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CN-122011891-A - Hydrogen-microorganism synergistic corrosion protection coating and preparation method and application thereof

CN122011891ACN 122011891 ACN122011891 ACN 122011891ACN-122011891-A

Abstract

The invention belongs to the technical field of metal corrosion protection, and discloses a hydrogen-microorganism synergistic corrosion protection coating, a preparation method and application thereof. The coating comprises, by weight, 100 parts of epoxy resin, 18-22 parts of liquid polysulfide rubber, 5-7 parts of palladium modified hexagonal boron nitride nanosheets, 6-10 parts of [ P 4444 ][Gly]@SiO 2 ] microcapsules, 2-4 parts of silane coupling agents and 35-45 parts of amine curing agents. The coating disclosed by the invention can be used for simultaneously and efficiently blocking hydrogen permeation and inhibiting microbial corrosion for a long time.

Inventors

  • YAN MAOCHENG
  • FAN WEIHUA
  • GAO BOWEN
  • ZHAO LIN

Assignees

  • 中国科学院金属研究所

Dates

Publication Date
20260512
Application Date
20260327

Claims (10)

  1. 1. The hydrogen-microorganism synergistic corrosion protection coating is characterized by comprising, by weight, 100 parts of epoxy resin, 18-22 parts of liquid polysulfide rubber, 5-7 parts of palladium modified hexagonal boron nitride nanosheets, 6-10 parts of [ P 4444 ][Gly]@SiO 2 ] microcapsules, 2-4 parts of silane coupling agents and 35-45 parts of amine curing agents.
  2. 2. The hydrogen-microorganism synergistic corrosion protective coating of claim 1, wherein palladium metal particles in the palladium modified hexagonal boron nitride nanosheets have a particle size of 6-10nm, the loading of the palladium metal particles being 4.8-5.2wt% based on the total weight of the palladium modified hexagonal boron nitride nanosheets; The preparation method of the palladium modified hexagonal boron nitride nanosheets comprises the following steps: Stripping the h-BN nano sheet, namely mixing and stirring hexagonal boron nitride powder and an acid solution, and sequentially centrifuging, washing with water and drying in vacuum to obtain the h-BN nano sheet; Pd loading, namely mixing the h-BN nano-sheets with water, performing ultrasonic dispersion to obtain a dispersion liquid, mixing and stirring the dispersion liquid and PdCl 2 aqueous solution under a protective atmosphere to obtain a mixed system, dropwise adding NaBH 4 aqueous solution into the mixed system for reduction reaction, and performing washing and vacuum drying to obtain the palladium modified hexagonal boron nitride nano-sheets.
  3. 3. The hydrogen-microorganism synergistic corrosion protective coating of claim 2, wherein the thickness of the h-BN nanoplatelets is 3-7nm.
  4. 4. The hydrogen-microorganism synergistic corrosion protective coating of claim 1, wherein, The diameter of the [ P 4444 ][Gly]@SiO 2 ] microcapsule is 160-200nm; The thickness of the mesoporous SiO 2 outer shell layer of the [ P 4444 ][Gly]@SiO 2 microcapsule is 20-30nm, the coating rate of the mesoporous SiO 2 outer shell layer is 80-85%, and the aperture of the mesoporous SiO 2 outer shell layer is 3-4nm; the preparation method of the [ P 4444 ][Gly]@SiO 2 ] microcapsule comprises the following steps: Mixing tetrabutyl phosphine bromide, glycine and water, reacting in the dark, rotary evaporating and vacuum drying to obtain tetrabutyl phosphine glycinate; the microcapsule coating comprises the steps of mixing tetrabutyl phosphine glycinate with absolute ethyl alcohol to obtain an ethanol solution of the tetrabutyl phosphine glycinate, mixing and homogenizing the ethanol solution of the tetrabutyl phosphine glycinate with a hexadecyl trimethyl ammonium bromide aqueous solution to obtain an emulsion, mixing and reacting the emulsion, tetraethoxysilane and alkali liquor, and sequentially centrifuging, washing and calcining to obtain the [ P 4444 ][Gly]@SiO 2 microcapsule.
  5. 5. The method for preparing the hydrogen-microorganism synergistic corrosion protective coating as claimed in any one of claims 1 to 4, characterized in that the preparation method comprises the following steps: s1, mixing and stirring preheated epoxy resin and preheated liquid polysulfide rubber to obtain a base material; S2, mixing the base material, the palladium modified hexagonal boron nitride nanosheets and the [ P 4444 ][Gly]@SiO 2 ] microcapsules under ice water bath, and performing ultrasonic dispersion to obtain a mixture; s3, mixing and stirring the mixture and the silane coupling agent to obtain a crosslinked material; and S4, mixing and stirring the cross-linked material and the amine curing agent to obtain the hydrogen-microorganism synergistic corrosion protection coating.
  6. 6. The method for preparing a hydrogen-microorganism synergistic corrosion protective coating according to claim 5, wherein, In the step S1: The preheating temperature of the epoxy resin and the liquid polysulfide rubber is respectively and independently 55-65 ℃, and the preheating time is respectively and independently 5-15min; The stirring speed is 2800-3200rpm, the stirring time is 25-35min, and the stirring temperature is 55-65 ℃; in the step S2: The ultrasonic dispersion power is 550-650W, each 2 seconds of operation is intermittent for 1 second, the total ultrasonic dispersion time is 25-35min, and the temperature of ultrasonic dispersion is controlled to be less than or equal to 45 ℃ through the ice water bath; In the step S3: The stirring speed is 750-850rpm, and the stirring time is 5-15min; in the step S4: the stirring speed is 650-750rpm, and the stirring time is 10-20min.
  7. 7. Use of a hydrogen-microorganism synergistic corrosion protective coating according to any one of claims 1 to 4 for the preparation of a protective coating for a pipeline, said pipeline being an oil and gas pipeline or a hydrogen energy pipeline.
  8. 8. The method according to claim 7, wherein the method for preparing the protective coating comprises spraying the hydrogen-microorganism synergistic corrosion protective coating on the surface of the pipeline after sand blasting, and curing to obtain the protective coating.
  9. 9. The use according to claim 7, wherein the curing temperature is 20-27 ℃ for 48 hours, or the curing temperature is 37-45 ℃ for 8 hours.
  10. 10. Use according to claim 7, wherein the protective coating has a dry film thickness of 280-320 μm.

Description

Hydrogen-microorganism synergistic corrosion protection coating and preparation method and application thereof Technical Field The invention belongs to the technical field of metal corrosion protection, and in particular relates to a hydrogen-microorganism synergistic corrosion protection coating, a preparation method and application thereof. Background In energy delivery pipeline systems, the synergistic effect of hydrogen corrosion and microbial corrosion (MIC) has become a significant technical challenge threatening the integrity of the pipeline. In hydrogen energy pipelines and sulfur-containing oil and gas pipelines, the special hydrogen corrosion problems such as Hydrogen Embrittlement (HE) and Hydrogen Induced Cracking (HIC) cause the rapid increase of pipeline corrosion and fracture risk. Meanwhile, the conveying medium (especially containing trace water, organic matters or sulfate) and the soil environment provide breeding environments for Sulfate Reducing Bacteria (SRB), acid Producing Bacteria (APB) and other corrosive microorganisms, and the metabolic product H 2 S and the organic acid of the conveying medium create local strong corrosive microenvironment to accelerate the pitting and cathode depolarization processes. The interaction of the two shows a remarkable synergistic effect that H 2 S generated by MIC not only promotes the penetration of hydrogen atoms and induces Sulfide Stress Corrosion Cracking (SSCC), but also prevents the diffusion of a corrosion inhibitor by a biological film to intensify the enrichment of hydrogen at a defect part, and microcracks generated by hydrogen embrittlement further become a detention area for the growth of microorganisms to form corrosion-hydrogen embrittlement vicious circle. Traditional anticorrosive coatings such as epoxy, polyurethane and the like have limited permeation and barrier capability to hydrogen, are easy to swell, bubble and peel under long-term service, have weak inhibition effect on microorganism adhesion and biofilm formation, and are easy to be degraded by microorganisms. Although the ceramic/metal hydrogen-resistant coating such as Al 2O3 and TiN has good hydrogen resistance, the brittleness is high, the binding force with a substrate is easily affected by stress, the coating has almost no protection effect on microbial corrosion, and the micro defect part of the coating is easy to become an MIC starting point. The ceramic hydrogen-resistant coating (such as Al 2O3) has the bending toughness of only 2-3 MPa.m 1/2 (GB/T21189) and cannot bear the stress deformation of the pipeline. Part of the hydrogen barrier coating adopts palladium-based catalyst to recombine hydrogen atoms, but H 2 generated by recombination accumulates in the coating to form high-pressure bubbles, so that the coating bubbles and peels off. The existing partial functional gradient coating has a good hydrogen resistance effect, but has the problems of weak interlayer bonding force, complex preparation process (multiple spraying and high-temperature sintering are needed), difficult repair and the like, and is difficult to meet the requirements of on-site construction and maintenance of pipelines. While the antibacterial coating is mainly aimed at microorganisms, the antibacterial agent is easy to run off, the long-term effect is poor, the barrier effect on hydrogen permeation is not achieved, and certain metal ions (such as Cu 2+) added can accelerate electrochemical corrosion. In the prior art, although the blending of the hydrogen-resistant filler and the antibacterial agent is attempted, the real 'hydrogen-microorganism synergistic protection' can not be realized due to the problems of poor interfacial compatibility, functional phase separation, insufficient long-acting property and the like. In summary, most of the prior art schemes are only aimed at a single corrosion type, and cannot cooperatively solve the coupling problem of hydrogen permeation and microbial corrosion, or have the defects of complex preparation process, insufficient mechanical properties, poor long-acting property and the like. Therefore, development of a novel pipeline protective coating capable of synchronously resisting hydrogen, inhibiting bacteria and having excellent mechanical properties and construction convenience is needed to ensure safe operation of the pipeline. Disclosure of Invention The invention aims at overcoming the defects of the prior art, and provides a hydrogen-microorganism synergistic corrosion protection coating, a preparation method and application thereof. The coating disclosed by the invention can be used for simultaneously and efficiently blocking hydrogen permeation and inhibiting microbial corrosion for a long time. In order to achieve the aim, the first aspect of the invention provides a hydrogen-microorganism synergistic corrosion protection coating, which comprises, by weight, 100 parts of epoxy resin, 18-22 parts of liquid polysulfide rubber, 5-7 parts of pall