Water-oil replacement type petrolatum anti-corrosion paste suitable for marine environment and preparation of water-oil replacement type petrolatum anti-corrosion paste

Abstract

The invention belongs to the field of anti-corrosion paste, and particularly relates to water-oil replacement type petrolatum anti-corrosion paste suitable for a marine environment and preparation of the water-oil replacement type petrolatum anti-corrosion paste. The anti-corrosion paste comprises the following components in percentage by weight: 20-30% of basic mineral oil, 5-15% of a water-oil displacer, 25-30% of a lubricant, 20-35% of a filler and 5-10% of an antirust agent. The anti-corrosion paste also contains a flame retardant. According to the petrolatum anti-corrosion paste used for underwater construction and having the good oil replacement performance, water and oil replacement agent components are used, underwater construction is achieved, meanwhile, water wrapped between a steel column object and the anti-corrosion paste is replaced, a good protection effect is achieved, and in addition, when the anti-corrosion paste contains a flame retardant, the corrosion resistance of the anti-corrosion paste is improved, and the service life of the anti-corrosion paste is prolonged. The composite petrolatum anti-corrosion paste which is used for underwater construction and has good oil replacement and flame retardant properties is formed, a good protection effect is achieved, and the flame retardant property of the anti-corrosion paste is remarkably improved by adding the flame retardant.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of anti-corrosion paste, and particularly relates to a water-oil displacement type mineral paste anti-corrosion paste suitable for marine environment and preparation thereof. BACKGROUND

[0002] The marine environment is one of the most complex corrosion environments, and the steel structure exposed to the marine environment is not only corroded by high salt, high humidity and other marine corrosive substances, but also subjected to the impact of sea waves. Compared with lake and river environments, metal materials in the marine environment often face more serious corrosion problems. Among the five zones of the sea, the corrosion in the splash zone is particularly serious. Often, the steel column in the splash zone has already undergone serious local corrosion before the other parts, with deep corrosion holes, becoming a short board for the protection of the steel column and a safety card for the steel casting. In the splash zone, the metal is in a humid state all year round, is exposed to the air and in contact with oxygen all year round, and is also subjected to the impact of sea waves all year round, so the corrosion rate is extremely high. However, it is difficult to protect some steel structures, because the traditional protection method is not suitable for this field, sacrificial anode protection cannot be used in the splash zone, and paint is difficult to implement in a humid and marine impact environment, and is easily damaged and lost under the impact of sea waves, causing greater damage to the steel casting.

[0003] Mineral fat has good adhesion, plasticity and corrosion resistance, so mineral substances are often used as anti-corrosion base rust-proof oil in the protection of steel structures such as steel piles, pipelines and bolts. However, the commonly used mineral rust-proof agents are mostly suitable for dry metal surfaces, and it is difficult to apply them to the surface of steel columns under water or in a humid environment, or their protection effect is poor. However, in actual marine engineering operations, especially for steel structures in the splash zone, the surface of the steel pile is humid all year round, and sometimes underwater construction is required, but the traditional mineral fat protection technology on the market is difficult to complete the underwater construction process, and even if it is applied to the metal surface, the protection effect is poor; this is because the traditional anti-corrosion paste will pack the water on the surface of the steel column inside the anti-corrosion paste when it is applied to the steel column in a humid environment, thereby causing greater corrosion to the metal.

[0004] In addition, with the development of offshore oil fields, the challenge of fire risk faced by offshore oil platforms has gradually increased. Since the platform operates in a high-temperature, flammable environment and often comes into contact with flammable and explosive substances such as oil and natural gas, the risk of fire accidents cannot be ignored. Therefore, the fire resistance grade of the protective material also faces more stringent standards. This not only tests the flame retardant properties of the material itself, but also promotes the entire protective material industry to continuously break through in formula upgrading and process optimization to meet the increasingly complex engineering fire protection scene requirements. Under this application background, high requirements are put forward for the underwater construction performance, water-oil displacement performance and fire resistance of the anti-corrosion paste. SUMMARY

[0005] In view of the above problems, the present application aims to provide a water-oil displacement type petrolatum anticorrosive paste suitable for marine environment and a preparation method thereof.

[0006] To achieve the above-mentioned purpose, the technical scheme adopted by the present application is as follows:

[0007] A water-oil displacement type petrolatum anticorrosive paste suitable for marine environment, the anticorrosive paste comprises, by weight percentage, 20-30% of base mineral oil, 5-15% of water-oil displacement agent, 25-30% of lubricant, 20-35% of filler, and 5-10% of rust inhibitor.

[0008] The water-oil displacement type petrolatum anticorrosive paste suitable for marine environment further comprises a flame retardant.

[0009] The mass amount of the flame retardant is 10-25% of the total mass of the anticorrosive paste.

[0010] The water-oil displacement agent is a mixture of barium petroleum sulfonate and zinc naphthenate; the mass ratio of the barium petroleum sulfonate to the zinc naphthenate is 2:1-3:2.

[0011] The base mineral oil is one or more of soap-based grease, hydrocarbon-based grease, inorganic grease, and organic grease.

[0012] The filler is calcium carbonate or silicon powder.

[0013] The lubricant is one or more of flow paraffin, white oil, phthalate ester, and vaseline.

[0014] The rust inhibitor is one or more of tannic acid, barium dinonylnaphthalene sulfonate, and sulfonate metal soap.

[0015] The flame retardant is at least one or more of phosphorus-based flame retardant, nitrogen-based flame retardant, phosphorus-nitrogen composite flame retardant, sodium methyl silicate, diatomite, magnesium hydroxide, and aluminum hydroxide.

[0016] A preparation method of a water-oil displacement type petrolatum anticorrosive paste suitable for marine environment, comprising the following steps:

[0017] (1) adding barium petroleum sulfonate and zinc naphthenate into a reaction kettle according to a proportion, heating at a temperature of 90-130℃, and stirring uniformly to obtain a water-oil displacement agent;

[0018] (2) adding mineral grease and lubricant into the water-oil displacement agent, heating to a temperature of 100-130℃, and stirring uniformly to obtain a base petrolatum anticorrosive paste;

[0019] (3) adding the filler and the rust preventive into the base petrolatum anticorrosive paste and heating in a blender to 110-130 DEG C, stirring for 1-2 hours to obtain the petrolatum anticorrosive paste;

[0020] (4) heating the petrolatum anticorrosive paste prepared in step (3) to 120 DEG C and continuously stirring to obtain the water-oil displacement type petrolatum anticorrosive paste.

[0021] When the anticorrosive paste contains the flame retardant, the flame retardant is added into the base petrolatum anticorrosive paste at the same time with the filler and the rust preventive.

[0022] The present application has the following advantages:

[0023] The present application provides a kind of for underwater construction and has good oil displacement type petrolatum anticorrosive paste, uses water-oil displacement agent component, realizes underwater construction at the same time, the water that is wrapped in steel column object and anticorrosive paste is displaced, reaches good protection effect, in addition, when the anticorrosive paste contains the flame retardant, forms the composite petrolatum anticorrosive paste for underwater construction and has good oil displacement and flame retardant performance, uses water-oil displacement agent component, realizes underwater construction at the same time, the water that is wrapped in steel column object and anticorrosive paste is displaced, reaches good protection effect, and by the addition of flame retardant, the flame retardant performance of anticorrosive paste is significantly improved, specifically:

[0024] (1) the water-oil displacement anticorrosive paste of the present application can be used for underwater construction, and adheres to the metal surface, and is well fitted, does not fall off, and does not affect the anticorrosive performance of the anticorrosive paste, and has good corrosion protection effect on the metal.

[0025] (2) the water-oil displacement anticorrosive paste of the present application has polar organic compounds, which not only contain polar (-OH, -COOH and -NH2, etc.) groups with the ability to adhere to metals and water, but also have non-polar groups that are lipophilic and hydrophobic. Under the synergistic action of the two groups, the water on the metal surface can be displaced, and the metal surface is in contact with the oily group. Even if there is water on the material surface, the material still has good protection. The steel structure in the environment of rivers, lakes and oceans can be further protected stably and effectively.

[0026] (3) the water-oil displacement anticorrosive paste of the present application closely fits the protected object, has good sealing performance, and has long rust and corrosion prevention life.

[0027] (4) the water-oil displacement anticorrosive paste of the present application has excellent environmental protection performance, no irritating odor during construction, no oil dripping phenomenon, and no environmental pollution.

[0028] (5) the water-oil displacement anticorrosive paste of the present application is suitable for corrosion protection of marine steel piles, bridge piers and other steel structures.

[0029] (6) When the corrosion-resistant paste contains a flame retardant, the corrosion-resistant paste realizes efficient fusion of fire resistance and corrosion resistance, and exhibits excellent integrated effects. In terms of corrosion resistance, it exhibits excellent protection capability, and can ensure that the metal surface remains completely rust-free in a harsh test environment for up to 200 hours, and can effectively resist the corrosion of moisture, salt and other corrosion factors; and in terms of fire resistance, the ignition point is significantly increased to 250 DEG C, which can delay the occurrence of combustion reaction compared with ordinary protective materials, and adds a solid safety barrier to the protected object.

[0030] (7) The water-oil displacement corrosion-resistant paste of the present application is closely matched with the protected object and has good sealing performance and long rust and corrosion prevention life. The integrated paste forms a dense and stable protective layer on the metal surface by means of the core technology of water-oil displacement, which can not only isolate the penetration of corrosion media such as water and oxygen and play a long-acting corrosion prevention role, but also enhance the fire resistance of the material by increasing the ignition point, thereby providing a solution that combines protection and safety guarantee for related application scenarios.

[0031] (8) When the corrosion-resistant paste is burned at high temperature, the flame retardant component decomposes at high temperature and generates non-flammable gas and free radicals. These free radicals can capture hydrogen free radicals and hydroxyl free radicals and interrupt the chain reaction of free radicals, thereby extinguishing the flame. DETAILED DESCRIPTION

[0032] Example 1

[0033] Preparation of water-oil displacement agent:

[0034] Barium petroleum sulfonate and zinc naphthenate were added to the reaction kettle in different proportions according to Table 1, heated to different temperatures, and stirred uniformly to obtain the water-oil displacement agent.

[0035] Table 1 Preparation of water-oil displacement agent

[0036]

[0037] As can be seen from Table 1, when the heating is insufficient, the compatibility of barium petroleum sulfonate and zinc naphthenate cannot make the two organic substances completely uniform, and when the temperature is too high, the substances will be oxidized and produce peroxide; when heated to 120 DEG C, the two substances can be completely dissolved and stirred uniformly; when the ratio of barium petroleum sulfonate to zinc naphthenate is 2:1 and 3:2, a dark brown paste-like substance is obtained. When the ratio of barium petroleum sulfonate to zinc naphthenate is too low or too high (such as 1:2 or 4:1), the texture of the water-oil displacement agent is not good; when the amount of barium petroleum sulfonate is too low (1:2), the paste-like texture is too soft; when the amount of barium petroleum sulfonate is too high (4:1), the paste-like texture is too hard, therefore, only when the ratio of barium petroleum sulfonate to zinc naphthenate is 2:1 and 3:2, the water-oil displacement agent is optimal.

[0038] Example 2

[0039] Preparation of water-oil displacement type corrosion protection paste:

[0040] (1) Water-oil displacement agent 2 in Example 1 is used as the water-oil displacement agent for preparing the water-oil displacement type corrosion protection paste;

[0041] (2) The base mineral oil and lubricant are added to the water-oil displacement agent in different proportions according to Table 2, heated to 110°C, and stirred uniformly to obtain a base mineral oil corrosion protection paste;

[0042] (3) The filler and rust inhibitor are added to the base mineral oil corrosion protection paste in different proportions according to Table 2 and stirred in a blender, heated to 120°C, and stirred uniformly to obtain a mineral oil corrosion protection paste;

[0043] (4) The mineral oil corrosion protection paste prepared in step (3) is heated to 120°C and continuously stirred to obtain a uniformly fused water-oil displacement type mineral oil corrosion protection paste.

[0044] The base mineral oil is a hydrocarbon-based grease, the lubricant is white oil, the filler is silicon powder (particle size 4000 mesh), and the rust inhibitor is barium dinonylnaphthalene sulfonate.

[0045] Table 2

[0046]

[0047] Comparative Example 1

[0048] According to the steps of Example 2, a common mineral oil corrosion protection paste is prepared according to the proportion of ingredients in Table 3. The base mineral oil is a hydrocarbon-based grease, the lubricant is white oil, the filler is silicon powder (particle size 4000 mesh), and the rust inhibitor is barium dinonylnaphthalene sulfonate.

[0049] Table 3

[0050]

[0051] In Comparative Example 1, ordinary mineral oil (e.g. vaseline) is used instead of water-oil displacement agent to prepare Comparative Example 1; at the same time, the water-oil displacement agent is removed to prepare Comparative Example 2.

[0052] According to the steps of Example 2, water-oil displacement agent 4 and water-oil displacement agent 5 in Table 1 are used to prepare mineral oil corrosion protection paste according to the mass ratio in Table 4. The base mineral oil is a hydrocarbon-based grease, the lubricant is white oil, the filler is silicon powder (particle size 4000 mesh), and the rust inhibitor is barium dinonylnaphthalene sulfonate.

[0053] Table 4

[0054]

[0055] The comparative corrosion-preventing paste 3 was prepared by using the water-oil displacement type corrosion-preventing paste No. 4 prepared in Table 1; the comparative corrosion-preventing paste 4 was prepared by using the water-oil displacement type corrosion-preventing paste No. 5 prepared in Table 1.

[0056] Example 3

[0057] Preparation of water-oil displacement type corrosion-preventing paste containing flame retardant

[0058] (1) The water-oil displacement agent 2 in Example 1 was used as the water-oil displacement agent for preparing the water-oil displacement type corrosion-preventing paste;

[0059] (2) The base mineral oil and the lubricant were added into the water-oil displacement agent in different proportions according to Table 5, heated to 110°C, and stirred uniformly to obtain the base mineral oil corrosion-preventing paste;

[0060] (3) The filler, the rust inhibitor, and the flame retardant were added into the base mineral oil corrosion-preventing paste in different proportions according to Table 5 and heated to 120°C in a stirring machine, and stirred uniformly to obtain the mineral oil corrosion-preventing paste;

[0061] (4) The mineral oil corrosion-preventing paste prepared in step (3) was heated to 120°C and continuously stirred to obtain the water-oil displacement type mineral oil corrosion-preventing paste containing flame retardant.

[0062] The base mineral oil was hydrocarbon-based grease, the lubricant was white oil, the filler was silicon powder (particle size 4000 mesh), the rust inhibitor was barium dinonylnaphthalene sulfonate, and the flame retardant was aluminum hydroxide.

[0063] Table 5

[0064]

[0065] Example 4

[0066] The water-oil displacement type corrosion-preventing paste 4 containing flame retardant was prepared according to the steps of Example 3 and the mass proportion ingredients in Table 6. The base mineral oil was hydrocarbon-based grease, the water-oil displacement agent was water-oil displacement agent No. 2 in Table 2, the lubricant was white oil, the filler was silicon powder (particle size 4000 mesh), the rust inhibitor was barium dinonylnaphthalene sulfonate, and the flame retardant was phosphorus-based flame retardant (microencapsulated red phosphorus).

[0067] Table 6

[0068]

[0069] Application Example 1

[0070] The corrosion experiment, temperature resistance and flowability experiment, and salt spray experiment of the water-oil displacement type anticorrosive paste 1-4 of Example 2 and the anticorrosive paste 1-4 of the comparative example were evaluated. The specific method refers to the national standard GB / T 32119-2023 “Marine steel structure complex mineral oil coating corrosion control technology”, and the anticorrosion test results are shown in Table 7.

[0071] Table 7

[0072]

[0073] Note: The corrosion conclusion refers to the relevant requirements of the national standard GB / T 32119-2023 “Marine steel structure complex mineral oil coating corrosion control technology”.

[0074] As can be seen from Table 7, the water-oil displacement anticorrosive paste 1-3 of the present application adds an oil-water displacement agent with water-oil displacement performance, and the adhesion to metal is significantly improved. The water on the surface of the metal can be displaced, and the paste still maintains good adhesion and corrosion protection effect with the metal. The amount of the water-oil displacement agent in the water-oil displacement type anticorrosive paste 4 is small. In the oil-water displacement experiment, the 24-hour vaseline floating phenomenon in distilled water was observed by visual inspection during the experiment, and the metal surface was severely corroded. In the oil-water displacement experiment of the anticorrosive paste 1-4 of the comparative example, the metal surface was severely corroded, which did not meet the requirements of the national standard GB / T 32119-2023 “Marine steel structure complex mineral oil coating corrosion control technology” for water-oil displacement performance. Significant corrosion occurred in the salt spray test, indicating that the addition of the water-oil displacement agent or the use of ordinary mineral oil instead cannot achieve good corrosion protection effect. The performance test results of the water-oil displacement performance show that when the ratio of barium petroleum sulfonate to zinc naphthenate is too low (or too high (such as 1:2 or 4:1)), the water-oil displacement performance and neutral salt spray resistance of the comparative anticorrosive paste 3 and the comparative anticorrosive paste 4 are reduced, which does not meet the performance requirements of the national standard GB / T 32119-2023 for mineral oil anticorrosive tape. In addition, the anticorrosive paste 1-3 of the comparative example does not meet the requirement of “vertically placed at (50±2) ℃ for 24 h without flowing” of GB / T 32119-2023 in the temperature resistance and flowability experiment. Therefore, the water-oil displacement anticorrosive paste of the present application can be used for underwater construction, and adheres to the metal surface and fits well without falling off, and does not affect the anticorrosive performance of the paste, and has good corrosion protection effect on the metal.

[0075] Application Example 2

[0076] The water-oil displacement type anticorrosive paste 1-4 containing a flame retardant of Examples 3 and 4 were respectively subjected to water-oil displacement and salt spray experiment and evaluation of corrosion protection performance. The specific method refers to the national standard GB / T 32119-2023 “Marine steel structure complex mineral oil coating corrosion control technology”, and the anticorrosion test results are shown in Table 8.

[0077] Table 8

[0078]

[0079] Note: The corrosion conclusion refers to the relevant requirements of the national standard GB / T 32119-2023 “Marine Steel Structure Coated with Complex Mineral Oil for Anticorrosion Technology”.

[0080] As can be seen from Table 8, when the flame retardant does not reach the required proportion, the water-oil displacement type anticorrosive paste 3 containing the flame retardant prepared has a significantly lower ignition point than the water-oil displacement type anticorrosive paste 1-2 containing the flame retardant, and has a greater risk of combustion, so it can be seen that the amount of flame retardant significantly affects the performance of the anticorrosive paste; in addition, the water-oil displacement type anticorrosive paste 4 containing the flame retardant prepared using a phosphorus-based flame retardant (microencapsulated red phosphorus) has a higher combustion temperature, reducing the risk of flammability, but its corrosion degree in neutral salt spray resistance (600 h) is B level, the reason is that this phosphorus-based flame retardant is a liquid, which reduces the connection between the organic functional groups in the original anticorrosive paste, dilutes the viscosity of the anticorrosive paste, and reduces the anticorrosive performance of the anticorrosive paste, thus indicating that the most preferred flame retardant is the aluminum hydroxide flame retardant.

[0081] Therefore, the water-oil displacement type anticorrosive paste containing the flame retardant of the embodiments of the present application adds a water-oil displacement agent with water-oil displacement performance and a flame retardant, on the one hand, the adhesion of the water-oil displacement agent to the metal is significantly enhanced, which can effectively displace the water wrapped around the metal surface, while still maintaining good adhesion and anticorrosive effect with the metal; on the other hand, the flame retardant will decompose to produce water vapor during heating, which can dilute the concentration of combustible and oxygen in the gas phase, thereby reducing the combustion speed. In addition, Al2O3 left over after heating of some flame retardants (such as aluminum hydroxide) will form a dense oxide film, which, when covering the surface of the material, not only blocks the transfer of heat, but also further enhances the corrosion resistance of the steel, and plays a role of mutual promotion and mutual synergy with the oil-water displacement agent. The water-oil displacement anticorrosive flame-retardant integrated paste of the present application can be constructed underwater, adheres to the metal surface, and is well fitted without falling off, and does not affect the anticorrosive performance of the anticorrosive paste, and has a good anticorrosive effect on the metal. In addition, the anticorrosive flame-retardant integrated paste greatly improves the ignition point and flame-retardant performance and corrosion resistance of the material, achieving the integrated effect of corrosion resistance and flame retardance.

[0082] Although the present disclosure is disclosed as above, the protection scope of the present disclosure is not limited to this. Those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present disclosure, and these changes and modifications will fall within the protection scope of the present disclosure.

Claims

1. A water-displacement type anticorrosive paste of petrolatum suitable for marine environments, characterized by: The anti-corrosion paste comprises, by weight percentage, 20-30% base mineral oil, 5-15% water-oil displacement agent, 25-30% lubricant, 20-35% filler, and 5-10% rust inhibitor.

2. The water-displacement petrolatum anticorrosion paste suitable for marine environments according to claim 1, characterized in that: The anti-corrosion paste further comprises a flame retardant.

3. The water-displacement petrolatum anticorrosion paste suitable for marine environments according to claim 2, characterized in that: The mass amount of the flame retardant is 10-25% of the total mass of the anti-corrosion paste.

4. A water-displacement petrolatum anticorrosive paste suitable for marine environments according to claim 1 or 3, characterized in that: The water-oil displacement agent is a mixture of barium petroleum sulfonate and zinc naphthenate.

5. A water-displacement petrolatum anticorrosive paste suitable for marine environments according to claim 1 or 3, characterized in that: The base mineral oil is one or more of soap-based grease, hydrocarbon-based grease, inorganic grease, and organic grease. The filler is calcium carbonate or silicon powder. The lubricant is one or more of flow paraffin, white oil, phthalate ester, and vaseline. The rust inhibitor is one or more of tannic acid, barium dinonylnaphthalene sulfonate, and sulfonate metal soap.

6. A water-displacement type anticorrosive paste for marine environments according to claim 4, characterized in that: The mass ratio of the barium petroleum sulfonate to the zinc naphthenate is 2:1-3:

2.

7. A water-displacement type anticorrosive paste for marine environments according to claim 3, characterized in that: The flame retardant is one or more of phosphorus-based flame retardant, nitrogen-based flame retardant, phosphorus-nitrogen composite flame retardant, magnesium hydroxide, and aluminum hydroxide.

8. A method for preparing the water-displacement type anticorrosive paste of petro- leum jelly suitable for marine environments according to claim 1, characterized by, The method comprises the following steps: (1) adding barium petroleum sulfonate and zinc naphthenate into a reaction kettle according to a ratio, heating to 90-130°C, and stirring uniformly to obtain a water-oil displacement agent; (2) adding mineral grease and lubricant into the water-oil displacement agent, heating to 100-130°C, and stirring uniformly to obtain a base mineral grease anti-corrosion paste; (3) adding filler and rust inhibitor into the base mineral grease anti-corrosion paste, and heating to 110-130°C in a stirring machine, stirring for 1-2 hours to obtain a mineral grease anti-corrosion paste; (4) heating the mineral grease anti-corrosion paste obtained in step (3) to 120°C and continuously stirring to obtain a fused and uniform water-oil displacement type mineral grease anti-corrosion paste.

9. The method of preparing a water-displacement petrolatum anticorrosive paste suitable for marine environments according to claim 8, characterized in that, When the anti-corrosion paste comprises a flame retardant, the flame retardant is added into the base mineral grease anti-corrosion paste at the same time as the filler and the rust inhibitor.

Images