CN108251754A - The anti-H of high-intensity and high-tenacity2S/CO2Corrode oil pipe and preparation method thereof - Google Patents

The anti-H of high-intensity and high-tenacity2S/CO2Corrode oil pipe and preparation method thereof Download PDF

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Publication number
CN108251754A
CN108251754A CN201711273914.5A CN201711273914A CN108251754A CN 108251754 A CN108251754 A CN 108251754A CN 201711273914 A CN201711273914 A CN 201711273914A CN 108251754 A CN108251754 A CN 108251754A
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oil pipe
intensity
temperature
iron
tenacity
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李晓
石晓霞
郭志文
高峰
赵艳辉
詹飞
田伟
马俊强
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Baotou Iron and Steel Group Co Ltd
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Baotou Iron and Steel Group Co Ltd
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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
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C37/00—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape
    • B21C37/06—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape of tubes or metal hoses; Combined procedures for making tubes, e.g. for making multi-wall tubes
    • 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
    • C22C33/06—Making ferrous alloys by melting using master 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
    • C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
    • 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
    • C22C38/04—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
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Heat Treatment Of Articles (AREA)
  • Heat Treatment Of Steel (AREA)

Abstract

The present invention provides a kind of anti-H of high-intensity and high-tenacity2S/CO2Corrode oil pipe and preparation method thereof.The chemical composition of the corrosion oil pipe includes by weight percentage：C 0.15~0.19%；Si 0.23~0.26%；Mn 0.45~0.55%；Cr 2.9~3.1%；Mo 0.45~0.55%；P≤0.010%；S≤0.006%；Al 0.015~0.025%；RE 0.0023~0.0052%, surplus are iron and inevitable impurity.In corrosion oil pipe provided by the invention and preparation method thereof, rational chemical composition, smelting continuous casting process, rolling mill practice and heat treatment process cause material to have higher anti-H2S/CO2Corrosive nature, the matching of rational high-intensity and high-tenacity, excellent product exploitativeness, preparation process production efficiency height is at low cost, good in economic efficiency, has good promotional value.

Description

The anti-H of high-intensity and high-tenacity2S/CO2Corrode oil pipe and preparation method thereof
Technical field
The present invention relates to iron and steel smelting technology field, more particularly to a kind of anti-H of high-intensity and high-tenacity2S/CO2Corrode oil pipe and Preparation method.
Background technology
CO2And H2S is that main etchant gas, related data are shown in oil and gas industry, and the global oil gas field there are about 1/2 to contain There is CO2And H2S gases.Carbon dioxide forms weak acid after being dissolved in water with hydrogen sulfide, defeated to oil, gas extraction, refining sum aggregate Equipment generates heavy corrosion, and the service life of equipment is caused to substantially reduce.The corrosion protection steps generally acknowledged both at home and abroad at present are main There are three types of, that is, it adds corrosion inhibiter, using anti-corrosion inner coating and use corrosion resistant alloy.However corrosion inhibiter and inner anticorrosioning coating are not Engineering desired effect can be fully achieved, corrosion resistant alloy material need to be used cooperatively, in addition corrosion inhibiter easily divides under high temperature and high pressure environment Solution denaturation.Corrosion resistant alloy mainly has 13Cr martensitic stain less steels, super 13Cr martensitic stain less steels and 22Cr two phase stainless steels, Although corrosion resistant alloy is with excellent anti-CO2Corrosive nature, still, expensive, cost of investment is very high, especially for some Corrosive gas content is not too high oil well, etchant gas content is higher but belongs to lean ore low permeability oil field, if selected resistance to Erosion alloy then seems conservative.In addition, corrosion resistant alloy is in high Cl-Under the conditions of corrosion resistance and anti-H2S stress corrosion crackings It can be undesirable.
Invention content
In view of this, the present invention provides a kind of anti-H of high-intensity and high-tenacity2S/CO2Corrode oil pipe and preparation method thereof.
The present invention provides a kind of anti-H of high-intensity and high-tenacity2S/CO2Corrode oil pipe, chemical composition is wrapped by weight percentage It includes：C 0.15~0.19%；Si 0.23~0.26%；Mn 0.45~0.55%；Cr 2.9~3.1%；Mo 0.45~ 0.55%；P≤0.010%；S≤0.006%；Al 0.015~0.025%；RE 0.0023~0.0052%, surplus for iron and Inevitable impurity.
Further, chemical composition includes by weight percentage：C 0.17~0.18%；Si 0.23~0.25%； Mn 0.48~0.55%；Cr 3.0~3.1%；Mo 0.51~0.53%；P≤0.009%；S≤0.006%；Al 0.015 ~0.019%；RE 0.0028~0.0052%, surplus are iron and inevitable impurity.
The present invention also provides a kind of above-mentioned anti-H of high-intensity and high-tenacity2S/CO2Corrode the preparation method of oil pipe, including：Smelting Refining, rolling and heat treatment；
The smelting includes：Molten iron pre-processes, converter smelting, LF refining, VD degassings, round billet continuous casting；Wherein, silicomanganese, manganese Iron, ferrochrome and molybdenum-iron carry out deoxidation alloying before addition；Converter terminal control targe：C >=0.06%, P≤0.015%； It is smelted using single slag technique, 200KG lime slag making, finishing slag basicity >=3.0 is added in before tapping；VD depth vacuum degrees desired value≤ 0.06Kpa, deep vacuum time >=15 minute, soft blow Ar are not less than 15 minutes, are added in after VD with rare earth alloy investing method Rare earth；Casting process uses electromagnetic agitation technique, and base type is Φ 210mm, and constant casting speed control is in 1.5M/min, molten steel overheat Δ T≤30 DEG C, are cooled down using way of stacking, while should avoid air port；
The rolling mill practice includes：Round billet, sawing are heated, and are felt relieved, perforation, tube rolling, stretch reducing, cooling, crop end, Aligning and inspection；Wherein, temperature is 1250~1280 DEG C when round billet is perforated；Temperature is 1160~1180 DEG C during tube rolling；Fixed subtracts Shi Wendu is 780~840 DEG C；
The heat treatment includes：Quenching and tempering；Wherein, hardening heat is 900 DEG C ± 10 DEG C, keeps the temperature 60~70 minutes； Temperature is 690 DEG C ± 10 DEG C, keeps the temperature 90~100 minutes.
The present invention provides a kind of anti-H of high-intensity and high-tenacity2S/CO2Corrode oil pipe and preparation method thereof, rational chemistry into Divide, smelting continuous casting process, rolling mill practice and heat treatment process cause material to have higher anti-H2S/CO2It is corrosive nature, rational High-intensity and high-tenacity matching, excellent product exploitativeness, preparation process production efficiency height is at low cost, good in economic efficiency, has Good promotional value.
Description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, to embodiment or will show below There is attached drawing needed in technology description to be briefly described.
Fig. 1 is microcosmic corrosion products film pattern of the steel of the preparation of the embodiment of the present invention 1 after corrosion resistance is examined Figure.
Specific embodiment
The invention discloses a kind of anti-H of high-intensity and high-tenacity2S/CO2Corrode oil pipe and preparation method thereof, people in the art Member can use for reference present disclosure, be suitably modified technological parameter realization.In particular, it should be pointed out that all similar substitutions and modifications Apparent to those skilled in the art, they are considered as being included in the present invention.The method of the present invention and application Be described by preferred embodiment, related personnel significantly can not depart from the content of present invention, in spirit and scope it is right Method described herein and application are modified or suitably changed with combining, to realize and using the technology of the present invention.
The present invention provides a kind of anti-H of high-intensity and high-tenacity2S/CO2Corrode oil pipe, chemical composition is wrapped by weight percentage It includes：C 0.15~0.19%；Si 0.23~0.26%；Mn 0.45~0.55%；Cr 2.9~3.1%；Mo 0.45~ 0.55%；P≤0.010%；S≤0.006%；Al 0.015~0.025%；RE 0.0023~0.0052%, surplus for iron and Inevitable impurity.
As the preferred embodiment of the present invention, the above-mentioned anti-H of high-intensity and high-tenacity2S/CO2Corrode the chemical composition of oil pipe by weight Percentages include：C 0.17~0.18%；Si 0.23~0.25%；Mn 0.48~0.55%；Cr 3.0~3.1%；Mo 0.51~0.53%；P≤0.009%；S≤0.006%；Al 0.015~0.019%；RE 0.0028~0.0052%, surplus For iron and inevitable impurity.
In above-mentioned chemical composition：
Cr is largely dissolved in solid solution, then is precipitated in corrosive environment in matrix surface, is enriched in matrix surface, with corroding ring The OH- ionized in border forms amorphous compound Cr (OH)3, chemical property is more stable.Cr(OH)3To matrix protective effect The reason of enhancing, mainly compares the corrosivity anion inhibition in medium since it is provided with cation selective Greatly.Carbon content is reduced, improves the efficiency of Cr elements to greatest extent, it is ensured that it is solid-solution in matrix to greatest extent, and material is improved with this Resistance to corrosion.Silicon can significantly improve yield of steel and tensile strength, and the combinations such as silicon and molybdenum, chromium are improved corrosion resistance Effect, but silicon can promote the column polycrystalline growing in cast steel, reduce plasticity, and in addition silicon easily makes to form banded structure in steel, reduces horizontal Vertical impulse ratio.Manganese is good deoxidier and desulfurizing agent, and manganese improves the hot-working character of steel, but manganese amount increases, and weakens the anti-of steel Corrosive power.The harm of phosphorus maximum is that segregation is serious, increases temper brittleness, significantly reduces the plasticity and toughness of steel, steel is caused to exist Cold working or by easy embrittlement during external force compared with big load.Sulphur makes steel generate red brittleness, reduces the ductility and toughness of steel, is rolling Crackle and micro-crack are caused when processed, the presence of crackle and micro-crack causes corrosive medium to be enriched with to form concentration cell and reduce material Corrosion resistance.Molybdenum can make the crystal grain refinement of steel, improve quenching degree, thermostrength, temper resistance, allow part in higher temperatures Degree is lower to be tempered, and so as to more effectively eliminate residual stress, improves performance.A small amount of aluminium is added in steel, can crystal grain thinning, improve punching Hit toughness.In addition Al can also fixed nitrogen so that the nitrogen of free state forms disperse compound, so as to improve the performance of steel.Rare earth has Cleaning molten steel, inclusion modification and refined crystalline strengthening effect, substantially improve anti-corrosion structure of steel and performance.Rare earth preferably uses lanthanum.
Correspondingly, the present invention also provides a kind of above-mentioned anti-H of high-intensity and high-tenacity2S/CO2Corrode the preparation method of oil pipe, Including：It smelts, rolling and heat treatment；
The smelting includes：Molten iron pre-processes, converter smelting, LF refining, VD degassings, round billet continuous casting；Wherein, silicomanganese, manganese Iron, ferrochrome and molybdenum-iron carry out deoxidation alloying before addition；Converter terminal control targe：C >=0.06%, P≤0.015%； It is smelted using single slag technique, 200KG lime slag making, finishing slag basicity >=3.0 is added in before tapping；VD depth vacuum degrees desired value≤ 0.06Kpa, deep vacuum time >=15 minute, soft blow Ar are not less than 15 minutes, are added in after VD with rare earth alloy investing method Rare earth；Casting process uses electromagnetic agitation technique, and base type is Φ 210mm, and constant casting speed control is in 1.5M/min, molten steel overheat Δ T≤30 DEG C, are cooled down using way of stacking, while should avoid air port；
The rolling mill practice includes：Round billet, sawing are heated, and are felt relieved, perforation, tube rolling, stretch reducing, cooling, crop end, Aligning and inspection；Wherein, temperature is 1250~1280 DEG C when round billet is perforated；Temperature is 1160~1180 DEG C during tube rolling；Fixed subtracts Shi Wendu is 780~840 DEG C；
The heat treatment includes：Quenching and tempering；Wherein, hardening heat is 900 DEG C ± 10 DEG C, keeps the temperature 60~70 minutes； Temperature is 690 DEG C ± 10 DEG C, keeps the temperature 90~100 minutes.
In smelting process, the effect that silicomanganese, ferromanganese, ferrochrome and molybdenum-iron carry out deoxidation alloying before addition is for suppression Gas content in prepared material；To ensure the cleanliness factor of material, during tapping must pushing off the slag, pushing off the slag failure must skim；In LF refining In link, can slag making desulfurization, composition adjustment and warming temperature be carried out according to converter molten steel ingredient and temperature.
The present invention provides a kind of anti-H of high-intensity and high-tenacity2S/CO2Corrode oil pipe and preparation method thereof, rational chemistry into Divide, smelting continuous casting process, rolling mill practice and heat treatment process cause material to have higher anti-H2S/CO2It is corrosive nature, rational High-intensity and high-tenacity matching, excellent product exploitativeness, the anti-H of high-intensity and high-tenacity provided by the invention2S/CO2Corrode oil pipe Preparation process and method, production efficiency height is at low cost, good in economic efficiency, have good promotional value.
With reference to embodiment, the present invention is further explained：
Embodiment 1-6
The smelting continuous casting manufacturing technique of steel is：Molten iron → molten iron pretreatment → converter smelting → LF refining → VD vacuum takes off Gas → round billet continuous casting.
Converter is smelted using desulphurised hot metal, and deoxidation alloying before silicomanganese, ferromanganese, ferrochrome, molybdenum-iron add in, addition is according to it Composition design content requirement is calculated in alloy content, steel in recovery rate, ferroalloy, vacuum degree desired value≤0.06KPa, Deep vacuum time >=15min, degree of supercooling Δ T≤30 DEG C.Each embodiment chemical composition is as shown in table 1.
1 steel product ingredient of the embodiment of the present invention of table (mass percent/%, RE are lanthanum)
Rolling mill practice：Round billet → sawing → heating → perforation → tube rolling → stretch reducing → cooling → crop end → aligning → Inspection → middle database.Embodiment 1-6 round billets perforate when temperature be followed successively by 1250 DEG C, 1260 DEG C, 1250 DEG C, 1260 DEG C, 1270 DEG C, 1280℃；Temperature is followed successively by 1160 DEG C, 1160 DEG C, 1170 DEG C, 1170 DEG C, 1170 DEG C, 1180 DEG C during embodiment 1-6 tube rollings；It is real It applies a 1-6 and opens temperature when subtracting surely and be followed successively by 780 DEG C, 830 DEG C, 800 DEG C, 820 DEG C, 810 DEG C, 840 DEG C.Using Ф 159mmPQF machines The seamless steel pipe that group rolling specs are Φ 101.6mm × 6.65mm.
Heat treatment process is：Quenching+tempering, embodiment 1-6 hardening heats be followed successively by 890 DEG C, 900 DEG C, 900 DEG C, 900 DEG C, 900 DEG C, 910 DEG C, soaking time is followed successively by 60 minutes, 60 minutes, 65 minutes, 65 minutes, 65 minutes, 70 minutes；Tempering temperature Spend to be followed successively by 690 DEG C, 690 DEG C, 700 DEG C, 700 DEG C, 700 DEG C, 710 DEG C, soaking time be followed successively by 90 minutes, 100 minutes, 95 Minute, 95 minutes, 95 minutes, 100 minutes.The results are shown in Table 2 for microstructure examination after heat treatment, the mechanical property after heat treatment It can be as shown in table 3.
2 steel microstructure of the embodiment of the present invention of table
3 steel mechanics performance of the embodiment of the present invention of table
From table 2 it can be seen that the steel field trash of various embodiments of the present invention preparation is tiny, is evenly distributed, institutional framework is fitted Preferably, crystal grain is ultra-fine grain, can reach 10 grades.From table 3 it can be seen that steel prepared by various embodiments of the present invention have well by force Degree, higher toughness with the seamless steel pipe of its preparation, have good high epistasis and high tenacity.
Corrosion resistance inspection is carried out in high temperature and high pressure kettle experiment to steel sample prepared by above-described embodiment, simulation is molten Liquid is Tarim Basin oil well environment, and PH 6, moisture content 70%, experimental period is 168 hours, and experimental temperature is 90 DEG C, carbon dioxide It divides as 1.5MPa, flow velocity 1.5m/s.Average corrosion rate is 1/3 of straight carbon steel or so compared with straight carbon steel.Experiment terminates Afterwards, specimen surface is smooth, and no pit and corrosion products film come off；Fig. 1 is that steel prepared by embodiment 1 pass through corrosion resistance Microcosmic corrosion products film shape appearance figure after inspection, from this figure, it can be seen that corrosion products film is extremely smooth, and particle is tiny It is even, it is tightly combined with matrix.
According to the NACE solution of NACE Standard TM 0177-2005 standard recommendations, the above-described embodiment that will be cleaned The steel sample of preparation is placed in injection experiments liquid and the corrosion container of sealing, is led to after inert gas purge experiment container and is carefully added It carries, stress loading amount is 469MPa, is passed through H2S gases and to its saturation, record experiment time started.It is continuous by NACE solution It impregnates within 720 hours, checks whether sample is broken or has destructive crackle in the case where amplifying 10 times.The experimental results showed that experience 720h The stretching of permanent load, sample remain intact, and do not occur corrosion cracking phenomenon, illustrate the anti-H of material2S stress corrosion crackings Ability reaches standard requirement.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications also should It is considered as protection scope of the present invention.

Claims (3)

1. a kind of anti-H of high-intensity and high-tenacity2S/CO2Corrode oil pipe, which is characterized in that its chemical composition is wrapped by weight percentage It includes：C 0.15~0.19%；Si 0.23~0.26%；Mn 0.45~0.55%；Cr 2.9~3.1%；Mo 0.45~ 0.55%；P≤0.010%；S≤0.006%；Al 0.015~0.025%；RE 0.0023~0.0052%, surplus for iron and Inevitable impurity.
2. the anti-H of high-intensity and high-tenacity according to claim 12S/CO2Corrode oil pipe, which is characterized in that its chemical composition is pressed Weight percent meter includes：C 0.17~0.18%；Si 0.23~0.25%；Mn 0.48~0.55%；Cr 3.0~ 3.1%；Mo 0.51~0.53%；P≤0.009%；S≤0.006%；Al 0.015~0.019%；RE 0.0028~ 0.0052%, surplus is iron and inevitable impurity.
3. the anti-H of high-intensity and high-tenacity described in claims 1 or 22S/CO2Corrode the preparation method of oil pipe, which is characterized in that packet It includes：It smelts, rolling and heat treatment；
The smelting includes：Molten iron pre-processes, converter smelting, LF refining, VD degassings, round billet continuous casting；Wherein, silicomanganese, ferromanganese, chromium Iron and molybdenum-iron carry out deoxidation alloying before addition；Converter terminal control targe：C >=0.06%, P≤0.015%；Using list Slag technique is smelted, and 200KG lime slag making, finishing slag basicity >=3.0 are added in before tapping；VD depths vacuum degree desired value≤0.06Kpa, it is deep Vacuum time >=15 minute, soft blow Ar are not less than 15 minutes, and rare earth is added in rare earth alloy investing method after VD；Continuous casting mistake Cheng Caiyong electromagnetic agitation techniques, base type are Φ 210mm, and constant casting speed control is in 1.5M/min, molten steel overheat Δ T≤30 DEG C, It is cooled down using way of stacking, while air port should be avoided；
The rolling mill practice includes：Round billet, sawing are heated, and are felt relieved, perforation, tube rolling, stretch reducing, cooling, crop end, aligning And inspection；Wherein, temperature is 1250~1280 DEG C when round billet is perforated；Temperature is 1160~1180 DEG C during tube rolling；It is fixed to open temperature when subtracting Spend is 780~840 DEG C；
The heat treatment includes：Quenching and tempering；Wherein, hardening heat is 900 DEG C ± 10 DEG C, keeps the temperature 60~70 minutes；Tempering Temperature is 690 DEG C ± 10 DEG C, keeps the temperature 90~100 minutes.
CN201711273914.5A 2017-12-06 2017-12-06 The anti-H of high-intensity and high-tenacity2S/CO2Corrode oil pipe and preparation method thereof Pending CN108251754A (en)

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CN112752862B (en) * 2018-09-28 2022-05-06 Posco公司 High-strength cold-rolled steel sheet having high hole expansibility, high-strength hot-dip galvanized steel sheet, and methods for producing these
US11753693B2 (en) 2018-09-28 2023-09-12 Posco Co., Ltd High-strength cold rolled steel sheet having high hole expansion ratio, highstrength hot-dip galvanized steel sheet, and manufacturing methods therefor
CN109355476A (en) * 2018-12-05 2019-02-19 江苏科技大学 A kind of anti-CO2Low-alloy steel material of corrosion and the preparation method and application thereof

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Application publication date: 20180706