CN106756537B - A kind of resistance to H2The excellent tough normalizing pipe line steel of height of S corrosive nature and production method - Google Patents
A kind of resistance to H2The excellent tough normalizing pipe line steel of height of S corrosive nature and production method Download PDFInfo
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- CN106756537B CN106756537B CN201611073339.XA CN201611073339A CN106756537B CN 106756537 B CN106756537 B CN 106756537B CN 201611073339 A CN201611073339 A CN 201611073339A CN 106756537 B CN106756537 B CN 106756537B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
-
- 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
-
- 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
-
- 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
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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
- C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
-
- 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
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/005—Ferrite
-
- 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
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/009—Pearlite
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Heat Treatment Of Steel (AREA)
Abstract
A kind of excellent tough normalizing pipe line steel of height of resistance to H2S corrosive nature, component and wt%:C 0.05 ~ 0.08%, Si 0.30 ~ 0.45%, Mn 0.85 ~ 1.0%, P≤0.010%, S≤0.0020%, Mo 0.10 ~ 0.20%, Nb 0.06 ~ 0.12%, B are no more than 0.0005%, RE and are no more than 0.0005%.Production stage: slab is heated；Roughing；Finish rolling；It is cooling；It batches；Normalizing.The present invention has except high-intensitive, high tenacity and good weldability, it is necessary to there is excellent hydrogen sulfide corrosion-resistant performance, loaded load be 0.80 × practical yield strength load-up condition under do not observe crackle.
Description
Technical field
The present invention relates to a kind of pipe line steel and production methods, particularly belong to a kind of resistance to H2The excellent height of S corrosive nature is tough
Normalizing pipe line steel and production method.
Background technique
Petroleum, natural gas are the important energy sources of the national economic development, and the specific gravity in energy-consuming increasingly increases.Work as front tube
Road conveying is still petroleum, natural gas long distance delivery mode the most economic, safe and efficient.However, with easy exploitation stone
The exhaustion of oil, natural gas resource, H2The high construction of natural gas fields dynamics of S content just continues to increase.
H2S is most one of the hazardous medium of corrosiveness in oil and natural gas.When pipe line steel is exposed to containing wet H2S
Pumped (conveying) medium in when, H easily occurs for material2S sour corrosion causes to send pipeline catastrophic failure, wherein hydrogen induced cracking (HIC) (HIC) and
Sulfide stress cracking (SSC) (SSCC) is H2The principal mode of S corrosion.
The H contained in China's major part oil gas field2S levels are higher, and the medium of gathering-line pipe conveying is without de-
The petroleum or natural gas of the processing such as salt, dehydration, desulfurization.Pipe line steel, which removes, requires it with good intensity, impact property and welding
Except performance, preferable anti-H it is also desirable to have2S corrosive nature.Normalizing state pipe line steel because of the uniform characteristic of its microstructure and property,
Compared to rolled more suitable for the manufacture of gathering line.Simultaneously in view of the demand of raising oil-gas transportation efficiency, need to develop
Have both high tough and excellent resistance to H2The normalizing state pipe line steel of S corrosive nature.
H is contained for conveying2The pipe line steel of S petroleum resources, the continuous Xiang Gangzhong defective locations of hydrogen atom for corroding generation are (band-like
Tissue, field trash, lattice defect etc.) assemble and generates hydrogen molecule.When rejected region hydrogen molecule concentration increases to a certain extent,
Habitat will be caused to occur to be permanently deformed and lead to pipe line steel actual effect, important form include hydrogen induced cracking cracking (HIC) and
Sulfide-stress cracking (SSCC).
Through retrieving, before making the present invention, Chinese Patent Application No. be CN201010235925.6 with
The document of CN201510297590.3 all refers to normalized steel X60N, and chemical component is all made of Mn system in middle C+, exists
Do not have the problem of corrosion resistance characteristic.
Chinese Patent Application No. is the document of CN201210271608.6, is related to normalized steel X52NS steel, uses Cu+
The system of Cr+Ni+V, there are the higher deficiencies of production cost.
Chinese Patent Application No. is the document of CN201610419909.X, the normalized steel being related to there are Mn content is higher,
The intensity of finished product only up to X52 rank, and do not have corrosion resistance characteristic.
Chinese Patent Application No. is the document of CN201310146465.3, is related to the manufacture of seamless steel pipe, exists and closes
Gold dollar cellulose content is high (Cr 1.0 ~ 9.0 wt%, W 0.1 ~ 0.2 wt%), does not have economic sexual clorminance.
Summary of the invention
The invention reside in the shortcomings of the prior art is overcome, providing a kind of has high-intensitive, high tenacity and good
Except weldability, it is necessary to which there is excellent resistance to H2The tough normalizing pipe line steel of height and production method of S corrosive nature.
Realize the measure of above-mentioned purpose:
A kind of resistance to H2The excellent tough normalizing pipe line steel of height of S corrosive nature, component and weight percent content are as follows: C
0.05 ~ 0.08%, Si 0.30 ~ 0.45%, Mn 0.85 ~ 1.0%, P≤0.010%, S≤0.0020%, Mo 0.10 ~ 0.20%, Nb
0.06 ~ 0.12%, B are no more than 0.0005%, RE and are no more than 0.0005%, and other is Fe and inevitable tramp element；Metallographic
Tissue are as follows: the ferrite+island disperse M/A+a small amount of pearlite.
Produce a kind of resistance to H2The method of the excellent tough normalizing pipe line steel of height of S corrosive nature, step:
1) slab after continuous casting is heated, controls its heating temperature at 1100 ~ 1150 DEG C；
2) roughing is carried out, and controlling roughing end temp is 1020 ~ 1070 DEG C；
3) finish rolling is carried out, and controls its start rolling temperature no more than 950 DEG C, finishing temperature is not less than 860 DEG C；
4) it is cooled down, is cooled to coiling temperature under the conditions of cooling velocity is not less than 55 DEG C/s；
5) it is batched, control coiling temperature is no more than 450 DEG C；
6) normalizing is carried out, and controls normalizing temperature and is kept the temperature at 860 ~ 900 DEG C, and again at a temperature of this according to 2min/mm,
And normalizing procedure cooling velocity is controlled in 5 ~ 8 DEG C/s.
Respectively change the effect and mechanism of Element-Level main technique in the present invention:
C:C is most basic, most economical intensified element, effectively improves the strong of steel by solution strengthening and precipitation strength
Degree.It is unobvious to the effect of the intensity of steel when C content is lower than 0.05%, when content is higher than 0.080%, then it can reduce the plasticity, tough of steel
Property and weldability, and the banded structure rank in steel can be aggravated.Therefore in the present invention content control of C for 0.050 ~
0.080%。
Si:Si improves the intensity of steel mainly with solution strengthening form, while being also the deoxidant element in steel, but content is too low
When strengthening effect it is unobvious, it is again unfavorable to the toughness of steel when too high levels.Therefore in the present invention content control of Si for 0.30 ~
0.45%。
Mn:Mn is solution strengthening element important in steel, conducive to the intensity and low-temperature flexibility for improving steel.But its too high levels
When, it will lead to that component segregation in its steel is serious, and then hard crisp pearlite or M/A banded structure in steel is promoted to be formed, deteriorate
The resistance to H of steel2S corrosive nature.Meanwhile high Mn content is easy to promote the generation of MnS ribbon field trash, becomes diffusible hydrogen in steel
Aggregation, be easy to induce hydrogen induced cracking (HIC).Therefore the content control of Mn is 0.85 ~ 0.10% in the present invention.
Mo:Mo can expand austenite phase transformation area, improve the harden ability of steel, improve steel in the even tissue of thickness x cross sectional
Property.Meanwhile the addition of Mo makes steel be easy to get equally distributed M/A tissue under lower cooling rate, improves the strength character of steel.
Mo element has Strengthening and Toughening effect similar with Mn element, and the addition of Mo avoids Mn content high in steel, and then avoids steel
Middle banded structure deteriorates, and improves the resistance to H of steel2S corrosive nature.Therefore the control of Mo content is 0.10 ~ 0.20% in the present invention.
Nb: Nb has strong Grain Refinement Effect and medium precipitation strength effect in course of hot rolling, can postpone Austria
Family name's body recrystallization, leads to the refinement of austenite grain and phase-change product and improves the obdurability of steel.In normalizing procedure, it is dissolved in steel
Nb element by solute drageffect prevent austenite grain excessively growing up, degree of grain refinement when hot rolling can be made to obtain
To largely heredity, and Nb element is precipitated in the form of second phase particles in normalizing cooling procedure, improves the strong of normalized steel
Degree.The control of Nb content is 0.06 ~ 0.12% in the present invention.
P, sulphur S:P can reduce the low-temperature flexibility of steel, deteriorate welding performance, and P is easy to be segregated in steel, promotes band-like group
The generation knitted is unfavorable for the resistance to H of steel2S etching characteristic.S is easy to be mingled with Mn formation strip MnS, is influencing the same of steel toughness
When, hydrogen atom tends to assemble at the tip MnS, to induce H2S corrosion cracking.Therefore, the present invention should reduce containing for P, S to the greatest extent
Amount is to reduce its adverse effect to steel, and the content control of P is P≤0.010%, and the content control of S is S≤0.0020%.
In view of user is to the common demands of pipeline steel chemical composition, B and RE element is not deliberately added in the present invention, and want
Ask B≤0.0005%, RE≤0.0005%.
The present invention is to obtain to take into account the normalizing state pipe line steel of high-strength tenacity and excellent anticorrosive performance, except to chemical component into
Production outside row optimization design, also in hot rolling stage (roughing, finish rolling, cooling etc.) and normalizing stage (temperature, time, cooling rate etc.)
Technique has carried out targeted design.Specific mentality of designing is as follows:
Why the present invention uses the low Mn system of low C+ to reduce the formation trend of banded structure in steel, while utilizing hot rolling
Fast cooling technology afterwards inhibits the diffusion and Local enrichment of phase transformation stage C element, to improve the corrosion resistance of steel.
Why the present invention adds suitable solution strengthening Mo element, hard in (normalizing is cooling) steel to promote under lower cooling rate
The transformation of phase constitution improves the strength character of normalized steel.
Why the present invention uses producing for the low C high Nb technology of TMCP+, by sufficient recrystallization softening and not again
The accumulation of crystalline dislocations density, to promote the Nb element being dissolved in austenite in the form of NbC in dislocation and grain boundaries disperse educt,
And then for normalizing stage austenite grain forming core provide advantage, thus realize austenite grain refinement and normalized steel it is strong
Toughness improves.
Why the present invention controls normalizing temperature and soaking time, avoids crystal grain mistake while guaranteeing complete austenitizing
Degree is grown up, in order to avoid deteriorate the intensity and toughness of normalized steel.
Why the present invention avoids because of plate thickness center cooling slow appearance when the cooling velocity in control normalizing cooling procedure
The hard phase constitution of ribbon, and then the corrosion resistance of severe exacerbation steel.
Compared with prior art, the present invention that is, surrender is strong having except high-intensitive, high tenacity and good weldability
Spend Rt0.5 >=415MPa, tensile strength Rm>=520MPa, -30 DEG C of ballistic work KV2The full-scale specification of >=200J(), -30 DEG C of DWTT
Section shearing rate SA >=90%.
Meanwhile the present invention has excellent resistance to H in NACE and solution A2S corrosive nature.It is embodied in, according to
0284 standard of NACE TM carries out HIC inspection, crack length rate CLR, the crackle of normalizing pipe line steel sample section in solution A
Thickness rate CTR, crackle the area ratio CSR value are 0, i.e. sample section flawless；According to 0177 standard of NACE TM, in solution A
In four-point bending method and constant load tensile be respectively adopted carry out SSCC inspection, normalizing pipeline steel curved beam is 0.80 in loaded load
Crackle is not observed under × practical yield strength load-up condition.
It can be used for the straight-line joint submerged arc welding tube of L415N rank or more at the normalizing pipe line steel of production using mentioned component and technique
Manufacture and production.
Detailed description of the invention
Fig. 1 is the metallographic structure figure of steel plate of the present invention.
Specific embodiment
The present invention is described in detail below:
Table 1 is the chemical component list of various embodiments of the present invention and comparative example；
Table 2 is the main technologic parameters list of various embodiments of the present invention and comparative example；
Table 3 is the tensile property and quality of coating experiment result list of various embodiments of the present invention and comparative example.
Various embodiments of the present invention follow the steps below production:
1) slab after continuous casting is heated, controls its heating temperature at 1100 ~ 1150 DEG C；
2) roughing is carried out, and controlling roughing end temp is 1020 ~ 1070 DEG C；
3) finish rolling is carried out, and controls its start rolling temperature no more than 950 DEG C, finishing temperature is not less than 860 DEG C；
4) it is cooled down, is cooled to coiling temperature under the conditions of cooling velocity is not less than 55 DEG C/s；
5) it is batched, control coiling temperature is no more than 450 DEG C；
6) normalizing is carried out, and controls normalizing temperature and is kept the temperature at 860 ~ 900 DEG C, and again at a temperature of this according to 2min/mm,
And normalizing procedure cooling velocity is controlled in 5 ~ 8 DEG C/s.
1 various embodiments of the present invention of table and comparison steel chemical composition comparative example (wt%)
The main technologic parameters value of 2 embodiment of the present invention of table and comparative example
3 various embodiments of the present invention of table and comparative example mechanical property list
From 3 data of table it is found that the mechanical property and HIC, SSCC performance of the embodiment of the present invention are superior to comparative example.
Present embodiment is only the best example, not to the restricted implementation of technical solution of the present invention.
Claims (1)
1. a kind of resistance to H2The excellent tough normalizing pipe line steel of height of S corrosive nature, component and weight percent content are as follows: C 0.054
~ 0.08%, Si 0.335 ~ 0.45%, Mn 0.85 ~ 1.0%, P≤0.010%, S≤0.0020%, Mo 0.10 ~ 0.198%, Nb
0.066 ~ 0.12%, other is Fe and inevitable tramp element；Metallographic structure are as follows: the ferrite+island disperse M/A+a small amount of pearly-lustre
Body；
Production method:
1) slab after continuous casting is heated, controls its heating temperature at 1100 ~ 1150 DEG C；
2) roughing is carried out, and controlling roughing end temp is 1020 ~ 1070 DEG C；
3) finish rolling is carried out, and controls its start rolling temperature no more than 950 DEG C, finishing temperature is not less than 875 DEG C；
4) it is cooled down, is cooled to coiling temperature under the conditions of cooling velocity is not less than 61 DEG C/s；
5) it is batched, control coiling temperature is no more than 450 DEG C；
6) normalizing is carried out, and controls normalizing temperature and is kept the temperature at 860 ~ 900 DEG C, and at this temperature according to 2min/mm, and
Normalizing procedure cooling velocity is controlled in 5 ~ 8 DEG C/s.
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| CN201611073339.XA CN106756537B (en) | 2016-11-29 | 2016-11-29 | A kind of resistance to H2The excellent tough normalizing pipe line steel of height of S corrosive nature and production method |
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| CN111254362B (en) * | 2020-03-31 | 2021-01-19 | 湖南华菱湘潭钢铁有限公司 | Production method of Gr.B-grade normalizing pipeline steel |
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|---|---|---|---|---|
| CN102392185A (en) * | 2011-10-28 | 2012-03-28 | 首钢总公司 | Normalized acid resistant hot-rolled steel plate and preparation method thereof |
| CN102732798A (en) * | 2012-03-31 | 2012-10-17 | 攀钢集团成都钢钒有限公司 | Boron-containing high-strength high-toughness thick-wall seamless line pipe steel and manufacturing method thereof |
| CN103556047A (en) * | 2013-10-22 | 2014-02-05 | 首钢总公司 | 450MPa-grade hydrogen-induced-cracking-resistant pressure vessel steel plate and production method thereof |
| CN103649351A (en) * | 2011-06-30 | 2014-03-19 | 杰富意钢铁株式会社 | High strength hot-rolled steel sheet for welded steel line pipe having excellent souring resistance, and method for producing same |
| CN103805844A (en) * | 2014-03-05 | 2014-05-21 | 江苏常宝钢管股份有限公司 | Boron-containing seamless pipe line pipe for ocean oil and gas exploitation |
| CN105132807A (en) * | 2015-10-10 | 2015-12-09 | 武汉钢铁(集团)公司 | Pipeline steel excellent in acid corrosion resistance on seabed and production method |
| CN105624554A (en) * | 2016-01-15 | 2016-06-01 | 宝山钢铁股份有限公司 | Steel plate for 70-grade SA671 electric fusion welding pipe with excellent HIC resistance and manufacturing method |
-
2016
- 2016-11-29 CN CN201611073339.XA patent/CN106756537B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103649351A (en) * | 2011-06-30 | 2014-03-19 | 杰富意钢铁株式会社 | High strength hot-rolled steel sheet for welded steel line pipe having excellent souring resistance, and method for producing same |
| CN102392185A (en) * | 2011-10-28 | 2012-03-28 | 首钢总公司 | Normalized acid resistant hot-rolled steel plate and preparation method thereof |
| CN102732798A (en) * | 2012-03-31 | 2012-10-17 | 攀钢集团成都钢钒有限公司 | Boron-containing high-strength high-toughness thick-wall seamless line pipe steel and manufacturing method thereof |
| CN103556047A (en) * | 2013-10-22 | 2014-02-05 | 首钢总公司 | 450MPa-grade hydrogen-induced-cracking-resistant pressure vessel steel plate and production method thereof |
| CN103805844A (en) * | 2014-03-05 | 2014-05-21 | 江苏常宝钢管股份有限公司 | Boron-containing seamless pipe line pipe for ocean oil and gas exploitation |
| CN105132807A (en) * | 2015-10-10 | 2015-12-09 | 武汉钢铁(集团)公司 | Pipeline steel excellent in acid corrosion resistance on seabed and production method |
| CN105624554A (en) * | 2016-01-15 | 2016-06-01 | 宝山钢铁股份有限公司 | Steel plate for 70-grade SA671 electric fusion welding pipe with excellent HIC resistance and manufacturing method |
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