CN107636185A - Ethanol stores and conveying equipment steel - Google Patents

Ethanol stores and conveying equipment steel Download PDF

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Publication number
CN107636185A
CN107636185A CN201680034328.2A CN201680034328A CN107636185A CN 107636185 A CN107636185 A CN 107636185A CN 201680034328 A CN201680034328 A CN 201680034328A CN 107636185 A CN107636185 A CN 107636185A
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ethanol
steel
corrosion
amounts
resistance
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CN107636185B (en
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寒泽至
盐谷和彦
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JFE Steel Corp
JFE Engineering Corp
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NKK Corp
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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
    • C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur
    • 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
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/005—Heat treatment of ferrous alloys containing Mn
    • 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
    • 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
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
    • 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
    • C22C38/008—Ferrous alloys, e.g. steel alloys containing tin
    • 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
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • 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
    • C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
    • 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
    • C22C38/14—Ferrous alloys, e.g. steel alloys containing 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
    • C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium 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
    • C22C38/24—Ferrous alloys, e.g. steel alloys containing chromium 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
    • C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
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    • 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

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  • Crystallography & Structural Chemistry (AREA)
  • Heat Treatment Of Steel (AREA)
  • Heat Treatment Of Sheet Steel (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The present invention provides a kind of ethanol storage and conveying equipment steel, and in terms of quality %, it contains C：0.02~0.3%, Si：0.01~1.0%, Mn：0.1~2.0%, P：0.003~0.03%, S：Less than 0.01%, Al：0.005~0.100%, N：0.0010~0.010%, and Al and N content also contains than meeting 2.0≤Al/N≤70.0 and is selected from W：0.010~0.5% and Mo：At least one of 0.010~0.5%, and contain and be selected from Sb：0.01~0.5% and Sn：At least one of 0.01~0.3%, surplus is made up of Fe and inevitable impurity.

Description

Ethanol stores and conveying equipment steel
Technical field
The present invention relates to the structural steel for being suitable as ethanol storage and conveying element of installation.That is, steel of the invention is fitted Cooperate as the raw material of ethanol storage facilities component, ethanol conveying equipment component.In addition, the present invention steel relate to containing Structure used under carboxylic acid, chlorion, the particularly ethanol of water, the corrosive environment of bio-ethanol, that resistance to ethanol corrosivity is excellent Use steel.
Background technology
The sugar of corn, wheat etc. is mainly decomposed, purified to manufacture by bio-ethanol.In recent years, bio-ethanol is made Alternative fuel for oil (gasoline) and be widely used as the fuel mixed with gasoline all over the world, its dosage have by Year increased tendency.Therefore, although in storage, the process of transporting biological ethanol or process for being mixed with gasoline etc., biological second The treating capacity of alcohol increased, but from the viewpoint of the corrosivity height of bio-ethanol, i.e. from generation spot corrosion, particularly stress corruption From the viewpoint of erosion cracking (SCC), it handles still difficult.
For bio-ethanol, contain in its manufacturing process acetic acid, chlorion as denier impurity situation, Absorb water, infiltrate the situation of dissolved oxygen in storage, turns into a reason of corrosivity enhancing.Particularly SCC caused by bio-ethanol, It will cause the danger of serious bio-ethanol leakage accident in the presence of once generation.Therefore, SCC caused by bio-ethanol is recognized To be the corrosion phenomenon of most serious problem, it is believed that it is important that preventing trouble before it happens in operation.
As described above, have the following disadvantages：Equipment, such as tank of the measure for resistance to ethanol are implemented, is only used The excellent organic coating material of resistance to ethanol corrosivity, stainless steel, the tank of stainless steel cladding steel could safely handle bio-ethanol. And the conveying that bio-ethanol be present the problem of can not also using pipeline etc. of existing transfer oil.So, in processing biology The equipment of ethanol needs very high cost aspect still leftover problem.
Solve the problems, such as above-mentioned method as desired, such as in patent document 1, as bio-fuel countermeasure, propose A kind of tank to the Ni containing 5~25 mass % steel are implemented zinc-nickel plating, implemented on the coating without 6 valency chromium The method of chemical conversion processing.According to this method, become good containing the corrosion resistance in ethanol petrol.
In addition, in patent document 2, it is proposed that for the pipe for the excellent corrosion resistance for handling the fuel vapo(u)rs such as bio-ethanol Road steel, the steel implement the Zn-Co-Mo that Co is 0.2~4.0at% relative to Zn proportion of composing to surface of steel plate and plated Apply.
In patent document 3, it was recently reported that a kind of excellent steel of resistance to alcohol corrosivity, the steel contain Cr in terms of quality %： 0.01~1.0%, and contain and be selected from Cu：0.05~1.0%, Sn：0.01~0.2% and Ni：Two kinds in 0.01~1.0% with On.
In addition, in non-patent literature 1, ammonium hydroxide is have studied for the steel in simulating liquid in bio-ethanol SCC (stress corrosion cracking) inhibitor effect.Non-patent literature 1 report by simulation liquid in add ammonium hydroxide come Suppress Crack Extension, slow down SCC technology.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2011-26669 publications
Patent document 2：Japanese Unexamined Patent Publication 2011-231358 publications
Patent document 3：Japanese Unexamined Patent Publication 2013-129904 publications
Non-patent literature
Non-patent literature 1：F.Gui, J.A.Beavers and N.Sridhar, Evaluation of ammonia hydroxide for mitigating stress corrosion cracking of carbon steel in fuel grade ethanol,NACE Corrosion Paper,No.11138(2011)
The content of invention
The invention problem to be solved
SCC refers to the seminess caused by the interaction of corrosive environment and static stress originally.Bio-ethanol SCC can be observed in the facility in variable load environment mostly, be showed result, it is believed that it is substantially corrosion fatigue As.Relative to caused SCC under static stress, under dynamic stress caused corrosion fatigue be crackle under lower stress, with The serious breakoff phenomenon of faster growth rate.That is, inventors believe that, in order to prevent bio-ethanol SCC, it is necessary to improve second Resistance to corrosion fatigue under alcohol environment.
It is considered that raising of the zinc-nickel plating to corrosion resistance disclosed in patent document 1 is effective.But the Zn-Ni is plated Applying needs to be handled using plating, therefore is had no problem for small-sized such as automobile fuel tank.But for Applied to large structure, the thick steel products of more than the thickness of slab 3mm such as amount of storage is more than 1000kL storage tank, pipeline and Speech, processing cost is huge, therefore can not apply plating.In addition, in the case of the bad grade there occurs plating, in the part on the contrary Spot corrosion easily occurs, easily causes corrosion fatigue, therefore be insufficient from the viewpoint of pitting corrosion resistance, resistance to corrosion fatigue 's.
On the Zn-Co-Mo platings disclosed in patent document 2, it is still desirable to handled using plating, therefore, according to The reason for identical with patent document 1, the thick steel products of large structure can not be applied to.In addition, according further to patent document 1 The reason for identical, from the viewpoint of pitting corrosion resistance, resistance to corrosion fatigue, it is considered as insufficient.
On the steel disclosed in patent document 3, although effective for pitting corrosion resistance, resistance to corrosion fatigue is not considered Property.It is thus impossible to the steel for thinking disclosed in patent document 3 can meet the resistance to ethanol corrosion required by actual structure Property.
In addition, in the record of non-patent literature 1, addition inhibitor has relaxed the corrosion phenomenons such as corrosion fatigue really, but Its effect is simultaneously insufficient.This is due to that inhibitor absorption plays effect on surface, but its absorption behavior can be by pH of surrounding etc. Very big influence.Therefore, in the case where locality corrosion occurs, it is insufficient to sometimes result in absorption.Suppress in addition, also existing The danger that agent pollutes to environment outflow, it is impossible to which the addition of inhibitor is referred to as suitable corrosion-resistant countermeasure.
As previously discussed, the anti-corrosion method based on plating is not suitable for large structure, in addition, on structural steel surface, Add inhibitor and inequality in terms of corrosive effect is reduced be present, and it is insufficient.Therefore, used as ethanol storage and conveying equipment On the way, it is highly desirable to contain carboxylic acid, chlorion and water as the corrosion resistance under the bio-ethanol environment of impurity, particularly corrosion resistant Lose the excellent steel of fatigability.
It is an object of the present invention to solves above-mentioned problem of the prior art, there is provided can also make under bio-ethanol environment Excellent steel pipe of resistance to ethanol corrosivity etc. is stored towards ethanol and the structural steel of conveying element of installation.Here, " resistance to second Alcohol corrosivity is excellent " refer to that the resistance to corrosion fatigue in the case where containing the alcoholic environment of carboxylic acid, chlorion and water as impurity is excellent.
For solving the method for problem
The present inventor etc. are in order to solve above-mentioned problem, for showing excellent resistance to corrosion fatigue under bio-ethanol environment Property ethanol storage and conveying equipment had made intensive studies with the exploitation of steel.Its result is found, for suppressing bio-ethanol ring It is effective containing Mo, W for corrosion fatigue under border, moreover, in addition to Mo, the W, contains Sb and/or Sn and Al It is effective.In addition, the present inventor etc. has found, resistance to corrosion fatigue can be significantly increased by the content for reducing N.Need to illustrate , these effects can also effectively act as acting on for the SCC under the static load environment of stress condition milder.This hair Bright is further to be studied and completed based on above-mentioned opinion, and its purport is as follows.
[1] a kind of ethanol storage and conveying equipment steel, in terms of quality %, it contains：
C：0.02~0.3%,
Si：0.01~1.0%,
Mn：0.1~2.0%,
P：0.003~0.03%,
S：Less than 0.01%,
Al：0.005~0.100%,
N：0.0010~0.010%, and Al and N content ratio meets 2.0≤Al/N≤70.0,
Also contain and be selected from W：0.010~0.5% and Mo：At least one of 0.010~0.5%,
And contain and be selected from Sb：0.01~0.5% and Sn：At least one of 0.01~0.3%, surplus is by Fe and can not keep away The impurity exempted from is formed.
[2] according to the ethanol storage described in [1] and conveying equipment steel, in terms of quality %, it also contains in following At least one：
Cu：0.05~1.0%,
Cr：0.01~1.0% and
Ni：0.01~1.0%.
[3] according to the ethanol storage described in [1] or [2] and conveying equipment steel, in terms of quality %, it, which also contains, is selected from down At least one of state：
Ca：0.0001~0.02%,
Mg：0.0001~0.02% and
REM：0.001~0.2%.
[4] the ethanol storage according to any one of [1]~[3] and conveying equipment steel, in terms of quality %, it also contains Have selected from least one of following：
Ti：0.005~0.1%,
Zr：0.005~0.1%,
Nb：0.005~0.1% and
V：0.005~0.1%.
[5] the ethanol storage according to any one of [1]~[4] and conveying equipment steel, it has below 825MPa Tensile strength, and with below 705MPa yield strength.
The effect of invention
In accordance with the invention it is possible to obtain containing carboxylic acid, chlorion, water bio-ethanol environment under can also use, The excellent ethanol storage of resistance to ethanol corrosivity and conveying equipment steel.Used storage tank of the invention as bio-ethanol, In the case of transfer pot and line construction steel, compared with prior art, can longer-term it use, and can avoid corroding Accident caused by fatigue phenomenon caused by bio-ethanol leakage, and then these various equipment can be inexpensively provided, in industry It is upper exceedingly useful.
Embodiment
Hereinafter, the present invention is specifically described.
In the present invention, to the composition composition of steel is defined in into above range the reason for, illustrates.Need what is illustrated It is that the unit of the constituent content in the composition composition of steel is " quality % ", below, just only to use unless otherwise specified " % " is represented.
C：0.02~0.3%
C (carbon) is to ensure that element necessary to the intensity of steel, in order to ensure preferable yield strength (350MPa in the present invention More than) and tensile strength (more than 400MPa), at least contain 0.02%.C amounts are preferably more than 0.03%.On the other hand, C amounts are super When 0.3%, weldability reduces, and is restricted in welding, therefore the upper limit is set into 0.3%.C amounts be preferably 0.20% with Under.In the present invention, from the viewpoint of good resistance to corrosion fatigue is obtained, C amounts are more preferably less than 0.10%.
Si：0.01~1.0%
Si (silicon) adds for deoxidation, when content is less than 0.01%, deoxidation effect deficiency, on the other hand, Si When amount is more than 1.0%, toughness, weldability can be made to be deteriorated, therefore Si contents are set to 0.01~1.0%.It should be noted that on The lower limit of Si amounts, preferably 0.03%, more preferably 0.05%, more preferably 0.20%, on the upper limit of Si amounts, preferably For 0.7%, more preferably 0.5%.
Mn：0.1~2.0%
Mn (manganese) in order to improve intensity, toughness and add, Mn amounts be less than 0.1% when, its effect is insufficient, another Aspect, when Mn amounts are more than 2.0%, weldability is deteriorated, therefore Mn contents are set to 0.1~2.0%.It should be noted that on The lower limit of Mn amounts, preferably 0.3%, more preferably 0.5%, on the upper limit of Mn amounts, preferably 1.6%, it is more preferably 1.3%, more preferably 1.0%.
P：0.003~0.03%
P (phosphorus) makes toughness and weldability be deteriorated, therefore P content is suppressed to less than 0.03%.P excessive reduction from desulfurization into It is unfavorable from the viewpoint of this, therefore the lower limit of P amounts is set to 0.003%.It should be noted that P amounts preferably 0.003~ 0.025% scope, more preferably 0.003~0.015% scope.
S：Less than 0.01%
S (sulphur) is the important element for influenceing corrosion resistance in the steel of the present invention.S inevitably contains, containing When amount increases, not only toughness and weldability reduce, and MnS etc. turns into the field trash increase of corrosion fatigue starting point, makes corrosion-resistant Fatigability reduces.Further, since the field trash as the starting point of corrosion fatigue also turns into preferential anode position, therefore can promote Spot corrosion.It is therefore preferable that reducing S amounts as far as possible, can allow for less than 0.01%.It should be noted that S amounts are preferably 0.005% Hereinafter, more preferably less than 0.003%.On the other hand, for these reasons, the lower limit of S amounts is not particularly limited.
Al：0.005~0.100%
Al (aluminium) adds as deoxidier, when content is less than 0.005%, drops toughness because of deoxidation deficiency It is low.On the other hand, when being welded, the toughness that can make welding metal portion containing the Al amounts for having more than 0.100% reduces, therefore will Al amounts are limited to less than 0.100%.
In addition, Al has the function that the raising acid resistance effect for further improving Sb, Sn for describing below.That is, with female The anodic solution of material and the Al of dissolution3+With a small amount of existing water in bio-ethanol hydrolysis occurs for ion, therefore in anode portion The pH of position is reduced, and can promote the formation of Sb oxides, Sn oxides described below.By containing more than 0.005% Al, The effect becomes apparent from.On the other hand, when containing Al more than 0.100%, being obviously promoted the pH at anode position reduces, and causes Low pHization is spent, corrosion resistance caused by the formation for promoting Sb oxides, Sn oxides can not be fully obtained and improve effect.From simultaneous From the viewpoint of caring for toughness and resistance to corrosion fatigue, the lower limit of Al amounts is preferably 0.010%, and more preferably 0.015%, further Preferably 0.020%, similarly, the upper limit of Al amounts is preferably 0.070%, and more preferably 0.060%, more preferably Less than 0.050%.
N：0.0010~0.010%, 2.0≤Al/N≤70.0
N (nitrogen) is the important element for influenceing resistance to corrosion fatigue in the steel of the present invention.Suppress shape by reducing N content Into thick nitride, corrosion fatigue life is improved.On the other hand, during containing N more than 0.010%, can promote to be formed thick AlN, it can not fully obtain resistance to corrosion fatigue caused by above-mentioned Al and improve effect, and thick AlN is in itself as corrosion The starting point of fatigue plays a role, therefore the increase of corrosion fatigue sensitiveness.Therefore, N amounts are defined to less than 0.010%.Need to illustrate , N amounts are preferably less than 0.007%, more preferably less than 0.005%.In addition, on N, to stably obtaining above-mentioned Al Caused resistance to corrosion fatigue raising effect has the function that important.That is, Al3+The low pHization that the hydrolysis of ion is brought can cause Because promoting resistance to corrosion fatigue caused by the formation of Sb oxides, Sn oxides to improve, on the other hand, excessively reduced in pH When, there is generally resistance to corrosion fatigue variation.Here, the N in steel consumes H with anodic solution+, form NH4 +, so as to show the cushioning effect for suppressing excessive pH and reducing.In order to obtain the cushioning effect, it is necessary to contain N at least 0.0010% More than.Therefore, the lower limit that the lower limit of N content is set to 0.0010%, N amounts is preferably 0.0015%.
In addition, as described above, performance that resistance to corrosion fatigue raising caused by Al and N and AlN formation, Al acts on etc. It is closely related, it is important that Al amounts/N amounts (mass ratio) in optimization steel.When Al amounts are excessive relative to N amounts, that is, exceed When 70.0, AlN formation speed dramatically increases, and causes AlN coarsening.Moreover, NH4 +Formation caused by cushioning effect without Method catches up with AlN formation.Therefore, the upper limit of Al amounts/N amounts is set to 70.0.The preferable upper limit of Al amounts/N amounts is 50.0, more preferably The upper limit be 20.0.On the other hand, when Al amounts/N amounts are less than 2.0, the Al in steel exists in the form of AlN mostly, Wu Fachong Divide the Al for producing and being generated with the anodic solution of mother metal3+Ion.That is, the raising that can not fully obtain Sb, Sn caused by Al is resistance to Acid effect.Therefore, the preferable lower limit that the lower limit of Al amounts/N amounts is set to 2.0, Al amounts/N amounts is 3.0, and preferred lower limit is 5.0。
Selected from W：0.010~0.5% and Mo：At least one of 0.010~0.5%
W (tungsten) is to improving the effective element of resistance to corrosion fatigue.W and Mo is similarly formed the oxyacid as corrosion product Ion, therefore there occurs during the crackle of the starting point as stress corrosion cracking, above-mentioned corrosion product, which is promptly adsorbed in, to be split Line front end, anode reaction activity is reduced, have the function that to suppress Crack Extension.In addition, pass through the oxidation quilt in steel surface W is imported in film, the oxidation quilt under the sour environment caused by the carboxylic acid contained in bio-ethanol in the form of impurity can be improved The dissolubility resistent of film, non-uniform corrosion is reduced, and have the effect for reducing pitting corrosion resistance concurrently.However, it is less than in W content When 0.010%, the improvement of resistance to corrosion fatigue and pitting corrosion resistance can not be fully shown.On the other hand, exceed in W amounts It is unfavorable in terms of cost when 0.5%, therefore it is set as 0.010~0.5% for W content.The lower limit of W amounts is preferably 0.05%, more Preferably 0.08%.In order to prevent cost from increasing, the upper limits of W amounts is preferably that the upper limit of 0.3%, W amounts is more preferably 0.2%.
Mo (molybdenum) is to improving the effective element of resistance to corrosion fatigue.Mo forms the oxygen-containing acid ion as corrosion product, Therefore there occurs during the crackle of the starting point as corrosion fatigue, above-mentioned corrosion product is promptly adsorbed in crackle front end, is made Anode reaction activity reduces, and has the function that to suppress Crack Extension.In addition, by being imported in the oxide film thereon of steel surface Mo, the resistance to molten of oxide film thereon under the sour environment caused by the carboxylic acid contained in bio-ethanol in the form of impurity can be improved Xie Xing, non-uniform corrosion is reduced, and have the effect for reducing pitting corrosion resistance concurrently.However, when Mo contents are less than 0.010%, nothing Method fully shows the improvement of resistance to corrosion fatigue and pitting corrosion resistance.On the other hand, when Mo amounts are more than 0.5%, into Present aspect is unfavorable, therefore Mo contents are set as 0.010~0.5%.The lower limit of Mo amounts is preferably 0.05%, more preferably 0.08%.In addition, in order to prevent cost from increasing, the upper limit of Mo amounts is preferably 0.4%, more preferably 0.3%.
It should be noted that from the viewpoint of good resistance to corrosion fatigue is obtained, above-mentioned W is preferably comprised in the present invention And Mo.
Selected from Sb：0.01~0.5% and Sn：At least one of 0.01~0.3%
Sb (antimony) is the element for improving acid resistance, is that important resistance to corrosion fatigue improves member in the steel of the present invention Element.Particularly to the effective element of Crack Extension for the corrosion fatigue crack front end for suppressing low ph conditions.Sb with mother metal sun Dissolve and remain in the form of the oxide, be enriched in anode position in pole.Thus, anode portion is protected, and is significantly inhibited molten The progress of reaction is solved, resistance to corrosion fatigue is improved.However, when Sb contents are less than 0.01%, its is not sufficiently effective, the opposing party Face, when Sb amounts are more than 0.5%, it is restricted in steel manufacture view, therefore Sb contents are set as 0.01~0.5% model Enclose.It should be noted that the lower limit of Sb amounts is preferably 0.02%, more preferably 0.05%.The upper limit of Sb amounts is preferably 0.4%, More preferably 0.30%.
Sn (tin) same with Sb is the element for improving acid resistance, is important resistance to corrosion fatigue in the steel of the present invention Property improve element.Particularly to the effective element of Crack Extension for the corrosion fatigue crack front end for suppressing low ph conditions.Sn is adjoint The anodic solution of mother metal and remain in the form of the oxide, be enriched in anode position.Thus, anode portion is protected, significantly The progress for inhibiting dissolving to react, resistance to corrosion fatigue are improved.However, when content is less than 0.01%, its is not sufficiently effective, On the other hand, when Sn amounts are more than 0.3%, it is restricted in steel manufacture view, therefore Sn contents are set as 0.01~0.3% Scope.It should be noted that the lower limit of Sn amounts is preferably 0.02%, more preferably 0.05%.The upper limit of Sn amounts is preferably 0.30%, more preferably 0.15%.
It should be noted that in the present invention, from the viewpoint of good resistance to corrosion fatigue is obtained, preferably comprise State Sb and Sn.
In the present invention, among above-mentioned each composition, it is important that by by the oxygen-containing acid ion of Mo oxygen-containing acid ion, W The surface protection effect of caused high quick-acting acts on strong surface protection caused by the oxide as Sb, Sn oxide It is combined.That is, in the case of Corrosion Fatigue Crack Propagation is fireballing, the Sb oxides of crackle front end, the shape of Sn oxides The extension of crackle front end can not be caught up with into script, Sn, Sb crackle portion surface protection effect can not be obtained.But by make Mo, W coexists, and the quick surface protection effect that the oxygen-containing acid ions of Mo, the W oxyacid ion band in crackle portion come plays a role first.By This, crack propagation velocity reduces, and the formation of Sb oxides, Sn oxides in crackle front end can catch up with the expansion of crackle front end Exhibition.As a result, crackle front end is by by this two layers firm sealer formed of oxyacid sheath and oxide skin(coating) Covering, can significantly suppress corrosion fatigue.Here, in order to promote the formation of Sb oxides, Sn oxides, it is important that control Al Amount and reduction N amounts.The reduction of N amounts helps to reduce corrosion fatigue starting point, therefore can obtain the superposition of resistance to corrosion fatigue raising Effect.
More than, basis is illustrated, but in the present invention, in addition, can also suitably contain as needed Composition as described below.
Selected from Cu：0.05~1.0%, Cr：0.01~1.0% and Ni：At least one of 0.01~1.0%
Cu (copper), Cr (chromium), Ni (nickel) are caused by the carboxylic acid contained to improvement in bio-ethanol in the form of impurity Sour environment under the effective element of resistance to corrosion fatigue.However, in the case of poor, its is not sufficiently effective, on the other hand, When content is more than 1.0%, it is restricted in steel manufacture view, therefore, Cu contents are set as 0.05~1.0%, Cr contents It is set as that 0.01~1.0%, Ni contents are set as 0.01~1.0% scope.The upper limit of Cu contents is preferably 0.5%, more excellent Elect 0.2% as.The upper limit of Cr contents is preferably 0.5%, and more preferably 0.2%.The upper limit of Ni contents is preferably 0.5%, more excellent Elect 0.2% as.
Selected from Ca：0.0001~0.02%, Mg：0.0001~0.02% and REM：At least one of 0.001~0.2%
As described above, MnS turns into spot corrosion, the starting point of corrosion fatigue, it is harmful, in order to be reduced, from control steel The form of sulfide, it is scattered from the viewpoint of, Ca (calcium), Mg (magnesium), REM (rare earth element) are effective.In poor feelings Under condition, the effect can not be fully obtained.On the other hand, in the case of more than content, Ca, Mg, REM form thick on the contrary in itself Field trash and as the starting point of spot corrosion and corrosion fatigue.Therefore, Ca contents are set as that 0.0001~0.02%, Mg contents are set as 0.0001~0.02%, REM content are set as 0.001%~0.2% scope.The lower limit of Ca contents is preferably 0.001%, Ca The upper limit of content is preferably 0.005%.The lower limit of Mg contents is preferably the upper limit preferably 0.005% of 0.001%, Mg contents.REM The upper limit of content is preferably 0.030%.
Selected from Ti：0.005~0.1%, Zr：0.005~0.1%, Nb：0.005~0.1% and V：In 0.005~0.1% At least one
In order to improve the mechanical property of steel, one be selected from Ti (titanium), Zr (zirconium), Nb (niobium) and V (vanadium) can also be contained Kind is two or more.When content is less than 0.005%, on the other hand it, exceedes these elements containing effective deficiency in content When 0.1%, the mechanical property of weld part reduces, therefore the content of each element is set as 0.005~0.1% scope.Need Illustrate, for each element, content is preferably 0.005~0.05% scope.
In the steel of the present invention, composition other than the above is Fe and inevitable impurity.As long as in addition, do not damaging In the range of effect of the present invention, it can allow comprising the composition other than the above inevitably contained.
It is molten in the ethanol containing more than carboxylic acid 0.02mmol/L, more than chlorion 0.02mg/L and more than water 0.05vol% In liquid, particularly spot corrosion position, crackle leading section are exposed under low ph conditions.Therefore, in addition to producing spot corrosion, crackle, Secondary rupture brittle as caused by hydrogen can be also superimposed.In order to suppress the hydrogen embrittlement sensitiveness of steel, the drawing for the steel of the present invention For stretching intensity, below 825MPa is preferably set to, for yield strength, is preferably set to below 705MPa.
The steel of the present invention is suitable to ethanol storage and conveying equipment purposes.In addition, the present invention steel be containing carboxylic acid, chlorine from The steel workable under son, the particularly ethanol of water, the corrosive environment of bio-ethanol, resistance to ethanol corrosivity is excellent.
In the present invention, carboxylic acid is aliphatic carboxylic acid, and carbon number is 1~5 scope.In the present invention, ethanol stores And the equipment that conveying equipment refers to store ethanol, conveys, transports, accumulating, distributing, reclaiming, mixing etc..Set as this It is standby, such as have tank, steel pipe, oil tanker, pipe arrangement, pipeline, nozzle, valve etc..The ethanol storage of the present invention and conveying equipment steel Shape can be selected suitably, preferably steel plate.The preferred thickness (wall thickness) of the steel of the present invention is 1~50mm, preferred thickness For 3~50mm, more preferably 5~50mm.
Then, the preferable manufacture method of steel of the present invention is illustrated.
Stove carries out melting to the molten steel with above-mentioned composition composition known to converter, electric furnace etc., passes through continuously casting The steel raw materials such as steel billet, blank are made in method known to method, ingot casting method etc..It should be noted that when carrying out melting, Ke Yishi Apply vacuum deaeration refining etc..
The method for adjusting compositions of molten steel can be carried out according to known method for making steel.
Then, when above-mentioned steel raw material is rolled into desired size shape, 1000~1350 DEG C are preferably heated to Temperature.When heating-up temperature is less than 1000 DEG C, deformation drag is big, the tendency for being difficult to hot rolling be present.On the other hand, more than 1350 DEG C Heating exist and turn into the reason for producing marks on surface, oxide skin loss, unit of fuel is consumed increased hidden danger.Heating-up temperature More preferably 1050~1300 DEG C of scope.It should be noted that the temperature in steel raw material is originally used for 1000~1350 DEG C , can also be without heating, and directly for hot rolling in the case of scope.
It should be noted that in hot rolling, generally hot fine rolling end temp is optimized.Hot fine rolling end temp It is preferably set to more than 600 DEG C and less than 850 DEG C.When hot fine rolling end temp is less than 600 DEG C, because of the increase of deformation drag, , the hidden danger for being difficult to carry out rolling be present in rolling load increase.On the other hand, when the temperature is more than 850 DEG C, can not obtain sometimes Desired intensity.Hot fine rolling terminate after cooling to be preferably set to the acceleration that air cooling or cooling velocity are less than 150 DEG C/sec cold But.Accelerate cooling during cooling to stop the scope that temperature is preferably set to 300~750 DEG C.It should be noted that can be cold But reheating processing is implemented afterwards.
Embodiment
Next, embodiments of the invention are illustrated.It should be noted that the present invention is not limited to these implementations Example.In addition, in the explanation of embodiment, table 1-1 and table 1-2 are referred to as table 1, table 2-1 and table 2-2 are referred to as table 2.
, with after vacuum fusion stove melting or after carrying out converter melting, it will pass through with the molten steel that the composition shown in table 1 forms Steel billet is made in continuously casting.Then, after being heated to 1230 DEG C, hot rolling is implemented under conditions of being 850 DEG C in finish rolling end temp, The thick steel plates of 15mm have been made.
Micro-tension test piece (parallel portion 6mm φ × 25mm) is gathered in the C directions (width) of the steel plate so obtained, Tension test is carried out according to JIS Z 2241 regulation at room temperature, has obtained yield strength (YS) and tensile strength (TS).Will As a result it is shown in table 1.
In addition, implement corrosion fatigue test as described below.
First, single shaft pole tension test sheet (parallel portion size is cut from steel plate：Length 25.4mm × diameter 3.81mm φ), to be polished equivalent to finishing for the standards of No. 2000 models to parallel portion.Then, carry out in acetone 5 minutes Ultrasonic degreasing, it is arranged on after air-drying on low strain dynamic speed tensile tester.Using with the addition of into ethanol 985ml water 10ml, Methanol 5ml, acetic acid 56mg, NaCl13.2mg and manufactured solution simulate liquid as bio-ethanol.Drawn to covering single shaft pole Stretch and bio-ethanol simulation liquid is filled in the groove of test film, based on the yield strength (YS) determined before experiment, in single shaft The stretching direction of principal axis of pole tension test sheet is with 8.3 × 10-4Hz cycle applies variable stresses to most long 240 hours, it is described can Maximum stress is set to yield strength × 110% by varying stress, and minimum stress is set into yield strength × 10%.
In evaluation, first, it is thus identified that fracture is whether there is in during experiment.Then, stretched for unbroken single shaft pole For test film, test film is taken out after experiment, implements to utilize microscopical visual inspection, it is thus identified that have flawless.To true Recognize the test film observation stretching direction of principal axis section of crackle, determine section maximum crack length.According to following benchmark to resistance to Corrosion fatigue is evaluated.In the case of crack length is less than 20 μm, it is judged as that Crack Extension is slow, is sent out in facilities and equipments The risk that raw corrosion fatigue destroys is low (qualified).
◎：Flawless
○：There is fine crack (crack length is less than 20 μm)
△：There is crackle (crack length is more than 20 μm)
×：Fracture
Obtained result is recorded in table 2.
As shown in Table 2, example clearly improves the degree of the corrosion fatigue crack in bio-ethanol simulation liquid. By contrast, all there occurs the degree of fracture or corrosion fatigue crack is big for the comparative example of composition Composition deviation invention scope.
It can be seen from the contrast of example and comparative example, improvement of the invention is obvious.In addition, by being split to generating The Auger spectrum analysis that the crackle front end of the example of line is implemented, it is thus identified that in crackle front end formed with superficial layer, the surface Layer is divided into the enriched layer of oxygen-containing acid ion formation element (W, Mo) and this two layers of the enriched layer of oxide forming elements (Sn, Sb). That is, in example, crackle front end is protected by firm protective layer.
Table 1-1
Table 1-2
Table 2-1
Table 2-2

Claims (5)

1. a kind of ethanol storage and conveying equipment steel, in terms of quality %, it contains：
C：0.02~0.3%,
Si：0.01~1.0%,
Mn：0.1~2.0%,
P：0.003~0.03%,
S：Less than 0.01%,
Al：0.005~0.100%,
N：0.0010~0.010%, and Al and N content ratio meets 2.0≤Al/N≤70.0,
Also contain and be selected from W：0.010~0.5% and Mo：At least one of 0.010~0.5%,
And contain and be selected from Sb：0.01~0.5% and Sn：At least one of 0.01~0.3%, surplus is by Fe and inevitably Impurity is formed.
2. ethanol according to claim 1 storage and conveying equipment steel, in terms of quality %, it also contains in following At least one：
Cu：0.05~1.0%,
Cr：0.01~1.0% and
Ni：0.01~1.0%.
3. ethanol storage according to claim 1 or 2 and conveying equipment steel, in terms of quality %, it, which also contains, is selected from down At least one of state：
Ca：0.0001~0.02%,
Mg：0.0001~0.02% and
REM：0.001~0.2%.
4. according to ethanol according to any one of claims 1 to 3 storage and conveying equipment steel, in terms of quality %, it also contains Have selected from least one of following：
Ti：0.005~0.1%,
Zr：0.005~0.1%,
Nb：0.005~0.1% and
V：0.005~0.1%.
5. according to ethanol according to any one of claims 1 to 4 storage and conveying equipment steel, it has below 825MPa's Tensile strength, and the yield strength with below 705MPa.
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