CN103305761A - Corrosion-resistant steel for bottom board in cargo oil compartment of crude oil tanker - Google Patents
Corrosion-resistant steel for bottom board in cargo oil compartment of crude oil tanker Download PDFInfo
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- CN103305761A CN103305761A CN201310236277XA CN201310236277A CN103305761A CN 103305761 A CN103305761 A CN 103305761A CN 201310236277X A CN201310236277X A CN 201310236277XA CN 201310236277 A CN201310236277 A CN 201310236277A CN 103305761 A CN103305761 A CN 103305761A
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Abstract
The invention relates to corrosion-resistant steel for a bottom board in a cargo oil compartment of a crude oil tanker, belonging to the field of steel for hot-rolled slab ship structure. The corrosion-resistant steel comprises the chemical components by mass percentage: 0.02-0.25% of C, 0.05-0.5% of Si, 0.1-2.0% of Mn, less than or equal to 0.025% of P, less than or equal to 0.01% of S, 0.05-2% of Cu, 0.05-2% of Ni, 0.001-1% of W, 0.001-0.1% of Zr, 0.005-0.1% of Ti, 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 bottom board in the cargo oil compartment of the oil tanker in a naked-state manner, has excellent local corrosion resistance capability under the service conditions of high Cl<-> concentration and lower pH value, is not required for coating protection, the maintenance cost can be lowered, and the service life of the compartment body can be effectively prolonged.
Description
Technical field
The invention belongs to hot rolled slab steel for ship structure technical field, particularly a kind of crude oil tanker oil cargo tank tank-top plate corrosion-resistant steel.Be applicable to common intensity and high strength steel plate for ship building.
Background technology
In recent years, oil accident takes place frequently in the marine operation process of oil tanker, causes great financial loss, and ocean environment caused severe contamination, in addition, the expense of inspection and maintenance oil carrier also is badly in need of reducing in shipping company, therefore, the etching problem of oil tanker receives increasing concern.The accident major cause is the corrosion failure of oil cargo tank tank-top plate, oil cargo tank is the main body container of carrying crude oil on the oil carrier, it uses the slab of steel normal operation A32-E36 level, specification is many between 20-50mm, according to statistics, find that the maximum pit degree of depth reaches 10mm when the tank-top plate detection was carried out in the oil tanker operation in 2.5 years, this will shorten the life-span of oil carrier greatly, threaten the safety of carried of crude oil.
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 of oil tanker is unique, mainly is crude oil and a small amount of H in the body of 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.There is certain thickness moisture film in the oil cargo tank bottom, contains the Cl of higher concentration
-, and dissolve a large amount of sour gas, form etchant solution.The cargo tank tank-top plate by oil film or mud covering, has certain provide protection to tank-top plate usually, but because fluid scouring and regular washing of tanks can cause the local failure of oil film; spot corrosion easily occurs in failure position; the pH value of pit inside is lower after deliberation, and about 0.85, spot corrosion speed is very fast.Also there are a large amount of corrosion products that fallen by upperdeck in tank-top plate, mainly is solid-state S, forms the corrosion galvanic couple with the exposed section, further accelerates the development of spot corrosion.
At present, coating or inhibiter are mainly taked in the corrosion prevention measure of oil ship goods tank, owing to having bracing frame, heating tube etc. in the body of cabin, coating complex procedures and cost are higher, the life-span of coating, with the larger gap of design service life (general 25 years) existence of hull, the process floating coat easily was damaged under arms generally at 10-15, under the acidic solution condition spot corrosion occurs, spot corrosion tempo even surpass naked steel without coating protection.The position that the pit degree of depth exceeds standard during the ship inspection needs spot welding maintenance or coating protection, brings the rising of maintenance cost.The use meeting of inhibiter significantly reduces the average corrosion rate of cabin body, but schedule of operation is loaded down with trivial details, and the protection cost is several times of coating, is not suitable for being widely used in oil carrier cabin body.Two kinds of means of defences all can not be in the spot corrosion problem of the military service cycle of oil carrier this solution of Rigen tank-top plate.
Summary of the invention
The object of the present invention is to provide a kind of crude oil tanker oil cargo tank tank-top plate corrosion-resistant steel.Solved the spot corrosion problem of tank-top plate in the crude oil storage and transport process.
A kind of crude oil tanker oil cargo tank tank-top plate corrosion-resistant steel, its chemical composition 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%, W:0.001-1%, Zr:0.001-0.1%, Ti:0.005-0.1%, Als:0.020-0.1%, surplus is Fe and inevitable impurity
This tank-top plate is 2-40 with the value of (Cu+Ni+W)/C in the corrosion-resisting steel.
Also contain by percentage to the quality Mo:0.001-1%, Cr:0.001-0.2%, Sb:0.005-0.3%, Sn:0.005-0.3%, Ce:0.0005-0.015%, Y:0.0005-0.015%, one or more among the Hf:0.0005-0.015% in the steel.
Also contain by percentage to the quality Ca:0.0002-0.01%, Mg:0.0002-0.01%, one or more among the Sr:0.0002-0.01% in the steel.
This tank-top plate is 10-850 with the value of Mn/(S+Ca+ Mg in the corrosion-resisting steel+Sr).
Also contain by percentage to the quality Nb:0.001-0.1%, V:0.001-0.1%, one or more among the B:0.001-0.01% in the steel.
C is the element that improves steel strength.The intensity that needs in order to obtain the present invention, C content need to 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 Si upper content limit is no more than 0.5wt%.
Mn is the element that improves steel strength.The intensity that needs in order to obtain the present invention, Mn content need to 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, affect 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 affects toughness and the weldability of steel, S surpasses 0.01wt%, anti-local corrosion ability, toughness and the weldability of steel sharply descend, thus S content be controlled at below the 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.P content is preferably 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.The sulfide of Cu is generation, the progress of suppressible point erosion also.Cu content should be higher than 0.05wt%, but is higher than 2wt%, affects cc billet surface quality, and further affects 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.Be higher than the genesis that 0.2wt% accelerates spot corrosion.Cr content preferably is controlled at 0.05-0.2wt%.
W, Mo can form WO in corrosive environment
4 2-, MoO
4 2-, form insoluble salt in the metallic surface of Fe, can stop Cl
-Deng the immersion of corrosive medium, reduce average corrosion rate.Content should be higher than 0.001wt%, above behind the 1wt%, will affect Drawing abillity and welding property, and W 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 affect 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%, affects 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%, affects 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%, affects 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%, affects 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 average corrosion rate and spot corrosion speed.Improve the pH on steel surface in Mg, the Sr acidic medium, reduce average corrosion rate and spot corrosion speed.Content is higher than 0.0002wt% and produces effect, but surpasses 0.01wt%, affects toughness and the welding property of material.Ca, Mg, Sr content should be below 0.01wt%.
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 affect toughness of material and welding property.Al content should be below 0.1wt%.
Zr is combined element with the S brute force, suppress the generation of MnS, reduces average corrosion rate, inhibition point pit quantity.Content is higher than 0.005wt% and produces effect, and obviously reduces toughness of material but surpass 0.1wt%.Zr 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%.Hf content should be below 0.015wt%.
Ce, Y purify crystal boundary element in the steel, improve the anti-corrosion capability of the crystal boundary of steel, and content is higher than 0.005% and produces effect, and obviously reduce toughness of material but surpass 0.015wt%.Ce, Y content should be below 0.015wt%.
For guaranteeing the tank-top plate of the present invention solidity to corrosion of corrosion-resistant steel, (Cu+Ni+W)/C should be higher than 2, but above 40 o'clock, processing characteristics and welding property were seriously deteriorated, and corrosion resisting property descends simultaneously, (Cu+Ni+W)/C should be at 2-40.
Size and morphology Control for the inclusion that guarantees tank-top plate Mn of the present invention, guaranteeing good pitting resistance, Mn/(S+Ca+ Mg+Sr) was 10-850, above 850 o'clock, the obvious alligatoring of inclusion morphology, Mn/(S+Ca+ Mg+Sr) is 10-850.
The invention has the advantages that: described corrosion-resistant steel can direct naked attitude be used in the construction of oil ship goods tank tank-top plate, at high Cl
-Have good anti-local corrosion ability under the service condition of concentration, low pH value, can be at inner fine and close, undissolved corrosion product, the intrusion of prevention corrosive ion, the genesis of inhibiting point corrosion of forming of pit; Oil carrier need not the protection of coating and inhibiter during one's term of military service, reduces maintenance cost and effectively prolongs cabin body work-ing life.
Embodiment
Comparative example test steel chemical composition is: C:0.14wt%, Si:0.28wt %, Mn:1.33wt %, P:0.015wt %, S:0.005wt %, Cr:0.15wt %, Als:0.035wt %, surplus is Fe and inevitable impurity, (Cu+Ni+W)/C=0 in the steel, and Mn/(S+Ca+ Mg+Sr)=207.
Embodiment 1: the test steel chemical composition is: C:0.12wt %, Si:0.23wt %, Mn:1.1wt %, P:0.010wt %, S:0.002wt %, Cu:0.1wt %, Ni:0.1wt %, W:0.05wt %, Zr:0.01wt %, Ti:0.015wt %, Als:0.047wt %, Sn:0.03wt %, Ce:0.0014wt %, Mg:0.002wt %, surplus is Fe and inevitable impurity.(Cu+Ni+W)/C=2.1 in the steel, Mn/(S+Ca+ Mg+Sr)=275.
Embodiment 2: the test steel chemical composition is: C:0.05wt %, Si:0.28wt %, Mn:1.05wt %, P:0.005wt %, S:0.0019wt %, Cu:0.3wt %, Ni:0.3wt %, W:0.08wt %, Zr:0.009wt %, Ti:0.02wt %, Als:0.026wt %, Mo:0.2wt %, Sr:0.001wt %, Ca:0.002wt %, also contain Nb:0.04wt %, surplus is Fe and inevitable impurity, (Cu+Ni+W)/C=13.6 in the steel, and Mn/(S+Ca+ Mg+Sr)=214.
The test steel of above composition is by industrial converter smelting, and continuously cast bloom heats, and the operations such as mill milling manufacture the Plate Steel of different thickness specification.Its mechanical property and sulfide mean sizes are as follows:
The thickness specification 18mm of comparative example test steel, yield strength 340MPa, tensile strength 470MPa, elongation after fracture 25% ,-20 ℃ of transverse impacts absorb merit 148J; Sulfide mean sizes: 4.5 μ m.
The thickness specification 18mm of embodiment 1 test steel, yield strength 360MPa, tensile strength 470MPa, elongation after fracture 27% ,-20 ℃ of transverse impacts absorb merit 178J; Sulfide mean sizes: 2.2 μ m.
The thickness specification 25mm of embodiment 2 test steel, yield strength 440MPa, tensile strength 519MPa, elongation after fracture 32% ,-20 ℃ of transverse impacts absorb merit 194J; Sulfide mean sizes: 1.8 μ m.
Contain the steel plate solidity to corrosion of embodiment composition of steel by 2 kinds of method evaluations, method 1 is simulation spot corrosion evaluation, and method 2 is the lacing film corrosion evaluation, and specific implementation method and corrosion evaluation result are as follows:
Method 1 specific implementation method and corrosion evaluation result: every kind of test steel plate prepares respectively 3 50 * 40 * 10mm samples, six faces carry out respectively the 600# sand papering, the acetone oil removing, alcohol wash, individual sample stays the aperture of a Φ 5mm at the center of 50 * 40mm face, rest position is coated with envelope with Resins, epoxy, stays the aperture face as test face.Sample places container bottom, and test faces up, and is immersed in 10% NaCl solution, passes into continuously 13 ± 2%CO
2-4 ± 1%O
2-500 ± 50ppmH
2S-100 ± 10ppmSO
2Gas mixture, test chamber is dipped in thermostat water bath, water temperature is set 40 ℃, test period 28 days.Aperture internal corrosion product is removed in off-test, measures corrosion pit depth.Corrosion evaluation result: comparative example test steel plate corrosion hole degree of depth 2.6mm; Embodiment 1 test steel plate corrosion hole degree of depth 0.32mm; Embodiment 2 test steel plate corrosion hole degree of depth 0.22mm.
Method 2 specific implementation methods and corrosion evaluation result: according to tank-top plate solidity to corrosion detection method of regulation in " the crude oil tanker oil cargo tank corrosion-resistant steel check guide " of China Classification Society promulgation in 2013, every kind of test steel plate prepares respectively 25 ± 1mm * 60 ± 1mm * 5 samples of 5 ± 0.5mm, beating Φ 2mm circular hole (being used for hanging) near 25mm one lateral edges place, surface 600# sand papering, the acetone oil removing, alcohol wash.Testing liquid is the NaCl solution of 10wt%, and regulating the pH value with HCl is 0.85, and sample hangs and is immersed in the solution sealed reaction vessel.The solution capacity is greater than 20ml/cm in the container
2, temperature remains on 30 ± 2 ℃, changes once in per 24 hours.The specimen surface corrosion product is removed in off-test, calculates average corrosion rate, observes specimen surface and has or not corrosion pit and measure its degree of depth.Corrosion evaluation result: comparative example test steel plate average corrosion rate 5.46mm/y, corrosion pit mean depth 1.8mm; Local corrosion does not occur in embodiment 1 test steel plate average corrosion rate 0.72mm/y; Local corrosion does not occur in embodiment 2 test steel plate average corrosion rate 0.42mm/y.
Claims (10)
1. an oil ship goods tank tank-top plate corrosion-resistant steel is characterized in that, its chemical composition 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%, W:0.001-1%, Zr:0.001-0.1%, Ti:0.005-0.1%, Als:0.020-0.1%, surplus is Fe and inevitable impurity.
2. corrosion-resistant steel according to claim 1 is characterized in that, the value of (Cu+Ni+W)/C is 2-40 in the corrosion-resistant steel.
3. corrosion-resistant steel according to claim 1, it is characterized in that, contain Mo:0.001-1% in the steel by percentage to the quality, Cr:0.001-0.2%, Sb:0.005-0.3%, Sn:0.005-0.3%, Ce:0.0005-0.015%, Y:0.0005-0.015%, one or more among the Hf:0.0005-0.015%.
4. corrosion-resistant steel according to claim 1 is characterized in that, contains Ca:0.0002-0.01% in the steel by percentage to the quality, Mg:0.0002-0.01%, one or more among the Sr:0.0002-0.01%.
5. corrosion-resistant steel according to claim 1 is characterized in that, the value of Mn/(S+Ca+ Mg in the corrosion-resistant steel+Sr) is 10-850.
6. 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%, one or more among the B:0.001-0.01%.
7. corrosion-resistant steel according to claim 1 is characterized in that, the mass percentage content of C is 0.04-0.2%.
8. corrosion-resistant steel according to claim 1 is characterized in that, the mass percentage content of Mn is 0.3-1.6%.
9. corrosion-resistant steel according to claim 1 is characterized in that, P :≤0.012wt%, S :≤0.002wt%.
10. corrosion-resistant steel according to claim 1 is characterized in that, the mass percentage content of Cu is 0.05-1%.
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Cited By (4)
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| CN103789630A (en) * | 2014-01-24 | 2014-05-14 | 杨学焦 | Production method of carbon steel workpiece for speed skating ice skate blade |
| CN104046919A (en) * | 2014-07-09 | 2014-09-17 | 南京赛达机械制造有限公司 | Long-life steam turbine blade and production process thereof |
| CN105506480A (en) * | 2015-11-24 | 2016-04-20 | 钢铁研究总院 | Method for controlling atmosphere corrosion resistance and alternate dry and wet oil gas corrosion resistance of corrosion-resistant steel |
| WO2023087350A1 (en) | 2021-11-19 | 2023-05-25 | 鞍钢股份有限公司 | High-heat-input-welding low-temperature-resistant corrosion-resistant steel for cargo oil tanks and manufacturing method therefor |
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Application publication date: 20130918 |