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CN102747279A - Oil casing capable of resisting hydrogen sulfide stress corrosion cracking and manufacturing method thereof - Google Patents

Oil casing capable of resisting hydrogen sulfide stress corrosion cracking and manufacturing method thereof Download PDF

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Publication number
CN102747279A
CN102747279A CN2012102239658A CN201210223965A CN102747279A CN 102747279 A CN102747279 A CN 102747279A CN 2012102239658 A CN2012102239658 A CN 2012102239658A CN 201210223965 A CN201210223965 A CN 201210223965A CN 102747279 A CN102747279 A CN 102747279A
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Prior art keywords
stress corrosion
steel
sulfide stress
corrosion cracking
oil casing
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董晓明
高展
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Baoshan Iron and Steel Co Ltd
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Baoshan Iron and Steel Co Ltd
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Abstract

An oil casing capable of resisting hydrogen sulfide stress corrosion cracking and a manufacturing method thereof. The oil casing comprises components of, by weight percentage, 0.2-0.3% of C, 0.1-0.5% of Si, 0.3-0.6% of Mn, no more than 0.012% of P, no more than 0.002% of S, 0.01-0.05% of Ti, 0.01-0.08% of Al, 0.0005-0.005% of Ca, 0.001-0.003% of B, and the balance of Fe and unavoidable impurities. The manufacture method comprises steps of: 1) smelting and casting: smelting and casting the above components into a tube billet; 2) rolling: rolling the tube into a steel tube; and 3) heat treatment: heating at 900-950 DEG C, and insulating for 30-60min; and carrying out water quenching and tempering at 710-730 DEG C, and insulating for 40-60min. The oil casing of the invention has low cost and good resistance to sulfide stress corrosion cracking, and can meet requirement of sulfide stress corrosion cracking resistance in gas field exploration and development.

Description

A kind of anti-H 2 S stress corrosion rimose tubing and casing and method of manufacture thereof
Technical field
The present invention relates to tubing and casing, be specifically related to a kind of anti-H 2 S stress corrosion rimose tubing and casing and method of manufacture thereof, that under hydrogen-sulfide environmental, uses has a good resistance H 2 S stress corrosion.
Background technology
Oil production much contains corrosive mediums such as hydrogen sulfide with the employed environment of tubing and casing; Not only can carry out uniform corrosion to the body surface, can also generate hydrogen with the iron and steel effect, it is inner to get into steel substrate; Make sleeve pipe generation stress corrosion fracture; In the extremely short time, lost efficacy, thereby brought great financial loss and potential safety hazard to oil field production, annual because of CO 2And H 2The accident that the S corrosion is produced brings financial loss up to more than hundred million yuan to the oil field.
The seamless tubing and casing technical process of producing hydrogen sulfide corrosion resistant is: pipe is smelted, is cast into to steel grade, rolling for carrying out the modified thermal treatment of homogeneous tube behind the seamless tube, processes the tubing and casing of anti-H 2 S stress corrosion at last through mechanical workout.
The tubing and casing that hydrogen sulfide corrosion resistant tubing and casing and general oil production are used is difference to some extent on selection and production technique, mainly is steel grade design and thermal treatment process.
In the steel grade design; Generally be to add the alloying element that improves hardening capacity and temper resistance; In the hope of in quenching process, obtaining more martensitic stucture and higher hardness; Guarantee the homogeneity of tissue,, simultaneously impurity elements such as P, S, O are carried out strictness control such as C, Mn, Cr, Mo, V etc.The main high temperature quenching-and-tempering process that adopts obtains average tempering sorbite tissue on thermal treatment process, and the tempered sorbite tissue has best anti-H 2 S stress corrosion performance in the various tissues of low alloy steel.
Like Chinese patent CN00136666.1, CN200510029218.0; CN200580019466.5 etc.; All adopt the steel grade of one or more alloying elements such as adding Cr, Mo, V, Ni, Cu, Nb and heat-treat the tubing and casing of producing anti-H 2 S stress corrosion; But along with alloying element price in recent years skyrockets, more and more stronger for the tubing and casing demand of anti-H 2 S stress corrosion cheaply, existing at present tubing and casing can not satisfy the requirement of user to product up-gradation.
Chemical ingredients, the product grade of steel of the existing hydrogen sulfide corrosion resistant oil bushing steel of table 1
Figure BDA00001831868400021
Summary of the invention
The objective of the invention is to design a kind of anti-H 2 S stress corrosion rimose tubing and casing and method of manufacture thereof; It is a kind of 80ksi steel grade sulfur resistant hydrogen-type corrosion tubing and casing of carbon manganese steel composition system; Performance index: press the API5CT standard; Rt0.5 (ys): 552-655MPa; Tensile strength: greater than 655MPa, unit elongation: greater than 15%, the hydrogen sulfide corrosion resistance ability: sulfur resistance adopts A method sample under the load that loads nominal ys more than 85% not ftracture through 720 hours according to the NACE0177-2005 standard; Have low-cost and good anti-H 2 S stress corrosion cracking performance, satisfy the needs of oilfield prospecting developing with anti-H 2 S stress corrosion requirement.
For reaching above-mentioned density, technical scheme of the present invention is:
The present invention adopts carbon manganese steel composition system and adds a small amount of B, does not add alloying elements such as Cr, Mo, Ni, V, Ni, Cu, controls the tubing and casing of lower inclusion content and anti-ization of the thermal treatment process production hydrogen stress corrosion of adopting high temperature, short time.In the composition design, optimize the content of C, Mn and do not add the higher alloying element of price, have advantage cheaply; Add B, utilize its strengthening effect, the crystal boundary free energy is reduced, hinder the formation of the hydrogenate that makes embrittlement of grain boundaries crystal boundary; The effect that utilize to improve hardening capacity has remedied the insufficient problem of hardening capacity of not adding alloying element and being brought, the content of the back martensitic stucture that guaranteed to quench; Because composition system of the present invention is a carbon manganese steel, does not add alloying elements such as Cr, Mo, anti-temper resistance is relatively poor; If adopt about two hours tempering heat treatment process of the anti-sulphur pipe of general alloy, mechanical property can not reach standard-required, and carbide particle can be thicker; Be unfavorable for anti-ization hydrogen stress corrosion performance, therefore adopt the prompt tempering thermal treatment process of high temperature, short time, the tempering heat treatment temperature of more general anti-sulphur pipe improves 10-20 ℃; Tempering time shortens over half; Guarantee to obtain tiny equally distributed carbide and change sufficient tempered sorbite tissue, improved anti-ization hydrogen stress corrosion performance, satisfy mechanical property requirements simultaneously; And can improve production efficiency greatly owing to shortened heat treatment time, reduce production cost.
Particularly; Anti-H 2 S stress corrosion rimose tubing and casing of the present invention; Its composition quality per-cent is: C:0.2 ~ 0.3%, Si:0.1 ~ 0.5%, Mn:0.3 ~ 0.6%, P≤0.012%, S≤0.002%, Ti:0.01 ~ 0.05%, Al:0.01 ~ 0.08%, Ca:0.0005 ~ 0.005%, B:0.001 ~ 0.003%, all the other are Fe and unavoidable impurities.
In composition design of the present invention:
C:0.2 ~ 0.3%, C are carbide forming element, can improve the intensity of steel, and DeGrain when too low can the remarkable anti-ization hydrogen stress corrosion performance that reduces steel when too high.
To improve the ys of steel, unsuitable too high, too high meeting worsens processing and toughness, is lower than 0.1% DeGrain in ferritic for Si:0.1 ~ 0.5%, Si solid solution.
Mn:0.3 ~ 0.6%, Mn are austenite former, can improve the hardening capacity of steel, and content is not obvious less than effect in 0.3 o'clock, and content with the microstructure segregation that significantly increases in the steel, influenced the homogeneity and the anti-ization hydrogen stress corrosion performance of hot rolling microstructure greater than 0.6% o'clock.
Ti:0.01 ~ 0.05%, Ti are strong carbonitride forming elements, remarkable refine austenite crystal grain, owing to added B, Ti can form TiN with N, and can prevent to form BN and the effect that influences B,, if content is too high, be prone to form thick TiN, reduce material property.
B:0.001 ~ 0.003; B can increase hardening capacity, can effectively strengthen crystal boundary, makes along the precipitate of crystal boundary to reduce; Can postpone the crackle forming process on the crystal boundary; Improve resisting sulfide stress corrosion crack performance, content is not obvious less than effect in 0.001% o'clock, and the too high then steel-making of content is difficult to accurate control.
Al:0.01 ~ 0.08%, Al have played the effect of desoxydatoin and crystal grain thinning in steel, also improved the stability and the solidity to corrosion of superficial film in addition.When add-on is lower than 0.01%, DeGrain, add-on surpasses 0.08%, the mechanical property variation.
Ca:0.0005 ~ 0.005%, Ca plays the effect of deoxidization desulfuration at steel grade, makes impurity S and Ca form the CaS of nodularization, prevents that S and Mn from generating the MnS of anti-H 2 S stress corrosion poor-performing, and add-on is above 0.005%, and the steel grade oxide impurity increases.
P: S≤0.012% :≤0.002%, P and S are the detrimental impurity elements in the steel, too high levels can worsen the toughness of resisting sulfide stress corrosion performance and steel, therefore should reduce phosphorus, the sulphur content in the steel as far as possible.
The method of manufacture of anti-H 2 S stress corrosion rimose tubing and casing of the present invention comprises the steps:
1) smelts, casts
Press mentioned component and smelt, be cast as pipe;
2) rolling
Pipe is rolled into steel pipe
3) thermal treatment
Heating, 900 ~ 950 ℃ of Heating temperatures, insulation 30 ~ 60min; Tempering after the shrend, 710 ℃ ~ 730 ℃ of tempering temperatures, insulation 40 ~ 60min.
The steel mechanical property of the above course of processing of process has reached the requirement of 80 grade of steels, and its sulfur resistance adopts A method sample under the load that loads 85%, 90% nominal ys not ftracture through 720 hours according to NACE 0177-2005 standard.The anti-H 2 S stress corrosion service check adopts the laboratory detection method of NACE TM0177-2005 resisting sulfide stress corrosion crack iron and steel to detect.
The advantage that the present invention compared with prior art has is:
1. oil annular tube steel provided by the invention, the high-frequency electric resistance welded petroleum casing pipe that it can be used to make the 80ksi grade of steel and have the good resistance sulfide-stress cracking under the condition of not adding alloys such as Cr, Mo, V, Ni, Cu.
2. adopt the tempering heat treatment process of high temperature, short time, it is half that the tubing and casing heat treatment time is shortened, and improved production efficiency greatly.
3. tubing and casing provided by the invention; It meets the requirement of 80ksi grade of steel; Performance index: press API 5CT standard, Rt0.5 (ys): 552-655MPa, tensile strength: greater than 655MPa; Unit elongation: greater than 15%, the hydrogen sulfide corrosion resistance ability: sulfur resistance adopts A method sample under the load that loads nominal ys more than 85% not ftracture through 720 hours according to NACE 0177-2005 standard; Can be widely used in oil production.
4. material alloys cost used in the present invention is very low, has great economic benefit.
Embodiment
Below in conjunction with embodiment the present invention is further specified.
Embodiment 1
Embodiment 1 chemical ingredients is seen table 2.Molten steel is through electrosmelting, and continuous casting is heated to 1250 ℃ of heating laggard eleven punch 11s and rolling; 900 ℃ of finishing temperatures are carried out homogeneous tube thermal treatment with hot-rolled tube, 950 ℃ of austenitizing temperatures; Shrend behind the insulation 30min; 710 ℃ of tempering temperatures, soaking time 60min, mechanical property and resisting sulfide stress corrosion crack performance are as shown in table 3.
Embodiment 2
Embodiment 2 chemical ingredientss are seen table 2.Molten steel is through electrosmelting, and continuous casting is heated to 1250 ℃ of heating laggard eleven punch 11s and rolling; 930 ℃ of finishing temperatures are carried out homogeneous tube thermal treatment with hot-rolled tube, 900 ℃ of austenitizing temperatures; Shrend behind the insulation 60min; 730 ℃ of tempering temperatures, soaking time 40min, mechanical property and resisting sulfide stress corrosion crack performance are as shown in table 3.
Embodiment 3
Embodiment 3 chemical ingredientss are seen table 2.Molten steel is through electrosmelting, and continuous casting is heated to 1250 ℃ of heating laggard eleven punch 11s and rolling; 950 ℃ of finishing temperatures are carried out homogeneous tube thermal treatment with hot-rolled tube, 920 ℃ of austenitizing temperatures; Shrend behind the insulation 40min; 720 ℃ of tempering temperatures, soaking time 40min, mechanical property and resisting sulfide stress corrosion crack performance are as shown in table 3.
Embodiment 4
Embodiment 4 chemical ingredientss are seen table 2.Molten steel is through electrosmelting, and continuous casting is heated to 1250 ℃ of heating laggard eleven punch 11s and rolling; 910 ℃ of finishing temperatures are carried out homogeneous tube thermal treatment with hot-rolled tube, 930 ℃ of austenitizing temperatures; Shrend behind the insulation 45min; 725 ℃ of tempering temperatures, soaking time 45min, mechanical property and resisting sulfide stress corrosion crack performance are as shown in table 3.
Comparative example 1
The higher alloying elements of price such as Cr, Mo have been to add with embodiment 1 difference on composition; Do not add micro-B; 950 ℃ of austenitizing temperatures, shrend behind the insulation 30min, 700 ℃ of tempering temperatures; Tempering insulation time 120min, other are made, and all consistent other manufacturings are all consistent with detection method with detection method.
Comparative example 2 does not add micro-B and Ti with embodiment 2 differences, and other manufacturings are all consistent with detection method.
Comparative example 3 is to adopt the conventional long time tempering heat treatment process with embodiment 3 differences, 920 ℃ of austenitizing temperatures, and shrend behind the insulation 40min, 680 ℃ of tempering temperatures, soaking time 120min, other manufacturings are all consistent with detection method.Mechanical property and resisting sulfide stress corrosion crack performance are as shown in table 3.
The existing 80 steel grade sulfur resistant pipe composition alloy contents of comparative example 1 are higher, and heat treatment efficiency is low, and production cost improves 800 yuan/ton than the present invention, and energy consumption per ton steel is higher, is unfavorable for energy-saving and emission-reduction.The steel grade resisting sulfide stress corrosion crack performance that does not add B and Ti in the comparative example 2 does not meet the demands.Comparative example 3 heat treatment efficiency are lower, and production cost improves more than 250 yuan/ton than the present invention, and energy consumption is higher, is unfavorable for energy-saving and emission-reduction.
It is thus clear that, adopt chemical ingredients and ME that the present invention designed, can stably produce and satisfy the well behaved tubing and casing of 80ksi steel grade sulfur resistant thing stress corrosion crack.
Table 2 unit: weight percent
Figure BDA00001831868400061
Table 2 is the chemical ingredients of embodiment and comparative example, and comparative example 1 is oil field 80 steel grade sulfur resistant hydrogen stress corrosion composition of steel commonly used at present, the composition system of comparative example 2 for not adding B and Ti.
Mechanical property, the corrosive nature of table 3 test steel
Figure BDA00001831868400071
Steel alloy of the present invention is because its low cost, less energy-consumption, production efficiency height and anti-H 2 S stress corrosion cracking performance are good; Can be widely used in the corrosion resistant flds of needs such as oil well pipe; It successfully designs and develops and will bring huge economic benefit, and its market outlook will be very huge.

Claims (2)

1. anti-H 2 S stress corrosion rimose tubing and casing; Its composition quality per-cent is: C:0.2 ~ 0.3%, Si:0.1 ~ 0.5%, Mn:0.3 ~ 0.6%, P≤0.012%, S≤0.002%, Ti:0.01 ~ 0.05%, Al:0.01 ~ 0.08%, Ca:0.0005 ~ 0.005%, B:0.001 ~ 0.003%, all the other are Fe and unavoidable impurities.
2. the method for manufacture of anti-H 2 S stress corrosion rimose tubing and casing as claimed in claim 1 comprises the steps:
1) smelts, casts
Press mentioned component and smelt, be cast as pipe;
2) rolling
Pipe is rolled into steel pipe
3) thermal treatment
Heating, 900 ~ 950 ℃ of Heating temperatures, insulation 30 ~ 60min; Tempering after the shrend, 710 ℃ ~ 730 ℃ of tempering temperatures, insulation 40 ~ 60min.
CN2012102239658A 2012-06-29 2012-06-29 Oil casing capable of resisting hydrogen sulfide stress corrosion cracking and manufacturing method thereof Pending CN102747279A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103045944A (en) * 2012-12-27 2013-04-17 江苏长强钢铁有限公司 High-toughness steel for petroleum casing and manufacturing method of petroleum casing
CN103060686A (en) * 2012-12-27 2013-04-24 江苏长强钢铁有限公司 Steel and seamless steel pipes used for high-performance N80 grade non-modulated oil casing, and a manufacturing method thereof
CN105986189A (en) * 2015-02-09 2016-10-05 宝钢特钢有限公司 Hydrogen sulfide and carbon dioxide corrosion resistant nickel base alloy strip and manufacturing method thereof
CN106319371A (en) * 2015-06-16 2017-01-11 鞍钢股份有限公司 90ksi steel-grade oil well pipe with excellent SSC (stress cracking resistance) performance and manufacturing method thereof
CN108004462A (en) * 2016-10-31 2018-05-08 宝山钢铁股份有限公司 A kind of tubing and casing and its manufacture method of anti-H 2 S stress corrosion cracking
CN109234555A (en) * 2018-10-24 2019-01-18 成都先进金属材料产业技术研究院有限公司 The preparation method of small-bore TA18 titanium alloy seamless pipe

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03268877A (en) * 1990-03-16 1991-11-29 Sumitomo Metal Ind Ltd Manufacture of sulfide stress cracking resistant welded steel pipe for oil well
CN101784680A (en) * 2007-11-14 2010-07-21 住友金属工业株式会社 Steel for steel pipes excellent in sour resistance and process for manufacturing the same
CN102199730A (en) * 2010-03-23 2011-09-28 宝山钢铁股份有限公司 Seamless oil bushing with steel grade higher than 140ksi and hydrogen sulfide corrosion resistance, and manufacture method thereof
CN101622368B (en) * 2007-02-26 2012-06-13 杰富意钢铁株式会社 Electric resistance welded steel pipe prior to heat treatment and process for manufacturing the same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03268877A (en) * 1990-03-16 1991-11-29 Sumitomo Metal Ind Ltd Manufacture of sulfide stress cracking resistant welded steel pipe for oil well
CN101622368B (en) * 2007-02-26 2012-06-13 杰富意钢铁株式会社 Electric resistance welded steel pipe prior to heat treatment and process for manufacturing the same
CN101784680A (en) * 2007-11-14 2010-07-21 住友金属工业株式会社 Steel for steel pipes excellent in sour resistance and process for manufacturing the same
CN102199730A (en) * 2010-03-23 2011-09-28 宝山钢铁股份有限公司 Seamless oil bushing with steel grade higher than 140ksi and hydrogen sulfide corrosion resistance, and manufacture method thereof

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103045944A (en) * 2012-12-27 2013-04-17 江苏长强钢铁有限公司 High-toughness steel for petroleum casing and manufacturing method of petroleum casing
CN103060686A (en) * 2012-12-27 2013-04-24 江苏长强钢铁有限公司 Steel and seamless steel pipes used for high-performance N80 grade non-modulated oil casing, and a manufacturing method thereof
CN103060686B (en) * 2012-12-27 2015-04-15 江苏长强钢铁有限公司 Steel and seamless steel pipes used for high-performance N80 grade non-modulated oil casing, and a manufacturing method thereof
CN103045944B (en) * 2012-12-27 2015-11-18 江苏长强钢铁有限公司 High toughness petroleum casing pipe steel and petroleum casing pipe manufacture method
CN105986189A (en) * 2015-02-09 2016-10-05 宝钢特钢有限公司 Hydrogen sulfide and carbon dioxide corrosion resistant nickel base alloy strip and manufacturing method thereof
CN106319371A (en) * 2015-06-16 2017-01-11 鞍钢股份有限公司 90ksi steel-grade oil well pipe with excellent SSC (stress cracking resistance) performance and manufacturing method thereof
CN106319371B (en) * 2015-06-16 2018-06-26 鞍钢股份有限公司 90ksi steel-grade oil well pipe with excellent SSC (stress cracking resistance) performance and manufacturing method thereof
CN108004462A (en) * 2016-10-31 2018-05-08 宝山钢铁股份有限公司 A kind of tubing and casing and its manufacture method of anti-H 2 S stress corrosion cracking
CN108004462B (en) * 2016-10-31 2020-05-22 宝山钢铁股份有限公司 Oil casing pipe capable of resisting hydrogen sulfide stress corrosion cracking and manufacturing method thereof
CN109234555A (en) * 2018-10-24 2019-01-18 成都先进金属材料产业技术研究院有限公司 The preparation method of small-bore TA18 titanium alloy seamless pipe
CN109234555B (en) * 2018-10-24 2020-08-18 成都先进金属材料产业技术研究院有限公司 Preparation method of small-caliber TA18 titanium alloy seamless tube

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Application publication date: 20121024