CN107557664A - A kind of anticorrosive Hi-grade steel submarine seamless line pipe and its manufacture method - Google Patents
A kind of anticorrosive Hi-grade steel submarine seamless line pipe and its manufacture method Download PDFInfo
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Abstract
The present invention relates to plant anticorrosive Hi-grade steel submarine seamless line pipe and its manufacture method.The chemical composition of the spool includes by weight percentage:C≤0.14;Si 0.20~0.35;Mn 0.10~1.10;P≤0.018;S≤0.006;Cr≤0.30;Mo≤0.15;Nb, V and Ti total amount≤0.10;Remaining is Fe and inevitable impurity.The reasonable selection that the present invention passes through microalloy element, appropriate constituent content proportioning, make steel grade that there is relatively low carbon equivalent, and it is readily produced, cost is low, and reasonably smelting continuous casting process, rolling mill practice and Technology for Heating Processing makes steel pipe have higher intensity, excellent low-temperature impact toughness, good corrosion resistance and high dimensional accuracy.The tubing can be used as delivery pipe, be widely used in conveying hydrogen sulfide containing acid hydrocarbon sub-marine field, have the characteristics of easily production, low cost, function admirable.
Description
Technical field
The present invention relates to iron and steel smelting technology field, more particularly to a kind of anticorrosive Hi-grade steel submarine seamless line pipe and its
Manufacture method.
Background technology
For Submarine linepipe as a kind of instrument of trandfer fluid medium, it is many excellent to have that continuous, quick, conveying capacity is big etc.
Point, since Brown&Root companies in 1954 U.S. Mexico gulf lay first Submarine linepipe since, nearly more than half
In century, the Submarine linepipe overall length of countries in the world laying is redeemed oneself and turns into offshore oil and gas up to more than ten0000 kms, Submarine linepipe
The major way that oil gas transmits in the exploitation of field.The construction of particularly nearly 2 years Submarine linepipes shows strong momentum, every year
All in more than 350km, and as the exploitation of offshore oil and gas, the construction of Submarine linepipe will increase at faster speed, its
Demand is growing day by day.At present, China's offshore oil has considerable part still to rely on import with pipe, and is given birth to offshore oil natural gas
The fast development of production is compared, and China's offshore oil is produced with pipe and lagged, and market potential is huge.
Due to being influenceed by soil property, corrosion around ocean current, wave, pipeline etc., submerged pipeline working environment is more harsh, loses
It is higher to imitate probability.From offshore oil with from the point of view of the specific buying of pipe and service condition, require tightened up with pipe than land oil, it is main
Show:It is tightened up to outward appearance processing dimension, required precision;To the corrosion resistance of tubing, in addition to hydrogen sulfide corrosion resistant, go back
Want the corrosion of resistant to sea water, marine environment.Ocean line pipe is to the stability of tubing inherent quality, the particularly control to carbon equivalent
The technical requirements of system and tube end maching precision, hence it is evident that higher than land oil field, only so, just can guarantee that the welding matter of submerged pipeline
Amount, avoids leaking.
Therefore, the exploitation of high intensity, high pressure, corrosion resistant pipe, low-temperature resistance line pipe has turned into what steel pipe manufacturing firm developed
Focus.
The content of the invention
In view of this, the present invention provides a kind of anticorrosive Hi-grade steel submarine seamless line pipe and its manufacture method.
The present invention provides a kind of anticorrosive Hi-grade steel submarine seamless line pipe, and its chemical composition is wrapped by weight percentage
Include:
C≤0.14;Si 0.20~0.35;Mn 0.10~1.10;P≤0.018;S≤0.006;Cr≤0.30;Mo≤
0.15;Nb, V and Ti total amount≤0.10;Remaining is Fe and inevitable impurity.
The present invention also provides a kind of manufacture method of above-mentioned anticorrosive Hi-grade steel submarine seamless line pipe, and it includes following step
Suddenly:
Steel-making, it includes successively:Molten iron pre-processes, converter smelting, LF refining, VD degassings and round billet continuous casting;
Tube rolling, it includes successively:Round billet sawing, annular stove heat, perforation, PQF tandem rollings, stretch reducing and cooling;Wherein,
Tandem rolling inlet temperature is 1250~1270 DEG C;
Heat treatment, it includes quenching and is tempered, wherein, hardening heat is 920 DEG C ± 10 DEG C, is incubated 40~60 minutes;Return
Fiery temperature is 600 DEG C~680 DEG C, is incubated 80~100 minutes or so;Sizing straightening temperature is not less than 500 DEG C after tempering.
Further, in the smelting procedure:
Deep vacuum desired value≤0.06Kpa of VD degassings, deep vacuum time >=15 minute, after VD degassings terminate, feeding
Silicon-calcium wire, soft blow Ar is not less than 15 minutes after feeding silk;Casting process uses electromagnetic agitation technique, molten steel overheat Δ T≤30 DEG C;
Enter burial pit after round billet continuous casting and carry out slow cooling, enter to cheat temperature more than 600 DEG C, temperature retention time is not less than 48 hours.
Further, in institute's tube rolling process:It is 1250~1270 DEG C to set annular furnace soaking zone temperature, temperature after round billet perforation
Spend for 1210~1230 DEG C;Temperature is 890~910 DEG C after stretch reducing.
The invention provides a kind of anticorrosive Hi-grade steel submarine seamless line pipe and its manufacture method, the conjunction of microalloy element
Reason selection, appropriate constituent content proportioning, makes steel grade have relatively low carbon equivalent, and is readily produced, and cost is low, rational to smelt
Continuous casting process, rolling mill practice and Technology for Heating Processing make steel pipe have higher intensity, excellent low-temperature impact toughness, good anti-
Corrosive nature and high dimensional accuracy.The tubing can be used as delivery pipe, be widely used in conveying hydrogen sulfide containing acid seabed oil
Gas field, there is the characteristics of easily production, low cost, function admirable.
Embodiment
The invention discloses a kind of anticorrosive Hi-grade steel submarine seamless line pipe and its manufacture method, those skilled in the art
Present disclosure can be used for reference, is suitably modified technological parameter realization.In particular, all similar replacements and change pair
It is it will be apparent that they are considered as being included in the present invention for those skilled in the art.The method of the present invention and application are
Through being described by preferred embodiment, related personnel substantially can not depart from present invention, in spirit and scope to this
Methods and applications described in text are modified or suitably changed with combining, to realize and using the technology of the present invention.
The present invention is using Submarine linepipe operating mode use condition as starting point, and the present invention is with low C, based on low Mn, by Cr,
The rational proportion of the microalloy elements such as Mo, Nb, Ti, go out yield strength by technique productions such as steel-making, tube rolling, heat treatment and processing
The full-scale side knock work(of V-type is higher than 100J, passes through HIC and SSC test evaluations under 450~600MPa, -50 DEG C of experimental situations
Anticorrosive Hi-grade steel submarine seamless line pipe.
The present invention provides a kind of anticorrosive Hi-grade steel submarine seamless line pipe, and its chemical composition is wrapped by weight percentage
Include:C≤0.14;Si 0.20~0.35;Mn 0.10~1.10;P≤0.018;S≤0.006;Cr≤0.30;Mo≤0.15;
Nb, V and Ti total amount≤0.10;Remaining is Fe and inevitable impurity.
In the chemical composition of anticorrosive Hi-grade steel submarine seamless line pipe provided by the invention:
Carbon (C):As intensified element most economical, most basic in steel, by solution strengthening and precipitation strength to improving steel
Intensity have obvious effect, but extension, toughness and weldability of the too high carbon content to steel adversely affect, while easily cause
Alloying element carbide separates out in crystal boundary, and so as to cause steel grade corrosion resistance to decline, especially sulfur resistance declines, the present invention
Appropriate control is carried out to carbon content, while intensity is ensured, improves the toughness and solderability of steel, for purposes of the invention, C
Content≤0.14%.
Manganese (Mn):Mn can greatly improve the intensity and toughness of steel grade by solution strengthening, be that compensation is drawn because C content reduces
The main and most economical intensified element of loss of strength, and effective deoxidier are played, and there is de- S, still
Too high Mn can promote the formation of carbide, so as to reduce the toughness of steel grade and corrosion resistance;Mn can be infinitely mutual with γ-Fe
It is molten, γ areas are expanded, increase the quenching degree of steel, but too high Mn has the tendency of increase austenite and grown up, and easily makes coarse grains, makes
Steel has superheated susceptivity and temper brittleness, while reduces the welding performance of steel.Therefore, for purposes of the invention, Mn content ranges are
0.10~1.10%.
Chromium (Cr):Cr can improve the thermodynamic stability of steel, block the anodic process of electrochemical corrosion, can be to a certain degree
The carbon dioxide corrosion-resistant of steel is improved, while improves the anti-local corrosion of steel grade and homogeneous corrosion ability, but Cr too high levels can be led
Steel grade welding performance is caused to decline, while Cr carbide easily causes steel grade sulfur resistance to decline in the segregation of crystal boundary, therefore, Cr
Content≤0.3%.
Molybdenum (Mo):Mo can reduce γ areas, the precipitation of strong inhibition pro-eutectoid ferrite and growth process, promote high density position
The formation of the acicular ferrite of wrong substructure, to control, phase-change organization plays an important role, and tissue is further refined, passes through tissue
Phase transformation strengthening improve the intensity of steel;In quenched and tempered steel, Mo can also improve the quenching degree of steel, prevent or reduce steel belt roof bolt
Fragility, improve steel belt roof bolt stability;It is a small amount of to add the anti-office that be effectively increased steel in addition because Mo is thick atom radius element
Portion corrodes and resisting corrosion of chlorine ion, can also improve the hydrogen sulfide corrosion resistant ability of steel.Therefore, Mo contents of the present invention≤
0.15%.
Niobium, vanadium, titanium (Nb, V, Ti):There is strong binding ability to form respective carbide, nitridation by Nb, V, Ti and C, N
Thing or carbonitride, there are strong crystal grain thinning and precipitation strength effect, greatly improve the mechanical property of steel grade.Nb is in steel
Feature is exactly to improve the recrystallization temperature of austenite, and so as to reach the purpose of fining austenite grains, micro Nb can make steel completely
Fabulous combination property is obtained, Nb too high levels cause steel mixed crystal easily occur;Ti's forms small stable in continuous-casting of steel billet
Precipitated phase, this precipitated phase can effectively hinder heating when Austenite Grain Growth, be favorably improved Nb in austenite
Solid solubility, while the impact flexibility to improving welding heat affected zone has obvious effect.But when Nb, V, Ti content exceed
It when 0.1%, can make it that precipitated phase particle is thick, and cause oxide is mingled with to increase, have a negative impact on the contrary, reduce simultaneously
The welding performance of steel grade.Therefore, Nb+V+Ti≤0.10% in the present invention.
Accordingly, the present invention also provides a kind of manufacture method of above-mentioned anticorrosive Hi-grade steel submarine seamless line pipe, and it is wrapped
Include following steps:
Steel-making, it includes successively:Molten iron pre-processes, converter smelting, LF refining, VD degassings and round billet continuous casting;
Tube rolling, it includes successively:Round billet sawing, annular stove heat, perforation, PQF tandem rollings, stretch reducing and cooling;Wherein,
Tandem rolling inlet temperature is 1250~1270 DEG C;
Heat treatment, it includes quenching and is tempered, wherein, hardening heat is 920 DEG C ± 10 DEG C, is incubated 40~60 minutes;Return
Fiery temperature is 600 DEG C~680 DEG C, is incubated 80~100 minutes or so;Sizing straightening temperature is not less than 500 DEG C after tempering.
In above-mentioned manufacturing process:
Steel-smelting production process is:Molten iron pretreatment → converter smelting → LF refining → VD degassings → round billet continuous casting.Supplied materials iron
Water must carry out molten iron pretreatment, so as to ensure to supply the molten steel quality of converter.To suppress gas content in material, silicomanganese, manganese
Iron, ferrochrome, molybdenum-iron, ferro-niobium and ferrotianium before addition must deoxidation alloyings;Converter terminal control targe:C >=0.06%, P
≤ 0.015%;Smelted using single slag technique, finishing slag basicity >=3.0;Necessary pushing off the slag during tapping, pushing off the slag failure must skim;In LF
Refine in link, slag making desulfurization, composition adjustment and warming temperature are carried out according to converter molten steel composition and temperature;Further, VD
Deep vacuum desired value≤0.06Kpa of degassing, deep vacuum time >=15 minute, after VD degassings terminate, appropriate silicon-calcium wire is fed,
Soft blow Ar is not less than 15 minutes after feeding silk, to ensure gas content relatively low in material;Casting process uses electromagnetic agitation technique,
Molten steel overheat Δ T≤30 DEG C, produced according to the suitable pulling rate perseverance pulling rate of different round billet section selections, enter slow cooling after round billet continuous casting
Hole carries out slow cooling, enters to cheat temperature more than 600 DEG C, temperature retention time is not less than 48 hours.Low P, low S, composition are obtained by this method
Uniform high quality round billet.
Tube-rolling technique is:Round billet → sawing → annular stove heat → perforation → PQF tandem rollings → stretch reducing (sizing) → cold
But.Preferably, it is 1250~1270 DEG C to set annular furnace soaking zone temperature, and temperature is 1210~1230 DEG C after round billet perforation;Even
Inlet temperature is rolled for 1090~1110 DEG C;Fixed subtracts rear temperature as 890~910 DEG C.Pass through three roller retained-mandrel MPM group PQF
Various sizes of high-precision high-quality body is obtained with reference to high-end controlling hot rolling technology.
Technology for Heating Processing is:Using modifier treatment, i.e. quenching+tempering.Wherein quenching uses the interior water spray side spray+drenched outside
Formula, to avoid tube bending, interior spray is than the outer leaching delay regular hour, and water is adjusted according to specification, by being reasonably heat-treated
Technology, control steel pipe residual stress technology, obtain the line pipe of surface quality and high comprehensive performance, not only with high intensity and
Good corrosion resistance, and there is excellent toughness.
The invention provides a kind of anticorrosive Hi-grade steel submarine seamless line pipe and its manufacture method, the conjunction of microalloy element
Reason selection, appropriate constituent content proportioning, makes steel grade have relatively low carbon equivalent, and is readily produced, and cost is low, rational to smelt
Continuous casting process, rolling mill practice and Technology for Heating Processing make steel pipe have higher intensity, excellent low-temperature impact toughness, good anti-
Corrosive nature and high dimensional accuracy.The tubing can be used as delivery pipe, be widely used in conveying hydrogen sulfide containing acid seabed oil
Gas field, there is the characteristics of easily production, low cost, function admirable.
With reference to embodiment, the present invention is expanded on further:
Embodiment 1-5
【Steel pipe tubing specification】Φ323.9×22.2mm
【Steel pipe tubing composition】It is listed in table 1.Steel pipe chemical composition fully meets requirement of the present invention to steel grade, P and S contents
It is relatively low, meet composition design requirement, and each stove component content deviation very little as can be seen from Table 1, stable component content have
Temperature control is carried out during beneficial to heat treatment, so as to have good tissue and performance to provide precondition for tubing.
The steel pipe chemical composition of the embodiment of the present invention of table 1, wt%
Embodiment | C | Si | Mn | P | S | Cr | Mo | Nb | Ti |
1 | 0.12 | 0.30 | 0.96 | 0.008 | 0.004 | 0.182 | 0.119 | 0.031 | 0.014 |
2 | 0.10 | 0.28 | 1.01 | 0.009 | 0.003 | 0.193 | 0.106 | 0.034 | 0.013 |
3 | 0.11 | 0.29 | 0.98 | 0.011 | 0.003 | 0.177 | 0.095 | 0.030 | 0.014 |
4 | 0.11 | 0.28 | 0.99 | 0.008 | 0.005 | 0.178 | 0.098 | 0.029 | 0.016 |
5 | 0.12 | 0.26 | 1.05 | 0.013 | 0.004 | 0.188 | 0.104 | 0.028 | 0.015 |
【Production procedure】
Temperature control is carried out during reason, so as to have good tissue and performance to provide precondition for tubing.
First, process for making:323.9 × 22.2mm of production specification Φ steel pipe, continuous cast round billets section is used as Φ 390mm,
Steel tube Co., Ltd of Baogang fan-shaped sections of steelmaking continuous casting machines arc radius is 12m.In order to overcome small arc radius production big cross section round billet easily to produce
The problem of raw round billet crizzle, the steel grade particularly containing microalloy elements such as Nb, V, Ti to crack-sensitivity, take a system
Row measure, such as appropriate Nb, V, Ti content and proportioning;The stable pulling rate of continuous casting, ensure that continuous casting billet crosses straightening section temperature not less than 900
℃;Using weak and uniform secondary cooling system;Suitable covering slag is selected, improves casting machine centering, arc aligning accuracy;After strand is offline,
Round billet enters burial pit slow cooling, enters to cheat temperature more than 600 DEG C, to eliminate structural stress and thermal stress.By above measure, obtain
High quality round billet.
2nd, tube-rolling technique:Round billet → sawing → annular stove heat → perforation → PQF tandem rollings → stretch reducing (sizing) → cold
But.Round billet heats in annular furnace, and furnace temperature is 1280 DEG C, heating of pipe blank temperature deviation ± 10 DEG C, and time inside furnace is unsuitable long, wears
Hole is bitten using low speed, the technique of high-speed rolling, wears rear temperature as 1220 DEG C, enters tandem mill temperature for 1100 DEG C, warm after sizing
Spend for 920 DEG C, cool down, sawing.
3rd, it is heat-treated:Using modifier treatment, i.e. quenching+tempering.Wherein quenching uses the interior spray mode spray+drenched outside, is
Tube bending is avoided, interior spray is adjusted than outer leaching delay regular hour, water according to specification, and temperature is 920 DEG C ± 10 DEG C, insulation
50 minutes or so;Temperature is 620 DEG C, is incubated 90 minutes or so, and sizing straightening temperature is best not less than 500 DEG C after tempering
Flaw detection.
【Line pipe physical dimension】
Diameter range:322.28~325.52 (- 0.5%D~+0.5%D)
Wall thickness range:21.09~23.86 (- 5%t~+7.5%t)
Out-of-roundness:Entirety≤1%OD
Straight degree:Overall≤0.15%, away from pipe end 1000mm, tip bend≤3.0mm.
The line pipe dimensional accuracy of the present invention is high, the weld job being easy between steel pipe, it is high-precision to meet Submarine linepipe
Spend the requirement of size.
【Mechanical properties of pipe】
Mechanical properties of pipe prepared by the embodiment of the present invention is as shown in table 2.As seen from Table 2, method of the invention can be very well
The requirement for meeting high tensile steel tube, 323.9 × 22.2mm of specification Φ steel strength reaches X80 steel-grade, yield tensile ratio very little, tool
There is excellent low-temperature impact toughness, -50 DEG C of side knocks are more than 100J, and hardness number is also very low, so as to ensure that it is very high that steel pipe has
Corrosion resistance.
The mechanical properties of pipe of the embodiment of the present invention of table 2
【Steel pipe field trash and tissue grain size】
The field trash and tissue grain size of steel pipe prepared by the embodiment of the present invention are as shown in table 3.
The steel pipe of the embodiment of the present invention of table 3 and debris and tissue grain size
Note:SReturnRepresent tempered sorbite
【HIC is tested】
The HIC result of the tests of steel pipe prepared by the embodiment of the present invention are as shown in table 4, from table 4, it can be seen that steel pipe flawless
And specimen surface shows there is excellent Properties of HIC resistance without hydrogen blister.The steel pipe of the present invention has also carried out SSC experiments, as a result such as
Shown in table 5,720 hours, sample did not ftractureed, is not cracked, and surface steel pipe has excellent resistance against sulfide stress cracking performance.
The steel pipe HIC result of the tests of the embodiment of the present invention of table 4
【HIC is tested】
The HIC result of the tests of steel pipe prepared by the embodiment of the present invention are as shown in table 5.
The steel pipe SSC result of the tests of the embodiment of the present invention of table 5
As shown in the above, X80 steel is reached using 323.9 × 22.2mm of specification Φ produced by the invention steel strength
Level, the reasonable selection of microalloy element, appropriate constituent content proportioning, make steel grade that there is relatively low carbon equivalent, and be readily produced,
Cost is low, and reasonably smelting continuous casting process, rolling mill practice and Technology for Heating Processing makes steel pipe have higher intensity, excellent low temperature
Impact flexibility, good corrosion resistance and high dimensional accuracy.Delivery pipe can be used as, is widely used in conveying hydrogen sulfide containing
Acid hydrocarbon sub-marine field, there is the characteristics of easily production, low cost, function admirable.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (4)
1. a kind of anticorrosive Hi-grade steel submarine seamless line pipe, it is characterised in that its chemical composition includes by weight percentage:
C≤0.14;Si 0.20~0.35;Mn 0.10~1.10;P≤0.018;S≤0.006;Cr≤0.30;Mo≤0.15;
Nb, V and Ti total amount≤0.10;Remaining is Fe and inevitable impurity.
2. the manufacture method of the anticorrosive Hi-grade steel submarine seamless line pipe described in claim 1, it is characterised in that it is included such as
Lower step:
Steel-making, it includes successively:Molten iron pre-processes, converter smelting, LF refining, VD degassings and round billet continuous casting;
Tube rolling, it includes successively:Round billet sawing, annular stove heat, perforation, PQF tandem rollings, stretch reducing and cooling;Wherein, tandem rolling
Inlet temperature is 1250~1270 DEG C;
Heat treatment, it includes quenching and is tempered, wherein, hardening heat is 920 DEG C ± 10 DEG C, is incubated 40~60 minutes;Tempering temperature
Spend for 600 DEG C~680 DEG C, be incubated 80~100 minutes or so;Sizing straightening temperature is not less than 500 DEG C after tempering.
3. the manufacture method of anticorrosive Hi-grade steel submarine seamless line pipe according to claim 2, it is characterised in that described
In smelting procedure:
Deep vacuum desired value≤0.06Kpa of VD degassings, deep vacuum time >=15 minute, after VD degassings terminate, feed silico-calcium
Line, soft blow Ar is not less than 15 minutes after feeding silk;Casting process uses electromagnetic agitation technique, molten steel overheat Δ T≤30 DEG C;Round billet
Enter burial pit after continuous casting and carry out slow cooling, enter to cheat temperature more than 600 DEG C, temperature retention time is not less than 48 hours.
4. the manufacture method of anticorrosive Hi-grade steel submarine seamless line pipe according to claim 2, it is characterised in that rolled
In plumber's sequence:It is 1250~1270 DEG C to set annular furnace soaking zone temperature, and temperature is 1210~1230 DEG C after round billet perforation;Tension force
Temperature is 890~910 DEG C after tube reducing.
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