EP3561126B1 - Steel material having excellent corrosion resistance in dew condensation environment containing sulfide and method for producing same - Google Patents
Steel material having excellent corrosion resistance in dew condensation environment containing sulfide and method for producing same Download PDFInfo
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- EP3561126B1 EP3561126B1 EP17885245.5A EP17885245A EP3561126B1 EP 3561126 B1 EP3561126 B1 EP 3561126B1 EP 17885245 A EP17885245 A EP 17885245A EP 3561126 B1 EP3561126 B1 EP 3561126B1
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- sulfide
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- 230000007797 corrosion Effects 0.000 title claims description 100
- 238000005260 corrosion Methods 0.000 title claims description 100
- 229910000831 Steel Inorganic materials 0.000 title claims description 76
- 239000010959 steel Substances 0.000 title claims description 76
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims description 32
- 239000000463 material Substances 0.000 title claims description 26
- 238000009833 condensation Methods 0.000 title claims description 18
- 230000005494 condensation Effects 0.000 title claims description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 61
- 239000010949 copper Substances 0.000 claims description 49
- 239000011572 manganese Substances 0.000 claims description 33
- 229910052750 molybdenum Inorganic materials 0.000 claims description 32
- 239000011651 chromium Substances 0.000 claims description 28
- 239000011575 calcium Substances 0.000 claims description 26
- 238000001816 cooling Methods 0.000 claims description 26
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 25
- 239000011733 molybdenum Substances 0.000 claims description 25
- 229910052802 copper Inorganic materials 0.000 claims description 24
- 229910052759 nickel Inorganic materials 0.000 claims description 22
- 230000035945 sensitivity Effects 0.000 claims description 21
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 18
- 229910052748 manganese Inorganic materials 0.000 claims description 18
- 229910052717 sulfur Inorganic materials 0.000 claims description 17
- 229910052804 chromium Inorganic materials 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 13
- 229910052791 calcium Inorganic materials 0.000 claims description 13
- 239000011593 sulfur Substances 0.000 claims description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- 239000010703 silicon Substances 0.000 claims description 12
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 238000005098 hot rolling Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 1
- 239000010779 crude oil Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 239000007789 gas Substances 0.000 description 11
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 11
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 5
- 238000005336 cracking Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- JGIATAMCQXIDNZ-UHFFFAOYSA-N calcium sulfide Chemical compound [Ca]=S JGIATAMCQXIDNZ-UHFFFAOYSA-N 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 101710178035 Chorismate synthase 2 Proteins 0.000 description 3
- 101710152694 Cysteine synthase 2 Proteins 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 238000004880 explosion Methods 0.000 description 3
- 229910001562 pearlite Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 238000009628 steelmaking Methods 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 1
- 229910000746 Structural steel Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910001566 austenite Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000008236 heating water Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- CADICXFYUNYKGD-UHFFFAOYSA-N sulfanylidenemanganese Chemical compound [Mn]=S CADICXFYUNYKGD-UHFFFAOYSA-N 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
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Classifications
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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
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
-
- 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
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
-
- 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
- C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
-
- 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
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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
- C21D9/085—Cooling or quenching
-
- 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
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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
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
-
- 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
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
Definitions
- the present invention relates to a steel material, having excellent corrosion resistance for use in an oil tanker, a crude oil tank, and the like, and particularly, to a steel material having excellent corrosion resistance in a dew condensation environment containing a sulfide gas and a method for producing the steel material.
- a steel material for use in a crude oil tank for an oil tanker may suffer from significantly serious corrosion damage due to an internal environment of the crude oil tank.
- various types of corrosion occur due to volatile components in crude, or inert gas, sent into the tank to achieve explosion proofing of mixed seawater, salt in oilfield brine or dew condensation, caused by an internal temperature difference, and the like.
- a corrosion rate is significantly higher than a corrosion rate in a typical brine environment.
- hydrogen sulfide gas evaporated from crude, and gas such as CO 2 , SO 2 , O 2 or the like in inert gas, introduced to achieve explosion proofing, may react with dew condensation, formed on a surface of a steel material by a temperature difference, to contain a large amount of hydrogen sulfide and sulfur dioxide components. Accordingly, corrosion occurs.
- Corrosion caused by the dew condensation i.e. condensed water
- condensed water is similar to atmospheric corrosion of atmospheric corrosion resistant steel because of the corrosion at the thin water film, and moisture is periodically and repeatedly condensed and dried due to a daily temperature range. For this reason the corrosion, caused by condensed water, may be separately classified as dew point corrosion.
- Patent Document 1 has been proposed to improve corrosion resistance of a steel material for a ship.
- a steel material for a ship of Patent Document 1 was designed without consideration of corrosion caused by hydrogen sulfide when crude oil contains the hydrogen sulfide, the steel material for ship is insufficient to be used in an actual crude oil tank.
- Patent Documents 1 Japanese Patent Publication Laid-Open 2000-017381 . Steels are disclosed in JP S53115611 A and JP H07188838 A . Other solutions are disclosed in JP 2010-222701 A , KR 2016-0085311 A , KR 2010-0067510 A .
- the present invention is to provide a steel material which may optimize steel components and may identify a relationship between components to secure improved corrosion resistance, even in a dew condensation environment including sulfides; and a method for producing the steel material.
- the steel material according to the invention is defined in the independent claim 1.
- the method for producing a steel material according to the invention is defined in the independent claim 3.
- the preferred embodiments are defined in the dependent claims.
- steel components are optimized to satisfy a sensitivity index of sulfide dew point corrosion.
- resistance against the sulfide dew point corrosion may be improved.
- the present inventors have conducted researches to address the above-described issues of the related art.
- the inventors found that in order to improve resistance against corrosion in a dew condensation environment containing sulfide gas, a composition of each component needs to be appropriately controlled, as set forth below.
- the inventors found that that relationships between components such as Ca, S, Cr, Mo, Ni, Mn, and the like, affecting sensitivity of dew point corrosion, needs to be appropriately controlled. For these reasons, the inventors conceived the present invention.
- the steel material comprises, by weight percent (wt%), 0.02 to 0.2% of carbon (C), 0.1 to 1.0% of silicon (Si), 0.2 to 2.0% of manganese (Mn), 0.03% or less of phosphorus (P), 0.03% or less of sulfur (S), 0.05 to 0.5% of copper (Cu), 0.05 to 0.5% of nickel (Ni), 0.02 to 0.5% of molybdenum (Mo), 0.1% or less of aluminum (Al), 0.05 to 0.5% of chromium (Cr), 0.001 to 0.01% of calcium (Ca), and a balance of iron (Fe) and inevitable impurities.
- C carbon
- Si silicon
- Mn manganese
- P phosphorus
- S sulfur
- Cu copper
- Ni nickel
- Mo molybdenum
- Al aluminum
- Cr chromium
- Ca calcium
- Fe iron
- Carbon (C) is an element added to improve strength.
- a content of carbon (C) is increased, hardenability may be increased to improve strength.
- general corrosion resistance is reduced.
- precipitation of carbide or the like is promoted, localized corrosion resistance is also affected.
- the content of carbon (C) should be decreased to improve the general corrosion resistance and the localized corrosion resistance.
- carbon (C) is less than 0.02 wt%, it is difficult to secure strength.
- carbon (C) is more than 0.2 wt%, weldability is deteriorated to be inappropriate for, in detail, steel for welded structure. Therefore, carbon (C) has a range, in detail, from 0.02 to 0.2 wt%.
- the content of carbon (C) may be set to, in detail, be 0.16 wt% or less and may be set to, in further detail, 0.14 wt% or less to improve casting cracking and to reduce a carbon equivalent.
- Silicon (Si) needs to be present in amount of 0.1 wt% or more to serve as a deoxidizer and to serve to increase strength of steel.
- silicon (Si) contributes to improvement in general corrosion resistance, it is advantageous to increase the content of silicon (Si).
- the content of silicon (Si) is greater than 1.0 wt%, toughness and weldability are deteriorated.
- the scale causes a surface defect. Therefore, the content of silicon (Si) is limited to, in detail, 0.1 to 1.0 wt%.
- silicon (Si) is added in an amount of 0.2 wt% or more to improve corrosion resistance.
- Manganese (Mn) is an element effect in increasing the strength without reducing toughness. However, when an excessive amount of manganese (MN) is added, an electrochemical reaction rate of a steel surface may be increased during a corrosion reaction to reduce corrosion resistance. When manganese (Mn) is added in an amount of less than 0.2 wt%, it is difficult to secure durability of a structural steel. When the content of manganese (Mn) is increased, hardenability is increased to improve strength. However, when manganese (Mn) is added in an amount greater than 2.0 wt%, weldability and corrosion resistance are reduced. Therefore, the content of manganese (Mn) is set to be, in detail, 0.2 to 2.0 wt%.
- Phosphorus (P) 0.03 wt% or less
- Phosphorus (P) is an impurity element.
- the phosphorous (P) is added in an amount greater than 0.03 wt%, weldability is significantly reduced and toughness is deteriorated. Therefore, the content of phosphorous (P) is limited to, in detail, 0.03 wt% or less.
- Sulfur (S) is also an impurity element.
- Sulfur (S) is apt to react with manganese (Mn) to form an elongated inclusion like manganese sulfide (MnS), and voids, formed on both ends of the elongated inclusion, may be a starting point of localized corrosion. Therefore, the content of sulfur (S) is limited to, in further detail, 0.01 wt% or less.
- copper (Cu) When copper (Cu) is contained in an amount of 0.05 wt% or more together with nickel (Ni), exudation of iron (Fe) is delayed, which is effective in improving general corrosion resistance and localized corrosion resistance.
- the amount of copper (Cu) is greater than 0.5 wt%, copper (Cu) in a liquid state melts into a grain boundary during production of a slab. Thus, cracking occurs during hot working, which is called “hot shortness” phenomenon. Therefore, the content of copper (Cu) is set to, in detail, be 0.05 to 0.5 wt%.
- a frequency of occurrence of the surface cracking may vary, depending on the content of each element, but the content of copper (Cu) is set to, in further detail, be 0.5 wt% or less.
- nickel (Ni) when nickel (Ni) is contained in an amount of 0.05 wt% or more, it is effective in improving general corrosion resistance and localized corrosion resistance. In addition, when nickel (Ni) is added together with copper (Cu), nickel (Ni) reacts with copper (Cu) in such a manner that formation of a copper (Cu) phase is suppressed to prevent hot shortness from occurring. Nickel (Ni) is also an element effective in improving toughness of a base material. However, since nickel (Ni) is an expensive element, the addition of nickel (Ni) in an amount of 0.5 wt% or more is disadvantageous in terms of economical efficiency and weldability. Therefore, the content of nickel (Ni) is set to, in detail, be 0.05 to 0.5 wt%.
- Ni nickel
- Cu copper
- the content of nickel (Ni) is limited to, in further detail, 0.3 wt% or less.
- Molybdenum (Mo) is an element contributing to improvement of corrosion resistance and strength and should be added in an amount of 0.02 wt% or more to achieve such an effect.
- molybdenum (Mo) should be dissolved in steel to improve corrosion resistance.
- the dissolved molybdenum (Mo) improves the corrosion resistance to the condensed water containing hydrogen sulfide.
- molybdenum (Mo) contained in an amount greater than a dissolution limit, may reacts with sulfur (S) in such a manner Mo 2 S is formed to reduce corrosion resistance. Therefore, when an excessive amount of molybdenum (Mo) is added, corrosion resistance against condensed water, containing hydrogen sulfide, may be reduced.
- an upper limit thereof is, in detail, 0.5 wt%.
- a precipitate of molybdenum (Mo) serves to improve strength, but coarsely precipitated molybdenum (Mo) may cause localized corrosion of the steel. Therefore, molybdenum (Mo) is added in an amount of, in further detail, 0.1 wt% or less.
- Aluminum (Al) is an element, added for deoxidation, and reacts with nitrogen (N) in the steel in such a manner that an aluminum nitride (AlN) is formed and austenite grains are refined to improve toughness.
- AlN aluminum nitride
- an inclusion is formed in a coarse oxide during a steelmaking process and a stretched inclusion, crushed and elongated during rolling, is formed according to aluminum oxide-based characteristics. Since the formation of such an elongated inclusion promotes the formation of a void around the inclusion and such a void serves as a starting point for localized corrosion, the elongated inclusion serves to reduce the localized corrosion resistance.
- the content of aluminum (Al) is set to, in detail, be 0.1 wt% or less. Since deoxidation effect may be obtained by another deoxidizing element such as silicon (Si) or the like even when aluminum (Al) is added, a lower limit of aluminum (Al) is not limited. However, in detail, at least 0.001 wt% or more of aluminum (Al) may be added to expect a deoxidation effect achieved by aluminum (Al).
- Chromium (Cr) is an element which increases the corrosion resistance by forming a chrome-containing oxide layer on a surface of the steel in a corrosive environment. Chromium (Cr) should be contained in an amount of 0.05 wt% or more to exhibit a corrosion resistance effect depending on addition of chromium (Cr). However, when chromium (Cr) is contained in an amount greater than 0.5 wt%, toughness and weldability are adversely affected. Therefore, the content of chromium (Cr) is set to, in detail, be 0.05 to 0.5 wt%.
- Calcium (Ca) reacts with aluminum (Al), silicon (Si), and oxygen (O) in a molten steel to form a composite oxide and then reacts with sulfur (S) to form calcium sulfide (CaS).
- CaS calcium sulfide
- Such a calcium sulfide (CaS) inclusion is dissolved in water in a dew condensation environment to increase pH of the surface of the steel.
- formation of a stable phase is promoted under suppress of an electrochemical reaction of the steel to improve corrosion resistance characteristics.
- calcium (Ca) should be added in an amount of at least 0.001 wt%. However, when the content of calcium (Ca) is greater than 0.01 wt%, refractories may be melted during a steelmaking process.
- the content of Ca is set to, in detail, be 0.001 to 0.01 wt%. Additionally, calcium (Ca) is added in an amount of, in further detail, 0.002 wt% or more to secure a sulfide dew point corrosion sensitivity index.
- the balance is iron (Fe) and inevitable impurities.
- the sulfide condensation corrosion sensitivity index defined as Relational Expression 1, satisfies, in detail, 1.78 to 2.25.
- Sensitivity Index of Sulfide Dew point corrosion 0.4 Ca / S + 5 Cr + 6Mo + 2 Cu + Ni ⁇ 0.5 Mn (where Ca, S, Cr, Mo, Cu, Ni, and Mn denote contents (wt%) of corresponding elements).
- the above Ca, Cr, Mo, Cu, Ni, and Mn are components affecting a corrosion resistance effect in a sulfide dew condensation environment depending on amounts of addition thereof.
- An influence of each of these components on the corrosion resistance was quantitatively derived, and a relationship between the components was expressed by Relational Expression 1.
- Relational Expression 1 When the sensitivity index of sulfide dew point corrosion, defined as Relational Expression 1, is 1.7 to 2.5, improved corrosion resistance may be secured in a corresponding environment.
- the sensitivity index of sulfide dew point corrosion defined as Relational Expression 1, is 1.78 to 2.25.
- the steel of the present invention having the advantageous composition, may be easily produced using knowledge in the art by a person of ordinary skill in the art without excessively repeated tests.
- a method for producing the steel material is proposed in the present invention .
- the method for producing a steel material according to the present invention is a method for producing a steel material through conventional hot rolling and cooling, and is characterized in that the cooling is performed at a cooling rate of 10°C/sec or higher in such a manner that cooling starting temperature is Ar3 temperature or higher and cooling stop temperature ranges from (Ae1-30°C) to 600°C.
- cooling conditions of the present disclosure will be described.
- Cooling Section cooled from Ar3 temperature or higher to (Ae1-30°C) - 600°C
- molybdenum (Mo) when molybdenum (Mo), added to achieve the advantageous effect, forms a great amount of precipitate, the added molybdenum (Mo) has an adverse influence on general corrosion, localized corrosion, or the like. Meanwhile, when an excessive amount of molybdenum (Mo) is dissolved, molybdenum (Mo) has an adverse influence on corrosion resistance in an environment containing hydrogen sulfide. Therefore, it is necessary to appropriately control a ratio of molybdenum (Mo), forming the precipitate, and the dissolved molybdenum (Mo).
- molybdenum (Mo) tends to form precipitates at temperature between 700 and 550°C, a portion of the section needs to be rapidly cooled to prevent that molybdenum (Mo) forms a precipitate and the other portions of the section need to be slowly cooled to prevent that molybdenum (Mo) is excessively dissolved.
- molybdenum (Mo) may bond to sulfur (S) at a condensed water atmosphere, containing hydrogen sulfide, to form MozS and may deteriorate corrosion resistance of the steel material. As a result, the cooling needs to be finished at temperature of 600°C or higher.
- Cooling Rate 10°C/s or higher
- the cooling rate needs to be 10°C/s or higher. Even if the cooling rate is high, there is no problem in achieving objects of the present disclosure. Accordingly, it is unnecessary to determine an upper limit of the cooling rate. However, since there may be a limitation in capability of cooling equipment, the upper limit may be determined to be 50°C/s in consideration of the limitation in capability to apply a significantly high cooling rate.
- a steel slab was produced using continuous casting after preparing molten steel having a composition (weight percent (wt%), the balance including iron (Fe) and inevitable impurities) listed in Table 1.
- the produced steel slab was hot-rolled under normal conditions and then cooled under conditions in Table 2.
- inventive steels refer to steel sheets having compositions satisfying a composition range defined in the present invention .
- comparative steels 1, 5, and 6 illustrate a case in which essential additive elements, selected in the present disclosure, such as Mo, Cu, and Cr are not added.
- Comparative steels 2, 3, 4, 7, and 8 illustrate a case in which essential elements are added but the sensitivity index of sulfide dew point corrosion, expressed as Relational Expression 1, does not satisfy a required range because the sensitivity index is less than 1.7 or more than 2.5, as described later.
- Such components of the comparative steels are significantly reduced in corrosion resistance than those of the inventive steels. Accordingly, since corrosion of the steel material cannot be prevented in the sulfide dew point corrosion environment, the corrosion resistance may be reduced and a replacement cycle may be increased.
- the reference steels do not satisfy the claimed Relational Expression 1.
- Table 3 below lists measurement results of sensitivity indices of sulfide dew point corrosion and corrosion rates of inventive steels and comparative steels.
- the corrosion rates listed in Table 3, were results measured by the test apparatus illustrated in FIG. 1 .
- an airtight container was filled with distilled water and a corrosive gas such as SO 2 , H 2 S, CO 2 , O 2 , or the like was continuously purged into the distilled water.
- a sample, having a size of 60mm ⁇ 20mm ⁇ 5mm, to measure a corrosion rate was polished with #600 sandpaper and located on top of the airtight container.
- a cover of the airtight container was provided with a gas inlet, an outlet, and a heating/cooling water circulation system. After being air-tightened, the airtight container was mounted in a thermostat and a temperature cycle of (50°C, 20 hours) ⁇ (25°C, 4 hours) was given for 100 days.
- a gas, introduced into the test apparatus, was a gas simulating the sulfide dew point corrosion environment of an upper deck of the crude oil tank, and has a composition below. Gas Composition: by volume percent, 5% of O 2 - 15% of CO 2 - 0.011% of SO 2 - 0.055% of H 2 S - balance N 2
- FIG. 2 is an image of samples of the inventive steels 1, 2, 5-7, and reference steels 3 and 4 and the comparative steels 1 to 8 observed after a sulfide dew point corrosion test performed for 100 days.
- Relational Expression 1 had a dense structure in which corrosion products had bright colors. In the case of the comparative steels 1 to 8, dark-colored corrosion products are visible to the naked eye.
- the sensitivity index of sulfide corrosion should be satisfied to to be between 1.7 and 2.3 to prevent sulfide dew point corrosion.
- the sensitivity index of sulfide dew point corrosion defined as Relational Expression 1, is 1.78 to 2.25.
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KR1020160177202A KR101889195B1 (ko) | 2016-12-22 | 2016-12-22 | 황화물을 포함하는 결로 환경에서 내식성이 우수한 강재 및 그 제조방법 |
PCT/KR2017/015294 WO2018117715A1 (ko) | 2016-12-22 | 2017-12-21 | 황화물을 포함하는 결로 환경에서 내식성이 우수한 강재 및 그 제조방법 |
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EP3561126A1 EP3561126A1 (en) | 2019-10-30 |
EP3561126A4 EP3561126A4 (en) | 2019-12-25 |
EP3561126B1 true EP3561126B1 (en) | 2023-08-30 |
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EP17885245.5A Active EP3561126B1 (en) | 2016-12-22 | 2017-12-21 | Steel material having excellent corrosion resistance in dew condensation environment containing sulfide and method for producing same |
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US (1) | US20200087766A1 (ja) |
EP (1) | EP3561126B1 (ja) |
JP (1) | JP6818145B2 (ja) |
KR (1) | KR101889195B1 (ja) |
CN (1) | CN110088345A (ja) |
WO (1) | WO2018117715A1 (ja) |
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CN114428051A (zh) * | 2020-10-29 | 2022-05-03 | 中国石油化工股份有限公司 | 一种冷凝温度可控的露点腐蚀评估装置 |
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JPS53115611A (en) * | 1977-03-19 | 1978-10-09 | Nippon Steel Corp | Method for low-alloyed steel of high carbon content for welding use excellent in weld crack resistance |
JPH07188838A (ja) * | 1993-12-27 | 1995-07-25 | Nippon Steel Corp | 湿潤硫化水素環境中の耐sohic特性の優れた圧力容器用厚鋼板 |
JP3860666B2 (ja) | 1998-07-03 | 2006-12-20 | 新日本製鐵株式会社 | カーゴオイルタンク用耐食鋼 |
JP3570376B2 (ja) * | 2000-12-04 | 2004-09-29 | Jfeスチール株式会社 | 耐原油タンク腐食性に優れた鋼材およびその製造方法 |
KR20060012952A (ko) | 2004-08-05 | 2006-02-09 | 엔에이치엔(주) | 개인화된 승리용 음향 효과 사용이 가능한 인터넷 게임서비스 시스템 및 그 방법 |
JP5014831B2 (ja) * | 2007-02-22 | 2012-08-29 | 新日本製鐵株式会社 | 拡管性能及び耐食性に優れた拡管油井用電縫鋼管及びその製造方法 |
KR101069981B1 (ko) * | 2008-12-11 | 2011-10-04 | 주식회사 포스코 | 황화수소를 포함하는 응축수 분위기에서 내식성이 우수한 강재 및 그 제조방법 |
JP5526859B2 (ja) * | 2009-02-26 | 2014-06-18 | Jfeスチール株式会社 | 原油タンカー用鋼材 |
JP5662894B2 (ja) * | 2011-07-27 | 2015-02-04 | 株式会社神戸製鋼所 | 耐食性に優れた原油タンカーのタンク上甲板用またはバラ積み船の船倉用鋼材 |
JP2014201759A (ja) | 2013-04-01 | 2014-10-27 | Jfeスチール株式会社 | 耐食性に優れる原油タンク用鋼材および原油タンク |
CN103286127B (zh) * | 2013-06-14 | 2015-06-24 | 首钢总公司 | 原油油船货油舱上甲板用耐腐蚀钢板的制造方法及钢板 |
JP6048385B2 (ja) * | 2013-12-12 | 2016-12-21 | Jfeスチール株式会社 | 耐食性に優れる原油タンク用鋼材および原油タンク |
CN106086641B (zh) * | 2016-06-23 | 2017-08-22 | 江阴兴澄特种钢铁有限公司 | 一种抗硫化氢腐蚀特大型石油储罐用高强钢及其制造方法 |
KR101696157B1 (ko) * | 2016-08-01 | 2017-01-13 | 주식회사 포스코 | 내황화물 응력균열성이 우수한 열연강판 및 그 제조방법 |
-
2016
- 2016-12-22 KR KR1020160177202A patent/KR101889195B1/ko active IP Right Grant
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- 2017-12-21 US US16/471,271 patent/US20200087766A1/en not_active Abandoned
- 2017-12-21 JP JP2019528916A patent/JP6818145B2/ja active Active
- 2017-12-21 CN CN201780078973.9A patent/CN110088345A/zh active Pending
- 2017-12-21 EP EP17885245.5A patent/EP3561126B1/en active Active
- 2017-12-21 WO PCT/KR2017/015294 patent/WO2018117715A1/ko unknown
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KR20180073414A (ko) | 2018-07-02 |
EP3561126A4 (en) | 2019-12-25 |
JP2020509164A (ja) | 2020-03-26 |
WO2018117715A1 (ko) | 2018-06-28 |
US20200087766A1 (en) | 2020-03-19 |
KR101889195B1 (ko) | 2018-08-16 |
EP3561126A1 (en) | 2019-10-30 |
CN110088345A (zh) | 2019-08-02 |
JP6818145B2 (ja) | 2021-01-20 |
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