KR100548116B1 - Crude oil tank having welding coupling excellent in corrosion resistance - Google Patents

Abstract

In the present invention, crude oil tanks including weld couplings are almost equivalent to crude oil corrosion occurring in a forced oil tank, and exhibit excellent corrosion resistance, and are capable of suppressing the generation of corrosion products (sludge) containing solid sulfur. It is to provide an oil bath, and in terms of mass% as a basic component, C: 0.001-0.2%, Si: 0.01-2.5%, Mn: 0.1-2%, Cu: 0.01-1.5%, Al: 0.001-0.1%, N: It is a crude oil tank which welded the steel member containing 0.001 to 0.01%, Mo: 0.01 to 0.5%, W: 0.02 to 1%, or two types, Cu content / of the weld metal of a weld coupling part. By setting the Cu content of the steel member and the (Mo content of the weld metal + W content) / (Mo content of the steel member + W content) to 0.15 to 3, local corrosion of the coupling is suppressed to improve the corrosion resistance of the entire crude oil tank. Made .

Dew point adjustment tank, test chamber, test piece, constant temperature heater plate, heater controller

Description

Crude oil tank with welded coupling with excellent corrosion resistance {CRUDE OIL TANK HAVING WELDING COUPLING EXCELLENT IN CORROSION RESISTANCE}

BRIEF DESCRIPTION OF THE DRAWINGS The figure which shows typically the test piece collection method in the corrosion resistance test of a coupling.

2 is a configuration diagram of a corrosion test apparatus.

3 is a diagram illustrating a temperature cycle added to a test piece.

<Explanation of symbols for main parts of the drawings>

2: dew point adjustment tank

3: test chamber

4: test piece

5: constant temperature heater plate

6: heater controller

In the present invention, the entire crude oil tank including the welding coupling is almost equal in the crude oil tanker tank formed by the welding structure, or the crude oil corrosive environment of the forced oil tank which transports or stores the crude oil such as the ground or underground crude oil tank. The present invention relates to a crude oil tank capable of exhibiting excellent corrosion resistance and suppressing the formation of corrosion products (sludge) containing solid sulfur powder.

As a tank for a crude oil tanker for transporting crude oil, or a forced tank for transporting or storing crude oil such as a ground or underground crude oil tank for storing crude oil, welded structural steel having excellent strength and weldability is used.

The steel is exposed to a corrosive environment by water, salt, and corrosive gas components contained in crude oil. In particular, in the oil tanker oil tank, due to volatile components in the crude oil, salt in the seawater, salt in the oil field, and inert gas transported into the oil tank for explosion protection, engine exhaust gas of a ship called condensation due to temperature fluctuations during the day and night, etc. It has a unique corrosive environment and the steel sheet is corroded and thinned. When the steel sheet corrodes and becomes thin, it becomes difficult to maintain the required hull strength, which requires the switching of the steel sheet (cutting the corroded member and welding and joining the new member), which is expensive. In addition to the corrosion damage, a large amount of solid sulfur powder (hereinafter referred to as solid S) is produced and precipitated on the steel surface of the inner surface of the forced oil tank. It is thought that iron rust on the back surface of the corroded deck becomes a catalyst and SO ₂ and H ₂ S in the gas phase react to generate a solid (S). Formation of new iron rust and precipitation of solid (S) are generated alternately by corrosion of steel, and layered corrosion products of iron rust and solid (S) precipitate. Since the solid (S) layer is soft, the product consisting of the solid (S) and iron rust is easily peeled off and dropped off, and is deposited as sludge on the bottom of the oil tank. The amount of sludge to be recovered by regular inspection is set to 300 tons or more in a super crude oil tanker, and the reduction of sludge mainly composed of solids (S) has been strongly demanded for maintenance.

That is, the corrosion resistant steel plate which has excellent corrosion resistance as a steel plate for crude oil tanks, and produces little sludge containing solid (S) was calculated | required.

As a technique for simultaneously reducing steel corrosion and reducing sludge mainly composed of solids (S), coating and lining corrosion prevention are common, and corrosion prevention by thermal spraying of zinc or aluminum is also proposed [for example, division Japanese Society of Shipbuilding Association No. 242 Research Group, March 2001, "A Study on the New Corrosion Behavior of Crude Oil Tankers" (2000 report)]. However, in addition to economic problems such as cost of construction, corrosion inevitably progresses due to micro defects in the construction of the anti-corrosion layer and deterioration with age, so that there are problems such as regular inspection and indispensability even when painting and lining. On the other hand, the technique which aims at the prevention of steel corrosion and sludge reduction by the characteristic of a steel member is not proposed.

There are still very few proposals for countermeasure techniques on the steel member side, and all are limited to improvement of corrosion resistance. For example, shipbuilding steels having excellent corrosion resistance to use environments such as ship shells, ballast tanks, cargo oil tanks, and coal mine cargo hold have been proposed (see, for example, Japanese Unexamined Patent Publication No. 2002-17381). . The corrosion resistance steel for shipbuilding contains an appropriate amount of C, Si, Mn, P, S and Al, and further contains Cu: 0.01 to 2.00% and Mg: 0.0002 to 0.0150%, thereby improving the overall corrosion resistance and local corrosion resistance. It is. In addition, a corrosion resistant steel for a lower oil tank has been proposed, which has excellent corrosion resistance for a lower oil tank application and excellent weldability as a shipbuilding steel. Corrosion-resistant steel is P-ultra low S-Cu-Ni-Cr-Al steel, which defines the upper limit of the total amount of alloy added in order to ensure weldability, and is applied to the explosion-proof prime mover exhaust gas introduced into the downstream tank. It is set as the steel which has the outstanding corrosion resistance with respect to corrosion in the downstream oil tank (for example, refer Unexamined-Japanese-Patent No. 2002-107l79). In addition, other corrosion-resistant steels are low P-ultra low S-Cu-Ni-Cr-Al steels, the upper limit of the total amount of alloy added to the formula value in order to ensure weldability, the explosion-proof prime mover introduced into the oil tank It is set as steel which has the outstanding corrosion resistance with respect to corrosion in the downstream tank by exhaust gas (for example, refer Unexamined-Japanese-Patent No. 2002-107180). In addition, there has been proposed a steel member having excellent crude oil tank resistance and a method for producing the same, which show excellent corrosion resistance against corrosion generated in a tank for oil or oil storage (for example, Japanese Patent Laid-Open No. 2002-173736). Publication). The corrosion resistant steel proposed here is 1.0 ≦ 0.3 in order to add Cu: 0.5 to 1.5%, Ni: 0.5 to 3.0%, and Cr: 0.5 to 2.0%, and to suppress the local corrosion caused by the increase in the amount of alloy addition. Cu + 2.0-Cr-0.5 Cu is limited to 3.8, and a steel having excellent corrosion resistance is provided in the gas phase portion and the liquid phase portion of the crude oil tank.

However, any of the above corrosion resistance and the corrosion resistance of the steel itself in the crude oil tank environment have been proposed, but in particular, the precipitation of solid S, which is produced and peeled off in large quantities in the gas phase part of the oil tank, is suppressed from the steel member side. The technique to do is not disclosed. Therefore, the use of welding structures such as tanks has been expected to develop structural steels excellent in corrosion resistance from the viewpoint of improving the reliability of the structure and extending the service life, and suppressing the production of sludge mainly composed of solid (S). .

On the other hand, the crude oil tank is generally a welded structure, and the welding coupling part is inevitably exposed to the crude oil tank environment unless the entire coating or lining is applied. In arc welding or electrogas welding, which is usually performed, the composition and structure of the weld metal are generally different from those of the steel member in order to dissolve the weld wire or the flux to form the weld metal. When metals of great chemical composition or structure are adjacent to each other in a corrosive environment, dissimilar metal corrosion is likely to occur in which one of the relatively electrochemically poor metals is selectively corroded. When selective corrosion occurs, there is a high possibility that a large local corrosion will occur.

When manufacturing crude oil tanks from ordinary steel that does not particularly improve corrosion resistance, the overwhelmingly large steel member of the surface area becomes electrochemically deteriorated regardless of the welding method or the welding material. The problem does not arise. However, if the crude oil tank is formed by a steel member having excellent corrosion resistance, the weld metal may be inferior depending on the welding method or the welding material, and the weld metal may be selectively corroded, and the overall corrosion of the crude oil tank may occur. . Therefore, in order to improve the corrosion resistance in the crude oil tank environment of the entire crude oil tank formed in the welded structure, it is necessary to consider not only the steel member but also the weld coupling part, but a technique that satisfies this requirement is found in the annular shape. It is not.

SUMMARY OF THE INVENTION The present invention has been made to solve such a problem, and an object thereof is a crude oil corrosive environment of an oil tank of a crude oil tanker formed by a welded structure or a forced oil tank which transports or stores crude oil such as a ground or underground crude oil tank. The present invention provides a crude oil tank capable of suppressing the formation of a corrosion product (sludge) containing a solid sulfur content, while the whole crude oil tank including the weld coupling is almost equivalent.

In order to solve the above problems, the inventors have investigated the influence of the chemical composition of the steel on the corrosion resistance of the steel behind the crude oil tank deck, which always becomes the gas phase part, and based on the chemical composition of the general welded structural steel, Cr is substantially free of By adding a specific amount of Mo, W, or both of the complex and Cu to limit the amount of P and S as impurities, the corrosion resistance in the environment can be improved, and the production of sludge can be greatly reduced. I have found that. In addition, as a result of studying the relationship between the presence state of Mo and W and the corrosion resistance in detail, it was found that Mo and W were more preferable for corrosion resistance in the solid molten state. Further, in welding the above steel members, the corrosion resistance of the weld coupling portion becomes equal to that of the steel member, and as a result of studying the chemical composition and the metal structure of the required weld metal and steel member in detail, the weld metal and steel Since the ratio of the content of Cu, Mo, and W between members is within a specific range, the weld coupling including the steel member and the weld metal exhibits equally good corrosion resistance, and also optimizes the steel member structure form. New knowledge has been found to be effective in improving corrosion resistance.

This invention is mainly made | formed based on the said knowledge, The summary is made as follows.

(1) by mass%

C: 0.001-0.2%,

Si: 0.01 to 2.5%,

Mn: 0.1 to 2%,

P: 0.03% or less,

S: 0.02% or less,

Cu: 0.01 to 1.5%,

Al: 0.001-0.3%,

N: 0.001% to 0.01%

Containing, and,

Mo: 0.01 to 0.5%,

W: 0.01 to 1%

Cu, Mo, and W contents of the weld metal in the weld coupling portion, respectively, when the steel components containing one or two kinds of metals, and the remaining portions are welded to steel members made of Fe and unavoidable impurities, form a crude oil tank. Crude oil tank with a weld coupling excellent in corrosion resistance characterized by satisfy | filling Formula 1 and Formula 2.

[Equation 1]                         

3 ≥ Cu content (mass%) of the weld metal / Cu content (mass%) of the steel member ≥ 0.15

[Equation 2]

3 ≥ [Mo content of weld metal + W content (mass%)] / [Mo content of steel member + W content (mass%)] ≥ 0.15

(2) Cu, Mo, and W content of the weld metal in the said welding coupling part satisfy | fills following Formula 3 and Formula 4, respectively, The crude oil which has the weld coupling excellent in corrosion resistance of said (1) characterized by the above-mentioned. Oil tank.

[Equation 3]

1.5 ≥ Cu content (mass%) of the weld metal / Cu content (mass%) of the steel member ≥ 0.3

[Equation 4]

1.5 ≥ [Mo content of the weld metal + W content (mass%)] / [(Mo content of the steel member + W content (mass%)] ≥0.3

(3) The crude oil tank having a weld coupling excellent in corrosion resistance according to any one of the above (1) or (2), wherein the amount of solid molten Mo and the amount of solid melt W of the steel member satisfy the following formula (5).

[Equation 5]

Solid Melt Mo + Solid Melt W ≥ 0.005%

(4) Cr oil content of a steel member is less than 0.1%, The crude oil tank which has the weld coupling excellent in the corrosion resistance in any one of said (1)-(3).

(5) the steel member is also in mass%,                         

Ni: 0.1 to 3%,

Co: 0.1 to 3%

Crude oil tank which has the weld coupling excellent in the corrosion resistance in any one of said (1)-(4) characterized by containing 1 type or 2 types of the said.

(6) the steel member is also in mass%,

Sb: 0.01 to 0.3%,

Sn: 0.01 to 0.3%,

Pb: 0.01 to 0.3%,

As: 0.01 to 0.3%,

Bi: 0.01 to 0.3%,

Se: 0.01 to 0.3%

Crude oil tank which has the weld coupling excellent in the corrosion resistance in any one of said (1)-(5) characterized by containing 1 type (s) or 2 or more types.

(7) the steel member is also in mass%,

Nb: 0.002 to 0.2%,

V: 0.005 to 0.5%,

Ti: 0.002-0.2%,

Ta: 0.005 to 0.5%,

Zr: 0.005 to 0.5%,

B: 0.0002 to 0.005%                         

Crude oil tank which has the weld coupling excellent in the corrosion resistance in any one of said (1)-(6) characterized by containing 1 type (s) or 2 or more types.

(8) the steel member is also in mass%,

Mg: 0.0001 to 0.01%,

Ca: 0.0005 to 0.01%,

Y: 0.0001 to 0.1%,

La: 0.005 to 0.1%,

Ce: 0.005 to 0.1%

Crude oil tank which has the weld coupling excellent in the corrosion resistance in any one of said (1)-(7) characterized by containing 1 type (s) or 2 or more types.

(9) The microstructure of the steel member is composed of at least one kind or two kinds of bainite and martensite, and the area ratio of the sum of the bainite and martensite is 30% or more, the above (1) to (8) Crude oil tank having a weld coupling excellent in corrosion resistance according to any one of

The present invention overcomes the above problems and achieves the object, and specific means thereof are shown below.

First, the reason for limitation is demonstrated about the component element of the steel member which forms a crude oil tank, and its content. The unit of% of component content in an article is mass%.

De-C to less than 0.001% of industrially impairs economic efficiency considerably industrially, so that C is contained in 0.001% or more, but more preferably 0.002% or more when used as a reinforcing element. On the other hand, when it contains exceeding 0.2% too much, deterioration of weldability, coupling toughness, etc. generate | occur | produce, and since it is not preferable for the weld structure, in this invention, 0.001 to 0.2% was made into the limited range.

Si is required as the deoxidation element, and in order to exhibit the deoxidation effect, 0.01% or more is required. Si is an element which is effective in improving the corrosion resistance of the whole surface and having a small but effective effect in improving local corrosion resistance. In order to express the said effect, it is preferable to contain 0.1% or more. On the other hand, when Si is excessively contained, fixation of the hot rolled scale (degradation of scale peelability) is caused, and damage due to the scale is increased. Therefore, the upper limit is made 2.5% in the present invention. In particular, when the weldability, the base material and the coupling toughness are stringent steels together with corrosion resistance, the upper limit is preferably 0.5%.

Mn is required at least 0.1% to secure the strength of the steel. On the other hand, when it exceeds 2%, since weldability deterioration and grain boundary embrittlement sensitivity are not preferable, the range of Mn is limited to 0.1 to 2% in this invention.

P is an impurity element, and if it exceeds 0.3%, the weldability is deteriorated, so it is limited to 0.03% or less. In particular, when it is 0.015% or less, since it has a favorable influence on corrosion resistance and weldability, it is preferable.

S is also an impurity element, and when it exceeds 0.02%, the amount of sludge produced tends to increase. Moreover, in order to remarkably deteriorate mechanical property, especially ductility, 0.02% is made into an upper limit. The amount of S is so preferable that it is small with respect to corrosion resistance and mechanical properties, and 0.01% or less is especially preferable.

When Cu and 0.01% or more are contained together with Mo and W, it is effective in improving corrosion resistance and is effective also in suppressing generation | occurrence | production of solid (S). Even if it contains more than 1.5%, these effects are almost saturated, On the contrary, since an adverse effect, such as improvement of the surface crack of a steel slab and deterioration of coupling toughness, also exists, an upper limit is made into 1.5% in this invention. 0.01 to 0.5% is more preferable from the balance of corrosion resistance, the sludge production suppression effect, and the manufacturing performance.

Al is an element useful for deoxidation and an element effective for miniaturizing the heating austenite grain size of the base material by AlN. In addition, it is advantageous to have a suppression effect of the generation of the corrosion product containing the solid (S). However, in order to exhibit these effects, it is necessary to contain 0.001% or more. On the other hand, if it contains excessively more than 0.3%, coarse oxides are formed to deteriorate ductility, and therefore it should be limited to 0.001% to 0.3% of range.

N is not preferable because it adversely affects ductility and toughness in the solid molten state, but in combination with V, Al, or Ti, it effectively acts to refine austenite grains and strengthen precipitation, so that a small amount is effective for improving mechanical properties. Moreover, it is impossible to remove N in steel completely industrially, and it is unpreferable to reduce more than necessary because it puts an excessive load on a manufacturing process. Therefore, it is a range which can tolerate the bad influence to ductility and toughness, is industrially controllable, and a minimum is made into 0.001% as a range which a load to a manufacturing process can tolerate. When it contains too much, since there is a possibility that solid melt N will increase and adversely affect ductility and toughness, an upper limit is made into 0.01% as an allowable range.

Mo and W are important elements similar to Cu for corrosion resistance and suppression of precipitation of solid (S), and it is necessary to contain Mo and W together with 0.01% or more of Cu. Mo and W have almost the same effect, Mo is 0.01 to 0.5%, W is 0.01 to 1% of range, and it is necessary to contain single or both, respectively. When Mo and W are contained together in an amount of 0.01% or more, a definite effect is exerted on corrosion resistance and suppression of precipitation of solid (S). On the other hand, even if Mo is 0.5% and W is more than 1%, the effect of improving the corrosion resistance and the inhibition of precipitation of the solid (S) is saturated, while Mo is 0.01 to 0.5% and W is 0.01 in order to deteriorate weldability and toughness. It is limited to 1%. Moreover, in order to suppress formation of precipitates and to ensure solid molten Mo and W reliably, the upper limit of Mo and W is more preferably set to 0.1% and 0.2%, respectively.

Although the range of said Mo and W is a necessary condition, in order to exhibit more effectively about corrosion resistance, it is more preferable to ensure the fixed amount of solids of Mo and W more than fixed after making content into the said range. That is, when Mo and W form coarse precipitates, depletion layers of the elements are generated around them, and the corrosion resistance effect is impaired. Therefore, Mo and W are preferably present as uniformly as possible. Since Mo and W in a solid molten state have an equivalent effect on corrosion resistance, as shown by Formula 5, when the sum total of the solid melt amounts of both elements is 0.005% or more, corrosion resistance will improve significantly.

In addition, solid melt Mo and solid melt W which are effective for the corrosion resistance improvement in this invention refer to the quantity which subtracted the precipitation amount calculated | required by extraction residue analysis from the total content. That is, as the extraction residue analysis, extremely fine precipitates, which are regarded as solid melting, can be regarded as being uniformly present in the steel in a nearly solid molten state, and thus function effectively for corrosion resistance.

Although the above is the basic requirement regarding the chemical composition in the steel of the present invention and the reason for the limitation thereof, in the present invention, the chemical composition is optionally limited for the purpose of improving various properties of the steel.

Cr is a reinforcing element, and it is possible to add it as necessary for the strength adjustment. However, Cr is an element which accelerates the local corrosion propagation rate most. Therefore, containing 0.1% or more deteriorates local corrosion resistance in the crude oil environment. Slightly promote the production of solid (S). Therefore, it is not preferable to contain 0.1% or more in this invention. Therefore, even if it does not intentionally contain or contains it, less than 0.1% is preferable.

Ni and Co are effective elements for improving the base metal and HAZ toughness, and are effective in improving corrosion resistance and suppressing sludge in steels containing Cu and Mo. By containing 0.1% or more with both elements, the toughness improvement and the corrosion resistance improvement effect are expressed clearly. On the other hand, excessively containing more than 3% with both elements is an element that is also expensive with both elements and is economically inadequate, and in the case of containing Ni and Co in the present invention in order to cause deterioration of weldability. The content is limited to 0.1 to 3%.

By containing 0.01% or more of Sb, Sn, Pb, As, Bi, and Se, respectively, the lower limit in the case of containing Sb, Sn, Pb, As, Bi, and Se as necessary, in order to have the effect of further suppressing the progress of local corrosion in the liquid part, is 0.01%. However, since the effect is saturated even if it contains too much more than 0.3%, respectively, there exists a possibility of the bad influence to another characteristic, and an upper limit is made into 0.3% in consideration of economical efficiency.

Nb, V, Ti, Ta, Zr, and B are elements that are effective in increasing the strength of the steel in trace amounts, and are mainly contained as necessary for the strength adjustment. In order to express an effect, it is necessary to contain Nb 0.002% or more, V 0.005% or more, Ti 0.002% or more, Ta 0.005% or more, Zr 0.005% or more, and B02 0.0002% or more. On the other hand, Nb is more than 0.2%, V is more than 0.5%, Ti is more than 0.2%, Ta is more than 0.5%, Zr is more than 0.5%, and N is more than 0.005%, so the toughness deterioration is not preferable. If necessary, when Nb, V, Ti, Ta, Zr, and B are contained, Nb is 0.002 to 0.2%, V is 0.005 to 0.5%, Ti is 0.002 to 0.2%, Ta is 0.005 to 0.5%, Zr is 0.005 to 0.5% and B is limited to 0.0002 to 0.005%.

Mg, Ca, Y, La, and Ce are effective for controlling the shape of inclusions, and are effective for improving the ductility characteristics, and are also effective for improving the HAZ toughness of the high heat input welding coupling, and the effect of suppressing sludge formation by fixing S Since it is weak, it is contained as needed. The lower limit of the content of each element in the present invention is determined from the lower limit at which the effect is expressed, and Mg is 0.0001%, Ca is 0.0005%, Y is 0.0001%, La is 0.005%, and Ce is 0.005%. . On the other hand, the upper limit is determined whether the inclusions coarsen and adversely affect the mechanical properties, particularly ductility and toughness. In the present invention, the upper limit is 0.01% for Mg and Ca, and 0.1 for Y, La, and Ce. Let it be%.

Although the above is the limitation reason regarding the chemical composition in this invention, it is also possible to reliably improve the internal corrosion characteristic of a welding coupling part by defining the microstructure form of a steel member. That is, when the steel members of the said composition range are welded, and the composition ratio of Cu, Mo, W between the weld metal and steel member in the said welding coupling is prescribed | regulated to an appropriate range as mentioned later, a weld metal and a steel member The welded heat affected substructure of is made of a low temperature transformation structure containing at least acyclic ferrite or bainite, in which case the microstructure of the steel member is composed of at least one kind or two kinds of bainite and martensite, and the bay It is preferable that the area ratio of the sum total of knight and martensite is 30% or more. When the area ratio of the total of bainite and martensite is less than 30% and becomes a ferrite or ferrite pearlite main structure, the corrosion on the steel member side selectively progresses, but the corrosion resistance of the steel member is slightly deteriorated. If the area ratio of the total of bainite and martensite is 30% or more, the weld metal, the weld heat-affected portion, and the steel member are roughly equal in view of corrosion resistance, so that local corrosion is hardly caused, and the corrosion resistance of the whole oil tank is stable. Is improved.

For the above reason, in forming a crude oil tank by welding steel members that have a composition and structure defined thereon, the uniform corrosion resistance of the weld coupling and the base material as a whole is increased, and the corrosion resistance of each of the weld metal and the steel member is effectively expressed so that the entire crude oil tank can be obtained. In order to improve the corrosion resistance, the balance of the chemical composition of the weld metal and the steel member is important, and in particular, the ratio of the weld metal and the steel member of Cu, Mo, and W, which are essential for the development of corrosion resistance, must satisfy the following formulas (1) and (2). have.

[Equation 1]

3 ≥ Cu content (mass%) of the weld metal / Cu content (mass%) of the steel member ≥ 0.15

[Equation 2]

3 ≥ [Mo content of weld metal + W content (mass%)] / [Mo content of steel member + W content (mass%)] ≥ 0.15

As shown by Equation 1 regarding Cu, when the mass% in the weld metal / mass% in the steel member exceeds 3, it is not preferable because the steel member from the weld heat affected zone near the weld metal to the base metal is selectively corroded. . On the other hand, when the mass% in the weld metal of Cu / mass% in the steel member is less than 0.15, the weld metal is electrochemically deteriorated and local corrosion of the weld metal becomes remarkable, so it should be avoided. Therefore, although 3 to 0.15 was set as mass%, 3 to 0.3 are preferable. In addition, Mo and W need to be defined in the same manner, but Mo and W may be defined in the total amount of Mo and W in order to have an almost equivalent effect on the corrosion behavior. Although it is a total amount, 3-0.15 is essential for the mass% in a weld metal / mass% in a steel member, but 3-0.3 are preferable. As for the total amount of Cu, Mo, and W, the mass% in each weld metal / mass% in a steel member, the one which is close to Formula 1 is less likely to selectively corrode either a weld metal or a steel member, Equations 3 and 4 As indicated by, the total amount of Cu, Mo, and W and the mass% in the mass% / steel member in each weld metal are more preferably in the range of 1.5 to 0.3.

Below, the effect of this invention is demonstrated in detail by an Example. In addition, this invention is not limited to the following Example.

<Example>

The effect of this invention is shown based on an Example. The test fabricated steel was melt manufactured by vacuum melting or converter, and an ingot or steel piece was produced on the steel sheet. The steel sheet was produced in a steel sheet having a sheet thickness of 15 to 50 mm adjusted to a predetermined strength and toughness by water-cooled processing heat treatment (TMCP) or reheat quenching and tempering (QT) after hot rolling. In a comparative example, the steel plate manufactured by normal hot rolling (AR) and control rolling (CR) is also included. Table 1 and Table 2 show the chemical composition of the steel.

Table 3 shows the production method, the structure form, the solid molten Mo, and the amount of W mechanical properties of the steel sheet. Measurements of bainite and martensite on the tissue were taken at 1000 to 5000 times magnification by a scanning electron microscope with a magnification of 2 mm under the surface, a quarter of the plate thickness, the center of the plate thickness, and 10 or more fields in each position. And the average area ratio (area ratio% in observation cross section) was calculated | required by the image analysis apparatus. Solid molten Mo and W amount were performed by extraction residue analysis about the steel plate whole thickness sample from which black skin was removed. The tensile property of the steel plate (base material) was measured at room temperature by taking a round bar tensile test piece from the sheet thickness center part in the direction perpendicular to the rolling direction. The toughness of the steel sheet was similarly taken from a sheet thickness center in a direction perpendicular to the rolling direction, and a standard 2 mm V notch Charpy impact test piece was taken, and tested at various temperatures to obtain the wavefront transition temperature (vTrs).

Coated arc welding (SMAW) or submerged arc welding (SAW) coupling using the welding material of the chemical composition shown in Table 4 with respect to the steel plate of Table 3 manufactured using the steel piece of the chemical composition of Table 1, Table 2. Was produced. The composition of Table 4 is the chemical composition of a handle bar in SMAW welding, and shows the composition of a welding wire in SAW welding. In addition, the flux equivalent to JIS Z3352 was used for SAW welding.

All improvements were made to V improvements. Table 5 shows the component ratios of the weld metal and the steel sheet to the amount of Cu, Mo and W in the welding conditions and the weld metal (WM), and the sum of the Cu, Mo and W (Mo + W). By changing a welding material, these component ratios are changed including the range outside of this invention.

Table 6 is a test for evaluating the corrosion resistance and selective corrosion tendency of the coupling, and Table 7 is mainly a test for evaluating the corrosion resistance and sludge formation behavior of the whole surface of the steel member.

Test conditions for evaluating the corrosion resistance as the coupling of Table 6 are as follows.

The test piece was extract | collected from the welding coupling of Table 5, and the corrosion test of the coupling in the environment which simulated the crude oil tank environment was done. As shown in FIG. 1, a test piece having a length of 80 mm, a width of 40 mm, and a thickness of 4 mm in order to include a weld metal (WM), a weld heat affected zone (HAZ), and a base material (BM) in a weld coupling. The sample was taken from a position of 1 mm of the steel sheet surface, and the entire test piece surface was mechanically ground, and after 600 wet polishing, only one side of the table of 80 mm × 40 mm was left to cover the end face and the back face with paint. The test piece was immersed in two kinds of corrosion solutions of 1 volume% HCl aqueous solution in which 20 mass% NaCl of pH 2.0 was dissolved. Immersion conditions were performed at 30 degreeC of liquid temperature, and immersion time 336h, and measured the maximum corrosion depth in each position of a welding metal (WM), a welding heat influence part (HAZ), and a base material (BM), and converted into corrosion rate (mm / Year).

Next, the corrosion test conditions for investigating the overall surface corrosiveness and sludge formation behavior of the steel member are as follows.

From the steel plate shown in Table 3, the test piece of length 40mm, width 40mm, and thickness 4mm was extract | collected so that the plate thickness 1/4 position of a steel plate may be the thickness center of a test piece. The whole surface of the test piece was mechanically ground, and after 600 wet polishing, the back surface and the end surface were covered with paint, leaving a surface of 40 mm × 40 mm. The corrosion rate of the test steel and the production rate of sludge mainly composed of solids (S) were evaluated using the test apparatus shown in FIG. Table 8 shows the composition of the gas used in the corrosion test.

The gas was adjusted to a constant dew point (30 ° C.) through the dew point adjustment tank 2 and then transferred to the test chamber 3. The NaCl aqueous solution was apply | coated and dried on the surface of the test piece 4 so that the adhesion amount of NaCl might be 1000 mg / m <2> before a corrosion test, and it installed horizontally in the constant temperature heater board 5 in a test chamber. By controlling the heater controller 6, a wet and dry repetition occurs on the surface of the test piece by giving a temperature cycle of 2 hours / cycle in total of 20 ° C × 1 hour and 40 ° C × 1 hour as shown in FIG. It was made. The sludge production rate was evaluated from the amount of material produced on the test piece surface from the corrosion loss after 720 cycles. In addition, it was confirmed by preliminary tests that the product is iron oxyhydroxide (iron rust) and solid (S) by chemical analysis and X-ray analysis.

Regarding mechanical properties among the examples, it is evident from Table 3 that the steel sheets Nos. A1 to A13 satisfying the requirements of the present invention, as shown in Table 3, all have sufficient base metal properties as weld structural steels. In the comparative examples, the steel sheets Nos. B3 and B4 have excessively low toughness compared to the steel sheets having the chemical composition of the present invention because Mo and C are excessively passed as component contents.

Regarding the corrosion resistance, first of all, the corrosion resistance of the couplings in Table 6 shows that the chemical composition of the steel member and the chemical composition ratio of the weld metal and the steel member satisfy the present invention. Regardless of the welding method or heat input, corrosion is generated almost uniformly over WM, HAZ, and BM, and the corrosion rate is also sufficiently low.

On the other hand, in the case of the welding coupling of the coupling numbers WB1 to WB8 of the comparative example, since it does not satisfy the requirements of the present invention as shown below, the corrosion rate of the specific site is selectively increased significantly, and the welding structure As a crude oil tank formed, it is clear that corrosion resistance is remarkably inferior compared with this invention.

That is, since the coupling numbers WB1 and WB2 do not contain all or part of the elements essential for securing corrosion resistance in the chemical composition of the steel member, and do not satisfy the present invention as a chemical composition, the corrosion resistance of the steel member itself It is falling, and the corrosion rate of HAZ, BM is significantly larger than that of WM.

Since Coupling Number WB3 contains too much Mo, as shown in Table 3, the toughness of the steel sheet is not sufficient, and with respect to the total content [(Mo + W)] of Mo and W, Since the composition ratio, that is, [Mo content of the weld metal + W content (mass%)] / [Mo content of the steel member + W content (mass%)] is too small, WM is selectively corroded in the corrosion test of the coupling. However, there is a problem in corrosion resistance as a crude oil tank.

Since the coupling number WB4 has an excessively large amount of C, the toughness of the steel member is not sufficient as structural steel.

Coupling number WB5 is not preferable because Cr is intentionally added and the content is too large.

When the coupling number WB6 is Cu and (Mo + W), the corrosion of WM is suppressed because the composition ratio between WM and the steel member is too large, but the corrosion rate of HAZ and BM near the WM is corroded only by the steel member. It is not preferred because it is larger than.

Coupling number WB7 is too small for Cu and (Mo + W), since the composition ratio of WM and steel member is too small, WM selectively corrodes and the corrosion rate of WM becomes remarkably large, and corrosion resistance as a crude oil tank is not enough. .

Coupling number WB8, like coupling number WB6, suppresses corrosion of WM because the composition ratio of WM and steel member becomes excessively large for Cu and (Mo + W), but the corrosion rate of HAZ and BM near WM is low. It is not preferable because the bay is larger than the case where it is corroded.

Next, according to the results of Table 6, which mainly investigated the corrosion resistance and sludge resistance of the whole surface of the steel sheet, the corrosion rate and sludge formation rate of the steel sheets of the steel sheets No. A1 to A13 having the chemical composition of the present invention are among Cu, Mo, and W. Compared to the steel plate of the steel sheet number B1 of the comparative example which does not contain any of them, it is reliably reduced to 30% or less at the same time, and it is clear that it has excellent whole surface corrosion resistance and sludge resistance, and therefore it is possible to use a steel that satisfies the requirements of the present invention. In the formed crude oil tank, good corrosion resistance and sludge resistance can be exhibited in base materials other than the coupling.

On the other hand, the steel sheets of the steel sheets Nos. B1, B2, and B5 of the comparative example do not satisfy the requirements regarding the chemical composition of the present invention, and thus either or both of the corrosion resistance and sludge resistance of the whole surface of the steel sheet itself are separated, and the requirements of the present invention. In crude oil tanks formed using steels that do not satisfy the requirements, it is clear that the entire oil tank cannot be expected to have sufficient corrosion resistance.

That is, since steel plate number B1 does not contain any of Cu, Mo, and W which are essential for corrosion resistance expression, corrosion resistance and sludge resistance of the steel plate itself are also inferior compared with the example of this invention.

Since steel plate number B2 does not contain Mo and W, and the requirements for corrosion-resistance expression are not achieved, corrosion resistance and sludge resistance of steel plate itself are inferior to the example of this invention.

Since steel sheet number B5 has a high Cr amount, the production of sludge is particularly noticeable, which is not preferable. The corrosion resistance is also slightly reduced.

In addition, in the comparative examples, the steel sheets Nos. B3 and B4 were improved in corrosion resistance because Mo and C were excessively passed as component contents, respectively, but the toughness was remarkably inferior to that of the steel sheet having the chemical composition of the present invention. Inadequate example.

According to the present invention from the above examples, it is clear that the entire crude oil tank including the weld coupling exhibits almost the same and excellent corrosion resistance, and can suppress the formation of corrosion products (sludge) containing solid sulfur.

According to the present invention, the entire crude oil tank including the welding coupling is almost equal in the crude oil tanker tank formed by the welding structure or the crude oil corrosion environment of the forced oil tank which transports or stores the crude oil such as the ground or underground crude oil tank. It is possible to provide a crude oil tank which exhibits excellent corrosion resistance and can suppress the formation of a corrosion product (sludge) containing solid sulfur powder, and improves the long-term reliability of a steel structure having a crude oil tank and a crude oil tank, a ship, It contributes to improved safety and economics.

Claims (10)

In mass%, C: 0.001-0.2%, Si: 0.01 to 2.5%, Mn: 0.1 to 2%, P: 0.03% or less, S: 0.02% or less, Cu: 0.01 to 1.5%, Al: 0.001-0.3%, N: 0.001% to 0.01% Containing, and, Mo: 0.01 to 0.5%, W: 0.01 to 1% In the case of forming a crude oil tank by welding steel members containing one or two kinds of residues, the remainder being made of Fe and unavoidable impurities, the Cu, Mo, and W contents of the weld metal in the weld coupling portion are as follows. Crude oil tank with a weld coupling excellent in corrosion resistance characterized by satisfy | filling Formula 1 and Formula 2. [Equation 1] 3 ≥ Cu content (mass%) of the weld metal / Cu content (mass%) of the steel member ≥ 0.15 [Equation 2] 3 ≥ [Mo content of weld metal + W content (mass%)] / [Mo content of steel member + W content (mass%)] ≥ 0.15 The steel according to claim 1, wherein the steel is in mass% of Cr: less than 0.1%, Ni: 0.1 to 3%, Co: 0.1 to 3%, Sb: 0.01 to 0.3%, Sn: 0.01 to 0.3%, Pb: 0.01 To 0.3%, As: 0.01 to 0.3%, Bi: 0.01 to 0.3%, Se: 0.01 to 0.3%, Nb: 0.002 to 0.2%, V: 0.005 to 0.5%, Ti: 0.002 to 0.2%, Ta: 0.005 to 0.5%, Zr: 0.005 to 0.5%, B: 0.0002 to 0.005%, Mg: 0.0001 to 0.01%, Ca: 0.0005 to 0.01%, Y: 0.0001 to 0.1%, La: 0.005 to 0.1%, Ce: 0.005 to 0.1 Crude oil tank having a welded joint excellent in corrosion resistance characterized by further containing one kind or two or more kinds in%. The crude oil tank according to claim 1 or 2, wherein the amount of solid molten Mo and the amount of solid melt W of the steel member satisfy the following formula (5). [Equation 5] Solid Melt Mo + Solid Melt W ≥ 0.005% delete delete delete delete delete The microstructure of the steel member is composed of at least one kind or two kinds of bainite and martensite, and the area ratio of the sum of the bainite and martensite is 30% or more. Crude oil tank with welded coupling with excellent corrosion resistance. The amount of solid molten Mo and the amount of solid molten W of a steel member satisfy | filling following Formula 5, and a microstructure consists of at least 1 type or 2 types of bainite and martensite, The said bay A crude oil tank having a weld coupling excellent in corrosion resistance, wherein the total area ratio of nitrate and martensite is 30% or more. [Equation 5] Solid Melt Mo + Solid Melt W ≥ 0.005%

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