CN103215513B - A kind of anticorrosive gathering-line pipe and manufacture method thereof - Google Patents
A kind of anticorrosive gathering-line pipe and manufacture method thereof Download PDFInfo
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Abstract
The invention discloses a kind of anticorrosive gathering-line pipe, its chemical element mass percentage is: C :≤0.1%, Si:0.1 ~ 0.5%, Mn:0.1 ~ 1.2%, Cr:1.0 ~ 9.0%, Al:0.01 ~ 0.10%, W:0.01 ~ 2.00%, Cu:0.30 ~ 0.45%, RE:0.05 ~ 0.10%, surplus is Fe and other inevitable impurity.Correspondingly, the invention also discloses the manufacture method of this anticorrosive gathering-line pipe.The anticorrosive gathering-line pipe that the present invention relates to has excellent anti-CO
2and H
2s corrosive nature, also takes into account good mechanical property simultaneously.
Description
Technical field
The present invention relates to a kind of steel alloy and manufacture method thereof, particularly relate to a kind of alloy steel pipe spool and manufacture method thereof.
Background technology
The medium of gathering-line pipe conveying is the oil or Sweet natural gas that process without desalination, dehydration, desulfurization etc., thus except requiring that it has except corresponding intensity, impact property and welding property, also requires that it has certain anti-H
2s/CO
2corrosive nature.
Publication date is on December 6th, 1994, and publication number is JP6336639, name is called " a kind of anti-H
2s/CO
2corrosion line pipe " Japanese documentation disclose a kind of line pipe, its chemical element consists of: C≤0.25%, Si0.01 ~ 0.50%; Mn0.1 ~ 2.0%, P≤0.01%, S≤0.003%; Cr0.25 ~ 1.0%, Al0.01 ~ 0.10%, Ca≤0.006%; Mo≤1.0%, Ti≤0.2%, Nb≤0.2%; V≤0.2%; B≤0.05%, and Zr≤0.2% comprises Cu and Ni in addition further.
Publication date is on October 15th, 1996, publication number is JP8269623, and the Japanese documentation that name is called " a kind of anticorrosive line pipe " also discloses a kind of line pipe, and its chemical element consists of: C≤0.06%, Si0.01 ~ 0.50%, Mn0.1 ~ 2.0%, P≤0.01%, S≤0.003%, Cr0.25 ~ 1.0%, Al0.01 ~ 0.10%, Ca≤0.006%, Pcm (%)≤0.18%.
Publication date is June 19 calendar year 2001, and publication number is US6248187, and the american documentation literature that name is called " one has the corrosive corrosion resisting steel of high resistance CO2 and rust-proof oil well casing " discloses a kind of line pipe, its chemical element consists of: C≤0.30%, Si≤1.0%, Mn0.2 ~ 2.0%, Cr2.1 ~ 5.0%, P≤0.03%, S≤0.02%, Al≤0.10%, N≤0.015%, comprises optional Cu in addition, Ni, Mo, Ti, Nb and B, its microtexture is martensite.
Summary of the invention
The object of the present invention is to provide a kind of anticorrosive gathering-line pipe and manufacture method thereof, its intensity is high and have excellent H
2s/CO
2corrosive nature.
To achieve the above object of the invention, the invention provides a kind of anticorrosive gathering-line pipe, its chemical element mass percentage is:
C：≤0.1%，
Si：0.1～0.5%，
Mn：0.1～1.2%，
Cr：1.0～9.0%，
Al：0.01～0.10%，
W：0.01～2.00%，
Cu：0.30～0.45%，
RE：0.05～0.10%，
Surplus is Fe and other inevitable impurity.
The chemical composition design principle of the technical program is as follows:
The interpolation of C:C effectively can improve the intensity of steel grade, but the too high alloying element carbide that easily makes of C content is separated out at crystal boundary, cause the appearance of crystal boundary local Cr-depleted region, thus cause steel grade corrosion resistance to decline, especially sulfur resistance declines, and too high C also can cause steel grade welding property to decline simultaneously.Therefore for the technical program, C content≤0.1%.
Si:Si is effective reductor, and in order to improve the intensity of steel grade, the technical program requires that the lower limit of Si content in steel is 0.1%, but too much Si can cause the reduction of steel grade toughness.Therefore, the upper limit of Si content is designed to 0.5% by the technical program.
Mn:Mn significantly can improve intensity and the toughness of steel grade, also be effective reductor, and there is the effect of de-S, but too much Mn also can promote the formation of carbide, thus reducing toughness and the erosion resistance of steel grade, too high Mn can reduce the welding property of steel grade simultaneously.Therefore, the content of Mn is defined as 0.1 ~ 1.2% by the present invention.
The interpolation of Cr:Cr significantly can improve the anti-local corrosion of steel grade and uniform corrosion ability, but the content of Cr is not more high better in the technical program, Cr too high levels can cause steel grade welding property to decline, the carbide of Cr easily causes steel grade sulfur resistance to decline in the segregation of crystal boundary simultaneously, therefore, the content of Cr is designed to 1.0 ~ 9.0%.
Al:Al is effective reductor, is the alloying element being difficult in steelmaking process avoid, but in the technical program, the content of Al will destroy toughness and the hot workability of steel grade more than 0.1%.Thus, the content of Al is limited to 0.01 ~ 0.1% by contriver.
Being added with of W:W helps improve steel grade resistance against sulfide stress cracking performance, also can improve steel grade mechanical behavior under high temperature simultaneously.The content of W is defined as 0.01 ~ 2% by the present invention.
Cu:Cu is added with the corrosion resistance helping improve steel grade, the antimicrobial corrosive nature of steel grade effectively can also be improved for subsea pipeline, but the content of Cu can reduce the mechanical property of steel grade more than 0.45% in the technical program, reduce hot workability and the sulfur resistance of steel grade simultaneously.Thus, the content of Cu is designed to 0.3% ~ 0.45%.
RE: the interpolation of rare earth element effectively can improve the toughness of steel grade, but in the technical program, the welding property of steel grade can be reduced when ree content is more than 0.10%, therefore its content is limited to 0.05% ~ 0.10%.
Inevitable impurity of the present invention mainly refers to P and S, and its content should be more low better.
Alternatively, anticorrosive gathering-line pipe of the present invention also have Ni≤0.5wt%, Nb≤0.1wt%, V≤0.1wt% and Ti≤0.1wt% at least one of them.
Ni element effectively can promote the corrosion-resistant effect of steel grade, therefore in order to improve the anticorrosion effect of the technical program further, can select to add Ni element, but contriver finds will reduce steel grade sulfur resistance when the content of Ni is more than 0.5%.
Nb, V, Ti and C, N have strong binding ability and form respective carbide, nitride or carbonitride, contribute to the mechanical property improving steel grade, Ti can also strengthen the corrosion resistance of steel grade simultaneously, but for the technical program, when the content of Nb, V, Ti is more than 0.1%, precipitated phase particle can be made thick, and oxide inclusion is increased, strength at break on the contrary, reduces the welding property of steel grade simultaneously.Thus the addition of Nb, V, Ti does not preferably all exceed 0.1%.
Further, in above-mentioned anticorrosive gathering-line pipe, Si content is 0.1 ~ 0.25%, Mn content be 0.5 ~ 1.2%, W content is 0.10 ~ 2.00%.
Correspondingly, present invention also offers the manufacture method of above-mentioned anticorrosive gathering-line pipe, it comprises the following steps:
(1) smelt, cast, obtain pipe;
(2) by heating of pipe blank;
(3) rolling;
(4) thermal treatment.
Further, the heat treatment mode in above-mentioned steps (4) is quenching+tempering.
Further, in above-mentioned steps (4), quenching temperature is 850-950 DEG C, and tempering temperature is 600-720 DEG C.
Or, in above-mentioned steps (4), also can take the heat treatment mode of normalizing.
Further, in step (4), normalizing temperature is 750-850 DEG C.
Further, in the step (2) of the manufacture method of above-mentioned anticorrosive gathering-line pipe, by heating of pipe blank to AC
3temperature and more than.
Anticorrosive gathering-line pipe of the present invention is compared with existing anticorrosive gathering-line pipe, and tool has the following advantages:
1) cost of alloy is low: the present invention is by adjustment Cr constituent content, and appropriate interpolation W and Cu element, instead of the precious metal elements such as Co, Zr, reduce cost of alloy simultaneously.
2) excellent anti-CO is possessed
2and H
2s corrosive nature: the technical program is ensureing that steel grade possesses excellent anti-CO
2while corrosive nature, steel grade is also made to have good anti-H2S hydrogen induced cracking (HIC) and stress corrosion crack performance.
3) controllability of high strength and intensity is possessed: the present invention, in order to ensure that steel grade possesses the component system that good welding property have employed Ultra-low carbon+low Fe content, does not lose the intensity of product simultaneously.
4) good welding property is possessed.
Embodiment
To be described further anticorrosive gathering-line pipe of the present invention and manufacture method thereof according to specific embodiment below, but specific embodiment and related description do not form the improper restriction for technical scheme of the present invention.
Embodiment 1-8
Anticorrosive gathering-line pipe of the present invention is manufactured according to following step:
1) smelt: use electric arc furnace or converter+secondary refining process, the proportioning controlling each chemical element is as shown in table 1;
2) continuous casting obtains pipe;
3) heat: use rotary heating furnace by heating of pipe blank to>=AC
3temperature;
4) rolling: adopt roll seamless steel tube technique that billet production is become seamless tube;
5) thermal treatment: the heat treatment mode taking quenching+tempering, or the heat treatment mode taking normalizing.
Table 1 shows the percent mass proportioning of each chemical element of this case embodiment 1-8 and comparative example 1-2.
Table 1.(wt.%, surplus is Fe and other inevitable impurity)
| C | Si | Mn | Al | Cr | W | Cu | Ni | Nb | V | Ti | RE | |
| 1 | 0.03 | 0.25 | 0.90 | 0.05 | 1.4 | 1.55 | 0.45 | 0.10 | 0.04 | 0.02 | 0 | 0.07 |
| 2 | 0.08 | 0.21 | 1.10 | 0.03 | 2.7 | 0.25 | 0.30 | 0.25 | 0 | 0.03 | 0.01 | 0.09 |
| 3 | 0.02 | 0.15 | 0.78 | 0.01 | 4.9 | 0.14 | 0.40 | 0.15 | 0.04 | 0.01 | 0 | 0.05 |
| 4 | 0.04 | 0.18 | 0.70 | 0.10 | 4.1 | 1.87 | 0.31 | 0.20 | 0.07 | 0 | 0.04 | 0.05 |
| 5 | 0.05 | 0.20 | 0.5 | 0.02 | 5.7 | 0.70 | 0.42 | 0.05 | 0 | 0.02 | 0 | 0.06 |
| 6 | 0.06 | 0.18 | 1.05 | 0.10 | 7.3 | 0.50 | 0.40 | 0.04 | 0 | 0.03 | 0 | 0.07 |
| 7 | 0.09 | 0.20 | 0.95 | 0.01 | 8.4 | 0.84 | 0.37 | 0.07 | 0.05 | 0 | 0.07 | 0.09 |
| 8 | 0.10 | 0.20 | 1.20 | 0.04 | 3.5 | 1.00 | 0.40 | 0.15 | 0.06 | 0 | 0.03 | 0.05 |
| 9 | 0.008 | 0.27 | 0.98 | 0.027 | 11.9 | / | 0.01 | 0.01 | / | / | / | / |
| 10 | 0.20 | 0.31 | 0.51 | / | 0.1 | / | 0.05 | 0.05 | / | / | / | / |
(in table 1, numbering 1-8 is embodiment, and numbering 9 and 10 is respectively comparative example 1-2, and wherein comparative example 2 also has the N element of 0.0036wt%)
Table 2 shows the heat treatment process parameter of this case embodiment 1-8.
Table 2.
| Sequence number | Heat treatment mode |
| Embodiment 1 | Normalizing: normalizing temperature 800 DEG C |
| Embodiment 2 | Normalizing: normalizing temperature 820 DEG C |
| Embodiment 3 | Quenching+tempering: quenching temperature 900 DEG C, tempering temperature 650 DEG C |
| Embodiment 4 | Normalizing: normalizing temperature 750 DEG C |
| Embodiment 5 | Normalizing: normalizing temperature 850 DEG C |
| Embodiment 6 | Quenching+tempering: quenching temperature 850 DEG C, tempering temperature 680 DEG C |
| Embodiment 7 | Quenching+tempering: quenching temperature 950 DEG C, tempering temperature 700 DEG C |
| Embodiment 8 | Quenching+tempering: quenching temperature 880 DEG C, tempering temperature 600 DEG C |
The steel pipe sampling being numbered 1-10 listed by his-and-hers watches 1, carries out V breach charpy impact test at tensile test at room temperature and 0 DEG C, detects the mechanical property obtained and lists in table 3.
Use Dynamic Corrosion weight-loss method to the steel pipe sampling being numbered 1-10, carry out anti-CO
2corrosive nature is tested, and detailed test conditions and solution medium composition are in table 4 and table 5, and test result is listed in table 3.
According to NACETM0284-2003 to the steel pipe sampling being numbered 1-10, carry out Properties of HIC resistance test, test result is listed in table 3.
Table 3. embodiment of the present invention and comparative example properties contrast
The anti-CO of table 4.
2corrosion test condition
Table 5. certain offshore gas field Produced Liquid component (mg/L) domestic
| Ion | K ++Na + | Mg 2+ | Ca 2+ | Cl － | SO4 2－ | HCO 3 － | CO 3 2－ | Total mineralization |
| Concentration | 18872 | 86 | 142 | 27632 | 1334 | 500 | 111 | 48677 |
As can be seen from Table 3, no matter anticorrosive gathering-line pipe of the present invention is tensile property and impact property, or anti-CO
2and H
2s corrosive nature, is all far superior to comparative example 2(i.e. numbering 10).In addition, relative to comparative example 1(i.e. numbering 9), anticorrosive gathering-line pipe of the present invention has the tensile property suitable with it, shock resistance, but the hic resistance ability of the technical program will be far superior to comparative example 1.
Those of ordinary skill in the art will be appreciated that, above embodiment is only used to the present invention is described, and be not used as limitation of the invention, as long as in essential scope of the present invention, all will drop in Claims scope of the present invention the change of the above embodiment or modification.
Claims (7)
1. an anticorrosive gathering-line pipe, is characterized in that, its chemical element mass percentage is:
C：≤0.1％，
Si：0.1～0.5％，
Mn：0.1～1.2％，
Cr：1.0～9.0％，
Al：0.01～0.10％，
W：0.01～2.00％，
Cu：0.30～0.45％，
RE：0.05～0.10％，
Surplus is Fe and other inevitable impurity.
2. anticorrosive gathering-line pipe as claimed in claim 1, is characterized in that, also have Ni≤0.5wt%, Nb≤0.1wt%, V≤0.1wt% and Ti≤0.1wt% at least one of them.
3. anticorrosive gathering-line pipe as claimed in claim 1, is characterized in that, wherein Si0.1 ~ 0.25%, Mn0.5 ~ 1.2%, W0.10 ~ 2.00%.
4., as the manufacture method of the anticorrosive gathering-line pipe in claim 1-3 as described in any one, it is characterized in that, comprise the following steps:
(1) smelt, cast, obtain pipe;
(2) by heating of pipe blank;
(3) rolling;
(4) thermal treatment: quenching+tempering, quenching temperature is 850-950 DEG C, and tempering temperature is 600-720 DEG C.
5. the manufacture method of anticorrosive gathering-line pipe as claimed in claim 4, is characterized in that, in step (2), by heating of pipe blank to AC
3temperature and more than.
6., as the manufacture method of the anticorrosive gathering-line pipe in claim 1-3 as described in any one, it is characterized in that, comprise the following steps:
(1) smelt, cast, obtain pipe;
(2) by heating of pipe blank;
(3) rolling;
(4) normalizing thermal treatment: normalizing temperature is 750-850 DEG C.
7. the manufacture method of anticorrosive gathering-line pipe as claimed in claim 6, is characterized in that, in step (2), by heating of pipe blank to AC
3temperature and more than.
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| EP3095886B1 (en) * | 2014-01-17 | 2020-04-08 | Nippon Steel Corporation | MARTENSITIC Cr-CONTAINING STEEL AND STEEL OIL COUNTRY TUBULAR GOODS |
| CN105200328A (en) * | 2015-08-24 | 2015-12-30 | 宝鸡石油钢管有限责任公司 | Straight seam welded oil casing pipe resisting H2S and CO2 corrosion and manufacturing method thereof |
| CN107177792A (en) * | 2016-03-10 | 2017-09-19 | 中国科学院金属研究所 | A kind of pipe line steel with resistance to sulfate reducing bacteria corrosion performance |
| CN106011666A (en) * | 2016-06-03 | 2016-10-12 | 深圳市樊溪电子有限公司 | Low alloy steel, steel pipe and manufacturing method of steel pipe |
| CN106987782B (en) * | 2017-03-17 | 2018-08-07 | 中国石油天然气集团公司 | A kind of resistance to a small amount of CO2And H2The continuous pipe and its manufacturing method of S corrosion |
| CN107619994B (en) * | 2017-04-27 | 2019-04-02 | 中国石油大学(北京) | A kind of anti-CO2/H2The seamless line pipe and its manufacturing method of S and sulfate reducing bacteria corrosion |
| CN107746934A (en) * | 2017-10-18 | 2018-03-02 | 舞阳钢铁有限责任公司 | A kind of corrosion-resistant low-alloy high-strength steel plate and production method |
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