invention is based on the basis of refining Clean Steel, add the microalloy composition, improved the through hardening performance of steel, after heat treatment form the equally distributed tempered sorbite tissue of tiny carbide particle, have good anti-SSC performance.
2, impelling strength height, hardness is low, and unrelieved stress is little.Adopt soft steel, improved the impelling strength of material, reduced the hardness of material, reduced structural stress after the steel pipe thermal treatment, reduced the problems such as dislocation desity increase that high-strength steel causes, reduced the speed of hydrogen atom, reduced the SSC sensitivity of corrosion to the material internal diffusion.
3, You Yi anti-sulfide stress cracking (SSC) performance, in the test of the TM0177-2005A of NACE method, at 25 ℃, feeding dividing potential drop is 1atm H
2The saturated A solution of S, actual load are the SSC test under the constant load stress of 85%SMYS, and 720h does not rupture, and show to satisfy the anti-SSC performance demands of the special-purpose pipe of C110 steel level oil fully.Behind the SSC test 720h, sample tension, impact property do not have considerable change.
Embodiment
In conjunction with the embodiments special-purpose pipe steel of the corrosive of anti-sulfide stress cracking (SSC) C110 steel level oil of the present invention and manufacture method thereof are illustrated.
It is alloying element that the special-purpose pipe steel of the corrosive of anti-sulfide stress cracking (SSC) C110 steel level oil of the present invention adopts Cr-Mo-Nb, to realize good anti-SSC performance.The mass percent of its composition is C 0.15～0.30%, Si 0.15～0.35%, and Mn 0.20～0.50%, P≤0.015%, S≤0.005%, Cr 0.80～1.50%, and Mo 0.60～1.00%, and Nb 0.01～0.05%, V 0～0.05%, Ni≤0.20%, Ca 〉=0.0015%, all the other are Fe and unavoidable impurities.
Chemical ingredients is formed detailed description:
C：0.15～0.30％
C is the important composition element of low alloy steel, is the important element that after heat treatment forms the equally distributed tempered sorbite tissue of tiny carbide particle.C content≤0.20% o'clock, M
sAnd M
fPoint is higher, causes that the required critical shear stress of slippage is lower, after the quenching, almost all changes lath martensite into, has also reduced the hardness of material simultaneously, has improved the toughness of material, all helps improving anti-SSC performance.For guaranteeing the necessary intensity of steel pipe, be limited to 0.15% under the C constituent content.C element preferred content is 0.15～0.25%.
Si：0.15～0.35％
Si is the necessary element of steel deoxidation.Too much can make the erosion resistance of steel and impelling strength reduce but add.So its content is controlled at 0.15～0.35%.
Mn：0.20～0.50％
Mn be in steel-making as the required element of deoxidation, the Mn element of certain content also can improve the hardening capacity and the toughness of steel.On the other hand, the interpolation of Mn is excessive, also can reduce the toughness of steel, promotes harmful element P, S, Sn, Sb etc. to grain boundary segregation in process of setting, thereby the crystal boundary linkage force is descended significantly, reduces anti-H
2The S performance.Therefore, Mn element preferred content is 0.20～0.50%.
P：≤0.015％
P is the impurity element in the steel, makes the erosion resistance of steel, toughness reduce.In order to obtain enough erosion resistances, toughness, the content of P is controlled at below 0.015%.
S：≤0.005％
S is the impurity element in the steel, makes hot workability, erosion resistance, the toughness of steel reduce.In order to obtain enough erosion resistances, the content of S is controlled at below 0.005%.
Cr：0.80～1.50％
The Cr element is the element that intensive stops bainite transformation in quenching process, can effectively improve the hardening capacity of steel.Have anti-temper softening, can improve the physical strength of steel, and reduce the erosion rate of steel.On the other hand, the Cr constituent content is too much, and the carbide that can cause crystal boundary to form thick chromium is separated out, and reduces anti-SSC performance and toughness.Therefore, Cr element preferred content is 0.80～1.20%.
Mo：0.60～1.00％
The Mo element has better anti-hydrogen performance than Cr element, and it can also reduce absorbed dose and the infiltration capacity of hydrogen in steel, improves the hardening capacity of steel.On the other hand, the Mo element easily produces segregation at crystal boundary, makes low alloy steel generation greying tendency.Therefore, Mo element preferred content is 0.60～0.80%.
Nb：0.01～0.05％
The Nb element is when high temperature deformation, produces strain inducing carbonitride precipitated phase, and refine austenite crystal grain also is the element that effectively strengthens the steel physical strength simultaneously.Nb element preferred content is 0.01～0.05%.
V：0～0.05％
A spot of V element makes the grain refining of steel, and impelling strength increases, and improves the tempering intensity of steel.On the other hand, too high levels when causing the accumulative carbide to be separated out, can reduce intensity, reduces room temperature impelling strength, causes that the mechanical property fluctuation is bigger.Therefore its content is controlled at 0～0.05% preferable.
Ca：≥0.0015％
External refining, after the vacuum outgas, feeding calcium silk, calcium fusing back moves up in liquation, with the molten steel reaction, carries out calcification processing, calcium contents 〉=0.0015% o'clock, making inclusion modification is nodule, improves the quality of steel.
The concrete manufacturing processed of the special-purpose pipe steel of the present invention's corrosive of anti-sulfide stress cracking (SSC) C110 steel level oil is as follows:
1, raw material adopts by above-mentioned composition mass percent preparation steel scrap, sponge iron, blast-melted, through the electric arc furnace fusion smelting, after the slag making dephosphorization, carry out ladle external refining, deoxidation, desulfurization, removal inclusion, vacuum outgas, guarantee condition of high vacuum degree≤66.7Pa, time 10-15min, feed the calcium silk and carry out the inclusion modification processing, become the circle base through continuous casting;
2, the round base of ring furnace heating steps (1), Heating temperature is 1250-1290 ℃, after the perforation, carries out tandem rolling, makes weldless steel tube;
3, to the modified thermal treatment of weldless steel tube of step (2), be heated to 900～960 ℃ and insulation through High Temperature Furnaces Heating Apparatus, make weldless steel tube organize complete austenitizing, the weldless steel tube homogeneous tube is quenched, carry out 〉=649 ℃ low temperature oven temper again, carry out hot straightening during in temperature 〉=500 ℃, detect a flaw behind the cool to room temperature, carry out mechanical property test and SSC test then.
Described in detail below in conjunction with embodiment:
It is blast-melted that raw material adopts steel scrap to add that sponge iron adds, through the electric arc furnace fusion smelting, after the slag making dephosphorization, through the ladle external refining, adjust chemical ingredients by table one requirement, vacuum outgas is under vacuum tightness≤66.7Pa, vacuum outgas 10-15min, feed Ca-Si silk inclusion modification and handle, after composition is qualified, become Φ 210-270mm circle base through continuous casting.1250 ℃ of insulations of ring furnace heat circle base are bored a hole, smart control tandem rolling, make weldless steel tube.Through modified thermal treatment, reach C110 grade of steel mechanical property (seeing Table two), and carry out anti-SSC performance test.
Table one chemical composition (Wt%)
| The steel grade class | C | Si | Mn | P | S | Ni | Cr | Mo | V | Nb | Cu | Ca |
| Embodiment 1 | 0.2 | 0.3 | 0.3 | 0.01 | 0.00 | 0.0 | 0.9 | 0.7 | 0.03 | 0.0 | 0.0 | 0.0017 |
| Embodiment 2 | 0.2 | 0.2 | 0.2 | 0.00 | 0.00 | 0.0 | 0.9 | 0.7 | 0.04 | 0.0 | 0.0 | 0.0023 |
| Embodiment 3 | 0.1 | 0.2 | 0.2 | 0.00 | 0.00 | 0.0 | 1.1 | 0.7 | 0.02 | 0.0 | 0.0 | 0.0024 |
| Embodiment 4 | 0.1 | 0.2 | 0.2 | 0.01 | 0.00 | 0.0 | 0.9 | 0.7 | 0.00 | 0.0 | 0.0 | 0.0016 |
| Embodiment 5 | 0.1 | 0.2 | 0.3 | 0.00 | 0.00 | 0.0 | 1.1 | 0.8 | 0.03 | 0.0 | 0.0 | 0.0019 |
| Comparative example 1 | 0.2 | 0.3 | 0.8 | 0.01 | 0.00 | 0.0 | 0.9 | 0.7 | 0.09 | 0.0 | 0.0 | 0.0012 |
| Comparative example 2 | 0.3 | 0.3 | 0.3 | 0.01 | 0.00 | 0.0 | 0.9 | 0.8 | 0.00 | 0.0 | 0.0 | 0.0022 |
| Comparative example 3 | 0.4 | 0.1 | 0.6 | 0.00 | 0.00 | 0.0 | 0.5 | 0.8 | 0.08 | 0.0 | 0.0 | 0.0013 |
| Comparative example 4 | 0.2 | 0.2 | 0.4 | 0.00 | 0.00 | 0.0 | 0.4 | 0.6 | 0.19 | 0.0 | 0.0 | 0.0015 |
| Comparative example 5 | 0.2 | 0.4 | 1.0 | 0.00 | 0.00 | 0.0 | 0.7 | 0.6 | 0.12 | 0.0 | 0.0 | 0.0019 |
Table two C110 grade of steel mechanical property and anti-SSC experimental performance *
| The steel grade class | Yield strength | Hardness (HRC) | SSC test-results * |
| Embodiment 1 | 812 | 27.6 | Crackle or fracture do not appear |
| Embodiment 2 | 797 | 26.3 | Crackle or fracture do not appear |
| Embodiment 3 | 776 | 25.9 | Crackle or fracture do not appear |
| Embodiment 4 | 781 | 26.0 | Crackle or fracture do not appear |
| Embodiment 5 | 779 | 26.3 | Crackle or fracture do not appear |
| Comparative example 1 | 803 | 27.4 | Fracture |
| Comparative example 2 | 815 | 28.7 | Fracture |
| Comparative example 3 | 799 | 28.1 | Fracture |
| Comparative example 4 | 808 | 29.1 | Fracture |
| Comparative example 5 | 811 | 29.0 | Fracture |
Anti-SSC performance test is pressed under the testing circumstance of TM0177-2005A method defined of NACE, and feeding dividing potential drop is 1atm H
2The saturated A solution of S (containing 5.0% the sodium-chlor of weight percent and the distilled water or the deionized water of 0.5% Glacial acetic acid), actual load are the stress corrosion resistant test of 720h under the permanent load of 110ksi * 85%.
Claims (3)
1. the special-purpose pipe steel of the corrosive of anti-a sulfide stress cracking (SSC) C110 steel level oil, its composition is C 0.15～0.30% by mass percentage, Si 0.15～0.35%, Mn 0.20～0.50%, P≤0.015%, S≤0.005%, Cr 0.80～1.50%, Mo 0.60～1.00%, Nb 0.01～0.05%, and V 0～0.05%, Ni≤0.20%, Ca 〉=0.0015%, all the other are Fe and unavoidable impurities.
2. the manufacture method of the special-purpose pipe steel of the corrosive of anti-sulfide stress cracking (SSC) C110 steel level oil according to claim 1, this method includes following steps:
(1), raw material adopts by above-mentioned composition mass percent preparation steel scrap, sponge iron, blast-melted, through the electric arc furnace fusion smelting, after the slag making dephosphorization, carry out ladle external refining, deoxidation, desulfurization, removal inclusion, vacuum outgas, guarantee condition of high vacuum degree≤66.7Pa, time 10-15min, feed the calcium silk and carry out the inclusion modification processing, become the circle base through continuous casting;
(2), the round base of ring furnace heating steps (1), Heating temperature is 1250-1290 ℃, after the perforation, carries out tandem rolling, makes weldless steel tube;
(3), to the modified thermal treatment of weldless steel tube of step (2), be heated to 900～960 ℃ and insulation through High Temperature Furnaces Heating Apparatus, make weldless steel tube organize complete austenitizing, the weldless steel tube homogeneous tube is quenched, carry out 〉=649 ℃ low temperature oven temper again, carry out hot straightening during in temperature 〉=500 ℃, detect a flaw behind the cool to room temperature, carry out mechanical property test and SSC test then.
3. according to claim 1, the special-purpose pipe steel of 2 described resisting sulfide stress corrosion high strength petroleums, it is characterized in that: this oil pipes tool has the yield strength more than the 758MPa, the performance index of resisting sulfide stress corrosion performance (SSC) 〉=85%SMYS with steel.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103667954A (en) * | 2013-12-06 | 2014-03-26 | 无锡西姆莱斯石油专用管制造有限公司 | Technology for quenching and tempering of C110 steel grade oil well tube by using Cr-Mo series steel |
| JP2018523012A (en) * | 2015-06-18 | 2018-08-16 | バオシャン アイアン アンド スティール カンパニー リミテッド | Ultra-high strength ultra-high toughness casing steel, oil casing and method for producing the same |
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| CN101250671A (en) * | 2008-03-26 | 2008-08-27 | 天津钢管集团股份有限公司 | Petroleum casing pipe with high-strength and high ductility as well as manufacturing method thereof |
| CN101586450A (en) * | 2009-04-29 | 2009-11-25 | 天津钢管集团股份有限公司 | Have high strength and high toughness petroleum casing pipe and manufacture method thereof |
| CN101629476A (en) * | 2009-08-05 | 2010-01-20 | 天津钢管集团股份有限公司 | High strength and high toughness petroleum casing pipe capable of bearing low temperature within -40 to -80 |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101250671A (en) * | 2008-03-26 | 2008-08-27 | 天津钢管集团股份有限公司 | Petroleum casing pipe with high-strength and high ductility as well as manufacturing method thereof |
| CN101586450A (en) * | 2009-04-29 | 2009-11-25 | 天津钢管集团股份有限公司 | Have high strength and high toughness petroleum casing pipe and manufacture method thereof |
| CN101629476A (en) * | 2009-08-05 | 2010-01-20 | 天津钢管集团股份有限公司 | High strength and high toughness petroleum casing pipe capable of bearing low temperature within -40 to -80 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103667954A (en) * | 2013-12-06 | 2014-03-26 | 无锡西姆莱斯石油专用管制造有限公司 | Technology for quenching and tempering of C110 steel grade oil well tube by using Cr-Mo series steel |
| JP2018523012A (en) * | 2015-06-18 | 2018-08-16 | バオシャン アイアン アンド スティール カンパニー リミテッド | Ultra-high strength ultra-high toughness casing steel, oil casing and method for producing the same |
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Application publication date: 20111116 |