CN102605242B - Steel capable of resisting hydrogen-induced cracking for pressure containers and manufacturing method for steel - Google Patents
Steel capable of resisting hydrogen-induced cracking for pressure containers and manufacturing method for steel Download PDFInfo
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- CN102605242B CN102605242B CN201210055848.5A CN201210055848A CN102605242B CN 102605242 B CN102605242 B CN 102605242B CN 201210055848 A CN201210055848 A CN 201210055848A CN 102605242 B CN102605242 B CN 102605242B
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Abstract
The invention relates to steel capable of resisting hydrogen-induced cracking for pressure containers. The steel comprises the following chemical components in percentage by weight: 0.15 to 0.25 percent of C, 0.10 to 0.30 percent of Si, 1.0 to 1.6 percent of Mn, less than or equal to 120ppm of P, less than or equal to 0.002 percent of S, 0.35 to 0.60 percent of Mo, less than or equal to 0.05 percent of V, 0.20 to 0.80 percent of Ni, 0.0013 to 0.0045 percent of Ca, 0.002 to 0.050 percent of Al, and the balance of iron and inevitable impurities. The invention also relates to a manufacturing method for the steel. The method comprises the following steps of: smelting in an LD converter, performing external refining and die casting, then heating the steel billet to the temperature of between 1100 and 1250 DEG C, and rolling with the deformation of at least over 80 percent; quenching the rolled steel plate, reheating the rolled steel plate at the temperature of between 860 and 940 DEG C, fully preserving the heat, and immediately spraying water after heat preservation of the steel plate to quickly cool the steel plate to the temperature of below 200 DEG C; and tempering the quenched steel plate at the temperature of between 600 and 700 DEG C, and cooling in air after the heat is preserved for long enough time to obtain steel with high strength, high toughness and excellent hydrogen-induced cracking resistance in a wet hydrogen sulfide environment. According to the invention, the yield strength is more than 485MPa, the tensile strength is 620-795MPa, and the elongation at the standard distance of 50 millimeters exceeds 16 percent; and the steel has excellent impact toughness, and is suitable for the pressure containers.
Description
Technical field
The present invention relates to steels for pressure vessel use, particularly relate to a kind of resistance against hydrogen cracking steels for pressure vessel use and manufacture method thereof.
Background technology
The patent relating to the steel in wet hydrogen sulfide environment with resistance against hydrogen cracking performance at present mainly concentrates on pipe line steel field, and the patent relating to steels for pressure vessel use is also few.
CN1914341A relates to the steel plate for the manufacture of pipeline that one has resistance against hydrogen cracking (HIC) performance, and wherein C content is in 0.03-0.15%, Mn, Cr, Mo, V, B, Nb alloying, and its Properties of HIC resistance is by realizing containing Cu or Ni.Be mingled with in this steel that TiN is maximum is no more than 30 μm.
CN1715435A relates to pipe line steel and the hot rolled plate making process thereof that one has hic resistance (hydrogen induced cracking (HIC)) performance, wherein C is no more than 0.055% at most, containing elements such as Si, Mn, Ti, V, Nb, B, for the hot-rolled sheet coil of pipeline, be generally no more than 20mm.
These two steel grades have larger difference with the present invention in purposes and steel plate thickness.
JP2008-007841A discloses and a kind ofly manufactures pipeline, ocean structure, the composition tissue of steels for pressure vessel use and manufacturing process.Utilize Nb and Ti element to improve intensity, composition meets relational expression 1.48-1.5*Si-14.3*Ti-73*N > 0.72.Technique adopt continuously cast bloom as raw material production steel plate.The area of cracks ratio (cracking area ratios, CAR) that resistance against hydrogen cracking (HIC) is tested is less than 4%.This patent is not containing Nb and Ti element, therefore simpler to the requirement of steel rolling process.This patent have employed the technique of die casting-cogging-rolling in addition, can better meet the large compression ratio of steel heavy plate for pressure vessels requirement.
JP60-228655A discloses a kind of low-carbon low-alloy steel, for pressurized vessel and oil and gas pipes.It contains element La, and effect is fixing P.The object of hic resistance is reached by meeting relational expression Mn+150P+2.5C≤44.But also seldom see in the STEELMAKING PRODUCTION of most of steel mill at present and add this element.
The pressurized vessel of petroleum chemical industry is called the collapse mode of hydrogen induced cracking (HIC) (HIC) because of the hydrogen-sulfide environmental (existing even without stress) of humidity.Therefore resistance against hydrogen cracking (HIC) performance that the pressurized vessel carbon steel and low alloy steel under this kind of service condition has had is required.Current industrial this type of conventional steel mainly contains 16MnR (HIC), SA516Gr.70 (HIC) etc.The yield strength general requirement of this kind of steel is greater than 280MPa, and tensile strength is greater than 480MPa, and alloy content is low, belongs to carbon steel.But the requirement that petrochemical equipment maximizes day by day makes the wall thickness of Steel Vessel constantly increase, thus increases the manufacture difficulty of this kind of steel plate, and brings a series of difficult problems such as transport, lifting, installation.Therefore the demand of the steel grade of the resistance against hydrogen cracking of more high intensity levels is proposed.That intensity is high, good toughness, resistance against hydrogen cracking performance are good to the performance requriements of this kind of material.
Summary of the invention
In order to solve the problems referred to above of prior art, the object of the present invention is to provide a kind of resistance against hydrogen cracking steels for pressure vessel use.
To achieve these goals, resistance against hydrogen cracking steels for pressure vessel use of the present invention, its chemical composition (% by weight) is: C:0.15-0.25%, Si:0.10-0.30%, Mn:1.0-1.6%, P≤0.012%, S≤0.002%, Mo:0.35-0.60%, V≤0.05%, Ni:0.20-0.80%, Ca:0.0015-0.0045%, Al:0.002-0.050%, all the other are iron and inevitable impurity.
The present invention devises a kind of low alloy steel of more high intensity levels, by effective composition proportion, makes invention steel grade be easy to smelt, adopts quenching to add the quenching-and-tempering process of tempering simultaneously, ensure mechanical property and the resistance against hydrogen cracking performance of steel plate.Product can manufacture cylindrical shell through curling, can manufacture end socket after spinning, for the manufacture of the pressurized vessel used under hydrogen sulfide Working environment.
Another object of the present invention is to provide the manufacture method of above-mentioned resistance against hydrogen cracking steels for pressure vessel use.The method comprises the steps:
LD converter smelting → external refining (LF desulfurization, RH vacuum outgas, hello silk Ca process) → die casting → Heating Steel Ingots → breaking down → finishing → heating → rolling → quenching → tempering.
Through LD converter smelting, after external refining and die casting, heating steel billet is rolled with more than at least 80% deflection after 1100-1250 DEG C;
Rolled sheet material carries out quench treatment, and rolled sheet material reheats at 860-940 DEG C, is fully incubated, and steel plate insulation terminates water spray immediately and is quickly cooled to less than 200 DEG C;
The metastable organizations such as quenched nickelclad then carries out temper, tempering temperature 600-700 DEG C, the martensite that during insulation sufficiently long, chien shih quenching is formed fully decompose, and carbide is fully separated out, and forms stabilizing tissue.The laggard line space of tempering is cold.
The mode of the present invention's heavy plate rolling-modifier treatment is produced a kind of high-intensity high-tenacity and is had the steels for pressure vessel use of excellent resistance against hydrogen cracking performance at wet hydrogen sulfide environment, its yield strength is made to be greater than 485MPa, tensile strength is in 620-795MPa, 50mm gauge length unit elongation more than 16%, and has good impact toughness.
Accompanying drawing explanation
Fig. 1 be the embodiment of the present invention 5 after Overheating Treatment, typical microtexture is tempering bainite.
Embodiment
Below in conjunction with embodiment and accompanying drawing, explain feature of the present invention and beneficial effect.
In the present invention, unless otherwise, content all refers to weight percent content.
In order to realize of the present inventionly providing that intensity is high, the object of good toughness, steels for pressure vessel use that resistance against hydrogen cracking performance is good, each element controls as follows:
Carbon: carbon is strengthening element the most basic in steel is that austenitic transformation becomes the requisite element of the strengthening phase such as martensite, bainite.When carbon content is too low, the hardening capacity of steel plate is poor, easily produces the tissues such as ferrite when quenching for thick steel plates, is difficult to the tissue reaching high strength needs; Otherwise the too high plasticity to steel of carbon content, toughness and weldability are unfavorable.The span of control of carbon content of the present invention is 0.15-0.25%.
Silicon: silicon plays desoxydatoin in steel, also plays solution strengthening, but too high levels then makes steel occur fragility.In the present invention, the span of control of silicone content is 0.10-0.30%.
Manganese: manganese plays solution strengthening effect, can improve intensity and the hardness of steel plate.Owing to being delayed ferrite, pearlitic formation, thus expand the scope of rate of cooling that cooling forms martensite, bainite structure, improve hardening capacity.Mn content range of the present invention is 1.0-1.6%.In order to improve armor plate strength, preferably, Mn:1.21-1.55%.
Sulphur and phosphorus: sulphur and phosphorus belong to inevitable impurity element in steel, should reduce content as far as possible.Sulphur forms plastic occluded foreignsubstance manganese sulfide with chemical combination such as manganese in steel, is the potential nucleation site of hydrogen induced cracking.By super low sulfur (being less than 15ppm) and Ca process, inclusion morphology control is carried out to sulfide, high impelling strength and good resistance against hydrogen cracking performance can be had by ten steel plates.In the present invention, P content is below 120ppm.
Molybdenum: molybdenum expands γ phase region, strongly inhibited perlite is formed, favourable to hic resistance, and promote that bainite is formed, to control, phase-change organization plays an important role.Certain Mo content can ensure the hardening capacity of Plate Steel, and meanwhile, Mo and C binding ability is comparatively strong, and the carbide formed during thermal treatment has contribution to room temperature strength and hot strength.Mo in addition in steel is conducive to alleviating temper brittleness.Mo content range 0.35-0.60% of the present invention.In order to ensure steel plate hardening capacity, avoid the formation of pearlitic structure, preferably, Mo:0.40-0.60%.
Vanadium: vanadium produces strengthening by Precipitation and crystal grain thinning, and in steel, the Carbonitride Precipitation of vanadium is on good terms and is significantly improved intensity.Add a small amount of vanadium in steel and just have significant strengthening effect, the present invention allows to add a small amount of V as required, and content controls below 0.05%, is preferably 0.002-0.05%.
Nickel: nickel is non-carbide forming element, mainly plays the effect of solution strengthening in steel.Add nickel in steel useful to toughness, the strength degradation that steel plate thickness increase causes can also be compensated simultaneously.The content range of Ni is 0.20-0.80%, Ni:0.25-0.80%.
Aluminium: aluminium is the main deoxidant element in steel, is conducive to crystal grain thinning, all containing a certain amount of in general steel.The aluminium added in the present invention is mainly used to deoxidation and crystal grain thinning, and adding aluminium content is 0.002-0.050%.In order to avoid inclusion content is too high, preferably, Al:0.004-0.035%.
Calcium: for making strip sulfide inclusion in steel be converted into spherical sulfide, adopts Ca process.In the present invention, the content range of Ca is 0.0013-0.0045, is preferably 0.0015-0.0045%.
Copper: copper can be played by formation protective membrane and hinder hydrogen atom spread in steel thus improve the resistance against hydrogen cracking performance of steel in steel, but when the pH value of sour environment is less than 4.5, this protective membrane will be damaged.Consider that the hydrogen-sulfide environmental of petrochemical industry is harsher, the present invention mainly relies on and adds Cu element and realize resistance against hydrogen cracking performance.
The mode of the present invention's heavy plate rolling and modifier treatment is produced above-mentioned high-intensity high-tenacity and is had the steels for pressure vessel use of excellent resistance against hydrogen cracking performance at wet hydrogen sulfide environment, its yield strength is made to be greater than 485MPa, tensile strength is in 620-795MPa, 50mm gauge length unit elongation more than 16%, and has good impact toughness.
Through LD converter smelting in the present invention, after external refining and die casting, heating steel billet makes austenite structure homogenizing to 1100-1250 DEG C, and make molybdenum in steel, the carbide of vanadium fully dissolves, the AlN precipitate high temperatures in steel can stop growing up of original austenite grains.Controlling the temperature drop of slab when Heating temperature lower limit is to consider rolling simultaneously, ensureing to complete rolling in specified temperature.Steel plate rolling time control compression ratio, is at least out of shape more than 80%.
Rolled sheet material needs through Overheating Treatment scalability energy, and typical thermal treatment process is quenching, temper.Rolled sheet material reheats 860-940 DEG C (being preferably 890-910 DEG C), abundant insulation (preferred soaking time is 30-300 minute) makes steel plate internal and external temperature consistent, form single uniform austenite structure, steel plate insulation terminates water spray immediately and cools until steel billet temperature is at least down to less than 100 DEG C fast.Quenched nickelclad then carries out temper to adjust final performance, tempering temperature 600-700 DEG C (being preferably 620-690 DEG C), the metastable organizations such as the martensite that insulation sufficiently long time (preferred soaking time is 60-600 minute) makes quenching be formed fully decompose, carbide is fully separated out, and is formed and stablizes bainite structure.Air cooling after tempering.
Described Composition Design is easy to implement, not only effectively plays strengthening effect by Alloying Treatment, and postpones the austenitic transformation incubation time, is convenient to thick steel plates thermal treatment process and implements.By the reasonable coordination of various alloying element, the steel plate of various thickness is made all to obtain desired properties.After mentioned component and production technique, various thickness steel plate heat treatment state yield strength is greater than 485MPa, and tensile strength is in 620-795MPa, and 50mm gauge length unit elongation more than 16%, and has excellent impelling strength.
The hydrogen induced cracking (HIC) of steel is closely related with wherein contained sulfide inclusion and banded pearlitic structure.The present invention, by strict control S constituent content, makes sulfide inclusion be reduced to very low level.Again by adding Ca element, make the sulfide inclusion nodularization of remaining minute quantity.These measures decrease the place that hydrogen atom can be assembled in steel, reduce destructive force when hydrogen atom changes to hydrogen molecule, thus improve the resistance against hydrogen cracking ability of steel.
Another measure that the present invention adopts adopts bainite structure to design within the scope of the heavy thickness of steel.In composition range of the present invention, quenching is adopted to add the quenching-and-tempering process of tempering, in the thickness range of very large steel, the basic bainite structure that all formed avoids the common appearance causing the banded pearlitic structure of hydrogen induced cracking (HIC), thus improves the resistance against hydrogen cracking performance of steel.
Embodiment
The chemical composition of embodiment of the present invention steel is in table 1, and main technologic parameters is in table 2.
The chemical composition of table 1 embodiment of the present invention steel, % by weight
The processing condition of table 2 embodiment of the present invention steel
| Embodiment | Thickness, mm | Quenching temperature, DEG C | Quench cooled | Tempering temperature, DEG C | Tempering cools |
| 1 | 30 | 910 | Water-cooled | 645 | Air cooling |
| 2 | 50 | 900 | Water-cooled | 655 | Air cooling |
| 3 | 57 | 905 | Water-cooled | 690 | Air cooling |
| 4 | 80 | 900 | Water-cooled | 640 | Air cooling |
| 5 | 90 | 890 | Water-cooled | 645 | Air cooling |
| 6 | 98 | 910 | Water-cooled | 650 | Air cooling |
| 7 | 110 | 890 | Water-cooled | 630 | Air cooling |
| 8 | 130 | 900 | Water-cooled | 620 | Air cooling |
Test example 1: mechanical property
According to GB/T 228-2002 and GB/T 229-2007 method, measure the mechanical property such as ballistic work of the yield strength of embodiment of the present invention steel, tensile strength, unit elongation and-20 DEG C, it the results are shown in Table 3.
The mechanical property of table 3 embodiment of the present invention steel
As can be seen from Table 3, the yield strength of embodiment of the present invention steel plate is all more than 485MPa, and tensile strength is positioned at 625-780MPa, 50mm calibration distance unit elongation is all more than 16%, level in kind reaches more than 24%, and have excellent low temperature impact properties ,-20 DEG C of ballistic works are more than 200J.
Test example 2: resistance against hydrogen cracking performance
According to HIC (hydrogen induced cracking) touchstone: NACE TM0284-2003, in solution A (containing saturated H
2the 5%NaCl+0.5%CH of S
3cOOH solution, PH=3.0) in, soak 96 hours, measure the resistance against hydrogen cracking performance of embodiment of the present invention steel, it the results are shown in Table 4.
The resistance against hydrogen cracking performance of table 4 embodiment of the present invention steel
As can be seen from Table 4, the equal flawless of embodiments of the invention steel, shows to have good resistance against hydrogen cracking performance.
Test example 3: metallographic structure
Fig. 1 is the metallographic structure of the embodiment of the present invention 5 steel.
As can be seen from the figure, the weave construction of steel plate of the present invention is tempering bainite.Other embodiments have also been obtained similar result.
The mode of the present invention's alloying, the heat treatment mode being added tempering by quenching produces pressurized vessel slab, steel plate is had intensity is high, good toughness, hydrogen-induced cracking resistance are good feature, production process simple possible.Alternative other carbon steel of current low intensity level of product, for the manufacture of the cylindrical shell, end socket etc. of the large-size chemical pressurized vessel worked in wet hydrogen sulfide environment.
Claims (15)
1. resistance against hydrogen cracking steels for pressure vessel use, its chemical composition is by weight percentage: 0.15% < C≤0.25%, Si:0.10-0.30%, Mn:1.0-1.6%, P≤0.012%, S≤0.002%, Mo:0.35-0.60%, V≤0.05%, Ni:0.35-0.80%, Ca:0.0013-0.0045%, Al:0.002-0.050%, all the other are iron and inevitable impurity; Described steel be organized as tempering bainite.
2. resistance against hydrogen cracking steels for pressure vessel use as claimed in claim 1, is characterized in that, Mn:1.21-1.55%.
3. the resistance against hydrogen cracking steels for pressure vessel use as described in as arbitrary in claim 1-2, is characterized in that, S≤0.0015%.
4. resistance against hydrogen cracking steels for pressure vessel use as claimed in claim 1, is characterized in that, Mo:0.40-0.60%.
5. resistance against hydrogen cracking steels for pressure vessel use as claimed in claim 1, is characterized in that, V:0.002-0.05%.
6. resistance against hydrogen cracking steels for pressure vessel use as claimed in claim 1, is characterized in that, Al:0.004-0.035%.
7. resistance against hydrogen cracking steels for pressure vessel use as claimed in claim 1, is characterized in that, Ca:0.0015-0.0045%.
8. resistance against hydrogen cracking steels for pressure vessel use as claimed in claim 1, its thickness is 30-130mm.
9. the manufacture method of the resistance against hydrogen cracking steels for pressure vessel use as described in as arbitrary in claim 1-8, comprises the steps:
Through LD converter smelting, after external refining and die casting, heating steel billet is rolled with more than at least 80% deflection after 1100-1250 DEG C;
Rolled sheet material carries out quench treatment, and rolled sheet material reheats at 860-940 DEG C, is fully incubated, and steel plate insulation terminates water spray immediately and is quickly cooled to less than 100 DEG C;
Quenched nickelclad then carries out temper, and tempering temperature is 600-700 DEG C, and the martensitic metastable organization that comprises that during insulation sufficiently long, chien shih quenching is formed fully decomposes, and carbide is fully separated out, and forms stabilizing tissue.
10. method as claimed in claim 9, it is characterized in that, the soaking time of quenching is 30-300 minute.
11. methods as described in claim 9 or 10, it is characterized in that, the soaking time of tempering is 60-600 minute.
12. methods as claimed in claim 9, is characterized in that, in quenching, steel plate insulation terminates water spray immediately and is quickly cooled to less than 100 DEG C.
13. method as claimed in claim 9, it is characterized in that, the steel plate after tempering carries out air cooling.
14. method as claimed in claim 9, it is characterized in that, rolled sheet material reheats at 890-910 DEG C.
15. methods as claimed in claim 9, it is characterized in that, tempering temperature is 620-690 DEG C.
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| CN102925814B (en) * | 2012-11-28 | 2014-07-23 | 武汉钢铁(集团)公司 | Steel for hydrogen sulfide stress corrosion resisting pressure container and production method of steel |
| CN103160740B (en) * | 2013-03-16 | 2015-08-26 | 南阳汉冶特钢有限公司 | A kind of pressure vessel steel 18MnMoNbR and 100mm thick plates production technique thereof |
| MX359834B (en) | 2013-10-01 | 2018-10-12 | Hendrickson Usa Llc | Leaf spring and method of manufacture thereof having sections with different levels of through hardness. |
| CN103866187A (en) * | 2014-03-24 | 2014-06-18 | 济钢集团有限公司 | Steel plate for 500MPa-level pressure container for resisting sulfide stress corrosion cracking and production method thereof |
| CN105603304B (en) * | 2016-01-15 | 2018-06-01 | 宝山钢铁股份有限公司 | It is a kind of that there is good hic resistance, the Q370R thick steel plate for pressure vessel of SSCC characteristics and manufacturing method |
| CN105886909B (en) * | 2016-04-19 | 2017-08-11 | 江阴兴澄特种钢铁有限公司 | A kind of resistance against hydrogen cracking steel plate of pressure vessel and its manufacture method |
| CN105803175B (en) * | 2016-05-31 | 2017-10-24 | 江阴兴澄特种钢铁有限公司 | Special thickness EH36 ship steels of a kind of low compression ratio and preparation method thereof |
| CN106086642B (en) * | 2016-06-23 | 2018-02-23 | 江阴兴澄特种钢铁有限公司 | A kind of 200mm thickness resistance against hydrogen cracking steel plate of pressure vessel and its manufacture method |
| CN108411196B (en) * | 2018-03-27 | 2019-11-26 | 武汉钢铁有限公司 | Tensile strength is 680MPa grades of large-scale mobile steelss for pressure vessel use and production method |
| CN114086083B (en) * | 2020-08-25 | 2023-01-20 | 宝山钢铁股份有限公司 | 1100 MPa-grade sulfur-resistant high-pressure gas cylinder steel, high-pressure gas cylinder and manufacturing method thereof |
| CN114737027B (en) * | 2022-04-15 | 2024-02-06 | 首钢集团有限公司 | 345 MPa-level container steel with excellent hydrogen induced cracking resistance and preparation method thereof |
| CN115418573A (en) * | 2022-10-09 | 2022-12-02 | 南京钢铁股份有限公司 | 80 mm-thick quenched and tempered high-toughness steel plate for pressure vessel and preparation method thereof |
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| CN1914341A (en) * | 2004-02-04 | 2007-02-14 | 住友金属工业株式会社 | Steel product for line pipe excellent in resistance to HIC and line pipe produced by using the steel product |
| CN101784680A (en) * | 2007-11-14 | 2010-07-21 | 住友金属工业株式会社 | Steel for steel pipes excellent in sour resistance and process for manufacturing the same |
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| JPH0941082A (en) * | 1995-07-28 | 1997-02-10 | Nkk Corp | Resistance welded tube excellent in hic resistance and sscc resistance and its production |
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| CN1914341A (en) * | 2004-02-04 | 2007-02-14 | 住友金属工业株式会社 | Steel product for line pipe excellent in resistance to HIC and line pipe produced by using the steel product |
| CN101784680A (en) * | 2007-11-14 | 2010-07-21 | 住友金属工业株式会社 | Steel for steel pipes excellent in sour resistance and process for manufacturing the same |
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