CN108277438A - Mo ultralow-carbon martensitic stainless steel seamless pipe and its manufacturing method - Google Patents

Mo ultralow-carbon martensitic stainless steel seamless pipe and its manufacturing method Download PDF

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Publication number
CN108277438A
CN108277438A CN201810269087.0A CN201810269087A CN108277438A CN 108277438 A CN108277438 A CN 108277438A CN 201810269087 A CN201810269087 A CN 201810269087A CN 108277438 A CN108277438 A CN 108277438A
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China
Prior art keywords
pipe
steel
temperature
ultralow
stainless steel
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CN201810269087.0A
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Chinese (zh)
Inventor
李阳
徐芳泓
方旭东
赵建伟
夏焱
张威
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Taiyuan Iron and Steel Group Co Ltd
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Taiyuan Iron and Steel Group Co Ltd
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Priority to CN201810269087.0A priority Critical patent/CN108277438A/en
Publication of CN108277438A publication Critical patent/CN108277438A/en
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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
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/18—Hardening; Quenching with or without subsequent tempering
    • 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
    • C21D8/10—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of tubular bodies
    • C21D8/105—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of tubular bodies 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
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/08—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for tubular bodies or pipes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/04—Making ferrous alloys by melting
    • 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
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • 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
    • 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

Abstract

The invention discloses a kind of Mo ultralow-carbon martensitic stainless steel seamless pipes, are made of Mo ultralow-carbon martensitic stainless steel, and Mo ultralow-carbon martensitic stainless steel includes following compositions, is calculated in mass percent：It is 0.2~0.5%, P≤0.015% that C≤0.03%, Si, which are 0.1~0.5%, Mn, and it be 5.2~5.7%, Mo be 1.9~2.1%, Cu is 0.1~1.6% that S≤0.002%, Cr, which are 12.2~13.2%, Ni, and surplus is Fe and other impurity.Above-mentioned seamless pipe is applicable to oil gas field.The present invention also provides a kind of manufacturing methods of above-mentioned seamless pipe, including step：Smelting, pipe hot-working, steel pipe hot-working and heat treatment, wherein, the hot worked heating temperature of pipe is 1200~1280 DEG C, and the heating temperature of extrusion tubulation is 1150~1250 DEG C, the heating temperature of perforation cold-rolling practice tubulation is 1200~1280 DEG C, and heat treating regime is：900~1050 DEG C of quenchings and 550~680 DEG C of tempering.Seamless pipe produced by the present invention is in CO2、Cl Coexisting has excellent intensity and corrosion resistance under corrosive environment and high-temperature and high-pressure conditions.

Description

Mo ultralow-carbon martensitic stainless steel seamless pipe and its manufacturing method
Technical field
The present invention relates to stainless steel field more particularly to a kind of Mo ultralow-carbon martensitic stainless steel suitable for oil gas field are seamless Pipe and its manufacturing method.
Background technology
With the development of global economy, demand of the countries in the world to petroleum resources constantly increases, and promotes the oil gas field of exploitation It is increasingly deeper, emerge many ultra-deep superelevation kill-jobs.High pressure-temperature and the difficulty of high pressure high temperature well exploration and development increase suddenly, Keep the drilling well problem more and more, is mainly concerned with design, tool, technique, equipment, well control, reservoir reconstruction, the peace of oil well A series of problems, such as complete and material selects, wherein most critical be exactly material select permeability.
High pressure-temperature and high pressure high temperature well usually all contain CO2、H2S、ClIon etc., the highest CO of content2Content is super Cross 10%, H2S is more than 60,000 ppm, ClIon is more than 100,000 ppm, therefore is corroded just as containing CO2、H2S and ClEnvironment in The main problem used.At present both at home and abroad for containing CO2、H2S and ClUnder oil well use material, according to environment severe degree according to Secondary is Cr13 types martensitic stain less steel, two phase stainless steel and nickel-base alloy.The Cr13 type martensitic stain less steel temperature in use limit are 150 DEG C, it is difficult to meet the requirement under existing harsh corrosive environment, there is down-hole oil tube fracture, gas collection main line leakage accident more Occur, causes many oil gas field wells to be discarded in advance less than 1 year in operation, not only cause huge economic losses, while also threatening To national energy strategic security.To avoid corrosion of the oil well pipe under such exacting terms, it is necessary to select anti-CO2、H2S and Cl The two phase stainless steel and nickel-base alloy of corrosion and stress corrosion cracking function admirable, but its price is very expensive, and rely primarily on Import keeps the input cost of construction oil well excessively high.
Chinese patent literature CN100368579C provides a kind of martensitic stain less steel, by adding 2.8~5.0% Mo, Form the Laves phases or the equal intermetallic compounds of σ of fine precipitation when the carbide being precipitated when tempered martensite, tempering and tempering Line and staff control, improve intensity and corrosion resistance.But the high Mo content of the invention steel grade can reduce toughness, and Laves phases or σ phases in use can deteriorated tissue, and cost is excessively high.
Chinese patent literature CN100453685C provides a kind of high Cr series stainless steel jointless oil well tube and its production method, It is 12~14%, Ni contents is 3.0~6.0% that wherein C content, which is 0.02~0.25%, Cr contents, is additionally added to simultaneously The member such as Mo, Cu, Nb, Cu, Al, Ti, V usually improves intensity.But the invention C content is excessively high, in CO2And ClUnder coexisted environment Corrosion resisting property it is inadequate, while alloying element type is excessive, and heat treatment process tissue change rule is excessively complicated, gives modifier treatment Bring difficulty.
In consideration of it, this field needs to develop a kind of novel anti-corrosion material of economy met under deep-well oil gas field use environment Material, to meet the demand of growing gas industries.
Invention content
In order to overcome the above-mentioned deficiency of existing martensitic stain less steel and its steel pipe, the object of the present invention is to provide one kind to be used for High concentration CO2、H2S and ClHigh temperature and pressure under corrosive environment coexists and superhigh temperature Ultra High Pressure Deep Wells Mo ultralow-carbon martensitic is stainless Steel seamless pipe, cost are less than two phase stainless steel and nickel-base alloy, and service life improves 2 than original Cr13 types martensitic stain less steel To 3 times.Also, the present invention also provides a kind of above-mentioned for high concentration CO2、H2S and ClThe high temperature coexisted under corrosive environment is high The manufacturing method of pressure and superhigh temperature Ultra High Pressure Deep Wells Mo ultralow-carbon martensitic stainless steel seamless pipe.
It emphasizes herein, it is unless otherwise indicated, the common meaning of various scientific and technical terminologies in terms used herein and this field, each The meaning of technical term defined in kind technology dictionary, textbook etc. is consistent.For example, herein, hp-ht well is usually With General Purpose Rubber sealing performance come what is defined, refer to the well that bottom hole temperature (BHT) is higher than 70MPa higher than 150 DEG C, pressure.Herein, surpass Superhigh-pressure high-temp well is usually to refer to bottom hole temperature (BHT) come what is defined with the electronic component operation limit higher than 205 DEG C, pressure to be higher than The well of 140MPa.Herein, deep-well generally refers to the well that well depth is more than 4500m or 15000ft.Mo ultralow-carbon martensitic stainless steel Generally refer on the basis of conventional martensitic stainless steel, by reduce carbon content (highest 0.07%), increase nickel (3.5%~ 6.5%) content, parent metal microscopic structure are the stainless steel of tempered martensite.Hot sending generally refers to steel material after being heated, It does not cool down, transfers while hot.
To achieve the goals above, present invention improves the ingredient of martensitic stain less steel in the prior art, technology structures Think as follows：On the component base of common 13Cr oil wells stainless steel, C content is greatly reduced, to improve resistance to general corrosion simultaneously Improve toughness；A certain amount of Ni is added, increases intensity to make up the loss of strength of C reductions, and improve resistance to CO2、H2S stress corrosions Property；It adds Mo and improves corrosion resistance；It adds a small amount of Cu and further increases corrosion resistance；In addition a small amount of N element is added to increase Martensitic phase stability.Finally, alloy system is formed：0.01C—13Cr—5.5Ni—2Mo—0.1Cu—0.04N.
Therefore, on the one hand, according to an embodiment of the present invention, a kind of Mo ultralow-carbon martensitic stainless steel seamless pipe is provided, In, the seamless pipe is made of Mo ultralow-carbon martensitic stainless steel, and the Mo ultralow-carbon martensitic stainless steel includes following compositions, with matter Measure percentage meter：C≤0.03%, Si are that 0.1~0.5%, Mn is 0.2~0.5%, P≤0.015%, and S≤0.002%, Cr are It is 1.9~2.1%, Cu is 0.1~1.6% that 12.2~13.2%, Ni, which are 5.2~5.7%, Mo, and surplus is Fe and other impurity.
Illustrate each alloys producing of Mo ultralow-carbon martensitic stainless steel of the present invention and the restriction reason of content range below By.
C can promote the precipitation of matrix carbide, when the C content of martensitic stain less steel is more than 0.03%, contain CO2、 H2Stainless steel corrosion resistance will significantly deteriorate under the corrosive environments such as S, while C content increases tempering sensitization caused by Ni.Cause This, 0~0.03% is chosen to be by C content.
Si is added in steel-making as deoxidier, but low-alloyed hot-working character and tough can drop in when additive amount is excessive Property, Si contents are limited thus as 0.1~0.5%.
Mn is the element to form austenite, can play the role of deoxidation, desulfurization in smelting process, while improving intensity And hot-workability.It if Mn contents are very few, can not have effect, if additive amount is excessive, influence whether the toughness of stainless steel, and high temperature Under corrosion resisting property also reduce.Therefore, the content range of Mn is chosen to be 0.2~0.5% in stainless steel of the invention.
P is impurity, can reduce stainless steel in CO2Corrosion resistance in environment and anticorrosion stress-resistant performance.Thus, P contains Amount is limited to 0.015% or less.
S is very unfavorable to the hot-working character in pipe and steel pipe manufacturing process, thus S constituent contents are limited to 0.002% or less.
Cr can form oxidation film on surface, be to ensure that and containing CO2、Cl、H2Corrosion resistant under the harsh corrosive environment of S etc. Important element necessary to corrosion and anticorrosion stress-resistant cracking behavior, achievees the effect that high-temperature corrosion resistance.The content of Cr must be 12.2% or more, but when Cr contents are more than after 13.2%, ferrite content increases, and hot-working character drastically deteriorates, simultaneously Strength reduction.Therefore, the content of Cr is chosen to be 12.2~13.2%.
Ni is the austenite former for typically improving resistance to general corrosion, can improve the stability of protective film, carry Height is in CO2、Cl、H2Corrosion resistance in S environment and anticorrosion stress-resistant performance, additive amount can just be played at 5.2% or more Said effect, whens too high levels, can improve residual austenite content, reduce alloy strength, while improving manufacturing cost.Therefore, originally In invention, the content of Ni is chosen to be 5.2%~5.7%.
Mo is a kind of ferrite former, and under the premise of containing enough Cr, martensite can be improved by adding appropriate Mo The corrosion resistance and anticorrosion stress-resistant performance of stainless steel, do not have an above-mentioned effect when content is below 1.9%, but Mo elements When content is more than 2.1%, stainless hardness of steel can be reduced while increasing cost.Consider, the content of Mo is chosen to be in the present invention 1.9~2.1%.
Cu can reduce martensitic stain less steel in H2Corrosion rate in S environment.However, Cu too high levels can significantly reduce The hot-workability of alloy.Therefore the Cu contents in the present invention are chosen to be 0.1~1.6%.
Above-mentioned Mo ultralow-carbon martensitic stainless steel seamless pipe is applicable to oil gas field.
The pipe diameter of above-mentioned seamless pipe could typically be Φ 76mm~Φ 220mm, and length is at least 6000mm.
On the other hand, it according to another embodiment of the present invention, additionally provides a kind of such as above-mentioned Mo ultralow-carbon martensitic stainless steel The manufacturing method of seamless pipe comprising following the step of implementing in order：
A) it smelts, wherein first regard molten iron as main material, smelting is at meeting the Mo ultralow-carbon martensitic stainless steel ingredient The ingredient of molten steel, i.e., the described molten steel reaches following ratios, is calculated in mass percent：C≤0.03%, Si are 0.1~0.5%, Mn For 0.2~0.5%, P≤0.015%, S≤0.002%, Cr be 12.2~13.2%, Ni be 5.2~5.7%, Mo be 1.9~ 2.1%, Cu are 0.1~1.6%,
Molten steel is cast into steel ingot again；
B) pipe hot-working, wherein first by Heating Steel Ingots, breaking down, forging, annealing and peeling, then cut into rodlike pipe；
C) steel pipe hot-working, wherein after heating of pipe blank, steel pipe is made in pipe；And
D) it is heat-treated, wherein it will quench and be tempered by the steel pipe of the steel pipe thermal work steps, production tube is made,
Wherein,
In the smelting step, pretreated molten iron is gone out by slightly refining, after vacuum oxygen decarburization and ladle refining Steel, wherein in vacuum oxygen decarburization, keep vacuum degree≤106.4Pa, wherein in ladle refining, adjust its in addition to C Its alloying component Si, Mn, P, S, Cr, Ni, Mo, Cu enter control range, under conditions of ensuring slag viscosity≤0.3P (pool), adjust Whole temperature is to after 1540 ± 10 DEG C, by ladle pouring at steel ingot；
In the pipe thermal work steps, in heating process, heating temperature is controlled according to 1200~1280 DEG C, finish to gauge temperature Degree and final forging temperature are more than 900 DEG C, rolling pass deformation amount controlling 20~40%, the control of forging pass deformation 30~ 40%, total forging ratio >=3；And
In the heat treatment step, hardening heat is 900~1050 DEG C, keeps the temperature 10~30min, with air-cooled above cold But speed is cooled to room temperature, and temperature is 550~680 DEG C of temperature, keeps the temperature 1~4 hour, is cooled to the air-cooled above speed Room temperature.
In one embodiment, in the steel pipe thermal work steps, after heating of pipe blank, steel is made using extrusion Pipe, wherein heating of pipe blank temperature is 1150~1250 DEG C, and extruding rate is 100~120mm/s, initial deformation temperature >=1050 DEG C, terminate deformation temperature≤1300 DEG C.
In another embodiment, in the steel pipe thermal work steps, after heating of pipe blank, using perforation cold rolling legal system At steel pipe, wherein heating of pipe blank temperature be 1200~1280 DEG C, perforation deflection be 50~70%, cold rolling reduction be 40~ 60%.
In one embodiment, in the smelting step, the pretreated molten iron slightly refines in top and bottom combined blown converter, It is refined in the decarburization of vacuum oxygen decarburization stove and in ladle refining furnace, and in vacuum oxygen decarburization stove decarburization, avoids over-blowing, Ensure aim carbon hit.
In one embodiment, in the smelting step, in vacuum oxygen decarburization, vacuum degree≤66.5Pa is kept.
Explain that the seamless pipe manufacturing method of Mo ultralow-carbon martensitic stainless steel according to the present invention includes in detailed below by suitable Four key steps that sequence is implemented, i.e. smelting, pipe hot-working, steel pipe hot-working and heat treatment.
One, smelting step
Pretreated molten iron is slightly refined by top and bottom combined blown converter, the decarburization of vacuum oxygen decarburization stove and ladle refining furnace refine Afterwards, the composition quality percentage of molten steel reaches requirement and can tap, and is then cast into steel ingot or continuous casting billet again.Here " molten steel Composition quality percentage reach requirement " refer to that each ingredient of molten steel reaches following ratios, be calculated in mass percent；C≤ 0.03%, Si are that 0.1~0.5%, Mn is 0.2~0.5%, P≤0.015%, and S≤0.002%, Cr are 12.2~13.2%, It is 1.9~2.1%, Cu is 0.1~1.6% that Ni, which is 5.2~5.7%, Mo,.
In vacuum oxygen decarburization stove decarburization, vacuum degree≤106.4Pa, preferably vacuum degree≤66.5Pa, true are kept Over-blowing is avoided in empty oxygen decarburization stove decarburization, ensures aim carbon hit.When ladle refining furnace refines, adjustment is other in addition to C Alloying component Si, Mn, P, S, Cr, Ni, Mo, Cu etc. enter control range so that Si be 0.1~0.5%, Mn be 0.2~ 0.5%, P≤0.015%, S≤0.002%, it be 5.2~5.7%, Mo is 1.9~2.1%, Cu that Cr, which is 12.2~13.2%, Ni, It is 0.1~1.6%.
Under conditions of ladle refining furnace ensures slag viscosity≤0.3P (pool), temperature is adjusted to after 1540 ± 10 DEG C, by steel Packet is cast into steel ingot.
Two, pipe thermal work steps
In pipe hot-working, first by Heating Steel Ingots, breaking down, forging, annealing and peeling, then rodlike pipe is cut into.
1, it heats
To the steel ingot soaking before breaking down cogging, heating temperature is：1200~1250 DEG C；Bloom continues to add before forging Heat, heating temperature are：1220~1280 DEG C.Total heating time in two stages is not less than 12 hours.
2, breaking down and forging
By the steel ingot after heating through blooming mill cogging breaking down, rolling pass deformation amount controlling is 20~40%, finishing temperature Control is at 900 DEG C or more so that rolls rear surface unfolded, crackle and serious scuffing defect.Bloom is forged after continuing heating To rod iron, forging deformation passage is determined according to pipe specification, total forging ratio >=3, and pass deformation control is 30~40%, finish-forging Temperature is controlled at 900 DEG C or more.Rod iron dimension D=(d+20) mm (d is pipe diameter) after forging, surface must not have folding, crackle With serious scuffing defect.
3, it machines
Rod iron after forging is annealed at 650~750 DEG C, the outer diameter dimension d of peeling processing excircles to pipe, cutting At pipe scale size L.D and L is the outer diameter, wall thickness, length according to fished pipe, after being calculated according to lengthening coefficient and lumber recovery It obtains.
Three, steel pipe thermal work steps
Extrusion or perforation two kinds of process routes of cold-rolling practice can be taken to be thermally processed into steel pipe.
A：Extrusion
1) blank prepares
Pipe is used into deep hole rig machining center through-hole, end face flat head chamfering processes horn mouth, horn mouth wherein Angle is 33.5 ± 5 °, and pipe surface flawless, pit after machining, are mingled with casting skin.
2) annular furnace preheats
Pipe is discharged into annular furnace in order and is preheated, heating furnace temperature is 950 DEG C ± 20 DEG C, and heating time presses pipe Wall thickness is set as 4~8min/cm, and soaking time is set as 1.0~1.5min/cm by pipe wall thickness.
3) sensing heating
Hot sending continues to heat to induction furnace after pipe is come out of the stove from annular furnace, primary induction elder generation heating temperature 1150~1200 DEG C, bringing-up section 600~800KW of heating power keeps the temperature 80~160KW of power, comes out of the stove after uniform after blank temperature, stable.
4) reaming
Pipe after sensing heating is subjected to reaming production using punch, pipe endoporus is expanded to more than production tube The size of internal diameter, reaming rate are 200~220mm/s.
5) secondary sensing heating
Pipe after reaming is heat-fed to the secondary sensing heating of induction furnace progress, 1180~1250 DEG C of heating target temperature, Bringing-up section power 200~300KW of heating power keeps the temperature 60~100KW of power, comes out of the stove after uniform after blank temperature, stable.
6) it squeezes
Pipe after secondary sensing heating is sent to horizontal extruder to the steel pipe for being squeezed into target size, extruding rate control It in 100~120mm/s, is lubricated using glass powder, water is entered after extruding and is cooled down.
B：Perforation cold-rolling practice
1) blank prepares
Internal point is beaten at pipe both ends, internal point outer diameter is 40~80mm, and depth is 5~10mm.It is required that internal point is eccentric ≤ 0.3mm, fillet smoothly transit.
2) annular furnace or wedged bottom stove heat
Pipe is sent to annular furnace or sloping hearth furnace and is heated, heating temperature is 1200~1280 DEG C, and heating time is by pipe Base wall thickness is set as 4~8min/cm, and soaking time is set as 1.0~1.5min/cm by pipe wall thickness.
3) hot piercing
Pipe after heating is sent to punch and is produced into hollow billet, roll away from for 70~120mm, top head front-extending quantity is 50~ 70mm, feed angle are 10~15 °.Hollow billet specification considers according to the deflection of production tube specification and following process process, greatly About 50~70%.
4) tube reducing is opened
Hollow billet after hot rolling is heat-fed to a tube reducing unit, water cooling or is air-cooled to room temperature, produces hollow forging.
5) cold rolling
Hollow forging is cold-rolled to target size, single pass heavy deformation 40~60%. by 1~2 passage
Four, heat treatment step
Steel pipe after cold rolling is subjected to quenching treatment first：By steel pipe be heated to 900~1050 DEG C temperature 10~ 30min is cooled to room temperature with the air-cooled above cooling velocity.By above-mentioned processing, tiny martensite and a small amount of can be obtained Residual austenite body tissue (referring to Fig. 1).If heating temperature at 900 DEG C hereinafter, if martensite generate it is insufficient, intensity is relatively low.If Heating temperature is more than 1050 DEG C, and martensitic structure is excessively coarse, can reduce toughness.
Then, quenched steel pipe is subjected to tempering heat treatment：It is heated to 550~680 DEG C of temperatures 1~4 hour, with The air-cooled above speed is cooled to room temperature, and tempered martensite and a small amount of retained austenite (referring to Fig. 2) is organized as, to become Seamless pipe with high intensity, high tenacity, outstanding corrosion resisting property.
Advantageous effect
The comparison such as table 1 of the main performance and existing steel pipe of the Mo ultralow-carbon martensitic stainless steel seamless pipe embodiment of the present invention It is shown.
Table 1：The Mo ultralow-carbon martensitic stainless steel seamless pipe embodiment of the present invention is compared with the main performance of existing 13Cr
It can be seen that, compared with traditional oil field is with martensitic stain less steel 13Cr, steel tensile strength and surrender are tested by table 1 Intensity is all higher than compared steel, is containing CO2And ClCorrosion rate in environment is much smaller than compared steel, and corrosion resistance is very It is outstanding, it is suitable for high concentration CO2、H2S and Cl—The deep-well under corrosive environment coexists.
Description of the drawings
Attached drawing described herein is used for providing further understanding the embodiment of the present invention, constitutes one of the present invention Point, the illustrative embodiments of the present invention and their descriptions are used to explain the present invention, does not constitute improper limitations of the present invention.Attached In figure：
Fig. 1 is the quenching state tissue metallograph according to the Mo ultralow-carbon martensitic stainless steel seamless pipe of one embodiment of the invention；
Fig. 2 is the tempering state tissue metallograph according to the Mo ultralow-carbon martensitic stainless steel seamless pipe of one embodiment of the invention； And
Fig. 3 is the manufacturing method flow chart according to the Mo ultralow-carbon martensitic stainless steel seamless pipe of one embodiment of the invention.
Specific implementation mode
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with the specific embodiment of the invention and Technical solution of the present invention is clearly and completely described in corresponding attached drawing.Obviously, described embodiment is only of the invention A part of the embodiment, instead of all the embodiments.Based on the embodiment of the present invention, those of ordinary skill in the art are not doing Go out the every other embodiment obtained under the premise of creative work, shall fall within the protection scope of the present invention.
The specific implementation mode for the description present invention that illustrates below by embodiment, but the specific implementation mode not office of the present invention It is limited to following embodiments.
First, the embodiment of the Mo ultralow-carbon martensitic stainless steel seamless pipe according to embodiment of the present invention is shown.
Table 2 lists seven different embodiments of the Mo ultralow-carbon martensitic stainless steel seamless pipe according to embodiment of the present invention Chemical composition.
Table 2：The chemical composition (quality %) of each embodiment
C Si Mn P S Cr Ni Mo Cu
Embodiment 1 0.005 0.12 0.5 0.008 0.001 12.2 5.7 1.91 1.6
Embodiment 2 0.011 0.15 0.45 0.010 0.001 12.4 5.6 1.94 1.4
Embodiment 3 0.012 0.13 0.42 0.007 0.001 12.6 5.5 1.95 1.1
Embodiment 4 0.015 0.16 0.4 0.007 0.001 12.7 5.5 2.01 0.9
Embodiment 5 0.022 0.29 0.35 0.006 0.001 12.8 5.4 2.03 0.5
Embodiment 6 0.025 0.43 0.3 0.009 0.001 13.0 5.3 2.08 0.3
Embodiment 7 0.030 0.50 0.2 0.008 0.001 13.2 5.2 2.1 0.1
Secondly, it illustrates and is implemented according to the manufacturing method of the Mo ultralow-carbon martensitic stainless steel seamless pipe of embodiment of the present invention Example.
It is described by taking the embodiment of two kinds of specifications as an example below stainless according to the Mo ultralow-carbon martensitic of embodiment of the present invention The manufacturing method of steel seamless pipe, one of which embodiment uses extrusion in the steel pipe thermal work steps, another real It applies example and then uses perforation cold-rolling practice in the steel pipe thermal work steps.
The manufacturing method of the Mo ultralow-carbon martensitic stainless steel seamless pipe of embodiment of the present invention, including following implement in order The step of：
1, it smelts
Pretreated molten iron is slightly refined by top and bottom combined blown converter, the decarburization of vacuum oxygen decarburization stove and ladle refining furnace refine Afterwards, the composition quality percentage of molten steel reaches target call and taps, and is then cast into steel ingot or continuous casting billet again.Here " steel The composition quality percentage of water reaches target call " refer to that each ingredient of molten steel reaches following ratios, it is calculated in mass percent；C It is 0.2~0.5%, P≤0.015% that≤0.03%, Si, which are 0.1~0.5%, Mn, S≤0.002%, Cr be 12.2~ It is 1.9~2.1%, Cu is 0.1~1.6% that 13.2%, Ni, which are 5.2~5.7%, Mo,.
When ladle refining furnace refines, tap when slag viscosity is 0.1P, temperature adjustment to 1543 DEG C of cast temperature, then ladle It is hoisted to and is molded into process and casts, tap, mold casting of molten steel is at 5.8 tons of steel ingots.Steel ingot specification is 500 × 650 × 2300mm.
2, pipe hot-working
Steel ingot heats 12 hours in soaking pit, and heating temperature is 1220 DEG C, it is ensured that steel ingot burning is grilled thoroughly.Through Φ The cogging of 1000mm blooming mills at 400*400mm bloom.Finishing temperature is 1032 DEG C during cogging, is lacked without surface after rolling It falls into.Bloom size is 400mm × 400mm × 3600mm after processing.
Bloom heating is sent heats into gas heating furnace, and 1250 DEG C of heating and temperature control, total heating time is 6 hours 30 points.After heating, 5 passages are passed through in 1800t diameter forging machines, are forged into Φ 239mm and Φ 230mm bars, slubbing time respectively Forging deformation amount is 30%, and final forging temperature is 1025 DEG C, Surface of Rod Bar no significant defect after forging.It is forged into after bar, peeling It is sawed into the pipe that size is Φ 219mm × 800mm and Φ 130mm × 1200mm.
3, steel pipe hot-working
A：Extrusion embodiment
According to finished size specification Ф 73.02*5.51mm, Φ 219mm × 800mm pipes are processed into using deep hole rig Ф 40mm central through holes, the horn mouth of end face flat head chamfering processing wherein, bell mouth angle is 33.5 °, the pipe after machining Base surface must not have crackle, pit, casting skin, be mingled with.Pipe passes through annular stove heat 3 hours to 950 DEG C, heating time 80min； Soaking time 20min.It is directly heat-fed to induction heater after coming out of the stove.By a sensing heating to 1180 DEG C, bringing-up section heats Power 700KW, heat preservation power 120KW.Endoporus is expanded to Ф 60mm after whole homogeneous heating, reaming rate is 200mm/s.Pass through Secondary induction is first heated to 1230 DEG C, bringing-up section power heating power 380KW, heat preservation power 85KW；It is squeezed into Ф 73.02* The steel pipe of 5.51mm, extruding rate 107mm/s enter to be water-cooled to room temperature immediately.
B：Perforation cold-rolling practice embodiment
Φ 130mm × 1200mm pipes are sent to annular furnace and are heated, heating temperature is 1230 DEG C, and heating time is 25min, soaking time 100min.Pipe after heating send to punch to the hollow billet for being produced into Φ 135*8.9mm, roll away from For 80mm, top head front-extending quantity 60mm, feed angle is 10 °.Hollow billet is heat-fed to a tube reducing unit and is processed as Ф 114*8.9mm famines Pipe, production tube Ф 89*7mm are cold-rolled to by a time.
4, heat treatment procedure
Steel pipe after hot-working is subjected to quenching and temper：Water cooling after 1020 DEG C of heating and thermal insulation 30min, then 630 DEG C heating and thermal insulation 4h is air-cooled obtains production tube.
It should be noted that herein, the terms "include", "comprise" or its any other variant are intended to non-row His property includes, so that the process, method, article or equipment including a series of elements includes not only those elements, and And further include the other elements being not explicitly listed, or further include for this process, method, article or equipment institute it is intrinsic Element.In the absence of more restrictions, the element limited by sentence "including a ...", it is not excluded that including institute State in the process, method, article or equipment of element that there is also other identical elements.
Finally it should be noted that：Above example is only used to illustrate the technical scheme of the present invention, rather than its limitations；Although Present invention has been described in detail with reference to the aforementioned embodiments, it will be understood by those of ordinary skill in the art that：It still may be used With technical scheme described in the above embodiments is modified or equivalent replacement of some of the technical features； And these modifications or replacements, the purport for various embodiments of the present invention technical solution that it does not separate the essence of the corresponding technical solution and Range.

Claims (8)

1. a kind of Mo ultralow-carbon martensitic stainless steel seamless pipe, which is characterized in that the seamless pipe is by Mo ultralow-carbon martensitic stainless steel It is made, the Mo ultralow-carbon martensitic stainless steel includes following compositions, is calculated in mass percent：C≤0.03%, Si be 0.1~ 0.5%, Mn are 0.2~0.5%, P≤0.015%, and S≤0.002%, Cr are that 12.2~13.2%, Ni is 5.2~5.7%, Mo It is 0.1~1.6% for 1.9~2.1%, Cu, surplus is Fe and other impurity.
2. Mo ultralow-carbon martensitic stainless steel seamless pipe as described in claim 1, which is characterized in that it is suitable for oil gas fields.
3. Mo ultralow-carbon martensitic stainless steel seamless pipe as described in claim 1, which is characterized in that the pipe diameter of the seamless pipe For Φ 76mm~Φ 220mm, length is at least 6000mm.
4. a kind of manufacturing method of Mo ultralow-carbon martensitic stainless steel seamless pipe as claimed any one in claims 1 to 3, including Following the step of implementing in order：
A) it smelts, wherein first using molten iron as main material, smelt into the steel for meeting the Mo ultralow-carbon martensitic stainless steel ingredient The ingredient of water, i.e., the described molten steel reaches following ratios, is calculated in mass percent：C≤0.03%, Si are that 0.1~0.5%, Mn is 0.2~0.5%, P≤0.015%, S≤0.002%, Cr be 12.2~13.2%, Ni be 5.2~5.7%, Mo be 1.9~ 2.1%, Cu are 0.1~1.6%,
Molten steel is cast into steel ingot again；
B) pipe hot-working, wherein first by Heating Steel Ingots, breaking down, forging, annealing and peeling, then cut into rodlike pipe；
C) steel pipe hot-working, wherein after heating of pipe blank, steel pipe is made in pipe；And
D) it is heat-treated, wherein it will quench and be tempered by the steel pipe of the steel pipe thermal work steps, production tube is made,
It is characterized in that,
In the smelting step, pretreated molten iron is tapped by slightly refining, after vacuum oxygen decarburization and ladle refining, In, in vacuum oxygen decarburization, keep vacuum degree≤106.4Pa, wherein in ladle refining, adjust other alloys in addition to C Ingredient Si, Mn, P, S, Cr, Ni, Mo, Cu enter control range, and under conditions of ensuring slag viscosity≤0.3P, adjustment temperature is extremely After 1540 ± 10 DEG C, by ladle pouring at steel ingot；
In the pipe thermal work steps, in heating process, heating temperature according to 1200~1280 DEG C control, finishing temperature and Final forging temperature is more than 900 DEG C, rolling pass deformation amount controlling 20~40%, the control of forging pass deformation 30~40%, Total forging ratio >=3；And
In the heat treatment step, hardening heat is 900~1050 DEG C, keeps the temperature 10~30min, with the air-cooled above cooling speed Degree is cooled to room temperature, and temperature is 550~680 DEG C of temperature, keeps the temperature 1~4 hour, room is cooled to the air-cooled above speed Temperature.
5. the manufacturing method of seamless pipe as claimed in claim 4, in the steel pipe thermal work steps, after heating of pipe blank, Steel pipe is made using extrusion, wherein heating of pipe blank temperature is 1150~1250 DEG C, and extruding rate is 100~120mm/s, just Deformation temperature≤1300 DEG C are terminated in beginning deformation temperature >=1050 DEG C.
6. the manufacturing method of seamless pipe as claimed in claim 4, in the steel pipe thermal work steps, after heating of pipe blank, Steel pipe is made using perforation cold-rolling practice, wherein heating of pipe blank temperature is 1200~1280 DEG C, and perforation deflection is 50~70%, Cold rolling reduction is 40~60%.
7. the manufacturing method of seamless pipe as claimed in claim 4, in the smelting step, the pretreated molten iron exists Top and bottom combined blown converter is slightly refined, is refined in the decarburization of vacuum oxygen decarburization stove and in ladle refining furnace, and in vacuum oxygen decarburization stove In decarburization, over-blowing is avoided, it is ensured that aim carbon is hit.
8. the manufacturing method of seamless pipe as claimed in claim 4, in vacuum oxygen decarburization, is protected in the smelting step Hold vacuum degree≤66.5Pa.
CN201810269087.0A 2018-03-29 2018-03-29 Mo ultralow-carbon martensitic stainless steel seamless pipe and its manufacturing method Pending CN108277438A (en)

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CN109234615A (en) * 2018-09-11 2019-01-18 中国科学院金属研究所 A kind of microbial corrosion resistance pipe for oil well use stainless steel and its manufacturing method
CN111346997A (en) * 2020-03-25 2020-06-30 攀钢集团江油长城特殊钢有限公司 Processing technology of shell for missile
CN111961816A (en) * 2020-09-15 2020-11-20 江阴市天虹金属铸造有限公司 Quenching process and quenching device for low-impurity ultralow-carbon stainless steel
CN112899445A (en) * 2021-01-18 2021-06-04 山西太钢不锈钢股份有限公司 Heat treatment method for super martensitic stainless steel medium plate
CN112955576A (en) * 2018-11-05 2021-06-11 杰富意钢铁株式会社 Martensitic stainless steel seamless steel pipe for oil well pipe and method for producing same
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

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CN109234615A (en) * 2018-09-11 2019-01-18 中国科学院金属研究所 A kind of microbial corrosion resistance pipe for oil well use stainless steel and its manufacturing method
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CN112955576A (en) * 2018-11-05 2021-06-11 杰富意钢铁株式会社 Martensitic stainless steel seamless steel pipe for oil well pipe and method for producing same
CN111346997A (en) * 2020-03-25 2020-06-30 攀钢集团江油长城特殊钢有限公司 Processing technology of shell for missile
CN111961816A (en) * 2020-09-15 2020-11-20 江阴市天虹金属铸造有限公司 Quenching process and quenching device for low-impurity ultralow-carbon stainless steel
CN111961816B (en) * 2020-09-15 2024-02-09 江阴市天虹金属铸造有限公司 Quenching process and quenching device for low-impurity ultralow-carbon stainless steel
CN112899445A (en) * 2021-01-18 2021-06-04 山西太钢不锈钢股份有限公司 Heat treatment method for super martensitic stainless steel medium plate
CN112899445B (en) * 2021-01-18 2022-05-10 山西太钢不锈钢股份有限公司 Heat treatment method for super martensitic stainless steel medium plate
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

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