WO2017203805A1 - Élément formé d'alliage d'aluminium et vaporisateur de gaz naturel liquide - Google Patents

Élément formé d'alliage d'aluminium et vaporisateur de gaz naturel liquide Download PDF

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Publication number
WO2017203805A1
WO2017203805A1 PCT/JP2017/010625 JP2017010625W WO2017203805A1 WO 2017203805 A1 WO2017203805 A1 WO 2017203805A1 JP 2017010625 W JP2017010625 W JP 2017010625W WO 2017203805 A1 WO2017203805 A1 WO 2017203805A1
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Prior art keywords
mass
aluminum alloy
corrosion
heat transfer
outer layer
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PCT/JP2017/010625
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English (en)
Japanese (ja)
Inventor
真司 阪下
亘 漆原
祐二 澄田
龍生 吉田
康行 堀家
大造 青木
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Kobe Steel Ltd
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Kobe Steel Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
    • C23C4/08—Metallic material containing only metal elements
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F13/00—Inhibiting corrosion of metals by anodic or cathodic protection
    • C23F13/02—Inhibiting corrosion of metals by anodic or cathodic protection cathodic; Selection of conditions, parameters or procedures for cathodic protection, e.g. of electrical conditions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F13/00—Inhibiting corrosion of metals by anodic or cathodic protection
    • C23F13/02—Inhibiting corrosion of metals by anodic or cathodic protection cathodic; Selection of conditions, parameters or procedures for cathodic protection, e.g. of electrical conditions
    • C23F13/06—Constructional parts, or assemblies of cathodic-protection apparatus
    • C23F13/08—Electrodes specially adapted for inhibiting corrosion by cathodic protection; Manufacture thereof; Conducting electric current thereto
    • C23F13/12—Electrodes characterised by the material
    • C23F13/14—Material for sacrificial anodes
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C9/00—Methods or apparatus for discharging liquefied or solidified gases from vessels not under pressure
    • F17C9/02—Methods or apparatus for discharging liquefied or solidified gases from vessels not under pressure with change of state, e.g. vaporisation

Definitions

  • the present invention relates to an aluminum alloy member and an LNG vaporizer. More specifically, the present invention is excellent in corrosion resistance in a corrosive environment such as a seawater environment, and is made of an aluminum alloy used for various vaporizers and heat exchangers such as members for vaporizers of liquefied natural gas and liquefied petroleum gas
  • the present invention relates to a member and an LNG vaporizer including the same.
  • heat transfer members such as heat transfer pipes and header pipes used for liquefied natural gas (hereinafter, also referred to as "LNG") vaporizers and various heat exchangers. It is used.
  • LNG liquefied natural gas
  • Such aluminum alloy members may locally undergo corrosion (pitting corrosion) by being exposed to the air or water for a long time, and as a result, they may lead to penetration of the members.
  • the cathodic protection method is often used.
  • a substrate made of an aluminum alloy is brought into contact with a substrate by applying a sacrificial coating such as an Al-Zn alloy or a fin material such as Al-Zn alloy, which has a lower corrosion potential than the substrate. It is the one that obtains the corrosion protection effect.
  • a method of adding a corrosion inhibitor (inhibitor) to circulating water is also used in combination.
  • Patent Document 1 proposes that a film made of an aluminum alloy having a Mg content higher than that of the base material of the heat transfer tube be formed on the surface of the base material as a sacrificial anticorrosive film.
  • Patent Document 2 the swelling and peeling of the sacrificial anticorrosive coating are prevented by adjusting the roughness at the interface between the sacrificial anticorrosive coating made of Al-Zn alloy or Al-Mg alloy and the substrate. Has been proposed.
  • An object of the present invention is to provide an aluminum alloy member excellent in sacrificial corrosion resistance and capable of more effectively suppressing the swelling of a film formed on the surface of a substrate, and an LNG vaporizer provided with the same. It is.
  • An aluminum alloy member includes a base made of an aluminum alloy, and a film formed on the surface of the base.
  • the film is formed between an outer layer made of an aluminum alloy containing magnesium in an amount of 1% by mass to 20% by mass, and the base and the outer layer, and contains 1% by mass to 20% by mass of zinc And an inner layer made of an aluminum alloy.
  • An LNG vaporizer according to another aspect of the present invention includes the above-described aluminum alloy member.
  • IFNV intermediate-medium type LNG vaporizer
  • the aluminum alloy member according to the present embodiment includes a base made of an aluminum alloy, and a film formed on the surface of the base.
  • the film is formed between an outer layer made of an aluminum alloy containing magnesium in an amount of 1% by mass to 20% by mass, and the base and the outer layer, and contains 1% by mass to 20% by mass of zinc And an inner layer made of an aluminum alloy.
  • the present inventors diligently studied the improvement of the durability of an aluminum alloy member exposed to a corrosive solution, such as seawater containing copper ions. Specifically, we carefully study measures to prevent the swelling of the film, which is the initial deterioration of the sacrificial anticorrosive film, and to ensure the corrosion resistance of the substrate even after the deterioration of the film progresses and the substrate is exposed.
  • a corrosive solution such as seawater containing copper ions
  • the present inventors form the outer layer which consists of an Al-Mg alloy which adjusted the component composition in the suitable range, and the inner layer which consists of an Al-Zn alloy as a film on the surface of a substrate, While finding that the swelling of the film which is the initial deterioration is suppressed, and the corrosion resistance of the substrate after the exposure of the substrate is improved, the present invention was conceived.
  • an outer layer made of an aluminum alloy containing 1% by mass or more and 20% by mass or less of magnesium is formed. Since magnesium is an element whose corrosion potential is lower than that of aluminum, its inclusion in an outer layer exposed to seawater can improve the sacrificial corrosion resistance of the film. That is, even after the corrosion progresses and the surface of the substrate is exposed, the corrosion resistance of the substrate can be secured by corroding the outer layer preferentially over the substrate.
  • the magnesium content of the outer layer is adjusted to 1% by mass or more.
  • the magnesium content of the outer layer is adjusted to 20% by mass or less.
  • the magnesium content of the outer layer is preferably 1.2% by mass or more, and more preferably 1.5% by mass or more.
  • the magnesium content of the outer layer is preferably 19% by mass or less, more preferably 18% by mass or less.
  • the sacrificial corrosion resistance of a film can be improved by forming the outer layer which adjusted magnesium content to a suitable quantity, when the single layer film by the said outer layer is formed, the following problems are mentioned.
  • the following problems are mentioned. That is, when a single layer coating consisting only of the outer layer is formed on the surface of the substrate, if local corrosion such as pitting occurs in the coating, the pH in the bottom of the hole decreases and the chloride is concentrated Corrosion rate increases. As a result, localized corrosion easily reaches the substrate. In this case, seawater entering from the pores of the coating reaches the interface between the substrate and the coating, and corrosion progresses at the interface. As a result, there is a problem that volumetric expansion of the film occurs due to the corrosion product generated at the interface, and the film swells.
  • the inventors of the present invention described the above local corrosion as described above by forming an inner layer containing a suitable amount of zinc whose corrosion potential is intermediate between magnesium and aluminum between the substrate and the outer layer. We found that we could suppress the progression.
  • Zinc has a lower corrosion potential than aluminum of the base material, but has a higher corrosion potential than magnesium of the outer layer, and therefore has an action of suppressing the progress of local corrosion of the outer layer made of an Al-Mg alloy. Therefore, by forming the inner layer, it is possible to prevent seawater from reaching the interface between the substrate and the film, and as a result, it is possible to suppress the swelling of the film due to the progress of corrosion at the interface.
  • the inner layer since the inner layer has a lower corrosion potential than the base material, it can be made to act as a sacrificial anticorrosive coating like the outer layer after the base material is exposed.
  • the zinc content of the inner layer is adjusted to 1% by mass or more.
  • the zinc content of the inner layer is adjusted to 20% by mass or less.
  • the zinc content of the inner layer is preferably 1.2% by mass or more, and more preferably 1.5% by mass or more.
  • the zinc content of the inner layer is preferably 19% by mass or less, more preferably 18% by mass or less.
  • the outer layer may further contain a smaller amount of zinc than magnesium.
  • the inner layer may further contain a smaller amount of magnesium than zinc.
  • the outer layer contains the same zinc as the element contained in the inner layer and also containing the same magnesium as the element contained in the outer layer, the affinity between the inner layer and the outer layer is improved. As a result, the adhesion between the layers can be improved.
  • the magnesium content in the outer layer may be larger than the magnesium content in the inner layer.
  • magnesium is contained more in the outer layer exposed to seawater than in the inner layer, since magnesium is an element that enhances the corrosion potential of the film to improve the sacrificial corrosion resistance.
  • At least one of the outer layer and the inner layer is 0.01% by mass or more and 1.0% by mass or less of silicon, and 0.01% by mass or more and 1.0% by mass or less Iron, 0.01% by mass or more and 1.0% by mass or less of copper, 0.01% by mass or more and 1.0% by mass or less of manganese, 0.01% by mass or more and 1.0% by mass or less of chromium and 0.01 It may further contain at least one element selected from the group consisting of titanium by weight or more and 1.0% by weight or less.
  • Silicon, iron, copper, manganese, chromium and titanium have the effect of reducing the film consumption rate by reducing the anodic reaction rate of aluminum.
  • content of these elements in the film is excessive, the corrosion potential may become noble and the sacrificial corrosion resistance may decrease.
  • content of these elements in an outer layer or an inner layer is 0.01 mass% or more and 1.0 mass% or less.
  • the base material may be made of any one of 3000 series, 5000 series and 6000 series aluminum alloys.
  • 3000 series, 5000 series and 6000 series are international aluminum alloy names.
  • the base material one made of an aluminum alloy having good thermal conductivity and no brittle fracture even at low temperatures is used.
  • the aluminum alloys those of the 2000 series, 3000 series, 5000 series, 6000 series or 7000 series can be suitably used from the viewpoint of strength, and particularly those of the 3000 series, 5000 series or 6000 series It is preferred to use.
  • good strength and corrosion resistance can be obtained.
  • A3003, A3203, A5052, A5154, A5083, A6061, A6063 or A6N01 can be used.
  • what heat-treated, such as hardening, tempering, and artificial aging may be used as needed.
  • the aluminum alloy member may be used in a low temperature environment of 0 ° C. or less.
  • the above aluminum alloy member has a coating excellent in sacrificial corrosion resistance formed on the surface of a substrate, so that it can be used continuously with long life even when used in a low temperature environment of 0 ° C. or less it can.
  • the aluminum alloy member may be configured as a heat transfer pipe or a header pipe of an LNG vaporizer.
  • the aluminum alloy member is a member having a coating excellent in sacrificial corrosion resistance formed on the surface of a substrate. For this reason, high corrosion resistance is achieved even when used under an environment where it is exposed to seawater, which is a corrosive medium, and is subjected to temperature change between low temperature and normal temperature, such as a heat transfer pipe or header pipe of an LNG vaporizer. You can get it.
  • the LNG vaporizer which concerns on this embodiment is provided with the said aluminum-alloy-made members.
  • the aluminum alloy member is excellent in sacrificial corrosion resistance and can suppress the swelling of the film. Therefore, the life of the LNG vaporizer can be further extended by providing the above-mentioned aluminum alloy member.
  • FIG. 1 schematically shows the configuration as viewed from the side of the LNG vaporizer 1.
  • FIG. 2 schematically shows the cross-sectional structure of the LNG vaporizer 1 along the line segment II-II in FIG.
  • the LNG vaporizer 1 is an open rack type vaporizer (ORV).
  • the LNG vaporizer 1 uses seawater as a heat source (fluid), and is liquefied liquefied gas of cryogenic temperature (-162 ° C. or less) flowing inside the heat transfer tube 13 and seawater at normal temperature flowing outside the heat transfer tube 13
  • the LNG is gasified by heat exchange between
  • the LNG vaporizer 1 includes a plurality of heat transfer pipe panels 11 which exchange heat between LNG and seawater, and a trough 12 which supplies the heat transfer pipe panels 11 with seawater.
  • Sea water may contain a trace amount of copper ions.
  • the heat transfer tube panels 11 are arranged at an interval in the lateral direction in a posture in which the heat transfer tube panels 11 are vertically erected.
  • the heat transfer pipe panel 11 includes a plurality of heat transfer pipes 13 spaced apart from one another, lower header pipes 14 connected to the lower ends of the heat transfer pipes 13, and heat transfer pipes 13. And an upper header pipe 15 connected to the upper end.
  • the lower header pipe 14 is connected to an inlet manifold 16 communicating therewith.
  • An outlet manifold 17 communicating with the upper header pipe 15 is connected to the upper header pipe 15.
  • the heat transfer pipe 13 and the lower header pipe 14 are heat transfer members, and are used in a low temperature environment of 0 ° C. or less because cryogenic LNG flows.
  • the heat transfer pipe 13 and the lower header pipe 14 are respectively made of the aluminum alloy members according to the present embodiment, and the details will be described later.
  • the trough 12 is comprised by the aluminum alloy member which concerns on this embodiment, upper direction opens, and consists of a container in which seawater accumulates. As shown in FIG. 2, the troughs 12 are disposed on the upper side (lower side than the upper header pipe 15) of the heat transfer pipe panel 11 between the adjacent heat transfer pipe panels 11. The trough 12 stores the seawater supplied from the seawater header pipe (not shown). Then, as shown by the arrows in FIG. 2, the seawater overflowing from the trough 12 flows down along the outer surface of the heat transfer tube 13 in each heat transfer tube panel 11. The details of the trough 12 will also be described later.
  • LNG flows in the order of the inlet manifold 16 and the lower header pipe 14, and then is diverted to each heat transfer pipe 13. Then, as shown in FIG. 2, the LNG flows from the lower side to the upper side in the flow path 7 inside each heat transfer pipe 13, while the seawater supplied from the trough 12 to the heat transfer pipe panel 11 is the outer surface of the heat transfer pipe 13. Flow down along.
  • LNG is vaporized by heat exchange with seawater (heat absorption from seawater) through the heat transfer tube 13 and becomes NG. Then, the NG gathers in the upper header pipe 15, passes through the outlet manifold 17, and is discharged as, for example, a gas at normal temperature.
  • a member through which seawater flows such as the heat transfer tube 13 constituted by an aluminum alloy member, the lower header tube 14 and the trough 12, etc. It is exposed to seawater which is a corrosive medium. Specifically, the outer surfaces of the heat transfer tube 13 and the lower header tube 14 and the inner surface of the trough 12 are exposed to seawater. For this reason, if the anticorrosion coating is not formed, the corrosion of aluminum progresses by being exposed to seawater for a long time during the operation of the LNG vaporizer 1, and the local corrosion such as pitting progresses. .
  • FIG. 3 shows the cross-sectional structure of the heat transfer tube 13 along the radial direction.
  • the heat transfer tube 13 is one in which a flow path 7 through which LNG flows is formed inside.
  • the heat transfer tube 13 includes a base 21 made of an aluminum alloy, and a coating 22 formed on the outer surface of the base 21.
  • the base 21 includes a hollow cylindrical tube main body 23 in which the flow path 7 is formed, and a plurality (10 in the present embodiment) of fins 24 protruding outward from the outer surface of the pipe main body 23 in the radial direction. And.
  • the fins 24 are provided to widen the heat transfer area of the heat transfer tube 13 and have the same shape and size. Further, as shown in FIG. 3, the fins 24 are formed at equal intervals along the circumferential direction on the outer surface of the tube main body 23.
  • the form of the fins 24 is not limited to this, and the plurality of fins 24 may have different shapes and sizes, or may be formed at different intervals along the circumferential direction.
  • the base material 21 is made of an aluminum alloy which is excellent in heat conductivity to increase the heat exchange efficiency between LNG and seawater, and from the viewpoint of strength and corrosion resistance, any one of the 3000 series, 5000 series and 6000 series aluminum alloys. It is composed of More specifically, the base 21 is made of an aluminum alloy such as A3003, A3203, A5052, A5154, A5083, A6061, A6063 or A6N01.
  • the coating 22 is a sacrificial anticorrosion coating for preventing the corrosion of the base 21, and is formed on the outer surface of the base 21 so as to conform to the shapes of the tube main body 23 and the fins 24.
  • the film 22 has a two-layer structure of the outer layer 26 made of an Al-Mg alloy and the inner layer 25 made of an Al-Zn alloy. It has the feature in the point.
  • the outer layer 26 is a layer including the outermost surface 22A of the coating 22, the seawater overflowing from the trough 12 (FIG. 2) mainly comes in contact with it.
  • the outer layer 26 contains 1 mass% or more and 20 mass% or less of Mg, and is comprised by the aluminum alloy which consists of remainder aluminum and an unavoidable impurity.
  • the "unavoidable impurities" are included in an amount that does not impair the anticorrosion performance of the outer layer 26, and examples thereof include elements such as H, O, C, and B.
  • Mg is an element having a lower corrosion potential than Al, and by enhancing the corrosion potential of the outer layer 26 relative to the base 21, the sacrificial corrosion resistance is improved. That is, even when corrosion progresses and the outer surface of the substrate 21 is exposed, the corrosion of the substrate 21 can be prevented by corroding the outer layer 26 preferentially over the substrate 21 (a sacrificial protection). .
  • the Mg content of the outer layer 26 is adjusted to 1 mass% or more. However, if the Mg content of the outer layer 26 is excessive, the consumption rate of the film increases and it becomes difficult to obtain the desired life, so the Mg content of the outer layer 26 is adjusted to 20% by mass or less. ing.
  • the Mg content of the outer layer 26 is preferably 1.2% by mass to 19% by mass, more preferably 1.5% by mass to 18% by mass, and 4% by mass to 6% by mass. It is more preferable that there be some, most preferably around 5% by mass. Further, as described above, the outer layer 26 is a layer including the outermost surface 22A of the coating 22 and higher sacrificial corrosion resistance than the inner layer 25 is required. Therefore, the Mg content in the outer layer 26 is the Mg content in the inner layer 25 It is more than that.
  • the film 22 when the film 22 is constituted by a single layer film of only the outer layer 26 made of an Al—Mg-based alloy, the corrosion rate in the depth direction of the outer layer 26 is large. Then, the holes 26A easily reach the substrate 21. In this case, seawater enters from the holes 26A formed in the outer layer 26, and corrosion progresses at the interface 21A between the base 21 and the outer layer 26. As a result, there is a problem that volumetric expansion of the coating 22 occurs due to the corrosion product 21B generated at the interface 21A, and the coating 22 is swollen.
  • the inner layer 25 made of an aluminum alloy containing an appropriate amount of Zn is formed between the base 21 and the outer layer 26. As shown in FIG. 3, the inner layer 25 is formed to be in contact with the outer surface of the base 21 (the tube body 23 and the fin 24), and the outer layer 26 is formed to be in contact with the outer surface of the inner layer 25. .
  • the inner layer 25 contains 1% by mass or more and 20% by mass or less of zinc, and is made of an aluminum alloy including the balance aluminum and unavoidable impurities.
  • the Zn of the inner layer 25 has a lower corrosion potential than the Al of the base material 21, but has a nobler corrosion potential than the Mg of the outer layer 26. Therefore, the inner layer 25 has a nobler corrosion potential than the outer layer 26. Therefore, as shown in FIG. 5, even if local corrosion in the outer layer 26 progresses to form the holes 26A, the inner layer 25 has a nobler corrosion potential than the outer layer 26, so that the holes 26A are formed of the substrate 21. It can prevent reaching the surface. That is, the inner layer 25 functions as a coating layer for preventing pitting of the coating 22 from reaching the substrate 21.
  • the Zn content of the inner layer 25 is 1% by mass or more and 20% by mass or less, preferably 1% by mass or more and 3% by mass or less, and most preferably 2% by mass It is near.
  • the corrosion potential of the inner layer 25 is more negative than the corrosion potential of the substrate 21, and the corrosion potential of the outer layer 26 is more negative than the corrosion potential of the inner layer 25.
  • the base 21, the inner layer 25, and the outer layer 26 are configured in this order (the outer layer 26, the inner layer 25, and the base 21 are nobled in order).
  • the heat exchanger tube 13 has the 1st anti-corrosion film (inner layer 25) and the 2nd anti-corrosion film (outer layer 26), and the 1st anti-corrosion film is the 2nd anti-corrosion film. It is formed at a position closer to the substrate than the film, and the corrosion potential of the first anticorrosion film is higher than the corrosion potential of the substrate and nobler than the corrosion potential of the second anticorrosion film. .
  • the coating 22 (the inner layer 25 and the outer layer 26) is formed on the outer surface of the substrate 21 by, for example, a thermal spraying method.
  • a thermal spraying method a usual method such as flame spraying, high speed flame spraying, detonation spraying, arc spraying, plasma spraying or laser spraying can be used.
  • a fuel for flame spraying a mixed gas of propane and oxygen, a mixed gas of acetylene and oxygen, or the like can be used.
  • the wire and powder of an aluminum alloy which have the same component composition as the film 22 (inner layer 25 and outer layer 26) can be used.
  • the adhesion between the base 21 and the inner layer 25 can be improved by performing an appropriate pretreatment on the outer surface of the base 21 before the formation of the inner layer 25 by thermal spraying.
  • the surface roughness of the outer surface of the substrate 21 may be adjusted to an appropriate range by shot blasting, grid blasting, or the like.
  • the surface roughness of the substrate 21 can be, for example, 1 ⁇ m to 30 ⁇ m in average roughness Ra, and can be 10 ⁇ m to 100 ⁇ m or less in maximum roughness Rmax.
  • the cleaning material used for the blast treatment remains on the outer surface of the substrate 21, the adhesion between the inner layer 25 and the substrate 21 is reduced when the inner layer 25 is formed by thermal spraying. For this reason, after blasting, it is preferable to remove the cleaning material by brushing or the like.
  • the thickness T of the coating 22 (the sum of the thickness T1 of the outer layer 26 and the thickness T2 of the inner layer 25) can be adjusted depending on the conditions at the time of thermal spraying, but is 100 ⁇ m to 1000 ⁇ m. If the thickness T of the coating 22 is too small, it will be difficult to sufficiently suppress the entry of corrosive substances such as chloride ions and oxygen into the substrate 21. Furthermore, since the coating 22 is dissolved early, it becomes difficult to obtain a sufficient anticorrosion effect over a long period of time. On the other hand, if the thickness T of the film 22 is too large, peeling of the film 22 occurs due to temperature change of low temperature and normal temperature, and cracks occur in the film 22 to make it difficult to obtain sufficient anticorrosion effect become.
  • the thickness T of the film 22 is adjusted in the range of 100 ⁇ m to 1000 ⁇ m, more preferably 980 ⁇ m or less, and still more preferably 950 ⁇ m or less.
  • the thicknesses T1 and T2 of the outer layer 26 and the inner layer 25 are adjusted in the range of 50 ⁇ m to 500 ⁇ m, preferably 60 ⁇ m or more, and more preferably 70 ⁇ m or more.
  • FIG. 6 shows a cross-sectional structure along the radial direction of the lower header pipe 14.
  • FIG. 7 shows the cross-sectional structure of the trough 12.
  • the lower header pipe 14 has a hollow cylindrical base 31 in which a flow path 33 through which LNG flows is formed, and a coating 32 formed on the entire outer surface of the base 31 by a method such as thermal spraying.
  • the trough 12 has a base 41 and a coating 42 formed on the entire surface of the base 41 by a method such as thermal spraying.
  • the base material 41 is comprised by the container in which the opening part 43 was formed.
  • the substrates 31 and 41 are made of an aluminum alloy having excellent thermal conductivity, as with the substrate 21 constituting the heat transfer tube 13.
  • the coatings 32 and 42 have the same characteristics as the coating 22 constituting the heat transfer tube 13 described above. That is, the coatings 32 and 42 are formed on the surfaces of the base members 31 and 41, and the inner layers 34 and 44 made of an aluminum alloy containing 1% by mass to 20% by mass of Zn, and the surfaces of the inner layers 34 and 44 And an outer layer 35, 45 made of an aluminum alloy containing 1% by mass or more and 20% by mass or less of Mg, and has a two-layer structure. Therefore, similar to the heat transfer tube 13, excellent sacrificial corrosion resistance can be exhibited, and the coating 32, 42 can be prevented from peeling off from the surface of the base material 31, 41 by swelling.
  • the aluminum alloy members (heat transfer pipe 13, lower header pipe 14, and trough 12) according to the first embodiment have the coatings 22, 32, 42 on the surfaces of the base members 21, 31, 41 made of aluminum alloy. It is formed. And the said film 22,32,42 contains Mg of 1 mass% or more and 20 mass% or less, Zn of 1 mass% or more and 20 mass% or less outer layer 26, 35, 45 which consists of remainder aluminum and an unavoidable impurity. And an inner layer 25, 34, 44 composed of the balance aluminum and inevitable impurities.
  • the outer layers 26, 35, 45 exhibit excellent sacrificial corrosion resistance even when used in an environment exposed to a corrosive medium such as seawater, subjected to temperature changes of low temperature and normal temperature. Can. Therefore, since corrosion degradation of the base materials 21, 31, 41 is difficult to progress, the life of the member can be extended, and the number of regular repairs can be reduced. Therefore, the safety of the LNG vaporizer 1 can be improved and the maintenance cost can be reduced. Further, by preventing the pitting corrosion of the coatings 22, 32, 42 from reaching the substrates 21, 31, 41 by the inner layers 25, 34, 44 (FIG. 5), the progress of corrosion at the interface 21A is suppressed, , 32, 42 can be prevented. As a result, it is possible to suppress peeling of the coatings 22, 32 and 42 from the surfaces of the substrates 21, 31 and 41.
  • the outer layers 26, 35, 45 may contain 1% by mass or more and 20% by mass or less of Mg and Zn in a smaller amount than Mg, and the balance may be made of aluminum and unavoidable impurities.
  • the Zn content of the outer layer 26 is, for example, 0.01% by mass or more and 1.2% by mass or less.
  • the inner layers 25, 34, 44 may contain 1% by mass or more and 20% by mass or less of Zn and Mg in a smaller amount than Zn, and may be composed of the balance aluminum and unavoidable impurities.
  • the Mg content of the inner layers 25, 34, 44 is, for example, not less than 0.01% by mass and not more than 0.52% by mass.
  • the same Zn as the element contained in the inner layers 25, 34, 44 is contained in the outer layers 26, 35, 45, and the same Mg as the element contained in the outer layers 26, 35, 45 is contained in the inner layers 25, 34, 44 By making it also contained, it is possible to improve the affinity between the inner layers 25, 34, 44 and the outer layers 26, 35, 45. Thereby, the adhesion between the inner layers 25, 34, 44 and the outer layers 26, 35, 45 is improved, and the durability of the aluminum alloy member can be improved.
  • At least one layer of the outer layers 26, 35, 45 and the inner layers 25, 34, 44 is 0.01% by mass or more and 1.0% by mass or less of Si, and 0.01% by mass or more and 1.0% by mass or less of Fe 0.01 mass% or more and 1.0 mass% or less Cu, 0.01 mass% or more and 1.0 mass% or less Mn, 0.01 mass% or more and 1.0 mass% or less Cr and 0.01 mass It may be made of an aluminum alloy further containing at least one element selected from the group consisting of Ti and 1.0% by mass or less.
  • the outer layers 26, 35, 45 are made of 1% by mass or more and 20% by mass or less of Mg, and 0.01% by mass or more and 1.0% by mass or less of the element M (Si, Fe, Cu, Mn, Cr, and Ti And at least one element), and the balance may be composed of aluminum and unavoidable impurities.
  • the inner layers 25, 34, 44 contain 1% by mass or more and 20% by mass or less of Zn, and 0.01% by mass or more and 1.0% by mass or less of the above-described element M, and the balance is aluminum and unavoidable impurities. It may be The outer layers 26, 35, 45 and the inner layers 25, 34, 44 may contain one type of element in the above group, or may contain a plurality of types of elements.
  • the present invention is not limited thereto.
  • the aluminum alloy member of the present invention may be applied. That is, in any member among the heat transfer tube 13, the lower header tube 14, and the trough 12, an outer layer made of an Al—Mg alloy (Mg: 1 to 20 mass%) and an Al—Zn alloy (Zn: 1 to A coating having a two-layer structure including an inner layer of 20% by mass) may be formed on the surface of the substrate.
  • the thickness of the coatings 22, 32 and 42 may be less than 100 ⁇ m or may exceed 1000 ⁇ m.
  • the base materials 21, 31 and 41 are made of 3000 series, 5000 series or 6000 series aluminum alloy has been described, but it is made of other types of aluminum alloys such as 2000 series and 7000 series. It is also good.
  • the heat transfer pipe 13 and the lower header pipe 14 are produced by forming the coatings 22 and 32 on the surfaces of the base members 21 and 31 by thermal spraying has been described, but the invention is not limited thereto. It may be a method of forming a tube. Thus, when manufacturing by a clad, the adhesiveness of the base materials 21 and 31 and the films 22 and 32 can be improved more.
  • the LNG vaporizer 2 is an intermediate medium vaporizer (IFV) that performs heat exchange via an intermediate medium 61 having a boiling point and a condensation point between the temperature of seawater as a heating source and the temperature of the LNG.
  • the LNG vaporizer 2 has an intermediate medium evaporation unit 51, a vaporization unit 52, and an NG heating unit 53.
  • the intermediate-medium evaporating unit 51 is a portion on the bottom side in the shell 70, and has a plurality of (three in the present embodiment) heat transfer pipes 71 disposed in the shell space on the bottom side.
  • the intermediate medium evaporation unit 51 exchanges heat between the seawater 72 flowing inside the heat transfer tube 71 and the liquid intermediate medium 61 accumulated at the bottom of the shell 70. By this heat exchange, the liquid intermediate medium 61 evaporates, and an intermediate medium gas 61A is generated. That is, the heat transfer tube 71 is a heat transfer member for performing heat exchange between the seawater 72 and the intermediate medium 61.
  • the vaporization unit 52 is an upper portion in the shell 70, and has an LNG pipe 73 including a flow path through which the LNG flows as shown by the arrows in FIG.
  • the vaporization unit 52 performs heat exchange between the LNG flowing inside the LNG pipe 73 and the intermediate medium gas 61A.
  • the LNG is vaporized to generate an NG.
  • the NG is sent to the NG heating unit 53 through the NG pipe 74.
  • the intermediate medium gas 61A is condensed by heat exchange with the LNG, and is accumulated at the bottom of the shell 70 as a liquid intermediate medium 61.
  • the NG heating unit 53 has a plurality of (three in the present embodiment) heat transfer tubes 81 through which seawater, which is a heating source, flows.
  • An NG is sent to the NG heating unit 53 from the vaporization unit 52 via the NG pipe 74, and the NG exchanges heat with the seawater 72 flowing inside the heat transfer tube 81. Thereafter, the NG heated by the seawater is discharged as a gas at normal temperature. That is, the heat transfer tube 81 is a heat transfer member for exchanging heat between the seawater 72 and the NG.
  • the heat transfer pipes 71, 81 are exposed to seawater 72 whose inner surface is a corrosive medium. For this reason, if the anticorrosive coating is not formed, problems such as pitting occur due to the progress of corrosion.
  • the heat transfer tubes 71 and 81 are made of the aluminum alloy members according to the present embodiment. That is, as in the first embodiment, in the heat transfer tubes 71 and 81, a coating having a two-layer structure including an outer layer containing an appropriate amount of Mg and an inner layer containing an appropriate amount of Zn is formed on the surface of the substrate It has been done. Specifically, as shown in the cross-sectional view of FIG.
  • the heat transfer tubes 71 and 81 extend along the inner surface of a hollow cylindrical base 91 having a flow path 91A through which seawater flows, and a base 91. And a coating 92 formed in the entire circumferential direction.
  • the film 92 is formed to be in contact with the inner surface of the base 91, and is formed to be in contact with the inner layer 93 made of an Al—Zn alloy (Zn: 1 to 20 mass%) and the inner surface of the inner layer 93.
  • an outer layer 94 made of an Al--Mg based alloy (Mg: 1 to 20% by mass).
  • the film 92 can prevent the corrosion of the base 91 and can prevent the peeling of the film 92. Therefore, the life of the heat transfer tubes 71 and 81 can be further lengthened.
  • the sacrificial anticorrosion coating having the above-described two-layer structure is formed on the members that may be corroded by being exposed to the seawater 72. It may be done.
  • the aluminum alloy member of the present invention can also be used as a heat transfer member in a liquefied petroleum gas (LPG) vaporizer, and also in plate heat exchangers in plate heat exchangers and plate fins in fin and tube type heat exchangers. It can also be used as a plate-like heat transfer member such as
  • LPG liquefied petroleum gas
  • such a plate-shaped aluminum alloy member can be produced by clad rolling. Specifically, first, an aluminum alloy base material and a coating material are respectively melted and cast, and if necessary, subjected to homogenization heat treatment to obtain respective ingots. Next, the ingots are integrated and rolled (hot rolling, cold rolling) or cut to obtain a plate of a desired size. Thereafter, these plate materials are stacked and pressure-bonded by hot rolling to form an integrated plate material, and cold rolling is performed until a predetermined final plate thickness is obtained.
  • Aluminum alloy members can be manufactured. At this time, the thickness of the film can be controlled by adjusting the thickness of the plate material corresponding to the film and the rolling reduction in the hot rolling.
  • FIGS. 10 and 11 are test materials 100 and 101 shown in FIGS. 10 and 11 .
  • FIG. 10 is a test material for evaluation of the anti-swelling property of a film, which assumes a sound portion of an aluminum alloy member, and was used to evaluate initial deterioration in practical use.
  • FIG. 11 is a test material for sacrificial-corrosion evaluation, Comprising: Deterioration of the aluminum alloy member progresses to a certain extent, and the state which the base material exposed is assumed.
  • the component compositions (% by mass) of the respective elements in the inner layer and the outer layer, the thicknesses ( ⁇ m) of the inner layer and the outer layer, and the types of aluminum alloys used for the substrate are as shown in Table 1 below.
  • the component composition of the inner layer and the outer layer was adjusted by the composition of the thermal spray material used.
  • the base-material exposed part 100A which is a circular hole of the size of 20 mm diameter was formed by cutting. Also, in all the test materials 100 and 101, the surfaces other than the 50 mm (L1) ⁇ 50 mm (L2) size on which the film is formed are sealed with a Teflon (registered trademark) tape, and then the next heat cycle corrosion is performed. Tested.
  • Thermal cycle corrosion test The following heat cycle corrosion test was conducted as a test to evaluate the corrosion resistance of aluminum alloy members against temperature change due to low temperature and normal temperature and corrosion action of seawater.
  • the artificial seawater adjusted to a liquid temperature of 35 ° C is sprayed on the surface of the test material 100, 101 on which the thermal spray coating is formed, and only the base portion of the test material 100, 101 is immersed in liquid nitrogen.
  • the cooling process was carried out once a day for a total of 6 months.
  • As artificial sea water what added copper chloride (II) so that a Cu ⁇ 2+ > ion concentration might be 1 ppm to aquamarine for metal corrosion tests by Yashima Co., Ltd. was used.
  • a photograph of the appearance of the test material 100 for evaluation of blister resistance was taken, and the area of the swollen portion of the film was measured by image analysis.
  • the corrosion product was removed by making 30% nitric acid of room temperature immerse. Thereafter, the substrate exposed portion 100A was observed with a laser microscope, and the depth of local corrosion was measured by the focal depth method to determine the deepest depth of local corrosion. Moreover, the amount of corrosion consumption of the test material 101 for sacrificial corrosion resistance evaluation was measured by the weight change before and behind a corrosion test. The weight after the corrosion test was the weight after removal of the corrosion product.
  • the evaluation criteria of each measurement item are as follows.
  • the ratio of corrosion consumption to 1 is less than 50% ⁇ : No.
  • the ratio of corrosion consumption amount to 1 is 50% or more and less than 75% ⁇ : No. Ratio of corrosion consumption to 1 is 75% or more and less than 100%.
  • X No. The ratio of corrosion consumption to 1 is 100% or more
  • the above No. 1 to 22 are cases where a base material made of a 7000 series aluminum alloy (A7072) is used. No. 1 using an aluminum alloy base material of any of 3000 series (A3003), 5000 series (A5083) and 6000 series (A6063). In 23 to 34, the above-mentioned No. As compared with 1 to 22, all of the effect of suppressing the swelling area, the effect of suppressing the corrosion depth, and the effect of reducing the amount of corrosion consumed became greater.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • General Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Heat-Exchange Devices With Radiators And Conduit Assemblies (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Filling Or Discharging Of Gas Storage Vessels (AREA)

Abstract

Cette invention concerne un tube de transfert de chaleur (13) (un élément formé à partir d'un alliage d'aluminium), comprenant une base (21) qui est formée à partir d'un alliage d'aluminium et un film de revêtement (22) qui est formé sur la surface de la base (21). Le film de revêtement (22) comprend : une couche externe (26) qui est formée à partir d'un alliage d'aluminium qui contient de 1 % en masse à 20 % en masse (inclus) de magnésium ; et une couche interne (25) qui est formée entre la base (21) et la couche externe (26) et qui est formée à partir d'un alliage d'aluminium qui contient de 1 % en masse à 20 % en masse (inclus) de zinc. Un vaporisateur de GNL selon la présente invention est pourvu dudit tube de transfert de chaleur (13), d'un tube collecteur inférieur (14) (un élément formé à partir d'un alliage d'aluminium) et d'une goulotte (12) (un élément formé à partir d'un alliage d'aluminium).
PCT/JP2017/010625 2016-05-25 2017-03-16 Élément formé d'alliage d'aluminium et vaporisateur de gaz naturel liquide Ceased WO2017203805A1 (fr)

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CN108977706B (zh) * 2018-07-28 2019-12-13 河南明泰铝业股份有限公司 一种液化气储气罐用铝合金板及其制备方法

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