CN102325909B - Method of manufacturing sheet steel for sour-resistant line pipe - Google Patents
Method of manufacturing sheet steel for sour-resistant line pipe Download PDFInfo
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- CN102325909B CN102325909B CN201080008173.8A CN201080008173A CN102325909B CN 102325909 B CN102325909 B CN 102325909B CN 201080008173 A CN201080008173 A CN 201080008173A CN 102325909 B CN102325909 B CN 102325909B
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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
- C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium
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- 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
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
- C21D8/0226—Hot rolling
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- 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
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
- C21D8/0263—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment following hot rolling
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- 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
- C21D9/14—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for tubular bodies or pipes wear-resistant or pressure-resistant pipes
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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
- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
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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
- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
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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
- 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
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- Organic Chemistry (AREA)
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- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Heat Treatment Of Steel (AREA)
- Metal Rolling (AREA)
Abstract
Disclosed is a method of manufacturing sheet steel for sour-resistant line pipe having excellent sour resistance that can withstand changes in heating temperature and plate thickness during hot rolling, since the temperature during hot rolling easily decreases when the billet heating temperature drops or the sheet steel is thin. The disclosed steel billets contain C, Si, Mn, Nb, and Ti, while Al, P, and N content is limited. The billets further contain Ca: 0.001-0.004%, there are limitations such that S: not more than 0.0008% and O: not more than 0.0030%, and the Ca, O, and S content meets the condition [Ca](1 - 124[O])/1.25[S] > 3.0. The billets are reheated to 1000-1250 DEG C, and then rough milled, finish rolled, and subjected to accelerated cooling. The cooling start temperature (Tc) of the accelerated cooling and the ratio of C content and Mn content [C/Mn] meet the condition 4 <= Tc [C/Mn] <= 32, the cooling rate of the accelerated cooling is 10-40 DEG C/s, and the stop temperature is 200-500 DEG C.
Description
Technical field
The present invention relates to containing hydrogen sulfide (H
2s) manufacture method that the resistance to hydrogen induced cracking (HIC) performance in environment is the steel plate of acid-proof.
Background technology
The steel pipe using in main line pipe for the sour oil that contains hydrogen sulfide in conveying, acid gas and the steel plate using in pipeline auxiliary facility etc., require to have acid resistance.In addition, so-called acid resistance, refers to the resistance to hydrogen induced cracking (HIC) performance (HIC) in containing the corrosive environment of hydrogen sulfide.
Known: acid resistance is because of deteriorated in the generation of MnS or the generation of bunch (cluster) shape inclusion of rolling direction extension.In addition, in order to improve the acid resistance in very harsh corrosive environment, proposed by reducing the content of P, S, O, N, and added Ca and the steel of having controlled MnS form carry out controlled rolling, then carried out the method (for example patent documentation 1) of water-cooled.As the inclusion that becomes the basic point of HIC, except MnS, also having Nb-Ti-C-N is inclusion, and people have proposed that to make Nb-Ti-C-N be the method (for example patent documentation 2) of the complete solid solution of inclusion by optimizing the heat-treat condition of steel.
In addition, from improving the transport efficiency of pipeline and considering by the angle that thin-walled property reduces costs etc., require the high strength of the effective steel plate of main line always.For such requirement, the intensity, the metal structure that have for example proposed to have X70 left and right are the manufacture method (for example patent documentation 3) at thickness direction steel plate even and fine bainite, acid-proof.
Moreover, when at cold district pipeline installation, need to improve the low-temperature flexibility of the effective steel plate of main line.For such problem, proposed to improve the manufacture method (for example patent documentation 4～6) of low-temperature flexibility and acid proof high tensile steel plate.They measure to suppress the rising of hardness by reducing C, by reducing S amount and adding Ca to control MnS form, measure to control the form of oxide compound, thereby seek taking into account of acid resistance and low-temperature flexibility by reducing Al.On the other hand, by containing certain carbon amount and adding Cr, in the situation that not making toughness drop, seek high strength, and by the specific miniaturization of creating conditions to seek crystal grain, thereby low-temperature flexibility (patent documentation 7) improved.
Prior art document
Patent documentation
Patent documentation 1: Japanese kokai publication sho 62-112722 communique
Patent documentation 2: TOHKEMY 2006-63351 communique
Patent documentation 3: Japanese kokai publication sho 61-165207 communique
Patent documentation 4: Japanese kokai publication hei 03-236420 communique
Patent documentation 5: Japanese kokai publication hei 05-295434 communique
Patent documentation 6: Japanese kokai publication hei 07-242944 communique
Patent documentation 7: Japanese kokai publication hei 06-136440 communique
Summary of the invention
Invent problem to be solved
In order to improve acid resistance, the growth that suppresses polygonal ferrite is necessary.Therefore, wish the temperature (Ar that is austenite one phase at metal structure
3more than point) under the acceleration that starts after hot rolling cooling., when the Heating temperature that makes steel billet reduces or when the thickness of slab of steel plate is thinner, in hot rolling, Yin Wendu declines and makes water-cooled start temperature lower than Ar
3point, damages acid resistance because generating polygonal ferrite sometimes.
The present invention has been for having addressed the above problem, using provide a kind of can be with the manufacture method of the Heating temperature of hot rolling and the effective steel plate of the change of thickness of slab main line that adapt, acid-proof as problem.
For solving the means of problem
The opinion of the present invention based on following completes, and by the content of strict restriction S and O, and adds Ca, thereby by with [Ca] (1-124[O])/1.25[S] the ESSP value of expression is controlled at higher level, to control the form of sulfide; Control the temperature of hot rolling and depress ratio, to make the cooling crystallization particle diameter before of acceleration starting after hot rolling become fine; And then C amount is limited in to lower level, increase Mn amount, and the ratio [C/Mn] of regulation C amount and Mn amount and the relation of accelerating cooling beginning temperature T c, thereby even if cooling beginning temperature T c reduces, also can suppress the generation of polygonal ferrite, prevent acid proof deteriorated.Main idea of the present invention is as follows.
(1) manufacture method for the effective steel plate of acidproof main line, is characterized in that:
Steel billet is being reheated after 1000～1250 ℃, carry out roughing, carry out again finish rolling, with C amount and the ratio [C/Mn] of Mn amount and the mode of satisfied 4≤Tc * [C/Mn]≤32 of cooling beginning temperature T c, from described cooling beginning temperature T c, beginning to cool down speed is that the acceleration of 10～40 ℃/s is cooling, and it is cooling at 200～500 ℃, to stop this acceleration; Wherein, described steel billet is in quality %, contain C:0.01～0.06%, Si:0.1～0.5%, Mn:1.0～1.5%, Nb:0.010～0.040%, Ca:0.001～0.004%, Ti:0.005～0.030%, following element is restricted to, below Al:0.08%, below P:0.015%, below S:0.0008%, below O:0.0030%, below N:0.0050%, and the content of Ca, O and S satisfied [Ca] (1-124[O])/1.25[S] > 3.0.
(2) according to the manufacture method of the effective steel plate of acidproof main line above-mentioned (1) Suo Shu, it is characterized in that: by final rolling temperature regulation, be more than 800 ℃, 950 ℃ of following depressing than R regulation are carried out to described finish rolling for surpassing 3.125, and make depressing than R and cooling beginning temperature T c of this finish rolling meet 20/ (R-3)+640≤Tc≤800.
(3) according to the manufacture method of the effective steel plate of acidproof main line above-mentioned (1) or (2) Suo Shu, it is characterized in that: described cooling beginning temperature T c is in the scope of 650～800 ℃.
(4) according to the manufacture method of the effective steel plate of acidproof main line above-mentioned (1) or (2) Suo Shu, it is characterized in that: described steel billet is in quality %, also contain that Ni:0.5% is following, Cu:0.5% is following, Cr:0.5% is following, Mo:0.3% is with lower one kind or two or more.
(5) according to the manufacture method of the effective steel plate of acidproof main line above-mentioned (1) or (2) Suo Shu, it is characterized in that: described steel billet, in quality %, also contains below V:0.10%.
(6) according to the manufacture method of the effective steel plate of acidproof main line above-mentioned (1) or (2) Suo Shu, it is characterized in that: described steel billet, in quality %, also contains below B:0.0020%.
(7) according to the manufacture method of the effective steel plate of acidproof main line above-mentioned (1) or (2) Suo Shu, it is characterized in that: described steel billet is in quality %, also contain Mg:0.01% with lower one or both.
The effect of invention
According to the present invention, even when the Heating temperature of hot rolling, thickness of slab change, also can provide the effective steel plate of main line of acid-proof.
Embodiment
The inventor has manufactured the steel plate that ESSP value is controlled, and has evaluated acid resistance, and described ESSP value is by the content of Ca, S and O, by [Ca] (1-124[O])/1.25[S] value obtained.
About acid resistance, carry out based on NACE (international corrosion and engineering association: the test of TM0284 National Association of Corrosion and Engineer), evaluate according to the having or not of generation of HIC (hydrogen induced cracking (HIC)).As long as HIC fracture rate, below 5% left and right, is just considered to acid-resistant property good.
NACE test is to make hydrogen sulfide saturated in the solution of 5%NaCl solution+0.5% acetic acid, pH=2.7, whether generates the test method of crackle at 96 hours " Invest, Then Investigate "s.To there is the tissue of the sample of HIC, be studied, result is learnt: in the deteriorated steel plate of acid resistance, generate and have polygonal ferrite.
Moreover, arranged the tissue of steel plate and create conditions between relation, result is learnt: even if reduce and also do not generate the steel plate of polygonal ferrite for making to accelerate cooling beginning temperature, say that qualitatively C amount is many, Mn measures few steel plate.
So the inventor thinks, if the ratio [C/Mn] of C amount and Mn amount is reduced, can make to accelerate cooling cooling beginning temperature T c and reduce, and arrange testing data.Consequently, so that obtained following opinion: as long as Tc and [C/Mn] meet the relation of 4≤Tc * [C/Mn]≤32, just can reduce cooling beginning temperature T c in the situation that not generating polygonal ferrite.
Moreover the inventor is following until depressing than regulation of finish rolling manufactured steel plate for surpassing 3.125 by 950 ℃, and should depress than and cooling beginning temperature T c between relation be studied.Result is learnt: if improved, depress ratio, and crystallization particle diameter miniaturization, even if reduce cooling beginning temperature T c, metal structure can not form lamellar structure yet, thus acid resistance is improved.
So the inventor is with regard to the condition of finish rolling and accelerate cooling cooling beginning temperature T c and the relation between acid resistance has arranged testing data.Consequently, so that obtained following opinion: if meet the relation of 20/ (R-3)+640≤Tc≤800, metal structure can not form lamellar structure, can obtain good acid resistance.
Below the present invention will be described in detail.In addition, following % refers to quality %.
C：0.01～0.06％
C:C is the element that improves hardness of steel, as its effective lower limit, need to add more than 0.01%.On the other hand, if increase C amount, promote the generation of carbide, thereby therefore infringement HIC-resistance seeks low carbonization in the present invention.In order to suppress the decline of HIC, weldability, toughness etc., preferably C gauge is decided to be below 0.06%, be preferably below 0.05%, more preferably below 0.038%.
Si：0.1～0.5％
Si:Si is deoxidant element, need to add more than 0.1%.On the other hand, if Si amount surpasses 0.5%, the toughness drop of welded heat affecting zone (HAZ), is therefore 0.5% by upper limit regulation.Preferred scope is 0.15～0.35%.
Mn：1.0～1.5％
Mn:Mn is the element that improves intensity and toughness, need to add more than 1.0%.On the other hand, Mn makes the deteriorated element of acid resistance by generating MnS, therefore in order to suppress HIC, need to be 1.5% by the upper limit regulation of Mn amount.Preferred scope is 1.1～1.4%.
Nb：0.010～0.040％
Nb:Nb makes the miniaturization of crystallization particle diameter by expanding non-recrystallization humidity province, form carbide, nitride, thereby the element that contributes to intensity to improve need to add more than 0.010%.On the other hand, in the present invention, it is very important preventing from generating thick carbide, need to be below 0.040% by upper limit regulation.The preferred scope of Nb is 0.011～0.025%, and preferred scope is 0.012～0.020%.
Ca：0.001～0.004％
Ca:Ca generates sulfide CaS, is suppressed at the generation of the MnS of rolling direction elongation, obviously contributes to the element of the improvement of HIC-resistance.At the addition of Ca, lower than 0.001% time, can not get effect, thereby undergage is decided to be to 0.001%.On the other hand, if the addition of Ca surpasses 0.004%, oxide compound gathers, and therefore infringement HIC-resistance is 0.004% by upper limit regulation.Preferred scope is 0.0025～0.0035%.
Ti：0.005～0.030％
Ti:Ti is as reductor and nitride forming element and for the element of grain refining, be necessary to add more than 0.005%.On the other hand, if add Ti superfluously, because forming thick nitride, making toughness drop, is therefore 0.030% by upper limit regulation.Preferred scope is 0.010～0.020%.
below Al:0.08%
Al:Al is deoxidant element, if but addition surpasses 0.08%, generate gathering bunch of Al oxide compound, and infringement acid resistance, is therefore limited in below 0.08%.In addition, when requiring toughness, preferably make Al amount below 0.03%.In preferred Al amount, be limited to 0.01%.There is no particular limitation for the lower limit of Al amount, but in order to reduce the oxygen amount in molten steel, preferably add more than 0.0005%.
below P:0.015%
P:P is impurity, if content surpasses 0.015%, damages HIC-resistance.Therefore by the upper limit regulation of P content, be, 0.015%.
below S:0.0008%
Thereby the element that the MnS that is created on rolling direction extension when S:S is hot rolling reduces HIC-resistance.Therefore, needing in the present invention to reduce S amount, is 0.0008% by upper limit regulation.S amount is more few more preferred, but make it, lower than 0.0001%, is difficult.In addition, from the angle of manufacturing cost, consider, also preferably make it more than 0.0001%.
below O:0.0030%
O:O is impurity, improves HIC-resistance for gathering of inhibited oxidation thing, need to be 0.0030% by upper limit regulation.For the generation of inhibited oxidation thing, improve toughness, preferably O gauge is fixed on below 0.0020%.
below N:0.0050%
N:N is impurity, if N content surpasses 0.0050%, the carbonitride of Ti and Nb easily gathers, infringement HIC-resistance.Therefore by the upper limit regulation of N amount, be, 0.0050%.In addition,, in the situation that requiring toughness etc., in order to suppress the coarsening of TiN, preferably make N amount below 0.0035%.In addition, during the miniaturization of the austenite particle diameter while seeking to heat utilizing the nitride such as TiN, NbN, preferably contain more than 0.0010% N.
[Ca](1-124[O])/1.25[S]＞3.0
In the present invention, need to increase [Ca] (1-124[O])/1.25[S] be ESSP value.ESSP value is to consider that Ca forms oxide compound, the Ca amount needing in order to generate CaS and the ratio of S amount.For by adding Ca, form CaS and fixing S, by ESSP value regulation, be to be necessary over 3.0.
In addition,, if S amount is 0, ESSP value reaches infinitely great, and in such cases, can not have MnS to generate.Therefore,, if Ca amount is in above-mentioned scope, do not need the upper limit of regulation ESSP value.
In the present invention, as the element that improves intensity and toughness, preferably add the one kind or two or more element in Ni, Cu, Cr, Mo, V, B.
below Ni:0.5%
Ni:Ni is effective element for improving toughness and intensity, also contributes to improve solidity to corrosion, therefore preferably adds more than 0.01%.On the other hand, Ni be high price element, in order to cut down manufacturing cost, preferably by ceiling restriction 0.5%.
below Cu:0.5%
Cu:Cu is effective element for improving intensity, also contributes to improve solidity to corrosion, therefore preferably adds more than 0.01%.On the other hand, Cu be also high price element, in order to cut down manufacturing cost, preferably by ceiling restriction 0.5%.
below Cr:0.5%
Cr:Cr is effective element for improving intensity, preferably adds more than 0.01%.On the other hand, if added in a large number, often hardening capacity improves, toughness drop, so the upper limit is preferably 0.5%.
below Mo:0.3%
Mo:Mo is when improving hardening capacity, forms carbonitride and improves the element of intensity, in order to obtain its effect, preferably adds more than 0.01%.On the other hand, Mo is the element of high price, in order to cut down manufacturing cost, preferably makes to be limited to 0.30%.In addition, if the intensity of steel rises, often HIC and toughness drop, be limited to 0.20% on therefore preferred.
below V:0.10%
V:V forms carbide, nitride, contributes to carry high-intensity element, in order to obtain additive effect, preferably adds more than 0.01%.On the other hand, if add the V that surpasses 0.10%, often cause toughness drop, so preferred upper limit is 0.10%.
below B:0.0020%
B:B obviously contributes to improve the element of hardening capacity by the grain boundary segregation to steel.In order to obtain this additive effect, preferably add more than 0.0001% B.On the other hand, if add B superfluously, superfluous to the segregation of crystal boundary, often cause toughness drop, so the upper limit is preferably 0.0020%.
below Mg:0.01%
Mg:Mg is the element playing a role as reductor and sweetening agent, particularly by producing fine oxide compound, suppresses the coarsening of particle diameter, for improving toughness, is therefore effective.In order to obtain this additive effect, preferably add more than 0.0001%.On the other hand, if add Mg, surpass 0.01%, the easy aggegation of oxide compound and coarsening often makes HIC and toughness drop, so preferred upper limit is 0.01%.
The steel that contains mentioned component, by after steel making working procedure melting, forms steel billet by casting continuously, by steel billet is heated, implements to comprise the heavy plate rolling of roughing and finish rolling, just forms steel plate.
heating temperature: 1000～1250 ℃
If the not solid solution of NbC that the Heating temperature of steel billet, lower than 1000 ℃, is separated out in steel billet, thick NbC remains in steel plate, and acid resistance is reduced.On the other hand, if the Heating temperature of steel billet surpasses 1250 ℃, the crystallization particle diameter of steel plate becomes thick, and the metal structure after finish rolling becomes lamellar structure, and acid resistance is reduced.Therefore, the Heating temperature of steel billet is defined in the scope of 1000～1250 ℃.
After finish rolling, accelerate cooling.Preferably acceleration is cooling carries out immediately after finish rolling., if the thickness of slab attenuate of steel plate, temperature easily reduces.Therefore, in the present invention, accelerate cooling condition for suppressing the generation of polygonal ferrite, the lamellar structure that prevents from becoming ferrite and low-temperature phase covert (bainite or martensite) is very important.
accelerate cooling cooling beginning temperature T c:
Accelerate cooling in order to make the tissue of steel plate become fine acicular ferrite or bainite ferrite carries out.If accelerate cooling cooling beginning temperature, reduce, promote polygonal ferrite phase transformation.On the other hand, by reducing C amount and increasing Mn, measure, can suppress polygonal ferrite phase transformation.
Therefore, in the present invention, in order to suppress the generation of polygonal ferrite, and make to accelerate cooling cooling beginning temperature and reduce, by the ratio [C/Mn] of C amount and Mn amount and cooling beginning temperature T c (℃) amass: it is below 32 that Tc * [C/Mn] stipulates.In addition, from making to accelerate the angle that cooling beginning temperature T c reduces, consider, the upper limit of Tc * [C/Mn] is preferably 30, and more preferably 27.
On the other hand, if cooling beginning temperature T c too reduces, even if make [C/Mn] to reduce in the scope being grouped at one-tenth of the present invention, can not avoid the generation of polygonal ferrite, therefore the undergage of Tc * [C/Mn] is decided to be to 4.In addition,, in order to suppress the generation of polygonal ferrite, Tc * [C/Mn] is preferably more than 4.5, more preferably more than 10.
In addition, if accelerate cooling cooling beginning temperature lower than 650 ℃, promote the generation of polygonal ferrite, therefore in order to ensure acid resistance, preferably will speed up cooling cooling beginning temperature and be defined in more than 650 ℃.
On the other hand, in order to improve acid resistance, preferably make the final rolling temperature of hot rolling be reduced to 900～800 ℃ of left and right, thereby tissue is homogenized.Owing to accelerating cooling cooling beginning temperature below the final rolling temperature of hot rolling, therefore preferably make to accelerate cooling cooling beginning temperature below 800 ℃.
accelerate cooling speed of cooling: 10～40 ℃/s
Accelerate cooling in order to make the tissue of steel plate become fine acicular ferrite or bainite ferrite carries out.In order to suppress polygonal ferrite phase transformation, prevent from generating perlite, making speed of cooling is necessary at 10 ℃/s above.
On the other hand, if accelerate cooling speed of cooling, surpass 40 ℃/s, because of surplus generate martensite and make hardness become inhomogeneous, acid resistance and toughness drop.Therefore, will speed up cooling speed of cooling regulation is 10～40 ℃/s.In addition, speed of cooling is the speed at the thickness of slab center of steel plate.
accelerate the cooling temperature that stops: 200～500 ℃
In order to suppress martensitic generation, will speed up cooling stopping in scope that temperature is defined in 200～500 ℃.In order to suppress polygonal ferrite phase transformation, prevent from generating perlite, making to accelerate the cooling temperature that stops is necessary at 500 ℃ below.
On the other hand, if accelerate cooling to stop temperature lower than 200 ℃, martensite generates superfluously, makes hardness become inhomogeneous, acid resistance and toughness drop.
Moreover, in order to suppress the generation of lamellar structure, preferably final rolling temperature, the cooling cooling beginning temperature of acceleration depressed after ratio, rolling are controlled.
final rolling temperature: more than 800 ℃
About the final rolling temperature of hot rolling, in order to make to organize homogeneous, preferably regulation is more than 800 ℃.This be because: the difference being grouped into according to one-tenth, when lower than 800 ℃, generate ferrite, often make the tissue of the steel plate after rolling become stratiform, thus infringement acid resistance.In addition, according to the difference of the condition of finish rolling, remaining processing ferrite in steel plate often, thereby infringement toughness.
950 ℃ of following depressing than R: surpass 3.125
In finish rolling, in order to make the miniaturization of crystallization particle diameter, controlled rolling temperature and depressing than being necessary.Particularly, by strengthening depressing than carrying out finish rolling under low temperature, can make steel plate tissue become fine.When rolling temperature surpasses 950 ℃, produce recrystallize, therefore 950 ℃ of following depressing are important than R.
In addition, if 950 ℃ of following depressing than below 3.125 are organized and do not reached homogeneous, acid resistance reduces sometimes.Therefore, preferably following until depressing of end finish rolling is to surpass 3.125 than regulation, more preferably more than 4 by 950 ℃.950 ℃ following depress than upper limit regulation not, but consider the thickness of slab after slab thickness and finish rolling, the 20th, the preferred upper limit.From below 950 ℃ until finish the depressing than the ratio that is thickness of slab the rolling thickness of slab during with 950 ℃ of finish rolling.
20/(R-3)+640≤Tc≤800
In the present invention, cooling owing to directly accelerating after hot rolling, therefore accelerate cooling cooling beginning temperature below the final rolling temperature of hot rolling.In order to improve acid resistance, preferably make the final rolling temperature of hot rolling be reduced to 900～800 ℃ of left and right.Therefore, preferably make to accelerate cooling cooling beginning temperature also below 800 ℃.
On the other hand, if strengthen the ratio of depressing of finish rolling, because thickness of slab attenuate makes to accelerate cooling starting, postpone, cooling beginning temperature reduces.Yet by increasing the ratio of depressing of finish rolling, the miniaturization of crystallization particle diameter, even if therefore cooling beginning temperature reduces, also can prevent from becoming lamellar structure.Therefore, if improved, depress ratio, cooling beginning temperature T c is reduced, the tolerable limit expanded of creating conditions while manufacturing the steel sheet of acid-proof.
Therefore, if 950 ℃ following, depressing than the relation of satisfied 20/ (R-3)+640≤Tc≤800 of the relation between R and cooling beginning temperature T c to finish rolling, good acid resistance can be in the situation that metal structure does not become lamellar structure, obtained, and the tolerable limit of creating conditions can be expanded.
Embodiment
With converter and there is the steel of the chemical composition shown in table 1 by secondary refining melting, by continuous casting, manufacture the steel billet that 250mm is thick.By the condition shown in table 2, the steel billet obtaining is carried out to hot rolling, thereby form steel plate.By NACE test evaluation the HIC of the steel plate after manufacturing.Condition as NACE test makes hydrogen sulfide saturated in the solution of 5%NaCl solution+0.5% acetic acid, pH=2.7, by dipping time regulation, is 96 hours, observes having or not of crackle, measures HIC fracture rate (CAR).
The results are shown in Table 2.In No.1～11, the composition of steel plate and creating conditions within the scope of the invention, CAR is below 5%, has good acid resistance.On the other hand, No.12 is that ESSP value is lower than scope of the present invention, the example that acid resistance reduces.In addition, No.13 and 14 is examples that C amount is many, Tc * [C/Mn] also increases, HIC-resistance reduces.No.15 is the example that cooling beginning temperature is low, HIC-resistance is deteriorated.
Utilizability in industry
As mentioned above, according to the present invention, even in the situation that the Heating temperature of hot rolling, thickness of slab change, also can provide the effective steel plate of main line of acid-proof.Therefore, the present invention is to the contribution highly significant in industry, and utilizability is industrially larger.
Claims (6)
1. a manufacture method for the effective steel plate of acidproof main line, is characterized in that:
Steel billet is being reheated after 1000～1250 ℃, carry out roughing, by the final rolling temperature regulation of finish rolling, be more than 800 ℃ again, depressing than R regulation of 950 ℃ of following finish rolling carried out to finish rolling for surpassing 3.125, with C amount, meet 4≤Tc * [C/Mn]≤24.0 with ratio [C/Mn] and the cooling beginning temperature T c of Mn amount, and make depressing than R and described cooling beginning temperature T c of described finish rolling meet 20/(R-3) mode of+640≤Tc≤800, from described cooling beginning temperature T c, beginning to cool down speed is that the acceleration of 10～40 ℃/s is cooling, and it is cooling at 200～500 ℃, to stop this acceleration,
Wherein, described steel billet is in quality %, contain C:0.01～0.06%, Si:0.1～0.5%, Mn:1.0～1.5%, Nb:0.010～0.040%, Ca:0.001～0.004%, Ti:0.005～0.030%, following element is restricted to, below Al:0.08%, below P:0.015%, below S:0.0008%, below O:0.0030%, below N:0.0050%, and the content of Ca, O and S satisfied [Ca] (1-124[O])/1.25[S] > 3.0.
2. the manufacture method of the effective steel plate of acidproof main line according to claim 1, is characterized in that: described cooling beginning temperature T c is in the scope of 650～800 ℃.
3. the manufacture method of the effective steel plate of acidproof main line according to claim 1 and 2, is characterized in that: described steel billet is in quality %, also contains that Ni:0.5% is following, Cu:0.5% is following, Cr:0.5% is following, Mo:0.3% is with lower one kind or two or more.
4. the manufacture method of the effective steel plate of acidproof main line according to claim 1 and 2, is characterized in that: described steel billet, in quality %, also contains below V:0.10%.
5. the manufacture method of the effective steel plate of acidproof main line according to claim 1 and 2, is characterized in that: described steel billet, in quality %, also contains below B:0.0020%.
6. the manufacture method of the effective steel plate of acidproof main line according to claim 1 and 2, is characterized in that: described steel billet, in quality %, also contains below Mg:0.01%.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009-035659 | 2009-02-18 | ||
| JP2009035659A JP4700740B2 (en) | 2009-02-18 | 2009-02-18 | Manufacturing method of steel plate for sour line pipe |
| PCT/JP2010/052586 WO2010095730A1 (en) | 2009-02-18 | 2010-02-16 | Method of manufacturing sheet steel for sour-resistant line pipe |
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| Publication Number | Publication Date |
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| CN102325909A CN102325909A (en) | 2012-01-18 |
| CN102325909B true CN102325909B (en) | 2014-04-23 |
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| CN201080008173.8A Active CN102325909B (en) | 2009-02-18 | 2010-02-16 | Method of manufacturing sheet steel for sour-resistant line pipe |
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| JP (1) | JP4700740B2 (en) |
| KR (2) | KR101601000B1 (en) |
| CN (1) | CN102325909B (en) |
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| EP2862954A4 (en) | 2012-06-18 | 2016-01-20 | Jfe Steel Corp | Thick, high-strength, sour-resistant line pipe and method for producing same |
| WO2014010150A1 (en) | 2012-07-09 | 2014-01-16 | Ｊｆｅスチール株式会社 | Thick-walled high-strength sour-resistant line pipe and method for producing same |
| JP6070642B2 (en) * | 2014-06-20 | 2017-02-01 | Ｊｆｅスチール株式会社 | Hot-rolled steel sheet having high strength and excellent low-temperature toughness and method for producing the same |
| KR101988771B1 (en) * | 2017-12-22 | 2019-09-30 | 주식회사 포스코 | Steel having excellent hydrogen induced cracking resistance and longitudinal strength unifomity and method for manufacturing the same |
| CN111607747A (en) * | 2020-07-01 | 2020-09-01 | 武汉科技大学 | Hydrogen sulfide corrosion resistant X70 grade pipeline steel for seabed and production method thereof |
| CN113083892B (en) * | 2021-03-29 | 2022-07-08 | 天津市新天钢联合特钢有限公司 | Preparation method of hot-rolled narrow strip steel for gas pipeline |
| CN113106354A (en) * | 2021-03-31 | 2021-07-13 | 五矿营口中板有限责任公司 | Easily-welded oil-gas corrosion-resistant shipbuilding structural steel and manufacturing method thereof |
| CN115612919B (en) * | 2022-08-28 | 2023-06-16 | 武汉科技大学 | Acid-resistant and hydrogen-resistant X70 pipeline steel and preparation method thereof |
| CN116288017B (en) * | 2023-05-22 | 2023-07-25 | 江苏省沙钢钢铁研究院有限公司 | Large thick-wall low-temperature-resistant pipeline steel and manufacturing method thereof |
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| JPS61165207A (en) | 1985-01-14 | 1986-07-25 | Nippon Steel Corp | Manufacture of unrefined steel plate excellent in sour-resistant property |
| JPS62112722A (en) | 1985-11-13 | 1987-05-23 | Nippon Steel Corp | Production of steel sheet having excellent resistance to hydrogen induced cracking and resistance to sulfide stress corrosion cracking |
| JPH075968B2 (en) * | 1990-02-13 | 1995-01-25 | 新日本製鐵株式会社 | Method for producing steel sheet excellent in hydrogen-induced cracking resistance, sulfide stress corrosion cracking resistance and low temperature toughness |
| JP2647302B2 (en) * | 1992-03-30 | 1997-08-27 | 新日本製鐵株式会社 | Method for producing high-strength steel sheet with excellent resistance to hydrogen-induced cracking |
| JPH05295434A (en) | 1992-04-20 | 1993-11-09 | Nippon Steel Corp | Production of high tensile strength steel plate excellent in hydrogen induced cracking resistance, sulfide stress corrosion cracking resistance, and toughness at low temperature |
| JPH0625743A (en) * | 1992-07-10 | 1994-02-01 | Nippon Steel Corp | Manufacture of sour resistant steel sheet having excellent low temperature toughness |
| JPH0625742A (en) * | 1992-07-10 | 1994-02-01 | Nippon Steel Corp | Manufacture of sour resistant steel sheet having excellent low temperature toughness |
| JPH06136440A (en) * | 1992-10-28 | 1994-05-17 | Nippon Steel Corp | Production of high strength steel sheet excellent in sour resistance |
| JP3009568B2 (en) * | 1993-10-06 | 2000-02-14 | 新日本製鐵株式会社 | Manufacturing method of high strength steel sheet with excellent hydrogen induced cracking resistance and low temperature toughness |
| JPH07173536A (en) * | 1993-12-16 | 1995-07-11 | Nippon Steel Corp | Production of steel sheet for high strength line pipe excellent in sour resistance |
| JP3274013B2 (en) * | 1994-03-04 | 2002-04-15 | 新日本製鐵株式会社 | Method for producing sour resistant high strength steel sheet having excellent low temperature toughness |
| JP4305216B2 (en) * | 2004-02-24 | 2009-07-29 | Ｊｆｅスチール株式会社 | Hot-rolled steel sheet for sour-resistant high-strength ERW steel pipe with excellent weld toughness and method for producing the same |
| JP2006063351A (en) | 2004-08-24 | 2006-03-09 | Sumitomo Metal Ind Ltd | High strength steel plate with excellent hydrogen induced cracking resistance, its manufacturing method, and steel pipe for line pipe |
| JP4969915B2 (en) * | 2006-05-24 | 2012-07-04 | 新日本製鐵株式会社 | Steel tube for high-strength line pipe excellent in strain aging resistance, steel plate for high-strength line pipe, and production method thereof |
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- 2010-02-16 WO PCT/JP2010/052586 patent/WO2010095730A1/en active Application Filing
- 2010-02-16 CN CN201080008173.8A patent/CN102325909B/en active Active
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| JP特开2007-314828A 2007.12.06 |
| JP特开平7-109519A 1995.04.25 |
| JP特开平7-242944A 1995.09.19 |
Also Published As
| Publication number | Publication date |
|---|---|
| BRPI1008927A2 (en) | 2016-03-15 |
| JP2010189720A (en) | 2010-09-02 |
| CN102325909A (en) | 2012-01-18 |
| KR101601000B1 (en) | 2016-03-08 |
| KR20140019483A (en) | 2014-02-14 |
| BRPI1008927B1 (en) | 2021-01-26 |
| KR20110102436A (en) | 2011-09-16 |
| JP4700740B2 (en) | 2011-06-15 |
| WO2010095730A1 (en) | 2010-08-26 |
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