Composite gas phase corrosion inhibitor for extreme marine atmospheric environment and preparation method thereof

Abstract

The application belongs to the technical field of metal corrosion protection, and particularly relates to a composite gas-phase corrosion inhibitor for extreme marine atmospheric environment, a preparation method thereof and application thereof in the protection of metal parts in the field of offshore wind power, ships, offshore platforms and other marine engineering. The composite gas-phase corrosion inhibitor comprises, by mass fraction, 1-2 parts of benzotriazole, 3-5 parts of cysteine, 0.5-1.5 parts of sodium phytate and 6-8 parts of cyclohexylamine carbonate. The application forms a stable and dense protective film on the surface of copper through the synergistic effect of the components, and can effectively block the coupling erosion of high temperature, high humidity, high salinity and strong radiation in the extreme marine atmospheric environment. Experiments show that the corrosion rate of copper sheets can be reduced by more than 95% in the simulated extreme marine atmospheric corrosion liquid. The application has the advantages of strong adaptability to extreme environment, excellent and long-lasting corrosion inhibition effect, environmental protection, non-toxicity, simple preparation, low cost and the like, and is suitable for long-term protection of copper metal components in the field of offshore wind power and other marine engineering, and has a wide application prospect.

Description

Technical Field

[0001] This invention belongs to the field of metal corrosion protection technology, specifically relating to a composite vapor phase corrosion inhibitor for use in extreme marine atmospheric environments (extreme marine atmospheric environments with superimposed high temperature, high humidity, high salinity and strong radiation), its preparation method, and its application in the protection of metal components in marine engineering fields such as offshore wind power, ships, and offshore platforms. Background Technology

[0002] In offshore wind power, shipbuilding, and other marine engineering fields, copper and copper alloys are widely used in the manufacture of core components such as electrical terminals, heat exchangers, and hydraulic pipelines due to their excellent electrical conductivity, thermal conductivity, and corrosion resistance. However, these components operate for extended periods in extreme marine atmospheric environments, facing high temperatures (temperatures inside engine rooms can reach over 60°C in summer), high humidity (relative humidity ≥90%), and high salinity (salt spray concentration ≥35mg / m³). 3 The combined corrosion of multiple factors, including oxidation, pitting, and crevice corrosion, on metal surfaces can easily lead to a decrease in the conductivity of components, a weakening of structural strength, and even safety accidents such as electrical short circuits and hydraulic system failures, seriously affecting the operational reliability and service life of marine engineering equipment.

[0003] Currently, marine corrosion protection methods for metals mainly include coating protection and electroplating protection, but both have significant shortcomings: coating protection is prone to cracking and peeling due to temperature and humidity fluctuations and ultraviolet aging in extreme environments, and it is difficult to adapt to the complex configurations of precision metal components such as tiny gaps and threaded interfaces, easily creating blind spots in protection; electroplating protection is complex and costly, and the coating is prone to peeling under strong salt spray and radiation environments, failing to achieve long-term protection. Although single vapor-phase corrosion inhibitors have certain vapor-phase protection capabilities, they suffer from low corrosion inhibition efficiency, short protection cycles, and poor environmental adaptability under the multi-factor coupled corrosion of extreme marine atmospheres, and some single corrosion inhibitors leave toxic residues, which is inconsistent with the trend of green and environmentally friendly industrial development.

[0004] Composite vapor-phase corrosion inhibitors, through the synergistic effect of multiple components, can compensate for the shortcomings of single corrosion inhibitors, making them a research hotspot in the field of marine corrosion protection. However, existing composite vapor-phase corrosion inhibitors are mostly designed for conventional marine environments and do not fully consider the special working conditions of extreme marine atmospheres such as high temperatures and strong radiation. In such environments, the corrosion-inhibiting components are prone to excessively rapid volatilization or failure. At the same time, some composite formulations have drawbacks such as poor component compatibility, complex preparation processes, and high raw material costs, making it difficult to meet the needs of large-scale industrial applications. Therefore, developing a copper metal composite vapor-phase corrosion inhibitor with a reasonable formulation, synergistic effect of each component, environmental friendliness and non-toxicity, simple preparation, and precise adaptability to extreme marine atmospheric environments has significant practical significance and engineering application value. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of the prior art and provide a composite vapor phase corrosion inhibitor for use in extreme marine atmospheric environments (extreme marine atmospheric environments with superimposed high temperature, high humidity, high salinity and strong radiation), its preparation method, and its application in the protection of metal components in marine engineering fields such as offshore wind power, ships, and offshore platforms.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows: A composite vapor phase corrosion inhibitor for use in extreme marine atmospheric environments, comprising, by mass parts: 1-2 parts benzotriazole, 3-5 parts cysteine, 0.5-1.5 parts sodium phytate, and 6-8 parts cyclohexylamine carbonate.

[0007] The composite vapor phase corrosion inhibitor, by mass parts, consists of 1.5 parts benzotriazole, 4 parts cysteine, 1 part sodium phytate, and 7 parts cyclohexylamine carbonate.

[0008] A method for preparing the composite vapor phase corrosion inhibitor involves gradient mixing of the pulverized components according to the above-mentioned proportions.

[0009] Specifically: (1) Raw material pretreatment: Vacuum dry, crush and sieve each raw material separately for later use; (2) Gradient mixing: Take the pretreated raw materials according to the mass fraction and perform gradient mixing in sequence to obtain a uniform mixture.

[0010] In step (2), the gradient mixing is as follows: first, benzotriazole and cysteine ​​are mixed at a speed of 150-250 r / min for 10-15 min, and after mixing, sodium phytate is added and mixing is continued for 8-12 min. Finally, cyclohexylamine carbonate is added and mixed at a speed of 250-350 r / min for 15-20 min.

[0011] In step (1), the vacuum drying temperature is 50~70℃, the drying time is 3~5h, and the sieve mesh size is 100~140 mesh.

[0012] An application of the aforementioned composite vapor phase corrosion inhibitor, wherein the composite vapor phase corrosion inhibitor is used in the corrosion protection of copper and copper alloy components in the fields of offshore wind power, ships, and offshore platforms.

[0013] The composite vapor phase corrosion inhibitor is used for corrosion protection of copper and copper alloy components in offshore wind power, ships, and offshore platforms in extreme marine atmospheric environments.

[0014] The extreme marine atmospheric environment is characterized by high temperatures of 50–80°C, relative humidity ≥90%, and salt spray concentration ≥35 mg / m³. 3 An environment with strong ultraviolet radiation.

[0015] Compared with the prior art, the composite vapor phase corrosion inhibitor of the present invention has the following advantages: 1. Excellent corrosion inhibition efficiency and strong synergistic effect: The components of this invention's composite vapor-phase corrosion inhibitor form a precise and synergistic protective system. Benzotriazole, as a copper-specific corrosion inhibitor, can form a dense chelated protective film on the copper surface through adsorption, blocking the erosion of corrosive media. Cysteine ​​coordinates with copper ions through its thiol group, further enhancing the stability of the protective film and improving the vapor-phase diffusion ability of the corrosion inhibitor. Sodium phytate has both corrosion inhibition and anti-radiation functions, which can alleviate the aging and damage of the protective film caused by ultraviolet rays in extreme environments, and can adsorb chloride ions in salt spray, reducing interfacial erosion. Cyclohexylamine carbonate, as the main vapor-phase component, can quickly volatilize and penetrate into the micro-gap, threads, and other complex configuration areas of copper components, filling the protection blind spots. By combining the above components in a specific way to achieve a balance between the components and achieve synergistic effect, experiments show that in simulated extreme marine atmospheric corrosion liquids, the corrosion inhibitor of this invention can reduce the corrosion rate of copper sheets by more than 95%, and the protective effect is significantly better than existing single or composite corrosion inhibitors.

[0016] 2. Strong adaptability to extreme environments: Designed for extreme marine atmospheric environments with high temperature, high humidity, high salinity, and strong radiation, each component of this invention has good thermal stability and radiation resistance. It can still maintain stable gas phase volatilization performance at high temperatures of 60~80℃. The protective film is not easily broken due to temperature and humidity changes or ultraviolet aging, and can achieve long-term stable protection. The protection cycle is extended by more than 50% compared with existing corrosion inhibitors.

[0017] 3. Environmentally friendly, non-toxic, and highly safe: All components in the corrosion inhibitor formula of this invention are environmentally friendly materials, free of heavy metal ions, toxic organic solvents, and other harmful ingredients. No toxic gases are released during use, so it will not harm the marine environment or the health of operators. At the same time, the corrosion inhibitor does not react adversely with copper metal and surrounding components (such as steel and aluminum), and will not cause galvanic corrosion, making it highly safe to use.

[0018] 4. Simple preparation and low cost: The corrosion inhibitor of this invention only requires conventional processes such as drying, pulverizing and gradient mixing, without the need for complex equipment; the raw materials used are all industrial-grade conventional reagents, which are readily available and inexpensive, and the unit cost of mass production is low, making it suitable for large-scale industrial applications.

[0019] 5. Wide range of applications: The corrosion inhibitor of this invention can be directly used for the protection of various copper metal components such as copper terminals of offshore wind turbine nacelles, copper heat exchangers of ships, and copper pipelines of offshore platforms. It is suitable for both the protection of components during standby storage and the auxiliary protection during service, and is especially suitable for the stringent protection requirements of extreme marine atmospheric environments. Attached Figure Description

[0020] Figure 1 This is a schematic diagram of a composite vapor phase corrosion inhibitor corrosion weight loss device.

[0021] Figure 2 The images provided for embodiments of the present invention are, from left to right, the blank group, the commercially available vapor phase corrosion inhibitor group, and the composite vapor phase corrosion inhibitor group obtained in the embodiments; wherein, (a) is the blank group, (b) is the commercially available vapor phase corrosion inhibitor group, and (c) is the composite vapor phase corrosion inhibitor group. Detailed Implementation

[0022] To make the technical solution of the present invention clearer, the present invention will be further described in detail below with reference to specific embodiments.

[0023] This invention relates to a composite vapor-phase corrosion inhibitor composed of benzotriazole, cysteine, sodium phytate, and cyclohexylamine carbonate. Through the synergistic effect of these components, a stable and dense protective film is formed on the copper surface, effectively blocking the coupled corrosion caused by high temperature, high humidity, high salinity, and strong radiation in extreme marine atmospheric environments. Experiments show that it can reduce the corrosion rate of copper sheets by more than 95% in simulated extreme marine atmospheric corrosive solutions. This invention has advantages such as strong adaptability to extreme environments, excellent and long-lasting corrosion inhibition effect, environmental friendliness and non-toxicity, simple preparation, and low cost. It is suitable for long-term protection of copper metal components in marine engineering fields such as offshore wind power, and has broad application prospects.

[0024] Example 1 The composite vapor-phase corrosion inhibitor for copper metal in extreme marine atmospheric environments has the following raw material composition by mass parts: Benzotriazole: 1.5 parts, cysteine: 4 parts, sodium phytate: 1 part, and cyclohexylamine carbonate: 7 parts.

[0025] Its preparation method is as follows: 1. Raw material pretreatment: Place each raw material in a vacuum drying oven at 60℃ for 4 hours according to the above proportions, cool, pulverize and pass through a 120-mesh sieve, and set aside for use; 2. Gradient mixing: Benzotriazole and cysteine ​​were added to a double-helix conical mixer according to the above proportions and mixed at 200 r / min at room temperature for 12 min to obtain the first mixture; then sodium phytate was added to the mixture and mixed for another 10 min. After mixing, cyclohexylamine carbonate was added, the speed was increased to 300 r / min, and mixed at room temperature for 18 min to obtain the composite vapor phase corrosion inhibitor.

[0026] Example 2 The composite vapor-phase corrosion inhibitor for copper metal in extreme marine atmospheric environments has the following raw material composition by mass parts: Benzotriazole: 1 part, cysteine: 3 parts, sodium phytate: 0.5 parts and cyclohexylamine carbonate: 6 parts.

[0027] The preparation method is the same as in Example 1.

[0028] Example 3 The composite vapor-phase corrosion inhibitor for copper metal in extreme marine atmospheric environments has the following raw material composition by mass parts: Benzotriazole: 2 parts, cysteine: 5 parts, sodium phytate: 1.5 parts, and cyclohexylamine carbonate: 8 parts.

[0029] The preparation method is the same as in Example 1.

[0030] Performance Testing: The composite vapor phase corrosion inhibitors prepared in Examples 1-3 were used as a control group, and copper-specific vapor phase corrosion inhibitors (VCI vapor phase corrosion inhibitor, model RTFD100) were used for copper sheet corrosion protection tests under simulated extreme marine atmospheric environments. The test schematic diagram is shown below. Figure 1 As shown, the test results are shown in Table 1 and Figure 2 .

[0031] Test conditions: Simulated extreme marine atmospheric corrosion liquid: containing 3.5% NaCl + 0.1% H2O2 (simulating salt spray and oxidative corrosion), pH value 5.5~6.5; test temperature 65℃, relative humidity 95%, and simultaneous application of ultraviolet radiation (intensity 30W / m²). 2 ); Test cycle 30 days; Copper sheet specifications 50mm×50mm×2mm.

[0032] Test method: The corrosion rate of copper sheet was determined according to the standard GB / T 16545-2015 "Determination of corrosion rate of metals and alloys by gravimetric method" and the corrosion inhibition rate was calculated. At the same time, the corrosion morphology of the copper sheet surface was observed by scanning electron microscopy (SEM) to evaluate the integrity of the protective film.

[0033] Table 1

[0034] Meanwhile, SEM analysis of the copper sheet corrosion rate obtained from Example 1 using the composite vapor phase corrosion inhibitor for copper sheet corrosion protection testing showed that... Figure 2 As shown in SEM image (c), the test results demonstrate that the composite vapor-phase corrosion inhibitor prepared in this invention exhibits excellent corrosion inhibition effects on copper metal under extreme marine atmospheric conditions, with inhibition rates exceeding 95%, significantly superior to existing commercially available corrosion inhibitors. Figure 2 (b); and the protective film can remain intact and dense even under high temperature, high humidity and strong radiation environments, and has strong adaptability to extreme environments.

[0035] Example 4: Protective Application of Copper Materials in Offshore Wind Turbine Nacelles This embodiment addresses the extreme marine atmospheric corrosion protection requirements for copper metals inside offshore wind turbine nacelles by conducting practical application verification of the composite vapor phase corrosion inhibitor of this invention.

[0036] Application method: The composite vapor phase corrosion inhibitor obtained in Example 1 above, as well as the different corrosion inhibitors prepared according to Table 2, and the commercially available copper-specific vapor phase corrosion inhibitor (VCI vapor phase corrosion inhibitor, model RTFD100) are placed near the copper material to ensure that the corrosion inhibitor molecules can freely volatilize and penetrate.

[0037] Table 2 describes the preparation process of different corrosion inhibitors according to Example 1.

[0038] Application effect test: Copper sheets coated with the corrosion inhibitor of this invention were installed at the Guangdong Energy Group Yue Dian Yangjiang Qingzhou Offshore Wind Farm (extreme marine atmospheric environment: summer maximum temperature in the nacelle 68℃, relative humidity 98%, salt spray concentration 42mg / m³). 3 Ultraviolet radiation intensity 35W / m 2 After 6 months of continuous service, the vehicle was disassembled and tested, with a blank control group included. The test results are as follows: Table 2

[0039] As can be seen from Table 2 above, the corrosion inhibitor obtained by mixing specific components of the present invention has excellent synergistic corrosion inhibition performance. Compared with existing products and corrosion inhibitors obtained by combining different components, it has obvious performance advantages and its comprehensive anti-corrosion performance is superior to various compound formulations and commercially available mature products.

[0040] In summary, the composite vapor phase corrosion inhibitor of this invention can penetrate into the protection blind zone through volatilization, forming a stable protective film in extreme marine atmospheric environments, effectively inhibiting corrosion. At the same time, the corrosion inhibitor does not affect the conductivity of the bonding material and has no adverse reaction with other equipment in the nacelle, making it suitable for the stringent protection requirements of offshore wind turbine nacelles and possessing significant engineering application value.

Claims

1. A composite vapor-phase corrosion inhibitor for use in extreme marine atmospheric environments, characterized in that, The composite vapor phase corrosion inhibitor, by mass parts, consists of 1-2 parts benzotriazole, 3-5 parts cysteine, 0.5-1.5 parts sodium phytate, and 6-8 parts cyclohexylamine carbonate.

2. The composite vapor phase corrosion inhibitor according to claim 1, characterized in that, The composite vapor phase corrosion inhibitor, by mass parts, consists of 1.5 parts benzotriazole, 4 parts cysteine, 1 part sodium phytate, and 7 parts cyclohexylamine carbonate.

3. A method for preparing the composite vapor phase corrosion inhibitor according to claim 1, characterized in that, The pulverized components are mixed in a gradient stirring process according to the above proportions to obtain the final product.

4. The method for preparing the composite vapor phase corrosion inhibitor according to claim 3, characterized in that, (1) Raw material pretreatment: Vacuum dry, crush and sieve each raw material separately for later use; (2) Gradient mixing: Take the pretreated raw materials according to the mass fraction and perform gradient mixing in sequence to obtain a uniform mixture.

5. The method for preparing the composite vapor phase corrosion inhibitor according to claim 4, characterized in that, In step (2), the gradient mixing is as follows: first, benzotriazole and cysteine ​​are mixed at a speed of 150-250 r / min for 10-15 min, and after mixing, sodium phytate is added and mixing is continued for 8-12 min. Finally, cyclohexylamine carbonate is added and mixed at a speed of 250-350 r / min for 15-20 min.

6. The method for preparing the composite vapor phase corrosion inhibitor according to claim 4, characterized in that, In step (1), the vacuum drying temperature is 50~70℃, the drying time is 3~5h, and the sieve mesh size is 100~140 mesh.

7. The application of the composite vapor phase corrosion inhibitor according to claim 1, characterized in that, The composite vapor phase corrosion inhibitor is used in the corrosion protection of copper and copper alloy components in offshore wind power, shipbuilding, and offshore platform fields.

8. The application of the composite vapor phase corrosion inhibitor according to claim 7, characterized in that, The composite vapor phase corrosion inhibitor is used for corrosion protection of copper and copper alloy components in offshore wind power, ships, and offshore platforms in extreme marine atmospheric environments.

9. The application of the composite vapor phase corrosion inhibitor according to claim 8, characterized in that, The extreme marine atmospheric environment is characterized by high temperatures of 50–80°C, relative humidity ≥90%, and salt spray concentration ≥35 mg / m³. 3 An environment with strong ultraviolet radiation.

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