Foam aluminum alloy sacrificial anode-solid corrosion inhibitor interpenetrating composite material and preparation method thereof

Abstract

The invention discloses a foam aluminum alloy sacrificial anode-solid corrosion inhibitor interpenetrating composite material and a preparation method, and relates to the technical field of anticorrosive materials.The preparation method comprises the steps that a refiner, a refining agent and a deslagging agent are sequentially added into a metal aluminum alloy solution, foam aluminum alloy is immersed into solid corrosion inhibitor suspension liquid, and vacuumizing is conducted in a vacuum drying environment; the method comprises the following steps: carrying out heat treatment on a vacuumized solid corrosion inhibitor suspension, carrying out heat preservation to remove a solvent in the corrosion inhibitor suspension, increasing the capacitance of the sacrificial anode by utilizing the large specific surface area of foam metal, improving the current efficiency, interpenetrating the solid corrosion inhibitor in the perforated aluminum alloy, and continuously releasing the corrosion inhibitor, thereby achieving the purpose of improving the corrosion resistance of the perforated aluminum alloy. The problem that the surface of the anode is stained and attached can be solved, meanwhile, the double corrosion prevention effects of the sacrificial anode and the corrosion inhibitor can be achieved, and the purpose of efficiently inhibiting corrosion failure of a metal component is achieved.

Description

Technical Field

[0001] The invention relates to the technical field of anti-corrosion materials, in particular to a foamed aluminum alloy sacrificial anode-solid corrosion inhibitor interpenetrating composite material and a preparation method thereof. Background Art

[0002] With the continuous exploration and development of oil and gas resources and the continuous advancement of the maritime power strategy, the corrosion and perforation failure problems of large-scale infrastructure such as oil and gas well pipelines, offshore platforms, and submarine pipelines caused by corrosive media and harsh service environments are becoming increasingly serious, resulting in a significant increase in oil field and marine development costs and increased production safety risks.

[0003] The sacrificial anode protects the cathode components through anode discharge dissolution. It is a cathodic protection material with simple and convenient construction and is widely used in corrosion protection of oil and gas fields and marine infrastructure. Aluminum alloy sacrificial anodes have been widely used due to their advantages such as light weight, large capacitance, high current efficiency, low price and environmental friendliness. However, in actual applications, traditional block aluminum alloy sacrificial anodes often fail to provide cathodic protection, such as anode self-corrosion, anode dissolution inhibition, and anode surface contamination and adhesion. Corrosion inhibitors are released and adsorbed on the surface of metal materials to form a protective film that isolates the metal surface from the corrosive medium, thereby preventing or slowing down the corrosion of metal materials. Among the anti-corrosion measures for oil wells, adding corrosion inhibitors is one of the most common protective measures, but the use of corrosion inhibitors has problems such as fast loss and short service life. Summary of the invention

[0004] The object of the present invention is to provide a foam aluminum alloy sacrificial anode-solid corrosion inhibitor interpenetrating composite material and a preparation method thereof, so as to overcome the deficiencies of the prior art.

[0005] To achieve the above purpose, the technical solution adopted by the present invention is as follows:

[0006] The method for preparing a foam aluminum alloy sacrificial anode-solid corrosion inhibitor interpenetrating composite material comprises the following steps:

[0007] S1, adding a refiner, a refining agent, and a slag remover to a metal aluminum alloy solution in sequence, and removing the slag after heat preservation to obtain a metal liquid A;

[0008] S2, maintaining the temperature of the molten metal at about 650-750°C, adding calcium as a thickener, and rapidly stirring it to fully mix with the molten metal to obtain molten metal B;

[0009] S3, add foaming agent TiH into the molten metal B 2 , so that the foaming agent is evenly distributed in the molten metal, and then naturally cooled and solidified to form foamed aluminum alloy;

[0010] S4, mixing the solid corrosion inhibitor particles in the liquid phase, and obtaining a suspension after ultrasonic dispersion;

[0011] S5, immersing the foamed aluminum alloy in a solid corrosion inhibitor suspension and evacuating the mixture under a vacuum drying environment;

[0012] S6, heat-treating the vacuum-evacuated solid corrosion inhibitor suspension to remove the solvent in the corrosion inhibitor suspension by heat preservation, and solidifying and forming the solid corrosion inhibitor particles in the foam aluminum alloy pore channels to obtain a foam aluminum alloy sacrificial anode-solid corrosion inhibitor interpenetrating composite material.

[0013] Preferably, the amount of alloying elements added to the metal aluminum alloy solution is 4.5%-6.5% of the total mass of the smelted metal.

[0014] Preferably, the alloy element is one or more of Zn, In, Mg, Cd, Ga, Al-Ti or Si.

[0015] Preferably, the amount of the refiner added is 0.5-1.0% of the total mass of the smelted metal.

[0016] Preferably, the amount of the refining agent added is 0.3-0.5% of the total mass of the smelting metal.

[0017] Preferably, the amount of the slag remover added is 0.1-0.2% of the total mass of the smelting metal.

[0018] Preferably, the refiner is titanium boron refiner.

[0019] Preferably, the refining agent is hexachloroethane refining agent, inorganic salt refining agent or sodium-free refining agent.

[0020] Preferably, the slag remover is silicon dioxide or aluminum oxide.

[0021] A method for preparing a foamed aluminum alloy sacrificial anode-solid corrosion inhibitor interpenetrating composite material is prepared based on the above method.

[0022] Compared with the prior art, the present invention has the following beneficial technical effects:

[0023] The present invention proposes a method for preparing a foam aluminum alloy sacrificial anode-solid corrosion inhibitor interpenetrating composite material, which utilizes the large specific surface area of ​​the foam metal to increase the capacitance of the sacrificial anode and improve the current efficiency. At the same time, the solid corrosion inhibitor is interpenetrating in the open-pored aluminum alloy. With the continuous release of the corrosion inhibitor, not only can the problem of contamination and adhesion on the anode surface be solved, but also the dual anti-corrosion effect of the sacrificial anode and the corrosion inhibitor can be exerted, thereby achieving the purpose of efficiently inhibiting the corrosion failure of metal components. DETAILED DESCRIPTION

[0024] In order to enable those skilled in the art to better understand the solutions of the present invention, the technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only embodiments of a part of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work should fall within the scope of protection of the present invention.

[0025] In one embodiment of the present invention, a method for preparing a foam aluminum alloy sacrificial anode-solid corrosion inhibitor interpenetrating composite material is provided, comprising the following steps:

[0026] a. Place a metal aluminum ingot in a crucible and heat it until the metal aluminum ingot is completely melted, then add alloying elements in sequence to obtain an aluminum alloy solution; the amount of alloying elements added is 4.5%-6.5% of the total mass of the smelted metal, and the mass fraction of the alloying elements is 4.5%-6.5%.

[0027] b. After step a is completed, keep the aluminum alloy solution at the molten temperature and add a refiner (mass fraction 0.5-1.0%), a refining agent (mass fraction 0.3-0.5%), and a slag remover (mass fraction 0.1-0.2%) in sequence, and remove the slag after keeping the temperature;

[0028] c. After step b is completed, the temperature of the molten metal is maintained at 650-750°C, calcium is added as a thickener (mass fraction 4-6%), and it is stirred rapidly to be fully mixed with the molten metal;

[0029] d. After step c is completed, add the foaming agent TiH 2 (mass fraction 1.5%), stir quickly to make the foaming agent evenly distributed in the molten metal;

[0030] e. After step d is completed, remove the stirrer, cover the furnace cover and keep warm for foaming at a temperature of 650-750°C;

[0031] f. After step e is completed, the crucible is removed and cooled, and the molten metal solidifies to form a foamed aluminum alloy;

[0032] g. After step f is completed, the solid corrosion inhibitor particles are mixed in a liquid solvent, ultrasonically dispersed at 25-35 ° C for 10-15min to prepare a solid corrosion inhibitor suspension with a concentration of 50% -75%, and poured into a container;

[0033] h. After step g is completed, the foamed aluminum alloy is immersed in the solid corrosion inhibitor suspension in the container and placed in a vacuum drying oven and evacuated at room temperature;

[0034] i. After step h is completed, the container is placed in a heat treatment furnace and kept at 80-100°C to remove the solvent in the corrosion inhibitor suspension, and the solid corrosion inhibitor particles are solidified and formed in the pores of the foam aluminum alloy to obtain a foam aluminum alloy sacrificial anode-solid corrosion inhibitor interpenetrating composite material.

[0035] In the specific implementation manner of the present application, the liquid phase solvent is specifically an organic solvent, specifically benzene.

[0036] In step a, the aluminum ingot is placed in a crucible and heated until the aluminum is completely melted. The heating temperature is 700-730°C and the heating rate is 10°C·s -1 The alloy element raw material is one or more of Zn, In, Mg, Cd, Ga, Al-Ti or Si.

[0037] In step b, a certain deformation is introduced through thermomechanical treatment to promote the proliferation reaction of low-energy special grain boundaries and the diffuse distribution of high-energy random grain boundaries.

[0038] In step b, the molten metal is kept at a temperature of 700-730°C.

[0039] The stirring speed in step c can be selected to be 700-1200 r / min.

[0040] Furthermore, in step d, the coated foaming agent and the ordinary TiH 2 Foaming agent: stirring speed can be selected from 1300-1700r / min.

[0041] Furthermore, in the step e, the furnace cover is closed for heat preservation and foaming, and the heat preservation time is 30 minutes.

[0042] Furthermore, in step f, the crucible is taken out and water-cooled.

[0043] Furthermore, in step g, solid corrosion inhibitor particles are mixed in the liquid phase, the solid corrosion inhibitor can be imidazoline solid corrosion inhibitor or quaternary ammonium salt corrosion inhibitor, and the liquid phase solvent is an organic solvent such as benzene. Ultrasonic dispersion is performed at a certain temperature, the temperature can be selected to be 30-70°C, and the dispersion time is 15 minutes.

[0044] Furthermore, in the step h, the foamed aluminum alloy is immersed in the solid corrosion inhibitor suspension in the container, and placed in a vacuum drying oven for evacuation at room temperature for 30 minutes to 2 hours.

[0045] Furthermore, in step i, the container is placed in a heat treatment furnace, and the solvent in the corrosion inhibitor suspension is removed by heat preservation at a certain temperature, and the solid corrosion inhibitor particles are solidified and formed in the pores of the foamed aluminum alloy, and the solidification and forming temperature is 100-200°C.

[0046] In another embodiment of the present invention, a foam aluminum alloy sacrificial anode-solid corrosion inhibitor interpenetrating composite material is provided, which is prepared by the above method.

[0047] Specifically, the refiner uses titanium-boron refiner. Titanium-boron refiner is composed of titanium and boron elements. It uses heterogeneous nucleation to achieve the purpose of grain refinement by introducing foreign nucleation particles. Specifically, the boron element in the titanium-boron refiner can significantly improve the stability of the crystal nucleus and produce more crystal nuclei during the crystal formation process; while the titanium element helps to increase the high temperature resistance and fluidity of the alloy, which is beneficial to reduce defects such as holes and shrinkage holes that may appear in castings.

[0048] The refining agent specifically uses hexachloroethane refining agent, inorganic salt refining agent (such as sodium chloride, calcium fluoride or sodium fluoroaluminate) or sodium-free refining agent (potassium chloride, potassium carbonate or lithium fluoride); reacts with hydrogen in the molten metal and removes inclusions through physical adsorption. The configuration is developed based on the principle of combining molten metal compounds, which reduces smoke and burn loss, and has the advantages of environmental protection and economy.

[0049] The slag remover is made of silicon dioxide or aluminum oxide, which has a high melting point and stability, and can effectively gather the infusible materials on the surface of the metal solution at high temperature, making it easy to remove.

[0050] Embodiment 1

[0051] A method for preparing a foam aluminum alloy sacrificial anode-solid corrosion inhibitor interpenetrating composite material, the processing steps are as follows:

[0052] a. Place a metal aluminum ingot in a crucible and heat it to 725°C to completely melt the metal aluminum, then add 4% Zn and 0.22% In ingots in turn and melt and stir to obtain solution A;

[0053] b. Add 1% titanium boron refiner, 0.5% hexachloroethane refining agent and 0.2% silicon dioxide to solution A at 730℃, keep warm and remove the slag;

[0054] c. Keep the temperature of the molten metal at 700°C, add 6% calcium as a thickener, and stir at 1200r / min to fully mix it with the molten metal so that the molten metal reaches a certain viscosity;

[0055] d. Add 2% TiH 2 , stirring at a speed of 1500r / min to make the foaming agent evenly distributed in the molten metal;

[0056] e. Take out the stirrer, cover the furnace and keep warm for 30 minutes;

[0057] f. Take out the crucible and cool it with water, and the molten metal solidifies to form a foamed aluminum alloy;

[0058] g. Mix the solid corrosion inhibitor particles in the liquid phase, disperse them ultrasonically at 30°C for 15 minutes to make a suspension of a certain concentration, and pour it into a container;

[0059] h. After step g is completed, the foamed aluminum alloy is immersed in the solid corrosion inhibitor suspension in the container and placed in a vacuum drying oven at room temperature for 30 minutes;

[0060] i. After step h is completed, the container is placed in a heat treatment furnace and kept at 100°C to remove the solvent in the corrosion inhibitor suspension. The solid corrosion inhibitor particles are solidified and formed in the pores of the foam aluminum alloy to obtain a foam aluminum alloy sacrificial anode-solid corrosion inhibitor interpenetrating composite material.

[0061] The invention prepares a porous foam aluminum alloy sacrificial anode and interpenetrates with a solid corrosion inhibitor to form a composite material, thereby overcoming the problems of aluminum alloy anode dissolution inhibition, anode surface contamination and adhesion, rapid loss of corrosion inhibitor, and short service life.

[0062] Embodiment 2

[0063] A method for preparing a foam aluminum alloy sacrificial anode-solid corrosion inhibitor interpenetrating composite material, the processing steps are as follows:

[0064] a. Place the aluminum ingot in a crucible and heat to 730°C to completely melt the aluminum. Then, add 4% Zn, 0.22% In, 0.1% Mg and 0.5% Al-Ti ingots to melt and stir.

[0065] b. Add 0.5% titanium boron refiner, 0.3% inorganic salt refining agent, and 0.1% aluminum oxide in sequence at 730°C, keep warm and remove the slag;

[0066] c. Keep the molten metal temperature at about 700°C, add 4% calcium as a thickener, and stir at 1200r / min to fully mix it with the molten metal so that the molten metal reaches a certain viscosity;

[0067] d. Add 2% TiH 2 , stirring at a speed of 1500r / min to make the foaming agent evenly distributed in the molten metal;

[0068] e. Take out the stirrer, cover the furnace and keep warm for 30 minutes;

[0069] f. Take out the crucible and cool it with water, and the molten metal solidifies to form a foamed aluminum alloy;

[0070] g. Mix the solid corrosion inhibitor particles in the liquid phase, disperse them ultrasonically at 30°C for 15 minutes to make a suspension of a certain concentration, and pour it into a container;

[0071] h. After step g is completed, the foamed aluminum alloy is immersed in the solid corrosion inhibitor suspension in the container and placed in a vacuum drying oven at room temperature for 30 minutes;

[0072] i. After step h is completed, the container is placed in a heat treatment furnace and kept at 100°C to remove the solvent in the corrosion inhibitor suspension. The solid corrosion inhibitor particles are solidified and formed in the pores of the foam aluminum alloy to obtain a foam aluminum alloy sacrificial anode-solid corrosion inhibitor interpenetrating composite material.

[0073] Embodiment 3

[0074] A method for preparing a foam aluminum alloy sacrificial anode-solid corrosion inhibitor interpenetrating composite material, the processing steps are as follows:

[0075] a. Place the aluminum ingot in a crucible and heat to 720°C. After the aluminum is completely melted, add 3.5% Zn, 0.25% In, and 0.2% Mg in sequence and melt and stir.

[0076] b. Add 0.7% titanium boron refiner, 0.4% sodium-free refining agent and 0.15% alumina in sequence at 730℃, keep warm and remove the slag;

[0077] c. Keep the molten metal temperature at 710°C, add 5% calcium as a thickener, and stir at 1200r / min to fully mix it with the molten metal so that the molten metal reaches a certain viscosity;

[0078] d. Add 2% TiH 2 , stirring at a speed of 1500r / min to make the foaming agent evenly distributed in the molten metal;

[0079] e. Take out the stirrer, cover the furnace and keep warm for 30 minutes;

[0080] f. Take out the crucible and cool it with water, and the molten metal solidifies to form a foamed aluminum alloy;

[0081] g. Mix the solid corrosion inhibitor particles in the liquid phase, disperse them ultrasonically at 30°C for 15 minutes to make a suspension of a certain concentration, and pour it into a container;

[0082] h. After step g is completed, the foamed aluminum alloy is immersed in the solid corrosion inhibitor suspension in the container and placed in a vacuum drying oven at room temperature for 30 minutes;

[0083] i. After step h is completed, the container is placed in a heat treatment furnace and kept at 100°C to remove the solvent in the corrosion inhibitor suspension. The solid corrosion inhibitor particles are solidified and formed in the pores of the foam aluminum alloy to obtain a foam aluminum alloy sacrificial anode-solid corrosion inhibitor interpenetrating composite material.

[0084] The present invention prepares a composite material of a porous sacrificial anode and an interpenetrating corrosion inhibitor, improves the capacitance and current efficiency of the sacrificial anode, realizes dual protection measures of sacrificial anode cathode protection and corrosion inhibitor, and achieves the purpose of efficiently inhibiting corrosion failure of metal components.

[0085] The data parameters of traditional aluminum alloy sacrificial anode are shown in Table 1:

[0086]

[0087]

[0088] Example 1 The data parameter table 2 of the foam aluminum alloy sacrificial anode-solid corrosion inhibitor interpenetrating composite material is as follows:

[0089]

[0090] Example 2 The data parameter table 3 of the foam aluminum alloy sacrificial anode-solid corrosion inhibitor interpenetrating composite material is as follows:

[0091]

[0092] Example 3 The data parameter table 3 of the foam aluminum alloy sacrificial anode-solid corrosion inhibitor interpenetrating composite material is as follows:

[0093]

[0094] In summary, referring to the data comparison of Table 1, Table 2, Table 3 and Table 4, the present invention overcomes the problems of aluminum alloy anode dissolution inhibition, anode surface contamination and adhesion, rapid loss of corrosion inhibitor, short service life, etc. by preparing a porous foam aluminum alloy sacrificial anode and interpenetrating with a solid corrosion inhibitor to form a composite material, thereby improving the capacitance and current efficiency of the sacrificial anode, realizing the dual protection measures of sacrificial anode cathodic protection and corrosion inhibitor, and achieving the purpose of efficiently inhibiting the corrosion failure of metal components.

[0095] The above shows and describes the basic principles and main features of the present invention and the advantages of the present invention. It is obvious to those skilled in the art that the present invention is not limited to the details of the above exemplary embodiments, and the present invention can be implemented in other specific forms without departing from the spirit or basic features of the present invention. Therefore, no matter from which point of view, the embodiments should be regarded as exemplary and non-restrictive. The scope of the present invention is defined by the appended claims rather than the above description, and it is intended that all changes falling within the meaning and scope of the equivalent elements of the claims are included in the present invention.

[0096] In addition, it should be understood that although the present specification is described according to implementation modes, not every implementation mode contains only one independent technical solution. This description of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment may also be appropriately combined to form other implementation modes that can be understood by those skilled in the art.

Claims

1. A method for preparing a foam aluminum alloy sacrificial anode-solid corrosion inhibitor interpenetrating composite material, characterized in that: The following steps are involved: S1, adding a refiner, a refining agent, and a slag remover to a metal aluminum alloy solution in sequence, and removing the slag after heat preservation to obtain a metal liquid A; S2, maintaining the temperature of the molten metal at about 650-750°C, adding calcium as a thickener, and rapidly stirring it to fully mix with the molten metal to obtain molten metal B; S3, adding a foaming agent TiH2 into the molten metal B, so that the foaming agent is evenly distributed in the molten metal, and then naturally cooling and solidifying to form a foamed aluminum alloy; S4, mixing the solid corrosion inhibitor particles in the liquid phase, and obtaining a suspension after ultrasonic dispersion; S5, immersing the foamed aluminum alloy in a solid corrosion inhibitor suspension and evacuating the mixture under a vacuum drying environment; S6, heat-treating the vacuum-evacuated solid corrosion inhibitor suspension to remove the solvent in the corrosion inhibitor suspension by heat preservation, and solidifying and forming the solid corrosion inhibitor particles in the foam aluminum alloy pore channels to obtain a foam aluminum alloy sacrificial anode-solid corrosion inhibitor interpenetrating composite material.

2. The method for preparing the foamed aluminum alloy sacrificial anode-solid corrosion inhibitor interpenetrating composite material according to claim 1, characterized in that: The amount of alloying elements added to the aluminum alloy solution is 4.5%-6.5% of the total mass of the molten metal.

3. The method for preparing the foamed aluminum alloy sacrificial anode-solid corrosion inhibitor interpenetrating composite material according to claim 2, characterized in that: The alloy element specifically includes one or more of Zn, In, Mg, Cd, Ga, Al-Ti or Si.

4. The method for preparing the foamed aluminum alloy sacrificial anode-solid corrosion inhibitor interpenetrating composite material according to claim 1, characterized in that: The amount of refiner added is 0.5-1.0% of the total mass of the molten metal.

5. The method for preparing the foamed aluminum alloy sacrificial anode-solid corrosion inhibitor interpenetrating composite material according to claim 1, characterized in that: The amount of refining agent added is 0.3-0.5% of the total mass of the molten metal.

6. The method for preparing the foamed aluminum alloy sacrificial anode-solid corrosion inhibitor interpenetrating composite material according to claim 1, characterized in that: The amount of slag remover added is 0.1-0.2% of the total mass of the smelting metal.

7. The method for preparing the foamed aluminum alloy sacrificial anode-solid corrosion inhibitor interpenetrating composite material according to claim 1, characterized in that: The refiner used is titanium boron refiner.

8. The method for preparing the foamed aluminum alloy sacrificial anode-solid corrosion inhibitor interpenetrating composite material according to claim 1, characterized in that: The refining agent specifically adopts hexachloroethane refining agent, inorganic salt refining agent or sodium-free refining agent.

9. The method for preparing the foamed aluminum alloy sacrificial anode-solid corrosion inhibitor interpenetrating composite material according to claim 1, characterized in that: The slag remover is made of silicon dioxide or aluminum oxide.

10. A method for preparing a foamed aluminum alloy sacrificial anode-solid corrosion inhibitor interpenetrating composite material, characterized in that: Prepared based on the method according to any one of claims 1 to 9.

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