CN106086645A - Hydrogen sulfide corrosion resistant tubing and casing and manufacture method thereof - Google Patents

Hydrogen sulfide corrosion resistant tubing and casing and manufacture method thereof Download PDF

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Publication number
CN106086645A
CN106086645A CN201610490248.XA CN201610490248A CN106086645A CN 106086645 A CN106086645 A CN 106086645A CN 201610490248 A CN201610490248 A CN 201610490248A CN 106086645 A CN106086645 A CN 106086645A
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casing
tubing
hydrogen sulfide
corrosion resistant
sulfide corrosion
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CN106086645B (en
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邓叙燕
刘珂
李英真
王学敏
胡楚江
冯莹
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DALIPAL PIPE Co
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DALIPAL PIPE Co
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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
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23P—METAL-WORKING NOT OTHERWISE PROVIDED FOR; COMBINED OPERATIONS; UNIVERSAL MACHINE TOOLS
    • B23P15/00—Making specific metal objects by operations not covered by a single other subclass or a group in this subclass
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/10—Handling in a vacuum
    • 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
    • C21D1/25—Hardening, combined with annealing between 300 degrees Celsius and 600 degrees Celsius, i.e. heat refining ("Vergüten")
    • 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
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
    • 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
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • 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
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • 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
    • C22C38/08—Ferrous alloys, e.g. steel alloys containing nickel
    • 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
    • C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
    • 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
    • C22C38/16—Ferrous alloys, e.g. steel alloys containing 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Abstract

The invention discloses hydrogen sulfide corrosion resistant tubing and casing and manufacture method thereof, in tubing and casing, the weight percent proportioning of chemical composition is: the Fe of 0.24%≤C≤0.28%, 0.15%≤Si≤0.35%, 0.4%≤Mn≤0.5%, S≤0.003%, P≤0.01%, 0.70%≤Cr≤1.10%, 0.25%≤Mo≤0.35%, 0.02%≤Al≤0.04%, Ca≤0.0025%, N≤0.08%, Ni≤0.1%, Cu≤0.1%, V≤0.005%, Nb≤0.005% and surplus and impurity element；Make through smelting procedure, tube rolling operation, Tempering and Quenching operation, screw thread process operation.The mechanical property of this kind of tubing and casing and hydrogen sulfide corrosion resistance can be excellent, can be widely used for the exploitation of sulfide hydrogen Oil/gas Well, have wide market prospect.

Description

Hydrogen sulfide corrosion resistant tubing and casing and manufacture method thereof
Technical field
The present invention relates to tubing and casing technical field.
Background technology
Predicting according to internal authority mechanism, from 2000-2030, the demand of world oil increases by 1.6% every year, the year two thousand thirty It is up to 57.69 hundred million tons；The demand of natural gas increases by 2.4% every year, and the year two thousand thirty is up to 42.03 hundred million tons of oil equivalents.Along with stone The quick growth of oil and gas demand, to common without H2The exploitation of the Oil/gas Well of S can not meet demand, containing H2S oil The exploitation of gas well is increasing.The northwest office of petrochemical industry, south exploration, Sichuan oilfield in China, the general smooth gas field of middle oil, long celebrating Oil field, Tarim Oilfield all contain H in various degree2S gas, the H in the oil gas field of eastern Sichuan Basin, in oil gas2S content reaches 15%~18%。
Conventional oil sleeve pipe stress under arms and H2Under the effect of S, often when stress is far below itself yield strength Suddenly there is brittle failure (this phenomenon is referred to as H 2 S stress corrosion), H can be caused2S is the most excessive with crude oil, natural gas, causes The considerable damage of ecological environment around.Therefore, exploit hydrogen sulfide containing petroleum resources to be necessary for using anti-H2The oil jacket of S corrosion Pipe, the demand of current China is at about 300,000 tons.Etching problem has become as restriction China Petroleum safely, surely at present Calmly, high-efficiency reform and the major obstacle of accumulating.The loss that China's oil causes due to corrosion with petrochemical industry accounts for oil work About the 6% of the industry output value, the 70% of Oil/Gas Pipe inefficacy is relevant with corrosion.Therefore, China Petroleum is in the urgent need to developing anti-H2S is rotten Erosion tubing and casing and manufacturing technology thereof.
Along with the rising of the strength of materials, the dislocation density of material also increases, and causes more hydrion to be assembled in dislocation, So that hydrogen sulfide splitting sensitivity is increased dramatically, the material therefore producing high strength sulfur resisting hydrogen-type corrosion is the most tired The aspects such as difficulty, needs at composition design, degree of purity control, roll control and heat treatment, microstructures Control consider.
Hydrogen sulfide corrosion resistant tubing and casing to intensity, toughness, corrosion resistance requirement the highest, to the surge requirements of performance very Narrow, the yield strength as required the yield strength of C90 to be 621～724 MPa, T95 in API standard is 655～758 MPa.Cause This, the chemical composition of hydrogen sulfide corrosion resistant oil annular tube pipe need to control in the narrowest scope, it is desirable to steel pipe has the highest Heat treatment stability.
In certain patent, the chemical component weight percentage ratio of tubing and casing is: C 0.24～0.32%, Si 0.17～0.40%, Mn 0.2～0.7%, Cr 0.80～1.20%, Mo 0.15～0.40%, Ni≤0.2%, Ti 0～0.06%, P≤0.015%, S≤ 0.01%, surplus is Fe and inevitable impurity.Use the Technology for Heating Processing of quenching+high tempering, it is thus achieved that tiny, uniform Tempered martensite.According to NACE TM-01 standard test, apply the stress value of regulation, be immersed in saturated sulfuration hydrogen salt molten In liquid, 720 hours without cracking.But the stress applied in Shi Yan is only the 80-85% of yield strength, if the sulfuration in oil gas field Hydrogen concentration content is higher, its performance it cannot be guaranteed that.It addition, the requirement of hydrogen sulfide corrosion resistant oil annular tube blank is relatively strict, but this Case is not announced the production method of blank.
In certain patent, the chemical component weight percentage ratio of tubing and casing is: C 0.20～0.40%, Mn 0～0.7%, Cr 0.4 ～1.6%, Mo 0.6～1.8%, V 0.05～0.20%, Nb 0.02～0.10%, Ti 0～0.04%, B 0～0.004%, P≤ 0.015%, S≤0.003%, surplus is Fe and inevitable impurity.By steel pipe being carried out twice quenched place in manufacturing process Reason (quenching+high tempering), the 125 KSI hydrogen sulfide corrosion resistant tubing and casing that availability is excellent.But in this technology, alloy Component system is complicated, manufacturing process is complicated, relatively costly.
Under the conditions of current receding economy situation and complicated international environment, the cost of winning budget of oil gas field is increasingly Low, that only R&D costs are low, dependable performance tubing and casing could improve enterprise competitiveness.Therefore, concrete according to oil gas field The demand of environment and user carries out product and becoming more meticulous of manufacturing process is intended to improve tubing and casing competitiveness with personalized designs Only way.
Summary of the invention
The technical problem to be solved in the present invention is for above-mentioned the deficiencies in the prior art, it is provided that the oil jacket of hydrogen sulfide corrosion resistant Pipe and manufacture method thereof, the alloying component system of this tubing and casing is simple, low cost of manufacture, mechanical property and hydrogen sulfide corrosion resistance Can be excellent.
For solving above-mentioned technical problem, the technical solution used in the present invention is:
Hydrogen sulfide corrosion resistant tubing and casing, in described tubing and casing, the weight percent proportioning of chemical composition is: 0.24%≤C≤0.28%, 0.15%≤Si≤0.35%、0.4%≤Mn≤0.5%、S≤0.003%、P≤0.01%、0.70%≤Cr≤1.10%、0.25%≤Mo ≤0.35%、0.02%≤Al≤0.04%、Ca≤0.0025%、N≤0.08%、Ni≤0.1%、Cu≤0.1%、V≤0.005%、Nb ≤ 0.005% and the Fe of surplus and impurity element；Through smelting procedure, tube rolling operation, Tempering and Quenching operation, screw thread process work Sequence is made.
Preferably, [C]+[Cr]/5 and the nominal-ultimate strength Y of described tubing and casing in tubing and casingminMeet following condition: [C]+[Cr]/5=(Ymin/ 200 ± 0.01)/100, wherein, [C] and [Cr] is respectively carbon and the weight of chromium content in described tubing and casing Amount percentage ratio, YminUnit be KSI；The nominal-ultimate strength of described tubing and casing is 80～95 KSI.
The manufacture method of hydrogen sulfide corrosion resistant tubing and casing, for manufacturing the tubing and casing of above-mentioned hydrogen sulfide corrosion resistant, including Following step: take and there is the continuous cast round billets of same composition through annular furnace heating → perforation → accurate oblique milling unit with described tubing and casing Rolling → micro-tension reducing → modifier treatment → screw thread process, makes described tubing and casing.
Preferably, continuous cast round billets is with steel scrap and the pig iron as raw material, true through arc melting → LF refine for the first time → VD Empty refine → LF refine for the second time → Calcium treatment → continuous casting → strand slow cooling operation is made.Wherein, LF refine i.e. ladle refining, VD Vacuum refining i.e. vacuum deaeration refining.
Preferably, the temperature of the departures of LF refine for the first time controls at 1610 ~ 1630 DEG C, the main task of LF refine for the second time It is to heat up, after temperature is adjusted in place, carries out Calcium treatment.
Preferably, Calcium treatment: feeding 200m silicon-calcium wire, then carry out the soft stirring of 12 ~ 18min.
Preferably, modifier treatment comprise the steps: by rolling state steel pipe be heated in high-temperature heater 860～ 880 DEG C and after being incubated, outer pouring is used to add the mode of interior spray and carry out water-cooled；Then steel pipe is heated to 640 in low-temperature heat stove ～660 DEG C and be incubated, then air cooling aligning；Steel pipe after aligning is heated to 660～680 DEG C again in low-temperature heat stove And be incubated, then air cooling.
Use and have the beneficial effects that produced by technique scheme:
The present invention can manufacture the tubing and casing that nominal-ultimate strength is 80～95 KSI, and its alloying component system is simple, be manufactured into This low, mechanical property and hydrogen sulfide corrosion resistance can be excellent.
The present invention can carry out minute design to the requirement of the strength of materials to chemical composition according to user, meets chemical composition Narrow fluctuation range, the requirement of Mechanical Fluctuation narrow range.
The present invention uses the smelting process of uniqueness, it is ensured that carry out VD vacuum refining at a lower temperature, alleviates true During the reason of vacancy, Ladle Furnace Lining material becomes field trash pollution molten steel in being washed erosion entrance molten steel, improves the pure of molten steel Cleanliness.
The present invention uses VD stove to be de-gassed process, and the hydrogen of ladle slag also drops to lower value in processing procedure, it is to avoid The increase of hydrogen content in molten steel in casting cycle.In addition, strand carries out slow cooling in burial pit, and the hydrogen in strand escapes further Go out, beneficially the raising of hydrogen sulfide corrosion resistance energy.
In the present invention, modifier treatment operation carries out double tempering, and the residual stress of steel pipe is substantially reduced, and structural homogenity is big Big raising, resisting sulfide stress corrosion ability significantly improves, and can pass through SSC evaluation test under the loading stress of 90%.
Accompanying drawing explanation
Fig. 1 is the metallographic structure figure of the 80 KSI anti-H 2 S tubing and casing that the embodiment of the present invention 1 prepares；
Fig. 2 is the metallographic structure figure of the 90 KSI anti-H 2 S tubing and casing that the embodiment of the present invention 2 prepares；
Fig. 3 is the metallographic structure figure of the 95 KSI anti-H 2 S tubing and casing that the embodiment of the present invention 3 prepares.
Detailed description of the invention
The present invention is further detailed explanation with detailed description of the invention below in conjunction with the accompanying drawings, but the protection model of the present invention Enclose and be not limited to the following stated.
Embodiment 1:
With steel scrap and the pig iron as raw material, through the LF essence of 80t arc melting → LF refine for the first time → VD vacuum refining → for the second time Refining → Calcium treatment → continuous casting → strand slow cooling, makes the continuous cast round billets of a diameter of Φ 180 mm, the weight percent of its chemical composition Ratio is: C 0.24%, Si 0.20%, Mn 0.42%, S 0.0011%, P 0.008%, Cr 0.80%, Mo 0.25%, Al 0.022%, Ca 0.0021%, N 0.008%, Ni 0.03%, Cu 0.04%, remaining is Fe and inevitable impurity.
Wherein, the temperature of the departures of LF refine for the first time controls at 1620 DEG C, and the main task of LF refine for the second time is to heat up, After temperature is adjusted in place, carry out Calcium treatment: feed 200m silicon-calcium wire, then carry out the soft stirring of 15 min.
Continuous cast round billets through annular furnace heat → perforation → accurate oblique milling unit rolling → micro-tension reducing → modifier treatment → Screw thread process, make external diameter be 177.8 mm, wall thickness be 10.36 mm, nominal-ultimate strength be the hydrogen sulfide corrosion resistant of 80 KSI Tubing and casing.
Wherein, the nominal-ultimate strength Ymin of the percentage by weight [C] of carbon and chromium content and [Cr] and tubing and casing meet with Lower condition: [C]+[Cr]/5=(Ymin/200 ± 0.01)/100.
Wherein, in annular furnace heating process, annular furnace heat the temperature of a section be 1149 DEG C, the temperature of heating two-stage nitration be 1247 DEG C, the heating temperature of three sections be 1263 DEG C, the temperature of soaking zone be 1257 DEG C.
In micro-tension reducing operation, entering temperature of steel pipe before mini-stretch reducing mill is 900 DEG C, and after sizing, temperature is 840 DEG C.
In modifier treatment operation, the steel pipe of rolling state is heated in high-temperature heater 880 DEG C and is incubated, during heating Between be 44 min, temperature retention time be 16 min, then use outer pouring to add the mode of interior spray and carry out water-cooled, outer trickle flow is 2680 m3/ h, interior jet flow amount are 1140 m3/h；Subsequently steel pipe is heated in low-temperature heat stove 640～660 DEG C and is incubated, heating Time is 53 min, temperature retention time is 40 min, then air cooling aligning；Finally by the steel pipe after aligning again at low-temperature heat stove In be heated to 660～680 DEG C and be incubated, heat time heating time is 53 min, temperature retention time is 40 min, then air cooling.
After the conditioned process of steel pipe, its tissue is mainly uniform tempered sorbite, as shown in Figure 1.
Sample from the tubing and casing that embodiment 1 prepares according to the requirement of standard API SPECIFICATION 5CT the 9th edition Analyzing its yield strength, tensile strength, elongation percentage, side knock merit, its statistic analysis result is as shown in table 1.Sample in table 1 The number of the number tubing and casing by being taken.The yield strength of tubing and casing prepared by above method is 583 ~ 637 MPa, tension is strong Degree is 704 ~ 750 MPa, elongation percentage >=25%, 0 DEG C of horizontal full-scale Xia Shi ballistic work >=120 J, and wherein yield strength is average Value is 610.1 MPa, standard deviation is 8.9 MPa, and tensile strength meansigma methods is 730.4 MPa, standard deviation is 8.2 MPa, extends Rate meansigma methods is 28.2%, standard deviation is 1.4%, and 0 DEG C of horizontal full-scale Xia Shi ballistic work meansigma methods is 142.5 J, standard deviation is 9.1 J。
According to the A method in examination criteria NACE TM0177-2005, the sample in embodiment 1 is carried out SSC performance evaluation Test, loading stress is 496.8 MPa(552 MPa × 90%), after 720h tests, sample all ruptures；10 times of amplifications Microscopic observation specimen surface does not finds to be perpendicular to the crackle in specimen surface tension direction.
Embodiment 2:
With steel scrap and the pig iron as raw material, through the LF essence of 80t arc melting → LF refine for the first time → VD vacuum refining → for the second time Refining → continuous casting → strand slow cooling, makes the continuous cast round billets of a diameter of Φ 180 mm, and the percentage by weight of its chemical composition is: C 0.25%、Si 0.21%、Mn 0.43%、S 0.0012%、P 0.008%、Cr 1.0%、Mo 0.26%、Al 0.023%、Ca 0.0022%, N 0.008%, Ni 0.03%, Cu 0.04%, remaining is Fe and inevitable impurity.
Wherein, the temperature of the departures of LF refine for the first time controls at 1622 DEG C, and the main task of LF refine for the second time is to rise Temperature, after temperature is adjusted in place, carries out Calcium treatment: feed 200m silicon-calcium wire, then carry out the soft stirring of 16 min.
Continuous cast round billets through annular furnace heat → perforation → accurate oblique milling unit rolling → micro-tension reducing → modifier treatment → Screw thread process, make external diameter be 177.8 mm, wall thickness be 10.36 mm, nominal-ultimate strength be the hydrogen sulfide corrosion resistant of 90 KSI Tubing and casing.
Wherein, the nominal-ultimate strength Ymin of the percentage by weight [C] of carbon and chromium content and [Cr] and tubing and casing meet with Lower condition: [C]+[Cr]/5=(Ymin/200 ± 0.01)/100.
Wherein, in annular furnace heating process, annular furnace heat the temperature of a section be 1152 DEG C, the temperature of heating two-stage nitration be 1251 DEG C, the heating temperature of three sections be 1265 DEG C, the temperature of soaking zone be 1258 DEG C.
In micro-tension reducing operation, entering temperature of steel pipe before mini-stretch reducing mill is 905 DEG C, and after sizing, temperature is 842 DEG C.
In modifier treatment operation, the steel pipe of rolling state is heated in high-temperature heater 880 DEG C and is incubated, during heating Between be 44 min, temperature retention time be 16 min, then use outer pouring to add the mode of interior spray and carry out water-cooled, outer trickle flow is 2680 m3/ h, interior jet flow amount are 1140 m3/h；Subsequently steel pipe is heated in low-temperature heat stove 640～660 DEG C and is incubated, heating Time is 53 min, temperature retention time is 40 min, then air cooling aligning；Finally by the steel pipe after aligning again at low-temperature heat stove In be heated to 660～680 DEG C and be incubated, heat time heating time is 53 min, temperature retention time is 40 min, then air cooling.
After the conditioned process of steel pipe, its tissue is mainly uniform tempered sorbite, as shown in Figure 2.
Sample from the tubing and casing that embodiment 2 prepares according to the requirement of standard API SPECIFICATION 5CT the 9th edition Analyzing its yield strength, tensile strength, elongation percentage, side knock merit, its statistic analysis result is as shown in table 2.Sample in table 2 The number of the number tubing and casing by being taken.The yield strength of tubing and casing prepared by above method is 644 ~ 691 MPa, tension is strong Degree is 760 ~ 814 MPa, elongation percentage >=24%, 0 DEG C of horizontal full-scale Xia Shi ballistic work >=125 J, and wherein yield strength is average Value is 669.2 MPa, standard deviation is 17.4 MPa, and tensile strength meansigma methods is 783.5 MPa, standard deviation is 15.9 MPa, prolongs The rate meansigma methods of stretching is 27.1%, standard deviation is 1.2%, and 0 DEG C of horizontal full-scale Xia Shi ballistic work meansigma methods is 170.2 J, standard deviation It is 8.2 J.
According to the A method in examination criteria NACE TM0177-2005, the sample in embodiment 2 is carried out SSC performance evaluation Test, loading stress is 558.9 MPa(621 MPa × 90%), after 720h tests, sample all ruptures；10 times of amplifications Microscopic observation specimen surface does not finds to be perpendicular to the crackle in specimen surface tension direction.
Embodiment 3:
With steel scrap and the pig iron as raw material, through the LF essence of 80t arc melting → LF refine for the first time → VD vacuum refining → for the second time Refining → continuous casting → strand slow cooling, makes the continuous cast round billets of a diameter of Φ 180 mm, and the percentage by weight of its chemical composition is: C 0.27%、Si 0.23%、Mn 0.45%、S 0.001%、P 0.007%、Cr 1.0%、Mo 0.28%、Al 0.025%、Ca 0.0024%, N 0.008%, Ni 0.03%, Cu 0.04%, remaining is Fe and inevitable impurity.
Wherein, the temperature of the departures of LF refine for the first time controls at 1623 DEG C, and the main task of LF refine for the second time is to heat up, After temperature is adjusted in place, carry out Calcium treatment: feed 200 m silicon-calcium wires, then carry out the soft stirring of 18 min.
Continuous cast round billets through annular furnace heat → perforation → accurate oblique milling unit rolling → micro-tension reducing → modifier treatment → Screw thread process, make external diameter be 177.8 mm, wall thickness be 10.36 mm, nominal-ultimate strength be the hydrogen sulfide corrosion resistant of 95 KSI Tubing and casing.
Wherein, the nominal-ultimate strength Ymin of the percentage by weight [C] of carbon and chromium content and [Cr] and tubing and casing meet with Lower condition: [C]+[Cr]/5=(Ymin/200 ± 0.01)/100.
Wherein, in annular furnace heating process, annular furnace heat the temperature of a section be 1160 DEG C, the temperature of heating two-stage nitration be 1250 DEG C, the heating temperature of three sections be 1268 DEG C, the temperature of soaking zone be 1259 DEG C.
In micro-tension reducing operation, entering temperature of steel pipe before mini-stretch reducing mill is 908 DEG C, and after sizing, temperature is 841 DEG C.
In modifier treatment operation, the steel pipe of rolling state is heated in high-temperature heater 880 DEG C and is incubated, during heating Between be 44 min, temperature retention time be 16 min, then use outer pouring to add the mode of interior spray and carry out water-cooled, outer trickle flow is 2680 m3/ h, interior jet flow amount are 1140 m3/h；Subsequently steel pipe is heated in low-temperature heat stove 640～660 DEG C and is incubated, heating Time is 53 min, temperature retention time is 40 min, then air cooling aligning；Finally by the steel pipe after aligning again at low-temperature heat stove In be heated to 660～680 DEG C and be incubated, heat time heating time is 53 min, temperature retention time is 40 min, then air cooling.
After the conditioned process of steel pipe, its tissue is mainly uniform tempered sorbite, as shown in Figure 3.
Sample from the tubing and casing that embodiment 3 prepares according to the requirement of standard API SPECIFICATION 5CT the 9th edition Analyzing its yield strength, tensile strength, elongation percentage, side knock merit, its statistic analysis result is as shown in table 3.Sample in table 3 The number of the number tubing and casing by being taken.The yield strength of tubing and casing prepared by above method is 671 ~ 725 MPa, tension is strong Degree is 781 ~ 832 MPa, elongation percentage >=23%, 0 DEG C of horizontal full-scale Xia Shi ballistic work >=125 J, wherein yield strength meansigma methods Be 695.3 MPa, standard deviation be 18.1 MPa, tensile strength meansigma methods is 806.2 MPa, standard deviation is 17.4 MPa, extend Rate meansigma methods is 25.5%, standard deviation is 1.3%, and 0 DEG C of horizontal full-scale Xia Shi ballistic work meansigma methods is 162.4 J, standard deviation is 10.1 J。
According to the A method in examination criteria NACE TM0177-2005, the sample in embodiment 3 is carried out SSC performance evaluation Test, loading stress is 589.5 MPa(655 MPa × 90%), after 720h tests, sample all ruptures；10 times of amplifications Microscopic observation specimen surface does not finds to be perpendicular to the crackle in specimen surface tension direction.
As can be seen here, after using technique scheme, the alloying component system of the tubing and casing of the hydrogen sulfide corrosion resistant prepared Simply, low cost of manufacture, mechanical property and hydrogen sulfide corrosion resistance can be excellent, can be widely used for opening of sulfide hydrogen Oil/gas Well Adopt, there is wide market prospect.

Claims (7)

1. hydrogen sulfide corrosion resistant tubing and casing, it is characterised in that: in described tubing and casing, the weight percent proportioning of chemical composition is: 0.24%≤C≤0.28%、0.15%≤Si≤0.35%、0.4%≤Mn≤0.5%、S≤0.003%、P≤0.01%、0.70%≤Cr ≤1.10%、0.25%≤Mo≤0.35%、0.02%≤Al≤0.04%、Ca≤0.0025%、N≤0.08%、Ni≤0.1%、Cu≤ 0.1%, the Fe of V≤0.005%, Nb≤0.005% and surplus and impurity element；At smelting procedure, tube rolling operation, quenched heat Science and engineering sequence, screw thread process operation are made.
Hydrogen sulfide corrosion resistant tubing and casing the most according to claim 1, it is characterised in that [C]+[Cr]/5 in described tubing and casing Nominal-ultimate strength Y with described tubing and casingminMeet following condition: [C]+[Cr]/5=(Ymin/ 200 ± 0.01)/100, its In, [C] and [Cr] is respectively carbon and the percentage by weight of chromium content, Y in described tubing and casingminUnit be KSI；Described oil jacket The nominal-ultimate strength of pipe is 80～95 KSI.
3. the manufacture method of hydrogen sulfide corrosion resistant tubing and casing, for the anti-H 2 S described in manufacturing claims 1 or claim 2 The tubing and casing of corrosion, it is characterised in that: comprise the steps: to take and there is the continuous cast round billets of same composition through ring with described tubing and casing Shape stove heating → perforation → accurate oblique milling unit rolling → micro-tension reducing → modifier treatment → screw thread process, makes described oil jacket Pipe.
The manufacture method of hydrogen sulfide corrosion resistant tubing and casing the most according to claim 3, it is characterised in that described continuous cast round billets It is with steel scrap and the pig iron as raw material, through arc melting → LF refine for the first time → VD vacuum refining → LF refine for the second time → calcium Process → continuous casting → strand slow cooling operation is made.
The manufacture method of hydrogen sulfide corrosion resistant tubing and casing the most according to claim 4, it is characterised in that described first time LF The temperature of refine departures controls at 1610 ~ 1630 DEG C, and the main task of LF refine for the second time is to heat up, after temperature is adjusted in place, Carry out Calcium treatment.
The manufacture method of hydrogen sulfide corrosion resistant tubing and casing the most according to claim 5, it is characterised in that described Calcium treatment: feed Enter 200m silicon-calcium wire, then carry out the soft stirring of 12 ~ 18min.
The manufacture method of hydrogen sulfide corrosion resistant tubing and casing the most according to claim 3, it is characterised in that described modifier treatment After comprising the steps: the steel pipe of rolling state is heated to 860～880 DEG C in high-temperature heater and is incubated, outer pouring is used to add The mode of interior spray carries out water-cooled；Then steel pipe being heated in low-temperature heat stove 640～660 DEG C and is incubated, then air cooling is also Aligning；Steel pipe after aligning is heated in low-temperature heat stove 660～680 DEG C again and is incubated, then air cooling.
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Publication number Priority date Publication date Assignee Title
CN108265231A (en) * 2017-12-30 2018-07-10 达力普石油专用管有限公司 A kind of complex geological condition oil gas well mining casing and preparation method thereof
CN111979498A (en) * 2020-09-23 2020-11-24 达力普石油专用管有限公司 Sulfide stress corrosion resistant oil sleeve material and preparation method thereof
CN116815072A (en) * 2023-06-12 2023-09-29 延安嘉盛石油机械有限责任公司 Sulfur-resistant oil sleeve joint and preparation method thereof

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CN1948538A (en) * 2006-11-03 2007-04-18 天津钢管集团有限公司 Petroleum steel tube capable of anti hydrogen sulfide stress corrosion and its manufacturing method
CN101418419A (en) * 2008-12-09 2009-04-29 山东墨龙石油机械股份有限公司 Middle and low intensity oil casing tube for resisting sulfurated hydrogen corrosion and method for producing the same
CN102277534A (en) * 2011-07-29 2011-12-14 攀钢集团有限公司 Hot rolled steel section for gas cylinders and production method thereof

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CN1948538A (en) * 2006-11-03 2007-04-18 天津钢管集团有限公司 Petroleum steel tube capable of anti hydrogen sulfide stress corrosion and its manufacturing method
CN101418419A (en) * 2008-12-09 2009-04-29 山东墨龙石油机械股份有限公司 Middle and low intensity oil casing tube for resisting sulfurated hydrogen corrosion and method for producing the same
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108265231A (en) * 2017-12-30 2018-07-10 达力普石油专用管有限公司 A kind of complex geological condition oil gas well mining casing and preparation method thereof
CN111979498A (en) * 2020-09-23 2020-11-24 达力普石油专用管有限公司 Sulfide stress corrosion resistant oil sleeve material and preparation method thereof
CN111979498B (en) * 2020-09-23 2021-10-08 达力普石油专用管有限公司 Sulfide stress corrosion resistant oil sleeve material and preparation method thereof
CN116815072A (en) * 2023-06-12 2023-09-29 延安嘉盛石油机械有限责任公司 Sulfur-resistant oil sleeve joint and preparation method thereof
CN116815072B (en) * 2023-06-12 2024-02-27 延安嘉盛石油机械有限责任公司 Sulfur-resistant oil sleeve joint and preparation method thereof

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