CN108118249A - A kind of crude oil carrier oil cargo tank upper deck anti-corrosion steel plate and its manufacturing method - Google Patents

A kind of crude oil carrier oil cargo tank upper deck anti-corrosion steel plate and its manufacturing method Download PDF

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Publication number
CN108118249A
CN108118249A CN201611077393.1A CN201611077393A CN108118249A CN 108118249 A CN108118249 A CN 108118249A CN 201611077393 A CN201611077393 A CN 201611077393A CN 108118249 A CN108118249 A CN 108118249A
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corrosion
steel plate
cargo tank
upper deck
tank upper
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高珊
张才毅
王炜
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Baoshan Iron and Steel Co Ltd
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Baoshan Iron and Steel Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0226—Hot rolling
    • C—CHEMISTRY; METALLURGY
    • 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
    • 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
    • C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
    • 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
    • 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
    • C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
    • 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
    • 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
    • C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
    • 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
    • C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
    • 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
    • C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
    • 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
    • C22C38/54—Ferrous alloys, e.g. steel alloys containing chromium with nickel with boron
    • 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
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/005—Ferrite
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/009—Pearlite

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  • Crystallography & Structural Chemistry (AREA)
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Abstract

A kind of crude oil carrier oil cargo tank upper deck anti-corrosion steel plate and its manufacturing method, ingredient percent are：C 0.015~0.15%, Si 0.10~0.50%, Mn 0.05~2.5%, P 0.005~0.030%, S≤0.008%, Cr 0.05~1.5%0%, Mo：0.003~1.00%, Cu 0.05~2.00%, Ni0.10~2.50%, Al 0.01~0.12%, and need to meet：100≤Cu/S≤300,0≤(0.58Ni+0.84Cu 2Cr 0.12Mo)≤0.6%, remaining Fe and inevitable impurity.The present invention utilizes the abundant crystal grain thinning tissue of big soft reduction process, ensure steel plate toughness and tenacity, control aggregation of the nano-precipitation in crystal boundary simultaneously, its microscopic structure adds a small amount of pearlitic structrure or ferrite to add a small amount of acicular ferrite structure for ferrite, steel plate yield strength >=235MPa, 400~660MPa of tensile strength, ballistic work >=120J at 60 DEG C, corrosion resistance is 25 annual corrosion rate ECL≤2.0mm, available for manufacture large-scale crude oil carrier oil cargo tank upper deck structure and other oceans, ships anticorrosion arbor etc..

Description

A kind of crude oil carrier oil cargo tank upper deck anti-corrosion steel plate and its manufacturing method
Technical field
The present invention relates to the anti-corrosion steel that crude oil carrier oil cargo tank is used in the state of not priming, and in particular to a kind of Crude oil carrier oil cargo tank upper deck anti-corrosion steel plate and its manufacturing method.
Background technology
For crude oil as strategic goods and materials, the appearance of energy crisis has further shown opening for crude resources in world wide especially The importance sent out, transport and utilized.Marine transportation is one of the main transport form of crude oil and important production link process, In recent years, since a lot of Crude Oil at Sea leakage accidents occur, extreme influence is caused to environment for human survival and marine ecology balance, Therefore the transportation safety performance of crude oil carrier is concerned.Safety, energy-saving and environmental protection requirement for crude oil carrier operation, International Maritime Association (IMO) is also increasingly strict for the anticorrosion requirement of Crude Oil at Sea shipload cargo tank, improves the standard of coating protection, simultaneously It proposes using corrosion resisting steel as effective bodyfixed frame for promoting oil cargo tank anticorrosive property.Corrosion-resisting steel is as crude oil carrier oil cargo tank The anti-corrosion measure of coating protection is substituted, there is economic, environmental protection, energy saving significant advantage, is the most important hair of crude oil ship plate Exhibition trend.
Show to tie on actual oilburg oil cargo tank top according to the crude oil corrosion condition investigation of crude oil carrier oil cargo tank In structure, there are the stripped shape corrosion of upper deck.Upper deck inner surface stripped shape corrosion product can uniformly come off, in the form of sludge Oil cargo tank bottom is deposited in, inspects periodically the sludge in recycling ultra large crude carrier more than 300 tons or more.For transporting the big of crude oil For type ship, the corrosion of oil carrier deck board greatly shortens oil carrier service life, and directly threatens safety of ship, so the deck of boat Corrosion resistance be the hull service life deciding factor.
In crude oil carrier, the gas compartment of oil cargo tank fuel tank is a corrosive environment for being full of passivation gas mixture, this A space is explosion and H in order to prevent why full of this gas2S is largely evaporated from crude oil.The inside of upper deck is sudden and violent It is exposed in this corrosive environment, under the periodically wet effects of humidity change done, with the change of temperature in daylight and at night Change, steel plate is constantly corroded, if erosion progress is fast, must just replace upper deck.The corrosion of oil cargo tank upper deck is predominantly strong Point hole corrosion under sour environment, and it is more to put the origin of hole corrosion and crude oil washing/COW, the precipitation of S simple substance, the connate water of crude oil tank etc. Kind external factor is related, these factors be easy to cause the local damage of oil cargo tank upper deck crude oil film or corrosion resistance and reduce, And then inspire and accelerate the generation of spot corrosion.
The composition of upper deck corrosion layer is mainly oxide iron rust and elemental sulfur, and corrosion product oxidation iron rust, which becomes, is precipitated list The soil of matter S, accelerates SO2And H2S reaction generation elemental sulfurs.The corrosive environment of upper deck causes the generation of steel plate corrosion iron rust And the precipitation of solid sulfur alternately occurs, due to S layers of more crisp layered distribution of cutting into slices of solid simple substance, therefore including easily causing iron rust The whole of corrosion product remove, come off.
From the perspective of oil carrier oil cargo tank corrosion protection, crude oil for inhibiting shipload cargo tank corrosion most straightforward approach be with The surface of crude oil contact steel carries out application, and steel with corrosive environment are isolated, and inspects periodically, repair.On corrosion-inhibiting coating, IMO has had mandatory standard.But since the area for needing to be coated with is huge, and since main body section such as oil cargo tank is opposite Closed, construction environment is severe, it is difficult to ensure coating quality, so coating needs are periodically coated with again, therefore the painting of oil carrier structure Layer will expend substantial amounts of construction cost and later maintenance expense.Therefore, actively seek a kind of more economical, environmentally friendly and facilitate construction Anti-corrosion measure, the corrosion resisting steel for exempting from coating are undoubtedly optimal selection scheme.
The corrosive environment of based on crude shipload cargo tank and corrosion mechanism, the corrosion resistance of crude oil carrier oil cargo tank upper deck corrosion-resisting steel It is mainly reflected in resist and contains H2S、SO2The homogeneous corrosion ability of environment.Improve the anti-oil cargo tank upper deck inner surface environment of steel plate Homogeneous corrosion, in composition design must so that surface of steel plate quickly formed under practical circumstances stablize, fine and close anti-acid environment it is rotten Product layer is lost, hinders the further oxidation corrosion of steel matrix, and will be dissolved with H2S、SO2Sour environment in keep stablize.This Outside, the content to field trashes such as the sulfide in steel, form are strictly controlled, it is necessary to including structural state, alloy member Element, grain size and heterogeneous microstructure and Phase Proportion etc. are controlled, and hinder the direct corruption of peracidity environment lower steel plate tissue Erosion reaction.
The content of the invention
It, should it is an object of the invention to provide a kind of crude oil carrier oil cargo tank upper deck anti-corrosion steel plate and its manufacturing method Yield strength >=235MPa of anti-corrosion steel plate, 400~660MPa of tensile strength, ballistic work >=120J under -60 DEG C of low temperature, corrosion resistant Corrosion can be 25 annual corrosion rate ECL≤2.0mm, have excellent general corrosion resistance and resistance to partial points corrosive nature, available for making Make large-scale crude oil carrier oil cargo tank upper deck structure and other oceans, ships anticorrosion arbor etc..
In order to achieve the above objectives, the technical scheme is that：
The Design of Chemical Composition of the present invention must take into consideration corresponding anti-corrosion environment, admittedly S compounds need to be reduced, particularly MnS's Quantity；Reduce the quantity of other types field trash；Complex inclusion is formed, the combination of particularly hard phase and soft phase ensures deformation It is tightly combined afterwards with matrix；Increase Ti, Nb precipitated phase, proof strength and refining grain size, while strengthen crystal boundary；Avoid Cr etc. The Carbide Precipitation of alloying element ensures solid solution to be quickly cooled down, controls the size of precipitated phase.In microstructure control aspect, Control microstructure is mainly ferrite or acicular ferrite structure, reduces the quantity and size on M-A islands；Crystal grain thinning is reduced Grain boundary precipitate strengthens grain boundary corrosion resistance energy.The defects of also needing to reduce the iron scale on surface, point, pit.
Specifically, a kind of crude oil carrier oil cargo tank upper deck anti-corrosion steel plate, ingredient percent are：C：0.015 ~0.15%, Si：0.10~0.50%, Mn：0.05~2.5%, P：0.005~0.030%, S≤0.008%, Cr：0.05~ 1.5%0%, Mo：0.003~1.00%, Cu：0.05~2.00%, Ni：0.10~2.50%, Al：0.01~0.12%, and Above-mentioned element need to meet following relation simultaneously：100≤Cu/S≤300,0≤(0.58Ni+0.84Cu-2Cr-0.12Mo)≤ 0.6%, surplus is Fe and inevitable impurity.
Further, also contain in the ingredient of the crude oil carrier oil cargo tank upper deck anti-corrosion steel plate：0 ＜ Nb≤ 0.15%, the 0 ＜ ＜ of Ti≤0.15%, V≤0.15%, 0 B≤0.0025%, 0 ＜ Zr≤0.25%, 0 ＜ REM (terres rares member Element)≤at least one of 0.020%, by percentage to the quality.
Crude oil carrier oil cargo tank upper deck of the present invention is ferrite+a small amount of pearlite with the microscopic structure of anti-corrosion steel plate Tissue or ferrite+a small amount of acicular ferrite structure, wherein, ferritic structure occupied area ratio is 75~95%, and ferrite is put down Equal crystallite dimension is 5~15 μm.
Yield strength >=235MPa of crude oil carrier oil cargo tank upper deck anti-corrosion steel plate of the present invention, tensile strength are 400~660MPa, ballistic work >=120J at -60 DEG C, corrosion resistance are 25 annual corrosion rate ECL≤2.0mm.
In the composition design of steel of the present invention：
C：C is to ensure that the essential elements of steel strength.For the TMCP techniques of controlled rolling and controlled cooling, in order to steadily keep Certain strength, the lower limit of C content is 0.015%.But with the increase of C content, the increase of cementite content will be caused, promoted Steel plate corrosion under sour environment, and cementite increases deterioration welding performance, therefore the upper limit of C content is defined to 0.15%.Cause This, C content scope is 0.015~0.15% in steel of the present invention.
Si：Si is required element during steel-making pre-deoxidation, and can play the role of strengthening base material, therefore Si The lower limit of content is 0.10%.But Si contents can reduce the toughness of base material and welding point when being more than 0.50%.Therefore, originally Si content ranges are 0.10~0.50% in invention steel.
Mn：Mn can be significantly improved the intensity of base material by solution strengthening and ensure the essential elements of steel strength, and It is of low cost, therefore Mn contents lower limit is 0.05%.But excessively high Mn deteriorates steel plate welding performance, and easily form slab The formation for increasing the field trash for also significantly increasing steel grade Mn of center segregation, in addition Mn contents promotes the corruption under sour environment Erosion aggravation, therefore, Mn content ranges are 0.05~2.5% in steel of the present invention.
P：P is typically impurity element in steel, is segregated in crystal boundary, can reduce the welding performance of steel plate, especially surpass in P content 0.03% is crossed, then welding performance is remarkably decreased, therefore the upper content limit of P is 0.03%.But then, P element, which has, improves The effect of the general corrosion resistance performance of crude oil carrier oil cargo tank upper deck, to improve steel plate corrosion resistance, P content is more than 0.003%. Therefore, P content scope is 0.003~0.030% in steel of the present invention.
S：S is the impurity element in steel, if S contents are more than 0.008% in steel, can increase the formation of MnS in steel, MnS easily becomes the starting point of corrosion, therefore preferably controls the content of S below 0.08%.
Al：Al is the element as deoxidier addition, adds more than 0.01% in the present invention, but Al content is more than 0.12%, steel plate toughness can be reduced, Gu the upper range of Al is 0.12%.Therefore, Al content scope is 0.01 in steel of the present invention ~0.12%.
Ni：Ni is the essential elements for ensureing low-temperature flexibility in steel, while Ni is also improved crude oil carrier oil cargo tank upper deck The effect of general corrosion resistance performance.Ni can promote the thermal stability of steel plate microscopic structure, delay the generation of steel plate homogeneous corrosion, and Ni and Cu is coupling in aggregation thickening distribution at corrosion interface, corrosion resistance of the steel plate under sour environment is improved, for crude oil Shipload cargo tank upper deck there are H2S+SO2The corrosion test environment of gas and condensation environment, these effects are in Ni contents It is embodied when more than 0.1%.But when Ni contents are more than 2.5%, the Overlay of Ni contents is not notable, and increases and be produced into This, therefore, preferred Ni content ranges are 0.1~2.5% in steel of the present invention.
Cu：Cu is the element for improving crude oil carrier oil cargo tank upper deck general corrosion resistance performance.Cu can promote surface of steel plate shape Into stable passivating film protective layer, delay the generation of steel plate spot corrosion, and Cu and Ni is coupling in aggregation thickening point at corrosion interface Cloth improves corrosion resistance of the steel plate under sour environment.Most importantly Cu is in H2S+SO2Gas and condensation environment it is uniform In corrosion process, fine and close CuS corrosion scales can be formed on corrosion surface layer, effectively hinder further expanding for corrosion.These Effect is embodied when Cu contents reach more than 0.05%, but when Cu contents are more than 2.0%, corrosion-resistant promotion effect is not shown It writes, and increases production cost, therefore, preferred Cu content ranges are 0.05~2.0% in steel of the present invention.
Cr：Cr, mostly in grain boundaries segregation, increases steel plate quenching degree, promotes steel plate toughness and tenacity in steel.Meanwhile a small amount of Cr Addition, can effectively delay the Initial Corrosion of steel plate, but when Cr contents are more than 1.5%, in H2S+SO2Gas and condensation environment Under the extension of etching time can reduce steel plate corrosion resistance.Therefore Cr needs to promote steel plate in sour environment with Cu, Ni cooperation Under resistance to spot corrosion performance.To obtain said effect, Cr content ranges are 0.05~1.5% in steel of the present invention.
Mo：Mo is the element for effectively improving quenching degree, but Mo can form stable resistance to H in surface of steel plate in the present invention- Sour corrosion, anti-dewing subacidity ion etching.Mo contents are less than 0.003%, said effect unobvious, but Mo contents are more than When 1.0%, corrosion proof promotion is no longer apparent, and increases production cost, and therefore, the addition scope of preferred Mo is in steel of the present invention 0.003~1.00%.
Nb：The recovery and recrystallization of deformed austeaite is hindered by NbC strain induced precipitates in course of hot rolling, is rolled through control The deformed austeaite that system and control cooling roll non-recrystallization zone, which is organized in, is changed into tiny phase-change product during phase transformation, to crystalline substance The effect of grain refinement is fairly obvious, and steel is made to have high intensity and high tenacity.Effective crystal grain thinning has to promoting corrosion resistance Benefit, when Nb contents are higher than 0.15%, grain refining effect promotion is no longer notable, and deteriorates toughness, therefore, present invention design Nb Content≤0.15%.
Ti：The strong N elements of Ti, the stoichiometric ratio of Ti/N is 3.42, can be fixed using 0.02% or so Ti in steel The N of below 60ppm can form the TiN precipitated phases of tiny high-temperature stable in sheet billet continuous casting.This tiny TiN particles can Austenite Grain Growth during slab reheating is effectively hindered, helps to improve solid solubility of the Nb in austenite, at the same it is right The impact flexibility for improving welding heat affected zone has obvious effect.But during Ti too high levels, will be formed coarse nitride or Cause the generation of TiC, reduce the toughness of base material and welding heat affected zone.The addition of Ti can also form TiS and avoid as corruption The formation of the MnS of starting point is lost, improves the resistance to spot corrosion performance of steel plate.Consider, present invention design Ti content≤0.15%.
V：V can play the role of solution strengthening in steel, and on the other hand, excessive V can generate the toughness of steel plate and welding Adverse effect, therefore consider, 0~0.15% V is added in the present invention, according to technique and making choice property is needed to add.
B：The strong quenching degree elements of B, especially for the steel plate that thickness is larger, steel plate center portion can effectively be enhanced by increasing B element Cooling capacity, enhance the toughness and tenacity of steel plate center portion, make the overall performance of big thickness steel plate uniformly, stablize, but B content is excessive It is unfavorable for the toughness of steel plate, therefore, present invention design B content≤0.0025%.
Zr：Zr preferentially can combine to form sulfide in steel with S, reduce the generation of MnS, improve the resistance to spot corrosion of steel plate Energy.Micro Zr can generate said effect, but when the content of Zr is more than 0.25%, can deteriorate steel plate toughness.Therefore, it is of the invention Zr content ranges are≤0.25% in steel.
REM：The addition of REM can improve the form of sulfide, while the oxide of REM and sulfide can inhibit to weld Austenite grain grows up in Thermal Cycling.But when REM contents are more than 0.02%, by generating portion grain size more than 5 μm Field trash reduces the impact flexibility of base material and welding heat affected zone.Therefore, REM content≤0.02% in steel of the present invention.
In addition, steel chemical composition of the present invention should also meet it is claimed below：100≤Cu/S≤300,0≤(0.58Ni+ 0.84Cu-2Cr-0.12Mo)≤0.6%, matched with ensuring to obtain good intensity and toughness, it is often more important that be applicable in crude oil Upper deck corrosive environment in shipload cargo tank needs to keep suitably adding between Cu, S element and between the elements such as Ni, Cu, Cr, Mo Add ratio and strengthen steel plate corrosion resistance to form the polymer of inhibition corrosion progress to cooperate with, this is also to obtain with excellent Adapt to the key of the highly corrosion resistant steel of crude oil carrier oil cargo tank upper deck corrosive environment.
The manufacturing method of crude oil carrier oil cargo tank upper deck anti-corrosion steel plate of the present invention, includes the following steps：
1) smelt, cast
It smelted, refined and continuous casting by mentioned component；
2) roll and cool down
Slab heating temperature is 1050~1250 DEG C；940 DEG C of roughing temperature ＞, single pass reduction ratio >=8% add up pressure Rate >=40%；Final rolling temperature is 740~900 DEG C, adds up reduction ratio >=60%；With the cooldown rate water cooling of 3~25 DEG C/s after rolling To 400~650 DEG C of final cooling temperature.
Further, the crude oil carrier oil cargo tank upper deck is ferrite+a small amount of pearly-lustre with the microscopic structure of anti-corrosion steel plate Body tissue or ferrite+a small amount of acicular ferrite structure, wherein, ferritic structure occupied area ratio is 75~95%, ferrite Average grain size is 5~15 μm.
Yield strength >=235MPa of crude oil carrier oil cargo tank upper deck anti-corrosion steel plate of the present invention, tensile strength are 400~660MPa, ballistic work >=120J at -60 DEG C, corrosion resistance are 25 annual corrosion rate ECL≤2.0mm.
The present invention is in rolling and cooling technique：
It is 1050~1250 DEG C that heating temperature is controlled before present invention rolling：When heating temperature before rolling is less than 1050 DEG C, The carbonitride of the microalloy elements such as Nb, Ti cannot be dissolved completely.When heating temperature is more than 1250 DEG C, austenite crystal will be caused Grain is grown up.
940 DEG C of present invention control roughing temperature ＞, single pass reduction ratio >=8% adds up reduction ratio >=40%, and recrystallization is filled Distribution life, fining austenite grains, and avoid abnormal grain! growth and reduce base metal tenacity.
Present invention control final rolling temperature is at 740~900 DEG C, the non-recrystallization region of austenite, formed in the operation of rolling Dislocation band becomes ferrite nucleation site, and the precipitation of carbonitride is promoted to increase precipitation strength effect.When the accumulative pressure of finish rolling When lower rate is less than 60%, steel plate deformed is insufficient, and the dislocation density formed is less, and nucleation site is reduced, steel plate crystal grain refinement Effect is not notable, influences the final toughness and tenacity of steel plate.Therefore, the present invention controls final rolling temperature to add up pressure for 740~900 DEG C Rate >=60%.
The present invention after finish rolling with the cooldown rate water cooling of 3~25 DEG C/s to 400~650 DEG C of final cooling temperature, work as cooling When rate is less than 3 DEG C/s, coarse grains, pearlitic structrure is reduced, and armor plate strength reduces.When cooldown rate is more than 25 DEG C/s, Bainite structure will be formed, reduces the toughness of base material, influence is will also result in particularly with the corrosion resisting property of steel plate.Work as final cooling temperature During more than 650 DEG C, the intensity of base material cannot be met the requirements, and when final cooling temperature is less than 400 DEG C, can increase steel plate internal stress and shape Into paralympic tissue, the toughness of base material is reduced, deteriorates steel plate corrosion resistance.
For oil cargo tank upper deck, there are H2S、SO2The homogeneous corrosion of gas and the water-soluble environment of condensation loses environment, the present invention By controlling the addition of the elements such as Ni, Cu, Cr, S, P, the dense distribution of the elements such as Ni, P, Cr is formed at steel plate corrosion interface, and With reference to the H in water-soluble environment2S+SO2The corrosion scales such as gas and then formation CuS, effectively delay the lasting progress of corrosion, and control The microscopic structure of steel plate processed adds a small amount of pearlitic structrure or ferrite to add a small amount of acicular ferrite structure for ferrite, wherein, 75%≤FA% (ferritic structure occupied area ratio)≤95%, ferrite average grain size d=5~15 μm are adapted to The highly corrosion resistant steel of crude oil carrier oil cargo tank upper deck corrosive environment.
Beneficial effects of the present invention：
The present invention is in terms of composition design, by designing the addition of low C, the adjusting elements such as Mn and Ni, Cu, Cr, Mo, Steel plate corrosion interface forms the thickening Assembled distribution of the elements such as Ni, Cu and the passivating film of Cu, and densification is formed in corrosion process CuS corrosion products, effectively delay corrosion continues occur, and utilize the abundant crystal grain thinning tissue of big soft reduction process, ensure steel Plate toughness and tenacity, while aggregation of the nano-precipitation in crystal boundary is controlled, controlled rolling obtains microscopic structure and adds on a small quantity for ferrite Pearlitic structrure or ferrite add a small amount of acicular ferrite structure, wherein, 75%≤FA%≤95%, ferrite average crystal grain ruler Very little is 5~15 μm, is obviously improved corrosion resistance of the steel plate under crude oil carrier oil cargo tank upper deck corrosive environment.
Steel plate thickness≤50mm produced by the present invention, yield strength >=235MPa, tensile strength 400~660MPa, -60 DEG C Under ballistic work >=120J, have excellent low-temperature impact toughness, it is resistance under crude oil carrier oil cargo tank upper deck corrosion test environment Corrosive nature is 25 annual corrosion rate ECL≤2.0mm, available for the large-scale crude oil carrier oil cargo tank upper deck structure of manufacture and other seas Ocean, ships anticorrosion arbor etc..
Description of the drawings
Fig. 1 is experiment sample processing dimension schematic diagram in the corrosion-resistant detection of the embodiment of the present invention.
Fig. 2 is experimental rig structure diagram in the corrosion-resistant detection of the embodiment of the present invention.
Fig. 3 is the top view of Fig. 2.
Specific embodiment
With reference to embodiment and attached drawing, the present invention will be further described.
Table 1 is the ingredient of steel of the embodiment of the present invention, and table 2 is the fabrication process parameters of steel of the embodiment of the present invention, and table 3 is this hair The mechanical property and corrosion resistance of bright embodiment steel, table 4 is corrosion sample and surveys testing requirements.
Manufacturing process of the embodiment of the present invention is as follows：
According to the chemical composition of table 1 using electric furnace or converter smelting, then external refining is carried out (including RH vacuum outgas+LF Desulfurization) and continuous casting, obtain strand；Then by heating strand to 1050~1250 DEG C, roughing temperature is 950~1150 DEG C, is added up Reduction ratio is 40~60%；Final rolling temperature is 770~880 DEG C, and it is >=60% to add up reduction ratio；With 3~25 DEG C/s after finish rolling Cooldown rate water cooling to 400~650 DEG C of final cooling temperature.Specific process parameter is referring to table 2.
Full thickness of slab stretching, the impact of Charpy v-notch, the corrosion-resistant inspection of crude oil carrier oil cargo tank upper deck environment are carried out to production board It surveys, the properties of acquisition are as shown in table 3.Specific corrosion sampling and experiment process are as follows：
(1) oil ship goods tank corrosion steel upper deck corrosion experiment cycle set is 21,49,77 and 98 days, it is necessary to which tradition is right Than the corrosion resistance test of steel progress 98 days to detect the validity of experimental rig corrosion atmosphere, corrode sample and survey and examine It surveys requirement and is specifically shown in Table 4.Experiment is with sample processing dimension schematic diagram referring to Fig. 1, and dimensional units are mm in Fig. 1, and sample position exists 1/4 position of steel plate thickness of slab, as shown in Figures 2 and 3, non-dimensioning unit is mm to experimental rig structure diagram in Fig. 2.
(2) using distilled water and simulation COT gases, being passed through gas componant is：(4 ± 1) %O2- (13 ± 2) %CO2-(100 ±10)ppmSO2-(500±50)ppmH2S- (83 ± 2) %N2, specimen surface has enough distances to prevent from distilling apart from the water surface The splashing of water.The flow of gas is：It is preceding 24 it is small when at least 100mL/ minutes, 24 it is small when after at least 20mL/ minutes.
(3) using cyclic corrosion experiment condition, the single cycle time is 1 hour, and wherein sample continues at 50 ± 2 DEG C 19 ± 2hr, then continues 3 ± 2hr at 25 ± 2 DEG C, the temperature transition time be at least 1 it is small when.Sample steams under the conditions of 50 DEG C The temperature of distilled water is not higher than 36 DEG C.
(4) size and weight of sample are recorded before test, weight loss (original weight and weight after test are recorded after experiment Difference), traditional steel be Wc, COT steel is W21、W49、W77、W98。
The corrosion loss amount (Corrosion Lost) of steel is calculated as follows：
CLi(mm)=10 × Wi/(S×D)
Wherein, S accumulates (cm for specimen surface2), D is the density (g/cm of sample3), WiFor weight loss (g), i is W subscripts, Corresponding C, 21,49,77,98 grade numbers.
If 0.05mm≤CLc≤ 0.11mm (the annual 0.2-0.4mm of corresponding corrosion rate), then device experiment condition is closed Reason.Simulate H in the gas of COT2The concentration of S can be according to CLcValue is adjusted.
COT steel corrosions lose formula：CL=A × tB
Wherein, A and B is coefficient, can be according to W21、W49、W77、W98Be calculated using least square method, t for the time (my god).
Corrosion loss after finally estimating 25 years：ECL (mm)=A × (25 × 365)B。
As shown in Table 3, the present invention can manufacture steel plate thickness≤50mm, yield strength >=235MPa, tensile strength 400- 660MPa, ballistic work >=120J at -60 DEG C, the crude oil carrier oil cargo tank upper deck of elongation percentage (A) >=30%, iron in microstructure Ferritic tissue occupied area ratio FA% is 75~95%, and ferrite average grain size d is 5~15 μm, corrosion test ring Corrosion resistance is 25 annual corrosion rate ECL≤2.0mm under border, available for the large-scale crude oil carrier oil cargo tank upper deck structure of manufacture and Other oceans, ships anticorrosion arbor etc..

Claims (7)

1. a kind of crude oil carrier oil cargo tank upper deck anti-corrosion steel plate, ingredient percent are：C：0.015~0.15%, Si：0.10~0.50%, Mn：0.05~2.5%, P：0.005~0.030%, S≤0.008%, Cr：0.05~1.5%0%, Mo：0.003~1.00%, Cu：0.05~2.00%, Ni：0.10~2.50%, Al：0.01~0.12%, and above-mentioned element needs Meet following relation simultaneously：100≤Cu/S≤300,0≤(0.58Ni+0.84Cu-2Cr-0.12Mo)≤0.6%, surplus Fe With inevitable impurity.
2. crude oil carrier oil cargo tank upper deck anti-corrosion steel plate according to claim 1, which is characterized in that the crude oil carrier Also contain in the ingredient of oil cargo tank upper deck anti-corrosion steel plate：0 ＜ Nb≤0.15%, 0 ＜ Ti≤0.15%, 0 ＜ V≤ At least one of 0.15%, 0 ＜ B≤0.0025%, 0 ＜ Zr≤0.25%, 0 ＜ REM≤0.020%, with mass percent Meter.
3. crude oil carrier oil cargo tank upper deck anti-corrosion steel plate according to claim 1 or 2, which is characterized in that the original Oil carrier oil cargo tank upper deck is ferrite+a small amount of pearlitic structrure or ferrite+a small amount of pin with the microscopic structure of anti-corrosion steel plate Columnar ferrite tissue, wherein, ferrite occupied area ratio is 75~95%, and ferrite average grain size is 5~15 μm.
4. according to claim 1-3 any one of them crude oil carrier oil cargo tank upper deck anti-corrosion steel plates, which is characterized in that institute State yield strength >=235MPa of crude oil carrier oil cargo tank upper deck anti-corrosion steel plate, tensile strength is 400~660MPa, -60 DEG C Lower ballistic work >=120J, corrosion resistance are 25 annual corrosion rate ECL≤2.0mm.
5. such as the manufacturing method of claim 1-4 any one of them crude oil carrier oil cargo tank upper deck anti-corrosion steel plates, bag Include following steps：
1) smelt, cast
Ingredient as described in claim 1 or 2 smelted, is refined and continuous casting；
2) roll and cool down
Slab heating temperature is 1050~1250 DEG C；940 DEG C of roughing temperature ＞, single pass reduction ratio >=8%, accumulative reduction ratio >= 40%；Final rolling temperature is 740~900 DEG C, adds up reduction ratio >=60%；With the cooldown rate water cooling of 3~25 DEG C/s to end after rolling Cold 400~650 DEG C of temperature.
6. the manufacturing method of crude oil carrier oil cargo tank upper deck anti-corrosion steel plate according to claim 5, which is characterized in that The crude oil carrier oil cargo tank upper deck with the microscopic structure of anti-corrosion steel plate be ferrite+a small amount of pearlitic structrure or ferrite+ A small amount of acicular ferrite structure, wherein, ferrite occupied area ratio is 75~95%, and ferrite average grain size is 5~15 μ m。
7. the manufacturing method of crude oil carrier oil cargo tank upper deck anti-corrosion steel plate according to claim 5 or 6, feature exist In, invent yield strength >=235MPa of the crude oil carrier oil cargo tank upper deck anti-corrosion steel plate, tensile strength for 400~ 660MPa, ballistic work >=120J at -60 DEG C, corrosion resistance are 25 annual corrosion rate ECL≤2.0mm.
CN201611077393.1A 2016-11-30 2016-11-30 A kind of crude oil carrier oil cargo tank upper deck anti-corrosion steel plate and its manufacturing method Pending CN108118249A (en)

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