CN103088347B - Aluminum alloy sacrificial anode material for storage tank coil and preparation method thereof - Google Patents

Aluminum alloy sacrificial anode material for storage tank coil and preparation method thereof Download PDF

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CN103088347B
CN103088347B CN201210577522.9A CN201210577522A CN103088347B CN 103088347 B CN103088347 B CN 103088347B CN 201210577522 A CN201210577522 A CN 201210577522A CN 103088347 B CN103088347 B CN 103088347B
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anode material
sacrificial anode
storage tank
alloy sacrificial
coil pipe
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CN103088347A (en
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郭亮
吴保玉
李世勇
张新发
陈怀兵
徐军
薛斌
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China National Petroleum Corp
CNPC Chuanqing Drilling Engineering Co Ltd
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CNPC Chuanqing Drilling Engineering Co Ltd
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Abstract

The invention discloses an aluminum alloy sacrificial anode material for a storage tank coil pipe and a preparation method thereof, wherein the aluminum alloy sacrificial anode material for the storage tank coil pipe comprises the following components in percentage by weight: zn: 3.0-5.5%; in: 0.02-0.03%; mg: 1.0-1.5%; ti: 0.03-0.05%; b: 0.01-0.09%; the balance of aluminum, and the impurity content is less than or equal to 0.1 percent. The invention has large capacitance, large driving potential, high current efficiency and uniform dissolution, and effectively solves the defects of easy passivation, failure and the like of the national standard Al-Zn-In anode material In the on-site high-temperature and high-mineralization corrosion environment, thereby effectively reducing the protective potential of the coil to be below-0.85V and prolonging the service life of the heating coil.

Description

Storage tank coil pipe aluminium alloy sacrificial anode material and preparation method thereof
Technical field
The present invention relates to oil field corrosion and protection technical field, relate generally to a kind of storage tank coil pipe aluminium alloy sacrificial anode material and preparation method thereof, for solving because corroding the storage tank heat coil pipe corrosion failure problem caused.
Background technology
Heating coil is one of important accessory in crude oil storage tank, and its function adds oil-water mixture in hot tank winter, to ensure that in tank, crude oil temperature is more than condensation point, prevents crude oil in storage tank from solidifying and accelerates oily water separation speed.Enter the crude oil water containing ratio high (water content >=50%) of storage tank, heating coil is generally arranged on tank bottom, and therefore external corrosion environments is mainly tank bottom connate water, the corrosive elements in the mainly connate water causing coil pipe to corrode.
The corrosive medium complicated component that bottom settlings water is formed, is characterized in: the higher (Cl of salinity -content>=30000mg/L), be dissolved with O 2, H 2s, CO 2deng corrosive gases, also cause the microorganism of corrosion in addition with SRB, TGB etc., cause coil pipe severe local corrosion, even bore a hole.The replacement charge of heating coil is huge, and one time expense is 40 ~ 500,000, and changing coil pipe frequently increases production cost, and tank cleaning work when simultaneously changing coil pipe more affects oily district and normally produces.
The anti-corrosion measure being applicable to on-the-spot heating coil corrosive environment is at present mainly coil surface coating protection technology and coil pipe outer wall galvanic anode protection technology.Wherein, coating has problems in application process at the scene: the strong and temperature high (controlling for a long time more than 80 DEG C) of corrosive medium, coating very easily occurs local shedding in this corrosive environment, is formed " large negative electrode, primary anode ", accelerates coil pipe matrix corrosion.The Al-Zn-In system anode that the sacrificial anode material that scene adopts for the galvanic protection of coil pipe outer wall provides for GB GB/T 4948-2002, measure this kind of anode electrochemical in the seawater functional, wherein electrical capacity >=2600Ah/kg, current efficiency >=90%, but this kind of anode material is applied in on-the-spot high temperature, high salinity corrosive environment, there is following problem: 1, anode material dissolves very fast, and work-ing life is short; 2, anode material surface dissolution is uneven, corrosion product difficult drop-off; 3, hot environment uses easy passivation, shielding failure; 4, cost is high, melting technology is complicated.
It take aluminium as raw material that CN101148767A discloses a kind of aluminum-zinc-indium series sacrificial anode material, Addition ofelements zinc, indium, magnesium, titanium and element silicon, adopt the preparation of argon shield induction melting, there is good chemical property, current efficiency >=92%, electrical capacity >=2650 Ah/kg; CN102002715A discloses the galvanic protection high-performance aluminium alloy sacrificial anode in a kind of ocean environment under equipment corrosion occasion, Al-Zn-In system basis with the addition of alloying element Mg, Sn, Si, realize anode electrochemical performance to improve, current efficiency >=92%, electrical capacity >=2700 Ah/kg; CN101619459A discloses a kind of quickly activating aluminum alloy sacrificed anticathode anode, adds the elements such as Ga, Mg, Mn, crystal grain thinning in aluminium alloy, makes sacrificial anode energy fast activating.Above-mentioned three kinds of sacrificial aluminium alloy anodes for metal corrosion and protection technical field possess the features such as excellent electrochemical performance, preparation technology be simple; but use for a long time in corrosive environment more than 80 DEG C; Yin Gaowen passivation is lost protected effect by sacrificial anode material, cannot be applied to high-temperature corrosion environment protection heating coil outer wall in storage tank.
Summary of the invention
The object of the invention is to overcome the problems referred to above that in prior art, the protection against corrosion of storage tank heat coil pipe exists; a kind of storage tank coil pipe aluminium alloy sacrificial anode material and preparation method thereof is provided; electrical capacity of the present invention is large, driving current potential is large, current efficiency is high and energy uniform dissolution; effective solution GB Al-Zn-In system anode material uses the defects such as easy passivation, inefficacy in high temperature, high salinity corrosive environment at the scene; thus effectively can reduce coil pipe protection potential to below-0.85V, extend the work-ing life of heating coil.
For achieving the above object, the technical solution used in the present invention is as follows:
A kind of storage tank coil pipe aluminium alloy sacrificial anode material, it is characterized in that, by weight percentage, composition is: Zn:3.0 ~ 5.5%; In:0.02 ~ 0.03%; Mg:1.0 ~ 1.5%; Ti:0.03 ~ 0.05%; B:0.01 ~ 0.09%; Surplus is aluminium, foreign matter content≤0.1%.
By weight percentage, composition is described aluminium alloy sacrificial anode material: Zn:4.0 ~ 5.0%; In:0.022 ~ 0.028%; Mg:1.2 ~ 1.4%; Ti:0.035 ~ 0.045%; B:0.04 ~ 0.07%; Surplus is aluminium, foreign matter content≤0.08%.
By weight percentage, composition is described aluminium alloy sacrificial anode material: Zn:5.5%; In:0.02%; Mg:1.5%; Ti:0.05%; B:0.03%, surplus is aluminium.
By weight percentage, composition is described aluminium alloy sacrificial anode material: Zn:3.5%; In:0.03%; Mg:1.0%; Ti:0.05%; B:0.015%, surplus is aluminium.
By weight percentage, composition is described aluminium alloy sacrificial anode material: Zn:5.0%; In:0.03%; Mg:1.5%; Ti:0.05%; B:0.05%, surplus is aluminium.
A preparation method for storage tank coil pipe aluminium alloy sacrificial anode material, is characterized in that: take alloying element and wrap in aluminium foil, being heated to whole fusing, after being uniformly mixed, be uniformly mixed after standing at least 10min, cast in a mold, naturally cooling solidifies.
The described alloying element taken wraps in aluminium ingot shape in aluminium foil, then puts into stove, and temperature is set at least 760 DEG C, is heated to whole fusing.
Describedly be heated to whole fusing, after being uniformly mixed, spreading one deck wood charcoal powder on fused solution surface, then leave standstill.
Employing the invention has the advantages that:
One, the present invention by weight percentage, and composition is: Zn:3.0 ~ 5.5%; In:0.02 ~ 0.03%; Mg:1.0 ~ 1.5%; Ti:0.03 ~ 0.05%; B:0.01 ~ 0.09%; Surplus is aluminium, foreign matter content≤0.1%, and have good activation performance, corrosion product easily comes off, and not easily occurs passivation, inefficacy in hot environment, meets hot environment service requirements; 0.01 ~ 0.09% trace B element, to adapt to the requirement that hot environment uses, adding of boron can form TiB2 refinement phase in the alloy, can effective crystal grain thinning, makes to organize dense uniform more, thus improve the erosion uniformity of anode material, in addition, the atomic radius of boron is 88Pm, has contraction to lattice, play and reduce from corrosion speed, improve the effect of current efficiency and anode capacity.
Two, in the present invention, by weight percentage, composition is described aluminium alloy sacrificial anode material: Zn:4.0 ~ 5.0%; In:0.022 ~ 0.028%; Mg:1.2 ~ 1.4%; Ti:0.035 ~ 0.045%; B:0.04 ~ 0.07%; Surplus is aluminium, foreign matter content≤0.08%, the aluminium alloy sacrificial anode material excellent electrochemical performance of this composition, after testing actual capacitance >=2650 Ah/kg, current efficiency >=90%.
Three, in the present invention: 1, described aluminium alloy sacrificial anode material by weight percentage, and composition is: Zn:5.5%; In:0.02%; Mg:1.5%; Ti:0.05%; B:0.03%, surplus is aluminium; 2, described aluminium alloy sacrificial anode material by weight percentage, and composition is: Zn:3.5%; In:0.03%; Mg:1.0%; Ti:0.05%; B:0.015%, surplus is aluminium; 3, described aluminium alloy sacrificial anode material by weight percentage, and composition is: Zn:5.0%; In:0.03%; Mg:1.5%; Ti:0.05%; B:0.05%, surplus is aluminium; The aluminium alloy sacrificial anode material of these three kinds of compositions; in process of the test, do not have appearance potential to decline or passivation failure phenomenon; anodic corrosion is even; corrosion product loosens Automatic-falling; chemical property is better than prior art products, have that protected effect is good, volume is little, lightweight, be easy to install, long service life and the feature such as cost is low.
Four, preparation method of the present invention, adopts conventional founding manufacture, technical maturity, and be convenient to manufacture, naturally cooling does not need artificial cooling, reduces energy consumption and cost of labor.
Five, in preparation method of the present invention, described in the alloying element that takes wrap in aluminium ingot shape in aluminium foil, then put into stove, temperature is set at least 760 DEG C, is heated to whole fusing, and this method is convenient to mixing of each composition, thus improves the quality of products.
Six, in preparation method of the present invention, described in be heated to whole fusing, after being uniformly mixed, spreading one deck wood charcoal powder on fused solution surface, then leave standstill, this method can prevent burning and reduce scaling loss, ensure that quality product.
Embodiment
Embodiment 1
The weight percent composition of the storage tank coil pipe aluminium alloy sacrificial anode material of the present embodiment is: Zn:5.5%; In:0.02%; Mg:1.5%; Ti:0.05%; B:0.03%, surplus is aluminium, foreign matter content≤0.1%.
According to formula, take various alloying element, pack tightly with aluminium foil.Temperature is set in 760 DEG C, aluminium ingot is heated to whole fusing with stove, different according to the fusing point of each alloying element, be pressed in the aluminium water of fusing at different temperatures, after repeatedly stirring, stir gently leave standstill 10min in stove after and mix, cast in cast iron die, naturally cooling solidifies.
Embodiment 2
The weight percent composition of the storage tank coil pipe aluminium alloy sacrificial anode material of the present embodiment is: Zn:3.5%; In:0.03%; Mg:1.0%; Ti:0.05%; B:0.015%, surplus is aluminium, foreign matter content≤0.1%.
According to formula, take various alloying element, pack tightly with aluminium foil.Temperature is set in 760 DEG C, aluminium ingot is heated to whole fusing with stove, different according to the fusing point of each alloying element, be pressed in the aluminium water of fusing at different temperatures, after repeatedly stirring, stir gently leave standstill 10min in stove after and mix, cast in cast iron die, naturally cooling solidifies.
Embodiment 3
The weight percent formula of the storage tank coil pipe aluminium alloy sacrificial anode material of the present embodiment is: Zn:5.0%; In:0.03%; Mg:1.5%; Ti:0.05%; B:0.05%, surplus is aluminium, foreign matter content≤0.1%.
According to alloy formula, take various alloying element, pack tightly with aluminium foil.Temperature is set in 760 DEG C, aluminium ingot is heated to whole fusing with stove, different according to the fusing point of each alloying element, be pressed in the aluminium water of fusing at different temperatures, after repeatedly stirring, stir gently leave standstill 10min in stove after and mix, cast in cast iron die, naturally cooling solidifies.
Embodiment 4
Carry out electrochemical property test to the aluminium alloy sacrificial anode material of preparation, reference standard GB/T17848-1999 specifies, adopts Princeton electrochemistry integrated test system to carry out electrochemical property test to aluminium alloy sacrificial anode material prepared by the present invention.
Test(ing) medium: natural sea-water, test temperature: 80 DEG C
Anode electrochemical the performance test results:
Shown by above-mentioned experiment, storage tank coil pipe aluminium alloy sacrificial anode material prepared by the present invention does not have appearance potential to decline or passivation failure phenomenon in process of the test, anodic corrosion is even, and corrosion product loosens Automatic-falling, and chemical property is better than prior art products.Have that protected effect is good, volume is little, lightweight, be easy to install, long service life and the feature such as cost is low.
Embodiment 5
A kind of storage tank coil pipe aluminium alloy sacrificial anode material, by weight percentage, composition is: Zn:4.0 ~ 5.0%; In:0.022 ~ 0.028%; Mg:1.2 ~ 1.4%; Ti:0.035 ~ 0.045%; B:0.04 ~ 0.07%; Surplus is aluminium, foreign matter content≤0.08%, and described impurity refers to the metal oxide remained in melt.
Adopt conventional founding manufacture, manufacturing process is according to formula, take various alloying element, pack tightly in aluminium ingot shape with aluminium foil, temperature is set in 760 DEG C, aluminium ingot is heated to whole fusing with stove, different according to the fusing point of each alloying element, be pressed in the aluminium water of fusing at different temperatures, after being repeatedly uniformly mixed, spread one deck wood charcoal powder gently on surface to prevent burning and to reduce scaling loss, stir gently leave standstill 10min in stove after and mix, use carbon-point drainage after skimming, cast in cast iron die, naturally cooling solidifies.
In preparation method, skimming refers to and removes the floating wood charcoal powder of bath surface and metal oxide products, and the existence because of scum silica frost can increase the air content of melt, and contaminated melt body.Skimming, it is steady, thorough to require, prevents scum silica frost to be involved in melt.
The aluminium alloy sacrificial anode material of the mentioned component adopting the method for the present embodiment to prepare; excellent electrochemical performance; electrical capacity >=2650 Ah/kg, current efficiency >=90%; have that protected effect is good, volume is little, lightweight, be easy to install, long service life and the feature such as cost is low; be applied in high temperature in storage tank, high salinity corrosive environment and effectively can reduce coil pipe protection potential to below-0.85V, extend the work-ing life of heating coil.
Embodiment 6
The weight percent composition of the storage tank coil pipe aluminium alloy sacrificial anode material of the present embodiment is: Zn:3.0%; In:0.025%; Mg:1.3%; Ti:0.03%; B:0.09%, surplus is aluminium, foreign matter content≤0.1%.
Adopt the aluminium alloy sacrificial anode material of the present embodiment mentioned component, be applied in high temperature in storage tank, high salinity corrosive environment and effectively can reduce coil pipe protection potential to below-0.85V, extend the work-ing life of heating coil.
Embodiment 7
The weight percent composition of the storage tank coil pipe aluminium alloy sacrificial anode material of the present embodiment is: Zn:4.0%; In:0.022%; Mg:1.2%; Ti:0.04%; B:0.01%, surplus is aluminium, foreign matter content≤0.07%.
Adopt the aluminium alloy sacrificial anode material of the present embodiment mentioned component, excellent electrochemical performance, electrical capacity >=2700 Ah/kg, current efficiency >=94%.Be mainly used in crude oil storage tank heating coil anticorrosion, also can be used for storage tank bottom in addition and tank skin is anticorrosion.Be applied in actual production; can effectively reduce coil pipe protection potential, suppress coil pipe to corrode outward, extend heating coil work-ing life; can save because of maintenance and the high expense changing coil pipe generation, the impact that tank cleaning work when changing coil pipe is normally produced oily district can be avoided again.

Claims (4)

1. a storage tank coil pipe aluminium alloy sacrificial anode material, is characterized in that: by weight percentage, composition is described aluminium alloy sacrificial anode material: Zn:4.0 ~ 5.0%; In:0.022 ~ 0.028%; Mg:1.2 ~ 1.4%; Ti:0.035 ~ 0.045%; B:0.04 ~ 0.07%; Surplus is aluminium, foreign matter content≤0.08%.
2. the preparation method of a kind of storage tank coil pipe aluminium alloy sacrificial anode material according to claim 1, it is characterized in that: take alloying element and wrap in aluminium foil, be heated to whole fusing, after being uniformly mixed, to leave standstill and be at least uniformly mixed after 10min, cast in a mold, naturally cooling solidifies.
3. the preparation method of storage tank coil pipe aluminium alloy sacrificial anode material according to claim 2, is characterized in that: described in the alloying element that takes wrap in aluminium ingot shape in aluminium foil, then put into stove, temperature is set at least 760 DEG C, is heated to whole fusing.
4. the preparation method of storage tank coil pipe aluminium alloy sacrificial anode material according to claim 2, is characterized in that: described in be heated to whole fusing, after being uniformly mixed, spreading one deck wood charcoal powder on fused solution surface, then leave standstill.
CN201210577522.9A 2012-12-27 2012-12-27 Aluminum alloy sacrificial anode material for storage tank coil and preparation method thereof Active CN103088347B (en)

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CN104480354B (en) * 2014-12-25 2017-01-18 陕西科技大学 Preparation method of high-strength dissolublealuminum alloy material
CN106834834B (en) * 2017-02-27 2018-10-16 东莞市铝美铝型材有限公司 A kind of use for electronic products high-strength aluminum alloy and preparation method thereof
CN107523721A (en) * 2017-05-08 2017-12-29 赵永韬 A kind of heat exchanger water-cooling system aluminum alloy anode and preparation method thereof

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CN101619459A (en) * 2009-08-11 2010-01-06 山东德瑞防腐材料有限公司 Sacrificial anode capable of quickly activating aluminum alloy

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CN101619459A (en) * 2009-08-11 2010-01-06 山东德瑞防腐材料有限公司 Sacrificial anode capable of quickly activating aluminum alloy

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Effective date of registration: 20201029

Address after: 100007 Dongcheng District, Dongzhimen, China, North Street, No. 9 Oil Mansion, No.

Patentee after: CHINA NATIONAL PETROLEUM Corp.

Patentee after: CNPC Chuanqing Drilling Engineering Co.,Ltd.

Address before: The 1 section of No. 3 company Chuanqing Drilling Technology Information Office Chenghua District Green Road 610051 Chengdu City, Sichuan Province

Patentee before: CNPC Chuanqing Drilling Engineering Co.,Ltd.