CN105745347B - Petroleum tank steel and petroleum tank - Google Patents

Petroleum tank steel and petroleum tank Download PDF

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Publication number
CN105745347B
CN105745347B CN201480062745.9A CN201480062745A CN105745347B CN 105745347 B CN105745347 B CN 105745347B CN 201480062745 A CN201480062745 A CN 201480062745A CN 105745347 B CN105745347 B CN 105745347B
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steel
corrosion
petroleum tank
quality
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CN105745347A (en
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钓之郎
小森务
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JFE Engineering Corp
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NKK Corp
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    • 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
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    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/08—Ferrous alloys, e.g. steel alloys containing nickel
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    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
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    • C22C38/16—Ferrous alloys, e.g. steel alloys containing 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
    • C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
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Abstract

A kind of petroleum tank steel, its make steel into following compositions are grouped into, thus the resistance to local corrosion both of which of the bottom plate of the resistance to whole face corrosivity of the top plate of the petroleum tank such as oil carrier oil groove portion and petroleum tank is excellent, and above-mentioned composition is：In terms of quality %, contain C：0.03%~0.18%, Si：0.03%~1.50%, Mn：0.1%~2.0%, P：Less than 0.025%, S：Less than 0.010%, Al：0.005%~0.10%, N：Less than 0.008% and Cu：0.05%~0.4%, remaining part is made up of Fe and inevitable impurity, also, makes the dislocation density of steel in the scope with meeting following formula (1) in the relation of Cu contents, α≤4 × 1016× [%Cu]2.8(1) [%Cu] is the Cu contents (quality %) in steel.

Description

Petroleum tank steel and petroleum tank
Technical field
The present invention relates to the oil groove for the crude oil carrier for forming welded steel, for conveying or storing the tank of crude oil (hereafter In be referred to as " petroleum tank ").In particular to alleviate whole face corrosion caused by the top of petroleum tank or side of sidewall portion and The petroleum tank of local corrosion caused by the bottom of petroleum tank is with steel and the petroleum tank being made up of the steel.
It should be noted that the petroleum tank of the present invention includes steel plate, sheet metal and shaped steel with steel.
Background technology
It is known to be produced in steel used in the petroleum tank inner surface of oil carrier, particularly the upper deck back side and side wall upper part Whole face corrosion.The reason for as the whole face corrosion occurs, following items etc. can be enumerated.
(1) repeated in the condensation of surface of steel plate and drying (dry and wet) caused by diurnal temperature difference；
(2) it is used for explosion-proof and is enclosed the inert gas in petroleum tank (with about 4vol%O2, about 13vol%CO2, about 0.01vol%SO2, remaining part N2To represent exhaust etc. of the boiler of composition or engine) in O2、CO2、SO2To the molten of dew Enter；
(3) from the H of crude oil volatilization2The corrosive gas such as S dissolve in dew；
(4) residual of the seawater used in petroleum tank cleaning.
These reasons can also peep from herein below to be known：Generally, in the dock of the every 2.5 years real ships carried out checks, Sulfate ion, chloride ion are detected in the dew of highly acid.
In addition, if the iron rust generated by corrosion makes H as catalyst2S is aoxidized, then solid S is generated in iron with stratiform In rust, but these corrosion products are easily peeled off and come off, and are deposited in petroleum tank bottom.Therefore, present situation be dock inspection in, A large amount of expenses are expended to carry out the repairing on tank top, the recovery of pot bottom deposit.
On the other hand, for the steel used in the bottom plate of the petroleum tank in oil carrier etc., thought to pass through crude oil in the past The corrosion of the effect of corrosion inhibition of itself, the protective coating (oil reservoir) from crude oil formed in petroleum tank inner surface suppresses to make With it will not produce corrosion.But the local corruption of bowl-type can be produced in the steel of tank bottom by being found out by nearest research Lose (spot corrosion).
The reason for as the local corrosion occurs, following items etc. can be enumerated.
(1) presence for the agglutinating water that the salt high concentration dissolving using sodium chloride as representative forms；
(2) oil reservoir caused by excessively cleaning departs from；
(3) high concentration of the sulfide contained in crude oil；
(4) the explosion-proof O with inert gas of dew is dissolved in2、CO2、SO2Deng high concentration.
In fact, when the dock of real ship checks, the water being trapped in petroleum tank is analyzed, as a result detects height The chloride ion and sulfate ion of concentration.
However, the most efficient method for preventing whole face corrosion as described above and local corrosion is by real in steel surface Apply recoating and cover (heavy coating), steel are separated from corrosive environment.But for the coating operation of petroleum tank, it is applied The area of cloth is huge, further, since film deteriorates, causes just to need within about 10 years to coat again 1 time, so checking, in coating Generate huge expense.And then it is noted through recoating the impaired part of the film covered under the corrosive environment of petroleum tank on the contrary Can promoting corrosion.
For etching problem as described above, it is proposed that some to improve crude oil by improving the corrosion resistance of steel in itself The technology of corrosion resistance of the tank under corrosive environment.
Such as following technology is disclosed in patent document l：C will be contained in terms of quality %：0.001%~0.2%, Si： 0.01%~2.5%, Mn：0.1%~2%, P：Less than 0.03%, S：Less than 0.02%, Cu：0.01%~1.5%, Al： 0.001%~0.3%, N：0.001%~0.01% and then contain Mo：0.01%~0.5% and W：1 in 0.01%~1% Kind or 2 kinds, the steel that are made up of Fe and inevitable impurity of remaining part are when being welded to one another and forming welding point, with welding metal In Cu, Mo, W content meet that the mode of following 3 formulas forms welding point.
Cu contents (quality %) >=0.15 of Cu contents (quality %)/steel of 3 >=welding metal
3 >=(Mo contents+W content (quality %) of welding metal)/(Mo contents+W contents (quality %) of steel) >= 0.15
Cu contents (quality %)≤0.5 of Cu contents (quality %)-steel of -0.3≤welding metal
In addition, Patent Document 2 discloses following technology：C will be contained in terms of quality %：0.001%~0.2%, Si： 0.01%~2.5%, Mn：0.1%~2%, P：Less than 0.03%, S：Less than 0.02%, Cu：0.01%~1.5%, Al： 0.001%~0.3%, N：0.001%~0.01% and then contain Mo：0.01%~0.5% and W：1 in 0.01%~1% Kind or 2 kinds, the steel that are made up of Fe and inevitable impurity of remaining part are when being welded to one another and forming crude oil tank, with welding metal In Cu, Mo, W content meet that the mode of following 2 formulas forms welding point.
Cu contents (quality %) >=0.15 of Cu contents (quality %)/steel of 3 >=welding metal
3 >=(Mo contents+W content (quality %) of welding metal)/(Mo contents+W contents (quality %) of steel) >= 0.15
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2005-21981 publications
Patent document 2：Japanese Unexamined Patent Publication 2005-23421 publications
The content of the invention
The invention problem to be solved
In order to protect the marine environment and crude oil carrier is safely navigated by water, crude oil is managed so that crude oil is not from original Tank leakage is critically important, it is necessary to the generation of through hole caused by preventing the corrosion in petroleum tank.Therefore, during every docking in 2.5 years pair The corrosion condition of petroleum tank bottom plate is investigated, and implements repairing for spot corrosion of the depth more than 4mm, as in reduction crude oil carrier Suppress one of means that spot corrosion of the depth more than 4mm occurs in the case of maintenance management expense, it is proposed that using resistance in oil carrier Corrode the scheme of steel.
But in the technology described in patent document l and 2, it is difficult to by caused office in oil carrier bottom plate and welding point Corrode (spot corrosion) and suppressed between 2.5 years in below 4mm in portion.That is in real ship Investigation On Corrosion in recent years, find out and resulted from The pH of solution inside the spot corrosion of oil carrier bottom plate and weld part is less than 1.0.It is generally known that be steel in Acidic Liquid Corrosion rate is controlled by hydrogen reduction reaction, and corrosion rate significantly increases while pH is reduced.Therefore, as above-mentioned patent document As described in l and 2 embodiment in the immersion test under the conditions of pH2.0, do not reflect the corrosive environment of real ship fully.
On the other hand, on the supression in whole face corrosion caused by oil carrier top plate, in the hair described in patent document 1 and 2 Also it is 0.11mm/ or so in the case that corrosion rate is minimum in bright example.On the other hand, in the case of the crude oil carrier of reality, Its durable years is 25 years, and the design corrosion allowance of oil carrier top plate is every one side 2mm or so, thus is required suitable for the resistance to of top plate The corrosion rate for corroding steel is below 0.08mm/.Particularly, for being welded on the small aggregate (ロ of cephalocaudal direction of oil carrier top plate Application ジ) for, because two sides is in the corrosive environment inside oil carrier, thus it is being applicable with the corrosion more than 0.1mm/ , it is necessary to be repaired in the case of the corrosion resisting steel of speed, so can not expect in the technology described in patent document 1 and 2 Omit coating.
The present invention be in view of above-mentioned present situation and developed, its object is to provide a kind of petroleum tanks such as oil carrier oil groove portion The resistance to whole face corrosivity of top plate and the excellent petroleum tank of both resistance to local corrosions of bottom plate of petroleum tank with steel and The petroleum tank being made up of the steel.
For solving the scheme of problem
Inventor's above-mentioned problem of solution has carried out in-depth study repeatedly.
As a result find, by suitably control steel composition form and steel dislocation density, particularly with Cu amounts or Sn Dislocation density is suitably controlled in the relation of amount, can significantly mitigate above-mentioned whole face corrosion and local corrosion.
The present invention is based on above-mentioned opinion.
That is, main points of the invention form as follows.
1. a kind of petroleum tank steel, the steel are contained in terms of quality %
C：0.03%~0.18%,
Si：0.03%~1.50%,
Mn：0.1%~2.0%,
P：Less than 0.025%,
S：Less than 0.010%,
Al：0.005%~0.10%,
N：Less than 0.008% and
Cu：0.05%~0.4%,
Remaining part is made up of Fe and inevitable impurity, and the dislocation density α of the steel in the relation of Cu contents with meeting Following formula (1).
α≤4×1016× [%Cu]2.8---(1)
Wherein, [%Cu] is the Cu contents (quality %) in steel.
2. the petroleum tank steel as described in above-mentioned 1, wherein, above-mentioned steel are further contained in terms of quality %
Sn：0.005%~0.4%,
Also, the dislocation density α of steel is with meeting following formula (2) in the relation of Cu and Sn contents.
α≤4×1016× ([%Cu]+[%Sn])2.8---(2)
Wherein, [%Cu], [%Sn] are respectively Cu, Sn content (quality %) in steel.
3. the petroleum tank steel as described in above-mentioned 1 or 2, wherein, above-mentioned steel are further contained in terms of quality % to be selected from
Ni：0.005%~0.4%,
Cr：0.01%~0.2%,
Mo：0.005%~0.5%,
W：0.005%~0.5%,
Sb：0.005%~0.4%,
Nb：0.001%~0.1%,
Ti：0.001%~0.1%,
V：0.002%~0.2%,
Ca：0.0002%~0.01%,
Mg：0.0002%~0.01% and
REM：0.0002%~0.015%
In it is one kind or two or more.
4. a kind of petroleum tank, it manufactures to obtain using the petroleum tank any one of above-mentioned 1~3 with steel.
The effect of invention
In accordance with the invention it is possible to effectively suppress the oil groove in crude oil carrier, conveying or store caused by tank of crude oil etc. Whole face corrosion or local corrosion, it is industrially exceedingly useful.
Brief description of the drawings
Fig. 1 is the figure for illustrating to be used in embodiments of the invention the experimental rig of whole face corrosion test.
Fig. 2 is the figure for illustrating to be used in embodiments of the invention the experimental rig of pitting test.
Embodiment
Below, the present invention is illustrated.
Said firstly, for the reasons why the petroleum tank of the present invention is defined into above range with the composition composition of steel It is bright.It should be noted that as long as no special declaration, then " % " relevant with composition expression refers to quality %.
C：0.03%~0.18%
C is the element for the intensity for improving steel, in the present invention, in order to ensure desired intensity (490MPa~ 620MPa), the C of addition more than 0.03%.But the C added more than 0.18% can make the tough of weldability and welding heat affected zone Property reduce.Thus, the scope that C amounts are 0.03%~0.18% is made.Preferably 0.06%~0.16% scope.
Si：0.03%~1.50%
Si is as deoxidier and the element that adds, and to improving the effective element of intensity of steel.Therefore, in the present invention In, in order to ensure desired intensity, the Si of addition more than 0.03%.But the Si added more than 1.50% can make the tough of steel Property reduce.Thus, Si amounts are 0.03%~1.50% scope.Preferably 0.05%~0.40% scope.
Mn：0.1%~2.0%
Mn is the element for the intensity for improving steel, in the present invention, in order to obtain desired intensity, addition more than 0.1% Mn.But the Mn added more than 2.0% can reduce the toughness of steel and weldability.Thus, Mn amounts are 0.1%~2.0% Scope.Preferably 0.80%~1.60% scope.
P：Less than 0.025%
P is to make the harmful element that the toughness of steel reduces in cyrystal boundary segregation, is preferably reduced as far as P.Particularly, if Containing the P for having more than 0.025%, then toughness is greatly reduced.In addition, if containing the P for having more than 0.025%, then can give in tank oil groove Corrosion resistance bring deleterious effect.Thus, P amounts are less than 0.025%.Preferably less than 0.015%.
S：Less than 0.010%
S can form the MnS as non-metallic inclusion, turn into the starting point of local corrosion, be to reduce resistance to local corrosion Harmful element, be preferably reduced as far as S.Particularly, if containing the S for having more than 0.010%, resistance to local corrosion can be caused Property significantly reduces.Thus, the permission upper limit of S amounts is 0.010%.Preferably less than 0.005%.
Al：0.005%~0.10%
Al is as deoxidier and the element that adds, in the present invention, the Al of addition more than 0.005%.But if addition Al more than 0.10%, then the toughness of steel reduces, so the upper limit of Al amounts is 0.10%.
N：Less than 0.008%
N is the harmful element for reducing toughness, is preferably reduced as far as N.Particularly, if containing having more than 0.008% N, then the reduction of toughness becomes big, so the upper limit of N amounts is 0.008%.
Cu：0.05%~0.4%
Cu can not only improve the intensity of steel, and be present in the rust generated by the corrosion of steel, can suppress to promote corrosion Cl- ions diffusion, thus be with improve corrosion resistance effect necessary addition element.These effects are less than in addition Can not fully it be obtained during 0.05% Cu, on the other hand, if Cu of the addition more than 0.4%, except improving corrosion resistance Outside effect saturation, the problems such as also causing face crack in hot-working.Thus, Cu amounts are 0.05%~0.4% scope. Preferably 0.06%~0.35% scope.
Sn：0.005%~0.4%
Sn corrosion when enter rusty scale in, formed densification rusty scale, so as to contribute to suppress steel local corrosion and The useful element of whole face corrosion.The effect shows when adding more than 0.005% Sn, but adds the Sn more than 0.4% When, not only low-temperature flexibility is reduced, and the generation of defect is also resulted in welding.Therefore, Sn amounts are 0.005%~0.4% model Enclose.Preferably 0.01%~0.2% scope, more preferably 0.01%~0.1% scope.
More than, basis is illustrated, but in the present invention, in addition to mentioned component, can also suitably contain Element described below.
Cr：0.01%~0.2%
Cr moves along with the progress of corrosion into rusty scale, by separating Cl-Suppress Cl to the intrusion of rusty scale-To rusty scale Concentrated with the interface of matrix, so as to contribute to the raising of corrosion resistance.In addition, when steel surface is coated with the priming paint containing Zn, Cr, the Zn that can be formed centered on Fe composite oxides, Zn is set to be present in surface of steel plate for a long time, thus, it is possible to tremendous Improve corrosion resistance in ground.The effect above contains high salt concentration what is separated the base plate as oil carrier oil groove with from crude oil oil The part of the liquid contact divided is particularly significant, by implementing the prime treatment containing Zn to the steel of the above-mentioned part containing Cr, So as to which compared with the steel for not containing Cr, corrosion resistance especially can be improved.For the effect of the Cr, if Cr amounts are less than 0.01% insufficient, on the other hand, the degraded toughness of weld part can be made if more than 0.2%.Therefore, Cr amounts be 0.01%~ 0.2% scope.Preferably 0.05%~0.20% scope.
Mg：0.0002%~0.01%
The toughness that Mg not only facilitates welding heat affected zone improves, and also has in the rust for being present in and being generated by the corrosion of steel And improve the effect of corrosion resistance.These effects can not be obtained fully when Mg amounts are less than 0.0002%, on the other hand, if addition Mg more than 0.01%, the reduction of toughness can be caused on the contrary, thus Mg amounts are 0.0002%~0.01% scope.
Ni：0.005%~0.4%
Ni has the rust Particle pollution for making generation and improves the corrosion resistance under naked state and yellow zinc chromate primer paint is implemented The effect of corrosion resistance in the state of epoxies coating.Therefore, in the case where needing further to improve corrosion resistance, add Add Ni.The effect above shows when adding more than 0.005% Ni.On the other hand, even if Ni of the addition more than 0.4%, Its effect also saturation.Thus, Ni is preferably added in 0.005%~0.4% scope.Preferably 0.08%~0.35% Scope.
Sb：0.005%~0.4%
Sb also has in addition to the effect with the spot corrosion for suppressing oil carrier oil groove portion bottom plate and suppresses oil carrier upper deck portion The effect of whole face corrosion.The effect above shows when adding more than 0.005% Sb.Even if addition is more than 0.4% Sb, its effect also saturation.Thus, Sb is preferably added with 0.005%~0.4% scope.
Nb：0.001%~0.1%, Ti：0.001%~0.1%, V：0.002%~0.2%
Nb, Ti and V be improve steel strength element, can intensity as needed properly select addition.In order to The effect above is obtained, preferably Nb, Ti adds more than 0.001%, V additions more than 0.002% respectively.But if Nb, Ti add respectively Add and added more than 0.1%, V more than 0.2%, then toughness can reduce.Thus, Nb, Ti and V are preferably added in above range respectively Add.
Ca：0.0002%~0.01%, REM：0.0002%~0.015%
Toughness raisings of the Ca and REM to welding heat affected zone is effective, can be added as needed.The effect above In addition Ca：More than 0.0002%, REM：Obtained when more than 0.0002%, if but adding the Ca more than 0.01% or adding super 0.015% REM is crossed, then can cause the reduction of toughness on the contrary.Thus, Ca and REM is preferably added in above range respectively.
Mo：0.005%~0.5%, W：0.005%~0.5%
Mo and W also has in addition to the effect with the spot corrosion for suppressing oil carrier oil groove portion bottom plate and suppresses oil carrier upper deck The effect of the whole face corrosion in portion.The Mo and W effect shows when adding more than 0.005% respectively, if but exceeding 0.5%, then the effect reach saturation.Thus, Mo and W amounts are preferably respectively 0.005%~0.5% scope.More preferably 0.01%~0.3%, more preferably 0.02%~0.2% scope.
It should be noted that Mo and W have the reasons why effect of raising corrosion resistance as described above as follows：Along with Steel plate corrosion and generate MoO in the rust that generates4 2-And WO4 2-, due to the MoO4 2-And WO4 2-Presence, chloride ion can be suppressed Invade surface of steel plate.Additionally, it is believed that by by MoO4 2-And WO4 2-To inhibitory action caused by the absorption of steel surface, also may be used Suppress the corrosion of steel.
Then, the dislocation density of steel specified in the present invention is illustrated.
The present invention corrosion resisting steel by the way that various corrosion resistance elements are added in steel with ormal weight as described above, from And in the rusty scale of the steel surface formed under corrosive environment of the various corrosion resistance elements in oil carrier oil groove portion's bottom plate and top plate Concentration, suppresses the diffusion of various corrosion factors, reduces the corrosion rate of steel.
On the other hand, for steel, the formation of the dislocation from its manufacturing process can not be avoided, the dislocation is in thermodynamics On be unstable, therefore under corrosive environment as dissolved ferric iron anode site play function.It is formed at the table of corrosion resisting steel The rusty scale in face has protectiveness, has the effect for the corrosion rate for reducing steel, but its function is not fully, the steel under rusty scale In the case that the dislocation density on material surface is big, the protectiveness of sufficient rusty scale can not be obtained, and then can not be obtained gratifying Corrosion resistance.
The protectiveness of rusty scale mainly determines by the Cu concentration in steel, or in the case of containing Sn, by the dense of Cu and Sn Degree determines that Cu and Sn concentration is more high, can obtain better protectiveness.Therefore, the dislocation density allowed is also according to Cu amounts, Sn Measure and change.
Then, inventor investigates for protectiveness and Cu amounts, the relation of Sn amounts of rusty scale, as a result finds out, according to steel In Cu amounts, Sn amounts, by dislocation density α controls in the scope given by following formula (1), (2), it can thus be concluded that to good rusty scale Protectiveness.
α≤4×1016× [%Cu]2.8---(1)
α≤4×1016× ([%Cu]+[%Sn])2.8---(2)
Wherein, [%Cu], [%Sn] are respectively Cu, Sn content (quality %) in steel.
The petroleum tank of the present invention is preferably manufactured by the following method with steel.
That is, steel of the invention are preferably as follows manufacture：Using refinery practice known to converter or electric furnace, vacuum outgas etc., Melting is carried out to the steel for being adjusted to mentioned component composition, steel billet is made using continuous casting process or ingot casting-split rolling method method (slab), then the material is reheated, then carries out hot rolling, so as to which steel plate, sheet metal and shaped steel etc. be made.
Relation reheating temperature before hot rolling is preferably 900 DEG C~1200 DEG C of temperature.Because heating-up temperature is less than 900 DEG C when, deformation drag is big, it is difficult to carries out hot rolling；On the other hand, if heating-up temperature is more than 1200 DEG C, austenite crystal is thick Change, cause the reduction of toughness, in addition, the oxidization burning loss (scale loss) caused by oxidation also becomes notable, yield rate Reduce.The scope that preferred heating-up temperature is 1000 DEG C~1150 DEG C.
In addition, when being rolled into the steel of desired shape, size in hot rolling, it is 700 DEG C preferably to make finish rolling end temp More than.Because when finish rolling end temp is less than 700 DEG C, the deformation drag of steel becomes big, rolling load increase, it is difficult to carry out Rolling, or the stand-by period produced untill rolling temperature as defined in rolling stock reaches, so rolling efficiency reduces.
The cooling of steel after hot rolling can utilize any means in air cooling, acceleration cooling, it is desirable to obtain higher intensity When, preferably carry out acceleration cooling.It should be noted that when accelerate cooling, cooling velocity is preferably set to 2 DEG C/s~80 DEG C/s, will cooling stop temperature being set to 650 DEG C~400 DEG C.Because cooling velocity is less than 2 DEG C/s, cooling stops temperature and surpassed When crossing 650 DEG C, accelerate cooling effect it is small, sufficient high intensity can not be realized, on the other hand, cooling velocity more than 80 DEG C/ S, when cooling stops temperature less than 400 DEG C, the toughness of obtained steel is reduced, or the shape of steel is deformed.
Embodiment
Steel is made to carrying out melting with the steel formed in table 1 with the various composition shown in No.1~37 with vacuum melting furnace Ingot, or melting is carried out with converter, plate slab is made by continuously casting, after they are heated into 1150 DEG C, with shown in table 2 Finish rolling end temp implement hot rolling, be made thickness of slab be 25mm steel plate after, be cooled to 10 DEG C/s of water cooling speed shown in table 2 Cooling stop temperature.
Condensation test and acid resistance test are carried out for the steel plate of so obtained No.1~37, evaluates its corrosion resistance. The dislocation density of steel is also determined in the lump.
That is, according to following main points, be simulated respectively the upper deck back side whole face corrosion test (condensation test) and Simulate the local corrosion resistance test (acid resistance test) of oil carrier backplane environment.
(1) the whole face corrosion test (condensation test) of oil carrier upper deck environment is simulated
In order to evaluate the corrosion resistance for being directed to the whole face at the oil carrier upper deck back side and corroding, for the thick steel of above-mentioned No.1~37 Plate, wide 25mm × long 60mm × thick 5mm rectangular particles are cut out from surface 1mm position respectively, with the sand paper of 600 granularities to it Surface is ground.Then, with the rubber belt sealing back side and end face, it is not corroded, use the corrosion testing apparatus shown in Fig. 1 Carry out whole face corrosion test.
The corrosion testing apparatus is made up of corrosion test groove 2 and temperature control panel 3, the implantation temperature in corrosion test groove 2 30 DEG C of water 6 is remained, in addition, importing CO by 13vol% by importing flue 4 in the water 62, 4vol% O2、 0.01vol% SO2, 0.05vol% H2S, remaining part N2The mixed gas of composition, tried with oversaturated vapor full of corrosion In check of foundation subsoil 2, the corrosive environment at the petroleum tank upper deck back side is reproduced.Also, corrosion test piece is set at the upper back side of the test flume 1, for the corrosion test piece 1, by built-in having heaters and the temperature control panel 3 of cooling device, by 25 DEG C × 1.5 hours+ 50 DEG C × 22.5 hours temperature changes as l cycle, assign 21,49,77 and 98 days repeatedly, produce the surface of test film 1 Raw dew, causes whole face to be corroded.In Fig. 1,5 represent the discharge flue by test flume.
After above-mentioned corrosion test, the rust on each test film surface is removed, is obtained by testing front and rear mass change because corroding institute The Mass lost of cause, the thickness of slab decrement (corrosion rate of one side) being converted into by the value in 1 year.Also, during being tested by 4 Value obtain 25 years after prediction waste, etching extent be below 2mm in the case of, it is good to be evaluated as resistance to whole face corrosivity (zero), in the case of more than 2mm, it is bad (×) to be evaluated as resistance to whole face corrosivity.
(2) local corrosion test's (acid resistance test) of oil carrier oil groove portion backplane environment is simulated
In order to evaluate the corrosion resistance for the spot corrosion for being directed to oil carrier oil groove portion bottom plate, for the steel plate of above-mentioned No.1~37, Wide 25mm × long 60mm × thick 5mm rectangular particles are cut out from surface 1mm position respectively, with the sand paper of 600 granularities to its table Face is ground.
Then, prepare and the 10%NaCl aqueous solution is adjusted to the examination that Cl ion concentrations are 10%, pH is 0.85 with concentrated hydrochloric acid Solution is tested, line is passed through and is opened in test film topHole and hung, for each test film, carry out 2L's The corrosion test of 168 hours is impregnated in testing liquid.It should be noted that testing liquid is heated in advance, is maintained at 30 DEG C, often 24 hours testing liquids more renewed.
The device used in above-mentioned corrosion test is shown in Fig. 2.The corrosion testing apparatus is corrosion test groove 8, thermostat 9 Dual structure device, above-mentioned testing liquid 10 is added into corrosion test groove 8, test film 7 is hung with line 11 and impregnated In wherein.The temperature of testing liquid 10 is kept by adjusting the temperature for the water 12 for being added to thermostat 9.
After above-mentioned corrosion test, generation is removed after the rust on test film surface, front and rear of poor quality of experiment is obtained, by the difference Converted according to whole table area, obtain the thickness of slab decrement (corrosion rate on two sides) of every 1 year.As a result, it is by corrosion rate Below 1.0mm/ situation is evaluated as resistance to local corrosion well (zero), and situation of the corrosion rate more than 1.0mm/ is evaluated It is bad (×) for resistance to local corrosion.
(3) measure of the dislocation density of steel
The test film of No.1~37 after acid resistance test has been carried out cuts out 20 × 20 × 5mmt test film, by script The face of the surface 1mm sides of steel is as aspect of measure.Using X-ray diffraction measure device, determine (110) of steel, (211) and (220) diffraction maximum in face, the respective θ of the angle of diffraction 2 and half width β m is obtained respectively for each test film.
Transverse axis is sin θ/λ, and the longitudinal axis is β cos θ/λ, and the measurement result of above-mentioned each crystal plane is mapped.
Wherein, λ represents X-ray wavelengthβ represents real diffraction half width at half-maximum (HWHM), according to (3) formula by actual measurement half-breadth Spend β m and obtained without strain half width β s.
It should be noted that as without strain standard specimen, having used Si powder standard specimen, (the β s at peak position are by base Obtained in the approximate interpolation calculation of parabola).
β=(β m2-βs2)0.5---(3)
For 3 points above-mentioned of curve, curve of approximation is drawn using least square method, as shown in (4) formula, by its slope Strain stress is obtained, dislocation density α is obtained by (5) formula.
β cos θ/λ=0.9/D+2 ε sin θs/λ --- (4)
The ε of α=14.42/b2---(5)
Wherein, b represents Bai Shi vector 0.25nm,
D represents crystallite dimension.
Resulting result is remembered in table 2 in the lump.
Table 2
As shown in table 2, meet that steel plate No.1~4 of the condition of the present invention, 7~10,13~36 are simulating upper deck Good corrosion resistance is shown in the whole face corrosion test at the back side and the local corrosion test for simulating oil carrier backplane environment.
On the other hand, steel plate No.5,6,11,12,37 of the condition of the present invention are unsatisfactory in any corrosion resistance test In can not obtain good result.
Symbol description
1st, 7 corrosion test piece
2nd, 8 corrosion test groove
3 temperature control panels
4 import flue
5 discharge flues
6th, 12 water
9 thermostats
10 testing liquids
11 lines

Claims (4)

1. a kind of petroleum tank upper plate and bottom plate steel, the steel are contained in terms of quality %
C：0.03%~0.18%,
Si：0.03%~1.50%,
Mn：0.1%~2.0%,
P：Less than 0.025%,
S：Less than 0.010%,
Al：0.005%~0.10%,
N：Less than 0.008%,
Cu：0.05%~0.4%,
Ca：0.0002%~0.01% and
Cr：0.05%~0.2%,
Remaining part is made up of Fe and inevitable impurity, and the dislocation density α of the steel in the relation of Cu contents with meeting following formula (1),
α≤4×1016× [%Cu]2.8---(1)
Wherein, [%Cu] is the Cu contents in steel, and unit is quality %, and dislocation density α unit is /m2。
2. petroleum tank upper plate as claimed in claim 1 and bottom plate steel, wherein, the steel are further contained in terms of quality % Have
Sn：0.005%~0.4%,
Also, the dislocation density α of steel is with meeting following formula (2) in the relation of Cu and Sn contents,
α≤4×1016× ([%Cu]+[%Sn])2.8---(2)
Wherein, [%Cu], [%Sn] are respectively Cu, Sn content in steel, and unit is quality %, dislocation density α unit For/m2。
3. petroleum tank upper plate as claimed in claim 1 or 2 and bottom plate steel, wherein, the steel enter one in terms of quality % Step, which contains, to be selected from
Ni：0.005%~0.4%,
Mo：0.005%~0.5%,
W：0.005%~0.5%,
Sb：0.005%~0.4%,
Nb：0.001%~0.1%,
Ti：0.001%~0.1%,
V：0.002%~0.2%,
Mg：0.0002%~0.01% and
REM：0.0002%~0.015%
In it is one kind or two or more.
4. a kind of petroleum tank, it is made to using the petroleum tank upper plate any one of claims 1 to 33 and bottom plate with steel Arrive.
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