CN103290337A - Corrosion-resistant steel for upper deck of cargo oil tank of crude oil tanker - Google Patents
Corrosion-resistant steel for upper deck of cargo oil tank of crude oil tanker Download PDFInfo
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- CN103290337A CN103290337A CN2013102349169A CN201310234916A CN103290337A CN 103290337 A CN103290337 A CN 103290337A CN 2013102349169 A CN2013102349169 A CN 2013102349169A CN 201310234916 A CN201310234916 A CN 201310234916A CN 103290337 A CN103290337 A CN 103290337A
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Abstract
The invention relates to corrosion-resistant steel for an upper deck of a cargo oil tank of a crude oil tanker, belonging to the technical field of hot rolling steel of flat ship body structures. The corrosion-resistant steel comprises the following chemical components in percentage by mass: 0.02-0.25% of C, 0.05-0.5% of Si, 0.1-2.0% of Mn, more than or equal to 0.025% of P, more than or equal to 0.01% of S, 0.05-2% of Cu, 0.05-2% of Ni, 0.01-5% of Cr, 0.001-1% of W, 0.001-0.1% of Zr, 0.0002-0.01% of Ca, 0.005-0.1% of Ti, 0.001-0.008% of N, 0.020-0.1% of Als, and the balance of Fe and inevitable impurities. The corrosion-resistant steel has the advantages that the corrosion-resistant steel can be directly used for building the upper deck of the cargo oil tank of the crude oil tanker in a bare state, the uniform corrosion rate of the upper deck in a cargo oil tank environment and the production of solid S in corrosion products are significantly reduced, coating protection is not needed, the inspection and maintenance frequencies of a ship body are reduced, and the service life of a cabin is effectively prolonged.
Description
Technical field
The invention belongs to hot rolled slab ship hull structure use steel technical field, particularly a kind of crude oil tanker oil cargo tank upperdeck corrosion-resistant steel.Be applicable to common intensity and high strength steel plate for ship building.
Background technology
Oil cargo tank is the main body container of carrying crude oil on the oil carrier, and it generally uses the slab of A32-E36 level with steel, and specification is many between 20-50mm.Along with the exploitation of marine oil and deep stratum oil, 80% is high-sulfur, the contour crude corrosively of peracid in the crude oil, and the crude oil tank internal corrosion circumstance complication uniqueness of oil tanker mainly is crude oil and a spot of H in the cabin
2O also contains O
2, CO
2, SO
2, N
2Etc. explosion-proof rare gas element, and by the H that evaporates in the crude oil
2S.After testing, H
2The peak concentration of S can surpass 0.2%, because O
2Oxidisability and H
2The reductibility of S makes the corrosive environment of oil cargo tank complicated and unique.The internal surface of upperdeck is owing to the variation of day and night temperature, and the water vapour in the steam forms condensate film at the upperdeck internal surface, makes internal surface be in the environment of alternation of wetting and drying H
2S, CO
2, SO
2Be dissolved in liquid film Deng corrosive gases, form acid attack solution (the pH value is at 2-4) and upperdeck is caused uniform corrosion, the H in the steam
2S and O
2Reaction generates solid-state S, is present in the corrosion product.Corrosion product mainly is product alpha-feooh and a small amount of S, the FeSO of oxygen corrosion
4, FeS etc., the corrosion product form is the synusia shape, constantly grows, peels off in dry, the moistening cycle changes.
At present, coating protection is mainly taked in oil tanker oil cargo tank upperdeck corrosion prevention measure, owing to have bracing frame, heating tube etc. in the body of cabin, coating complex procedures and cost are higher, the life-span of coating is generally at 10-15, has big gap with the design of hull cycle (general 25 years) of being on active service, thus in the oil carrier operation process because ship inspection and a large amount of expenses of coating maintenance generation, along with the prolongation of operating time, the corrosion thinning problem of upperdeck also can threaten the safe operation of oil carrier.
Summary of the invention
The object of the present invention is to provide a kind of crude oil tanker oil cargo tank upperdeck corrosion-resistant steel.Solved the uniform corrosion problem of upperdeck under the oil cargo tank corrosive environment.
A kind of crude oil tanker oil cargo tank upperdeck corrosion-resistant steel, its chemical ingredients is by percentage to the quality: C:0.02-0.25%, Si:0.05-0.5%, Mn:0.1-2.0%, P :≤0.025%, S :≤0.01%, Cu:0.05-2%, Ni:0.05-2%, Cr:0.01-5%, W:0.001-1%, Zr:0.001-0.1%, Ca:0.0002-0.01%, Ti:0.005-0.1%, N:0.001-0.008%, Als:0.020-0.1%, surplus is Fe and unavoidable impurities.
Also contain Mo:0.001-1%, Co:0.001-1%, one or more among the Hf:0.0005-0.015% by percentage to the quality in the steel.
Also contain Sb:0.005-0.3%, Sn:0.005-0.3%, Se:0.005-0.3%, As:0.005-0.3%, Bi:0.005-0.3%, one or more among the Pb:0.005-0.3% by percentage to the quality in the steel.
Also contain Mg:0.0002-0.01%, Ce:0.0005-0.015%, Y:0.0005-0.015%, one or more among the Sr:0.0002-0.01% by percentage to the quality in the steel.
Also contain Nb:0.001-0.1%, V:0.001-0.1%, B:0.001-0.01%, one or more among the Ta:0.001-0.01% by percentage to the quality in the steel.
C is the element that improves steel strength.In order to obtain the intensity that the present invention needs, C content need be more than 0.02wt%, and when C content surpassed 0.25wt%, the toughness of base metal tenacity and welded heat affecting zone descended, in order to take into account base metal tenacity and welding heat influence area toughness, the preferred 0.04-0.2wt% of C content.
Si at steelmaking process usually as reductive agent and reductor, also can improve the intensity of steel, in order to guarantee the intensity of deoxidation effect and steel, need Si content more than 0.05wt%, if surpass 0.5wt%, can significantly reduce toughness and the welding property of steel, for guaranteeing toughness and the weldability of steel, the upper limit of Si is no more than 0.5wt%.
Mn is the element that improves steel strength.In order to obtain the intensity that the present invention needs, Mn content need be more than 0.1wt%, when Mn content surpasses 2.0wt%, the toughness of base metal tenacity and welded heat affecting zone descends, the quantity that forms the MnS inclusion increases, influence the matrix solidity to corrosion, in order to take into account mother metal solidity to corrosion, base metal tenacity and welding heat influence area toughness, the preferred 0.3-1.6wt% of Mn content.
S is harmful element remaining in the steel, form the MnS inclusion with the Mn in the steel, it is the origin of local corrosion, and S influences toughness and the weldability of steel, S surpasses 0.01wt%, anti-local corrosion ability, toughness and the weldability of steel sharply descend, so the control of S content is below 0.01wt%, preferably below 0.002wt%.
P is easy grain boundary segregation element, increases with P content, and the toughness of steel, solidity to corrosion reduce, and P content surpasses 0.025wt%, the center segregation aggravation, and toughness, welding property sharply descend.When P content was lower than 0.003wt%, steel-making cost can significantly increase, and therefore preferred P content is below 0.012wt%.
Cu is the solidity to corrosion element that improves steel, is the element that the present invention must add, and Cu is containing H
2Can form the sulfide rete on the steel surface under the S environment, can suppress general corrosion.Cu content should be higher than 0.05wt%, but is higher than 2wt%, influences cc billet surface quality, and further influences hot workability and the welding property of later stage steel plate, so the preferred 0.05-1wt % of the content range of Cu.
Ni improves steel toughness element, also is simultaneously to improve the solidity to corrosion element, and the compound interpolation of General N i, Cu suppresses Cu and adds the material fragility that causes.Generally be higher than 0.05wt%, be lower than 2wt%, be higher than 2wt% and cause that processing characteristics and welding property worsen Ni content 0.05-2wt%.
Cr can improve the strength of materials, is simultaneously to significantly improve material corrosion proof element under acidic conditions, and is better with the compound additive effect of Cu, Ni.But Cr content is higher than 5wt% will make material welding performance significantly worsen, and Cr content is preferably controlled at 0.01-5wt%, preferred 0.05-2wt%.
W, Mo can form WO in corrosive environment
4 2-, MoO
4 2-, form insoluble salt in the metallic surface of Fe, reduce general corrosion speed.Content should be higher than 0.001wt%, above behind the 1wt%, will influence Drawing abillity and welding property, and W content is at 0.001-1wt%.
Co can improve the solidity to corrosion of material under the dry wet alternating environment acidic conditions, and content should be higher than 0.001wt%, above behind the 1wt%, will influence Drawing abillity and welding property, and Co content is at 0.001-1wt%.
Sn, Sb element can improve steel at H
2SO
4, the corrosion resisting property under the environment such as HCl, and form oxide compound on the steel surface, reduce the anode dissolution zone.Content should be higher than 0.005wt%, above behind the 0.3wt%, will influence toughness and the welding property of material, and Sn, Sb content are at 0.005-0.3wt%.
The Nb element is to significantly improve the hardness of steel element, and crystal grain thinning improves solidity to corrosion, and content is higher than 0.001wt% and produces effect, but surpasses 0.1wt%, influences toughness and the welding property of material.Nb content 0.001-0.1wt%.
V element is to significantly improve the hardness of steel element, and crystal grain thinning improves solidity to corrosion, and content is higher than 0.001wt% and produces effect, but surpasses 0.1wt%, influences toughness and the welding property of material.V content 0.001-0.1wt%.
The Ti element is to significantly improve the hardness of steel element, and crystal grain thinning improves solidity to corrosion, and content is higher than 0.001wt% and produces effect, but surpasses 0.1wt%, influences toughness and the welding property of material.Ti content 0.001-0.1wt%.
The B element is to significantly improve the hardness of steel element, and crystal grain thinning improves solidity to corrosion, and content is higher than 0.0003wt% and produces effect, but surpasses 0.01wt%, influences toughness and the welding property of material.B content 0.001-0.01wt%.
Ca can improve the steel inclusion form, improves toughness of material, further reduces the spot corrosion incidence, improves the pH on steel surface in acidic medium, reduces general corrosion speed.Improve the pH on steel surface in Mg, the Sr acidic medium, reduce general corrosion speed.Content is higher than 0.0002wt% and produces effect, but surpasses 0.01wt%, influences toughness and the welding property of material.
Al is the deoxidant element in the steel, also is the element that improves erosion resistance under the material acidic conditions, and being higher than 0.1wt% can influence toughness of material and welding property.
Zr is combined element with the S brute force, suppress the generation of MnS, reduces general corrosion speed, suppresses spot corrosion.Content is higher than 0.005wt% and produces effect, and obviously reduces toughness of material but surpass 0.1wt%.Content should be below 0.1wt%.
Hf is the element of anti-crevice corrosion that significantly improves steel, and content is higher than 0.005wt% and produces effect, and obviously reduces toughness of material but surpass 0.015wt%.
Ce, Y purify crystal boundary element in the steel, improve the anti-corrosion capability of the crystal boundary of steel, reduce general corrosion speed, and content is higher than 0.005wt% and produces effect, and obviously reduce toughness of material but surpass 0.015wt%.
The invention has the advantages that: described corrosion-resistant steel can direct naked attitude be used in the construction of crude oil tanker oil cargo tank upperdeck; the growing amount of solid-state S in the uniform corrosion speed of upperdeck and the corrosion product under the remarkable reduction oil cargo tank environment; need not coating protection; reduce hull inspection and maintenance number of times, effectively prolong cabin body work-ing life.
Embodiment
Comparative example test steel its chemical ingredients by percentage to the quality is: C:0.14%, and Si:0.28%, Mn:1.33%, P:0.015%, S:0.005%, Cr:0.15%, Als:0.035%, surplus is Fe and unavoidable impurities.
Embodiment 1: test steel its chemical ingredients by percentage to the quality is: C:0.05%, Si:0.25%, Mn:1.1%, P:0.005%, S:0.0008%, Cu:0.15%, Ni:0.1%, Cr:0.10%, W:0.08%, Nb:0.04%, Zr:0.009%, N:0.006%, Hf:0.001%, Sr:0.001%, Ca:0.002%, Ti:0.02%, Als:0.026%, surplus is Fe and unavoidable impurities.
The test steel of above composition is by industrial converter smelting, and continuously cast bloom heats, and operations such as mill milling manufacture the 18mm Plate Steel, and its mechanical property is as follows:
The yield strength 340MPa of comparative example test steel plate, tensile strength 470MPa, elongation after fracture 25% ,-20 ℃ of transverse impacts absorb merit 148J.
Embodiment tests the yield strength 430MPa of steel plate, tensile strength 506MPa, and elongation after fracture 28% ,-20 ℃ of transverse impacts absorb merit 264J.
The steel plate solidity to corrosion evaluation specific implementation method and the evaluation result that contain comparative example and embodiment composition of steel are as follows:
Upperdeck solidity to corrosion detection method according to regulation in " the crude oil tanker oil cargo tank corrosion-resistant steel check guide " of China Classification Society promulgation in 2013 is carried out corrosion evaluation.For carrying out the corrosive nature contrast more accurately, comparative example and example are tested under the identical test parameter simultaneously, should carry out respectively 21,49,77 and 98 days.Each experimental stage should have 5 samples, and each sample is of a size of 25 ± 1mm * 60 ± 1mm * 5 ± 0.5mm, specimen surface 600# sand papering, acetone oil removing, alcohol wash.Test simulation is the operating mode on deck in fact, with distilled water and simulation oil cargo tank gas (4 ± 1%O
2-13 ± 2%CO
2-100 ± 10ppmSO
2-500 ± 50ppmH
2S-83 ± 2%N
2) test.For preventing that distilled water from spilling, should keep sufficient distance between specimen surface and the distilled water.Minimum gas flow in the 1st 24h is the 100ml per minute, is the 20ml per minute behind 24 h.Sample should be heated to 50 ± 2 ℃ and keep 19 ± 2h, and 25 ± 2 ℃ keep 3 ± 2h, and should be at least 1h switching time between two temperature.The time of 1 test period is 24h.The temperature of distilled water should keep not being higher than 36 ℃, and this moment, the temperature of sample was 50 ℃.
21,49,77 and 98 days test-results is coefficient A and the B that method of least squares obtains corrosion-resistant steel.
The corrosive wear of test steel are expressed as follows formula (1):
CL = A×t
B （1）
A(mm) and B: coefficient;
T: test period (fate);
Calculate corrosive wear estimated value (ECL) after 25 years by following formula (2).
ECL（mm）= A ×（25×365）
B （2）
Corrosion evaluation result: after the off-test of comparative example steel plate corrosion, test steel corrosion form is uniform corrosion, solid-state S content is 3wt% in the XRD analysis corrosion product, 21,49,77 and 98 days test-results is the coefficient A:0.00138 that method of least squares obtains testing steel, B:0.92752.Carry out corrosive wear estimated value ECL:6.5mm after 25 years according to formula (2).After the off-test of embodiment steel plate corrosion, test steel corrosion form is uniform corrosion, solid-state S content is 1wt% in the XRD analysis corrosion product, and 21,49,77 and 98 days test-results is the coefficient A:0.00246 that method of least squares obtains testing steel, B:0.73110.Carry out corrosive wear estimated value ECL:1.93mm after 25 years according to formula (2).
Claims (10)
1. a crude oil tanker oil cargo tank upperdeck corrosion-resistant steel is characterized in that its chemical ingredients is by percentage to the quality: C:0.02-0.25%, Si:0.05-0.5%, Mn:0.1-2.0%, P :≤0.025%, S :≤0.01%, Cu:0.05-2%, Ni:0.05-2%, Cr:0.01-5%, W:0.001-1%, Zr:0.001-0.1%, Ca:0.0002-0.01%, Ti:0.005-0.1%, N:0.001-0.008%, Als:0.020-0.1%, surplus is Fe and unavoidable impurities.
2. corrosion-resistant steel according to claim 1 is characterized in that, contains Mo:0.001-1% in the steel by percentage to the quality, Co:0.001-1%, one or more among the Hf:0.0005-0.015%.
3. corrosion-resistant steel according to claim 1 is characterized in that, contains Sb:0.005-0.3% in the steel by percentage to the quality, Sn:0.005-0.3%, Se:0.005-0.3%, As:0.005-0.3%, Bi:0.005-0.3%, one or more among the Pb:0.005-0.3%.
4. corrosion-resistant steel according to claim 1 is characterized in that, contains Mg:0.0002-0.01% in the steel by percentage to the quality, Ce:0.0005-0.015%, Y:0.0005-0.015%, one or more among the Sr:0.0002-0.01%.
5. corrosion-resistant steel according to claim 1 is characterized in that, contains Nb:0.001-0.1% in the steel by percentage to the quality, V:0.001-0.1%, B:0.001-0.01%, one or more among the Ta:0.001-0.01%.
6. corrosion-resistant steel according to claim 1 is characterized in that, the content of C is 0.04-0.2wt%.
7. corrosion-resistant steel according to claim 1 is characterized in that, the content of Mn is 0.3-1.6wt%.
8. corrosion-resistant steel according to claim 1 is characterized in that, P :≤0.012wt%, S :≤0.002wt%.
9. corrosion-resistant steel according to claim 1 is characterized in that, the content of Cu is 0.05-1wt %.
10. corrosion-resistant steel according to claim 1 is characterized in that, the content of Ni is 0.05-2wt%.
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Application publication date: 20130911 |