Pipeline anti-corrosion material and construction process

Abstract

The invention belongs to the technical field of pipeline anti-corrosion material preparation, and particularly relates to a pipeline anti-corrosion material and a construction technology. The anti-corrosion material is obtained by mixing raw materials of modified alkyd resin, a benzotriazole loaded hydrotalcite Co-MOFs compound, zinc oxide, a drier and a solvent, when a coating is damaged, a Co-MOFs frame firstly plays a preliminary anti-corrosion role through physical barrier and metal ion release, then a benzotriazole corrosion inhibitor between hydrotalcite layers is released through ion exchange, and the corrosion resistance of the coating is improved. An adsorption film is formed on the metal surface, and multi-level collaborative corrosion prevention is achieved; the boron-containing silicon resin and the alkyd resin are subjected to a grafting reaction to obtain the modified alkyd resin, and the mechanical property of the anticorrosive coating is effectively enhanced through modification.

Description

Technical Field

[0001] The present invention belongs to the technical field of pipeline anti-corrosion material preparation, and in particular relates to a pipeline anti-corrosion material and a construction process. Background Art

[0002] In industrial production and daily life, pipelines are widely used to transport various liquids and gases, many of which are corrosive substances, such as acid and alkali solutions and sulfur-containing gases. These corrosive substances will cause continuous erosion on the inner and outer walls of the pipeline, causing the pipeline to gradually become thinner, perforated, and eventually leak. Pipeline leakage not only causes waste of materials, but may also cause serious consequences such as environmental pollution and safety accidents, bringing great harm to production and life. In the prior art, in order to prevent pipeline corrosion, an anti-corrosion coating is usually applied to the pipeline surface. However, most of the anti-corrosion coatings currently used have problems such as insufficient corrosion resistance and low bonding strength with the pipeline surface.

[0003] Chinese patent publication number CN114539871B discloses an anti-corrosion powder coating for deep-well pipelines, its preparation method, and application. The coating is prepared from epoxy resin, curing agent, modified graphene, additives, and pigments and fillers, and is mixed and extruded to obtain the anti-corrosion coating. The combination of epoxy resin and curing agent effectively increases the cross-linking density and rigid group content. Furthermore, bisphenol A epoxy and phenolic curing agents provide some toughness, ensuring that the coating itself can withstand high and low temperature fluctuations, better meeting the anti-corrosion requirements of deep-well oil pipelines. Chinese patent publication number CN115044273B discloses a high-temperature and high-pressure fused epoxy powder for pipeline corrosion protection. The powder is made of composite epoxy resin, composite filler, adhesion promoter, degassing agent, curing agent, leveling agent, and pigment filler. By using a combination of phenolic modified epoxy resin and o-cresol epoxy resin as the composite epoxy resin, the coating can meet the requirements of high Tg and high flexibility. The mixture of wollastonite and sericite is used as the composite filler to increase the corrosion resistance and flexibility of the coating. The needle-shaped or rod-shaped wollastonite easily forms a mutually intersecting three-dimensional structure during the stacking process, which can echo the three-dimensional network structure formed by the cross-linking and curing of the epoxy resin to form a tighter coating.

[0004] However, the anti-corrosion coating prepared in the prior art is prone to falling off and cracking after a period of use. Therefore, it is of great practical significance to develop an anti-corrosion material with excellent corrosion resistance and high bonding strength with pipelines and a corresponding construction process. Summary of the Invention

[0005] The purpose of the present invention is to provide a pipeline anti-corrosion material and a construction process to solve the problems existing in the prior art.

[0006] In order to solve the above technical problems, the present invention provides the following technical solutions: A method for preparing a pipeline anti-corrosion material comprises the following steps: S100, using raw materials including zinc nitrate, aluminum nitrate, sodium nitrate, and benzotriazole to prepare benzotriazole-loaded hydrotalcite by an ion exchange method; S200, preparing Co-MOFs powder using raw materials including cobalt nitrate hexahydrate and trimesic acid, and then compounding it with benzotriazole-loaded hydrotalcite to obtain a benzotriazole-loaded hydrotalcite@Co-MOFs composite; S300, using raw materials including phenyltriethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, and boric acid to obtain a boron-containing silicone resin, and then mixing it with raw materials including alkyd resin, propylene glycol methyl ether acetate, and tetrabutyl titanate to obtain a modified alkyd resin; S400, the anti-corrosion material is obtained by mixing raw materials including a modified alkyd resin, a benzotriazole-loaded hydrotalcite@Co-MOFs composite, zinc oxide, a drying agent and a solvent.

[0007] Furthermore, step S100 specifically includes: S110, under an inert atmosphere, dissolving zinc nitrate and aluminum nitrate in deionized water and adding the solution to a sodium nitrate solution to obtain a mixed solution, adding an alkaline solution to the mixed solution, controlling the pH of the system to maintain at 9.0-10.0, and after the addition, crystallizing in a water bath at 70-80° C. for 20-28 hours, then washing by centrifugation and drying to obtain a Zn-Al-NO3 powder; S120, dissolving benzotriazole in deionized water, adding sodium hydroxide and stirring until completely dissolved to obtain a benzotriazole anion solution; S130, dispersing Zn-Al-NO3 powder in deionized water to obtain a suspension, adding benzotriazole anion solution thereto, stirring at 25-35°C for 20-28 hours, and after completion of the reaction, centrifuging, washing, and drying to obtain benzotriazole-loaded hydrotalcite.

[0008] Furthermore, step S200 specifically includes: S210, adding cobalt nitrate hexahydrate to N,N-dimethylformamide, stirring until completely dissolved, then adding trimesic acid thereto, stirring for 1-2 hours, and then placing the mixture in a reactor at 200-240° C. for 4-6 hours. After the reaction, cooling to room temperature, washing, and drying to obtain Co-MOFs powder; S220. Add Co-MOFs powder to deionized water, add benzotriazole-loaded hydrotalcite after ultrasonic dispersion, continue ultrasonication to mix evenly, then raise the temperature to 30-60°C and stir for 4-8 hours, centrifugally wash, and dry to obtain a benzotriazole-loaded hydrotalcite@Co-MOFs composite.

[0009] Furthermore, in step S210, the mass ratio of cobalt nitrate hexahydrate to trimesic acid is 1.5-3:1.

[0010] Furthermore, step S300 specifically includes: S310, adding phenyltriethoxysilane, methyltriethoxysilane and dimethyldiethoxysilane to a reactor, raising the temperature to 70-80° C., adding hydrochloric acid thereto while stirring, continuing the reaction for 2-4 hours after the addition is completed, then adding an anhydrous ethanol solution of boric acid thereto, reacting for 4-6 hours, and after the reaction is completed, distilling under reduced pressure to obtain a boron-containing silicone resin; S320, adding boron-containing silicone resin, alkyd resin, propylene glycol methyl ether acetate and tetrabutyl titanate into a reactor, raising the temperature to 100-120° C. and dehydrating for 1-2 hours. After the dehydration is completed, raising the temperature to 115-135° C., and performing reduced pressure distillation for 20-40 minutes after the reaction is completed to obtain a modified alkyd resin.

[0011] Furthermore, in step S310, the mass ratio of phenyltriethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane and boric acid is 30-40:20-35:15-25:5-15.

[0012] Furthermore, in step S320, the mass ratio of the boron-containing silicone resin, the alkyd resin, the propylene glycol methyl ether acetate and the tetrabutyl titanate is 10-25:50-70:10-20:1-5.

[0013] Furthermore, in step S400, the mass ratio of the modified alkyd resin, the benzotriazole-loaded hydrotalcite@Co-MOFs composite, the zinc oxide, the drying agent, and the solvent is 45-50:10-12:5-8:1-2:33-36.

[0014] The present invention also provides a pipeline anti-corrosion material, which is prepared using the pipeline anti-corrosion material preparation method described in any of the above technical solutions.

[0015] The present invention also provides a pipeline anti-corrosion construction process, the construction process steps are: rust and oil removal on the pipeline surface, then coating the pipeline anti-corrosion material on the treated pipeline surface, and leaving the coated pipeline at room temperature for 24-48 hours to allow it to cure naturally.

[0016] The present invention has the following beneficial effects: Nitrate-intercalated zinc-aluminum hydrotalcite was synthesized by a hydrothermal method, and benzotriazole-loaded hydrotalcite was prepared by anion exchange using the organic corrosion inhibitor benzotriazole. When the hydrotalcite releases benzotriazole anions due to the penetration of the corrosive medium, the benzotriazole anions can form stable chelates with metal ions on the metal surface, forming a dense protective film on the metal surface, blocking direct contact between the metal and the corrosive medium, thereby achieving a synergistic corrosion effect between the inherent properties of the hydrotalcite and the corrosion inhibition of the loaded benzotriazole. The hydroxyl-rich surface of the benzotriazole-loaded hydrotalcite layer formed hydrogen bonds with Co-MOFs to obtain a benzotriazole-loaded hydrotalcite@Co-MOFs complex. When the coating is damaged, the Co-MOFs framework first exerts an initial anti-corrosion effect through physical barriers and metal ion release. Subsequently, the benzotriazole corrosion inhibitor between the hydrotalcite layers is released through ion exchange, forming an adsorption film on the metal surface, achieving multi-level synergistic corrosion protection.

[0017] Using dimethyldiethoxysilane, methyltriethoxysilane, phenyltriethoxysilane, and boric acid as raw materials, a siloxane network is formed through a silane hydrolysis-condensation reaction. Boric acid is then introduced for cross-linking modification. Furthermore, tetrabutyl titanate is used as a catalyst to graft a boron-containing silicone resin onto an alkyd resin to produce a modified alkyd resin. The low surface energy and hydrophobic groups of the silicone resin reduce the water absorption of the coating, while the three-dimensional network structure of the silicone resin and the introduction of boron enhance the mechanical properties of the coating. DETAILED DESCRIPTION

[0018] The following will be combined with the embodiments of the present application to clearly and completely describe the technical solutions in the embodiments of the present application. Obviously, the embodiments described are only part of the embodiments of the present application, not all of the embodiments. Based on the embodiments of the present application, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of this application.

[0019] Metals and their alloys have advantages such as high strength, good machinability and plasticity, and have been widely used in various fields. However, metals easily react with certain substances or components in the environment, which can lead to damage to the metal surface substrate. Severe corrosion not only destroys the structural integrity of the metal material, but also causes serious safety accidents and economic losses. Therefore, anti-corrosion treatment is necessary for metal surfaces. Alkyd resins are oil-modified polyesters with high adhesion. Due to their low price, flexible formulation, and excellent gloss and flexibility of the coating film, they are used in the preparation of anti-corrosion materials. However, single alkyd resins are easily corroded and degraded by harmful substances in the environment.

[0020] Based on this, the present invention provides a method for preparing a pipeline anti-corrosion material, which comprises the following steps: S100, using raw materials including zinc nitrate, aluminum nitrate, sodium nitrate, and benzotriazole to prepare benzotriazole-loaded hydrotalcite by an ion exchange method; S200, preparing Co-MOFs powder using raw materials including cobalt nitrate hexahydrate and trimesic acid, and then compounding it with benzotriazole-loaded hydrotalcite to obtain a benzotriazole-loaded hydrotalcite@Co-MOFs composite; S300, using raw materials including phenyltriethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, and boric acid to obtain a boron-containing silicone resin, and then mixing it with raw materials including alkyd resin, propylene glycol methyl ether acetate, and tetrabutyl titanate to obtain a modified alkyd resin; S400, the anti-corrosion material is obtained by mixing raw materials including a modified alkyd resin, a benzotriazole-loaded hydrotalcite@Co-MOFs composite, zinc oxide, a drying agent and a solvent.

[0021] Step S100 specifically includes: S110, under an inert atmosphere, dissolving zinc nitrate and aluminum nitrate in deionized water and adding the solution to a sodium nitrate solution to obtain a mixed solution, adding an alkaline solution to the mixed solution, controlling the pH of the system to maintain at 9.0-10.0, and after the addition, crystallizing in a water bath at 70-80° C. for 20-28 hours, then washing by centrifugation and drying to obtain a Zn-Al-NO3 powder; S120, dissolving benzotriazole in deionized water, adding sodium hydroxide and stirring until completely dissolved to obtain a benzotriazole anion solution; S130, dispersing Zn-Al-NO3 powder in deionized water to obtain a suspension, adding benzotriazole anion solution thereto, stirring at 25-35°C for 20-28 hours, and after completion of the reaction, centrifuging, washing, and drying to obtain benzotriazole-loaded hydrotalcite.

[0022] In this step, nitrate-intercalated zinc-aluminum hydrotalcite was synthesized by hydrothermal method, and benzotriazole-loaded hydrotalcite was prepared by anion exchange using organic corrosion inhibitor benzotriazole. Hydrotalcite is a two-dimensional layered material with a high aspect ratio. When it is dispersed in an anti-corrosion coating, it can distort and extend the penetration path of the corrosive medium, thereby reducing the penetration rate of the corrosive medium. Benzotriazole can form a stable protective film on the metal surface, thereby blocking the contact between the corrosive medium and the metal. In this step, the exchangeability of anions between the hydrotalcite layers is utilized to exchange the NO3 between the Zn-Al-NO3 layers. -The loading of benzotriazole is achieved by replacing it with benzotriazole anions. When the hydrotalcite releases benzotriazole anions due to the penetration of the corrosive medium, the benzotriazole anions can form a stable chelate with the metal ions on the metal surface, forming a dense protective film on the metal surface, blocking direct contact between the metal and the corrosive medium. This achieves a synergistic corrosion effect of the inherent properties of the hydrotalcite and the corrosion inhibition effect of the loaded benzotriazole.

[0023] Step S200 specifically includes: S210, adding cobalt nitrate hexahydrate to N,N-dimethylformamide, stirring until completely dissolved, then adding trimesic acid thereto, stirring for 1-2 hours, and then placing the mixture in a reactor at 200-240° C. for reaction for 4-6 hours. After the reaction is completed, cooling to room temperature, washing, and drying to obtain Co-MOFs powder; wherein the mass ratio of cobalt nitrate hexahydrate to trimesic acid is 1.5-3:1; S220. Add Co-MOFs powder to deionized water, add benzotriazole-loaded hydrotalcite after ultrasonic dispersion, continue ultrasonication to mix evenly, then raise the temperature to 30-60°C and stir for 4-8 hours, centrifugally wash, and dry to obtain a benzotriazole-loaded hydrotalcite@Co-MOFs composite.

[0024] In this step, Co is used as the metal source and trimesic acid is used as the organic ligand. The two are coordinated by a solvent thermal method to prepare a cobalt-based metal organic framework compound. Co-MOFs contain a large amount of coordinated Co 2+ Central metal ions, in a corrosive environment, some Co 2+ It can be slowly released by cleavage of coordination bonds or dissolution of the framework. 2+ It can competitively adsorb on the metal surface, occupy the active sites on the metal surface, inhibit the metal atoms from losing electrons, and at the same time Co 2+ It can combine with corrosion products to form insoluble oxides or hydroxides, which deposit on the metal surface to form a secondary protective film, thereby hindering further oxidation.

[0025] The surface of the benzotriazole-loaded hydrotalcite is rich in hydroxyl groups, and unreacted hydroxyl groups from the trimesic acid ligands may remain on the surface of the Co-MOFs. This allows hydrogen bonds to form between the two, further strengthening the interfacial bonding. Furthermore, ultrasonic treatment fully disperses the Co-MOFs and benzotriazole-loaded hydrotalcite, increasing the contact area. This allows the benzotriazole-loaded hydrotalcite to adhere to the porous surface or pores of the Co-MOFs via physical adsorption, forming a stable composite. This composite process does not destroy the main structures of the two, but rather achieves synergistic loading through interfacial interactions, preserving the corrosion inhibitor release properties of the benzotriazole-loaded hydrotalcite and the porous adsorption properties of the Co-MOFs. When the coating is damaged, the Co-MOFs framework first exerts its initial anti-corrosion effect through physical barriers and metal ion release. Subsequently, the benzotriazole corrosion inhibitor between the hydrotalcite layers is released through ion exchange, forming an adsorption film on the metal surface, achieving multi-level synergistic corrosion protection.

[0026] Step S300 specifically includes: S310, adding phenyltriethoxysilane, methyltriethoxysilane and dimethyldiethoxysilane to a reactor, raising the temperature to 70-80° C., adding hydrochloric acid thereto while stirring, continuing the reaction for 2-4 hours after the addition is completed, then adding an anhydrous ethanol solution of boric acid thereto, reacting for 4-6 hours, and distilling under reduced pressure to obtain a boron-containing silicone resin after the reaction is completed; wherein the mass ratio of phenyltriethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane and boric acid is 30-40:20-35:15-25:5-15; S320. Add boron-containing silicone resin, alkyd resin, propylene glycol methyl ether acetate and tetrabutyl titanate into a reactor, mix well and then increase the temperature to 100-120° C. for dehydration for 1-2 hours. After the dehydration is completed, increase the temperature to 115-135° C. and perform reduced pressure distillation for 20-40 minutes to obtain a modified alkyd resin; wherein the mass ratio of the boron-containing silicone resin, alkyd resin, propylene glycol methyl ether acetate and tetrabutyl titanate is 10-25:50-70:10-20:1-5.

[0027] In this step, the polar groups contained in the alkyd resin molecules can form strong physical or chemical adsorption with the metal surface, allowing the coating to adhere tightly to the substrate surface and reducing the penetration of corrosive media caused by poor adhesion. At the same time, after the resin dries, it forms a continuous film that can physically block the contact of corrosive media such as water, oxygen, and chloride ions with the metal. However, the alkyd resin molecules contain a large number of ester bonds, which can cause hydrolysis and cause the coating to swell or crack. Silicone resin has a Si-O-Si skeleton. Because Si-O has a high bond energy, organic silicon polymers have excellent thermal stability and water resistance. Furthermore, the BO bond energy is higher than the Si-O bond energy, so introducing boron into the organic silicon backbone can further improve its adhesion and thermal stability. Therefore, in the present invention, dimethyldiethoxysilane, methyltriethoxysilane, phenyltriethoxysilane and boric acid are used as raw materials. A siloxane network is formed through a silane hydrolysis-condensation reaction, and boric acid is introduced for cross-linking modification. Further, using tetrabutyl titanate as a catalyst, the boron-containing silicone resin is grafted onto the alkyd resin to obtain a modified alkyd resin. Through modification, the low surface energy and hydrophobic groups of silicone resin can reduce the water absorption rate of the coating, and the three-dimensional network structure of silicone resin and the introduction of boron element can enhance the mechanical properties of the coating.

[0028] Step S400 is specifically as follows: S400, adding a modified alkyd resin, a benzotriazole-loaded hydrotalcite@Co-MOFs composite, zinc oxide, a drying agent, and a solvent into a reactor, stirring at a speed of 2000-2800 r / min for 15-25 minutes, and obtaining the pipeline anticorrosion material after being fully blended.

[0029] In step S400, the mass ratio of the modified alkyd resin, benzotriazole-supported hydrotalcite@Co-MOFs composite, zinc oxide, drier, and solvent is 45-50:10-15:5-8:1-2:33-46. The drier is one or more of manganese naphthenate, cobalt isooctanoate, cobalt neodecanoate, nickel naphthenate, cobalt octoate, and cobalt acetylacetonate; and the solvent is one or more of ethanol, isopropanol, sec-butyl alcohol, butanone, ethylene glycol butyl ether, propylene glycol methyl ether, and toluene.

[0030] A pipeline anti-corrosion material is prepared by the preparation method of the pipeline anti-corrosion material as described in any of the above technical solutions.

[0031] A pipeline anti-corrosion construction process comprises the following steps: rust and oil removal is performed on the pipeline surface, a pipeline anti-corrosion material is then coated on the treated pipeline surface, and the coated pipeline is left to stand at room temperature for 24-48 hours to allow it to cure naturally.

[0032] In this step, the pipeline surface is first derusted by sandblasting. Sandblasting can remove rust, scale, oil and other impurities on the pipeline surface, and at the same time form a certain degree of roughness on the pipeline surface. The pipeline surface is then cleaned with an organic solvent to further remove surface oil and residual impurities. The evenly mixed pipeline anti-corrosion material is then sprayed or brushed on the treated pipeline surface. Finally, the coated pipeline is placed at room temperature for 24-48 hours to allow it to cure naturally.

[0033] In the present invention, phenyltriethoxysilane, methyltriethoxysilane, and boric acid were all analytically pure and purchased from Shanghai Aladdin Biochemical Technology Co., Ltd., dimethyldiethoxysilane (analytical pure) was purchased from Shanghai MacLean Biochemical Technology Co., Ltd., and alkyd resin (analytical pure) and propylene glycol methyl ether acetate (industrial grade) were purchased from Hangzhou Jihua Polymer Materials Co., Ltd. All reagents used in the present invention are commercially available.

[0034] Example 1 A method for preparing a pipeline anti-corrosion material, the method comprising the following steps: S1. Under a nitrogen atmosphere, 24 parts by weight of zinc nitrate and 10 parts by weight of aluminum nitrate were dissolved in 100 parts by weight of deionized water, and the mixture was added to 75 parts by weight of a 1.5M sodium nitrate solution to obtain a mixed solution. A 1.5M sodium hydroxide solution was added to the mixed solution, and the pH of the system was controlled to be maintained at 9.0-10.0. After the addition was completed, the mixture was crystallized in a water bath at 75°C for 24 hours, and then centrifuged, washed with deionized water three times, and placed in a vacuum drying oven at 60°C for 12 hours to obtain Zn-Al-NO3 powder; S2, dissolving 2 parts by weight of benzotriazole in 50 parts by weight of deionized water, adding 0.4 parts by weight of sodium hydroxide and stirring until completely dissolved to obtain a benzotriazole anion solution; dispersing 1 part by weight of Zn-Al-NO3 powder in 50 parts by weight of deionized water and ultrasonically dispersing for 10 minutes to obtain a suspension, slowly adding 50 parts by weight of the benzotriazole anion solution thereto, stirring at 30°C for 24 hours, centrifuging after completion of the reaction, washing 3 times with deionized water, and then drying in a vacuum drying oven at 60°C for 12 hours to obtain a benzotriazole-loaded hydrotalcite; S3. Add 1.8 parts by weight of cobalt nitrate hexahydrate to 50 parts by weight of N,N-dimethylformamide, stir until completely dissolved, then add 1 part by weight of trimesic acid, stir for 2 hours, and then place in a reactor to react at 220° C. for 5 hours. After the reaction, cool to room temperature, wash with anhydrous ethanol three times, and then dry in a vacuum drying oven at 60° C. for 6 hours to obtain Co-MOFs powder; S4. Add 15 parts by weight of Co-MOFs powder to 50 parts by weight of deionized water, ultrasonically disperse for 20 minutes, then add 1.5 parts by weight of benzotriazole-loaded hydrotalcite, continue ultrasonicating for 10 minutes to mix evenly, then heat to 45°C and stir for 6 hours, centrifuge, wash with deionized water three times, and dry in a vacuum drying oven at 60°C for 8 hours to obtain a benzotriazole-loaded hydrotalcite@Co-MOFs composite; S5, adding 35 parts by weight of phenyltriethoxysilane, 32 parts by weight of methyltriethoxysilane and 18 parts by weight of dimethyldiethoxysilane to the reactor, raising the temperature to 75° C., adding 6 parts by weight of 4M hydrochloric acid thereto under stirring, continuing the reaction for 3 hours after the addition is completed, and then adding 100 parts by weight of a 10 wt% boric acid anhydrous ethanol solution thereto and reacting for 5 hours. After the reaction is completed, distilling under reduced pressure to obtain a boron-containing silicone resin; S6, adding 22 parts by weight of boron-containing silicone resin, 65 parts by weight of alkyd resin, 15 parts by weight of propylene glycol methyl ether acetate and 3 parts by weight of tetrabutyl titanate into the reactor, mixing evenly and then raising the temperature to 110° C. for dehydration for 1.5 hours. After the dehydration is completed, raising the temperature to 120° C. and performing reduced pressure distillation for 20-40 minutes after the reaction is completed to obtain a modified alkyd resin; S7. Add 48 parts by weight of modified alkyd resin, 12 parts by weight of benzotriazole-loaded hydrotalcite@Co-MOFs composite, 6 parts by weight of zinc oxide, 1 part by weight of manganese naphthenate, and 42 parts by weight of isopropyl alcohol into the reactor, and stir at a speed of 2200 r / min for 20 minutes. After fully blended, the pipeline anticorrosion material is obtained.

[0035] A pipeline anti-corrosion construction process comprises the following steps: sandblasting the pipeline surface to remove rust, wherein the abrasive used for sandblasting is quartz sand, the sandblasting pressure is 0.5 MPa, and the pipeline surface roughness is 50 μm; then the pipeline surface is cleaned and degreased with gasoline; the above-mentioned anti-corrosion materials are evenly mixed and then brushed on the pipeline surface, with a coating thickness of 100±5 μm; and finally, the coated pipeline is left to stand at room temperature for 24 hours to allow it to cure naturally.

[0036] Example 2 This embodiment has the following differences compared to the first embodiment: In step S1, 18 parts by weight of zinc nitrate and 5 parts by weight of aluminum nitrate are dissolved in 60 parts by weight of deionized water and then added to 32 parts by weight of a 1.5M sodium nitrate solution to obtain a mixed solution; In step S2, 1.2 parts by weight of benzotriazole is dissolved in 30 parts by weight of deionized water, and 0.15 parts by weight of sodium hydroxide is added and stirred until completely dissolved to obtain a benzotriazole anion solution; 0.65 parts by weight of Zn-Al-NO3 powder is dispersed in 30 parts by weight of deionized water and ultrasonically dispersed for 10 minutes to obtain a suspension, to which 30 parts by weight of the benzotriazole anion solution is slowly added, and stirred at 25°C for 20 hours; In step S3, 1.5 parts by weight of cobalt nitrate hexahydrate was added to 30 parts by weight of N,N-dimethylformamide, and the mixture was stirred until completely dissolved. Then, 1 part by weight of trimesic acid was added thereto, and the mixture was stirred for 1 hour to mix thoroughly. After that, the mixture was placed in a reactor at 200° C. and reacted for 4 hours. In step S4, 12 parts by weight of Co-MOFs powder was added to 30 parts by weight of deionized water, and after ultrasonic dispersion for 20 minutes, 1 part by weight of benzotriazole-loaded hydrotalcite was added, and ultrasonic dispersion was continued for 10 minutes to mix uniformly, and then the temperature was raised to 30° C. and stirred for 4 hours; In step S5, 30 parts by weight of phenyltriethoxysilane, 20 parts by weight of methyltriethoxysilane and 15 parts by weight of dimethyldiethoxysilane were added to the reactor, the temperature was raised to 70° C., 4 parts by weight of 4M hydrochloric acid were added thereto under stirring, and the reaction was continued for 2 hours after the addition was completed. Then, 80 parts by weight of a 10 wt% boric acid anhydrous ethanol solution was added thereto and the reaction was carried out for 4 hours. After the reaction was completed, the reaction was carried out by vacuum distillation to obtain a boron-containing silicone resin; In step S6, 10 parts by weight of boron-containing silicone resin, 50 parts by weight of alkyd resin, 10 parts by weight of propylene glycol methyl ether acetate, and 1 part by weight of tetrabutyl titanate are added to the reactor, mixed evenly, and then the temperature is raised to 100° C. for dehydration for 1 hour. After the dehydration is completed, the temperature is raised to 115° C., and after the reaction is completed, reduced pressure distillation is performed for 20 minutes to obtain a modified alkyd resin; In step S7, 45 parts by weight of modified alkyd resin, 10 parts by weight of benzotriazole-loaded hydrotalcite@Co-MOFs composite, 5 parts by weight of zinc oxide, 1 part by weight of manganese cyclohexane, and 33 parts by weight of isopropanol were added to the reactor and stirred at a speed of 2000 r / min for 15 minutes. After being fully blended, the pipeline anticorrosion material was obtained.

[0037] A pipeline anti-corrosion construction process comprises the following steps: sandblasting the pipeline surface to remove rust at a sandblasting pressure of 0.6 MPa and a pipeline surface roughness of 65 μm, then cleaning the pipeline surface with gasoline to remove oil; mixing the above-mentioned anti-corrosion materials evenly and then applying the materials to the pipeline surface by brushing to a coating thickness of 100±5 μm; and finally allowing the coated pipeline to stand at room temperature for 36 hours to allow it to cure naturally.

[0038] The rest are all referred to Example 1.

[0039] Example 3 This embodiment has the following differences compared to the first embodiment: In step S1, 28 parts by weight of zinc nitrate and 15 parts by weight of aluminum nitrate are dissolved in 140 parts by weight of deionized water and then added to 100 parts by weight of a 1.5M sodium nitrate solution to obtain a mixed solution; In step S2, 2.5 parts by weight of benzotriazole are dissolved in 80 parts by weight of deionized water, and 0.6 parts by weight of sodium hydroxide are added and stirred until completely dissolved to obtain a benzotriazole anion solution; 1.25 parts by weight of Zn-Al-NO3 powder is dispersed in 80 parts by weight of deionized water and ultrasonically dispersed for 10 minutes to obtain a suspension, to which 80 parts by weight of the benzotriazole anion solution is slowly added, and stirred at 35°C for 28 hours; In step S3, 3 parts by weight of cobalt nitrate hexahydrate were added to 80 parts by weight of N,N-dimethylformamide, and the mixture was stirred until completely dissolved. Then, 1 part by weight of trimesic acid was added thereto, and the mixture was stirred for 2 hours until completely mixed. After that, the mixture was placed in a reactor at 240° C. and reacted for 6 hours. In step S4, 18 parts by weight of Co-MOFs powder was added to 80 parts by weight of deionized water, and ultrasonic dispersion was performed for 20 minutes. Then, 2.1 parts by weight of benzotriazole-loaded hydrotalcite was added, and ultrasonic dispersion was continued for 10 minutes to mix the mixture evenly. Then, the temperature was raised to 50° C. and stirred for 8 hours. In step S5, 40 parts by weight of phenyltriethoxysilane, 35 parts by weight of methyltriethoxysilane and 25 parts by weight of dimethyldiethoxysilane were added to the reactor, the temperature was raised to 80° C., 8 parts by weight of 4M hydrochloric acid were added thereto under stirring, and the reaction was continued for 4 hours after the addition was completed. Then, 120 parts by weight of a 10 wt% boric acid anhydrous ethanol solution was added thereto and the reaction was carried out for 6 hours. After the reaction was completed, the reaction was carried out by vacuum distillation to obtain a boron-containing silicone resin; In step S6, 25 parts by weight of boron-containing silicone resin, 70 parts by weight of alkyd resin, 20 parts by weight of propylene glycol methyl ether acetate, and 5 parts by weight of tetrabutyl titanate are added to the reactor, mixed evenly, and then the temperature is raised to 120° C. for dehydration for 2 hours. After the dehydration is completed, the temperature is raised to 135° C., and after the reaction is completed, the reaction is distilled under reduced pressure for 40 minutes to obtain a modified alkyd resin; In step S7, 50 parts by weight of modified alkyd resin, 15 parts by weight of benzotriazole-loaded hydrotalcite@Co-MOFs composite, 8 parts by weight of zinc oxide, 2 parts by weight of manganese cyclohexane, and 46 parts by weight of isopropanol were added to the reactor and stirred at a speed of 2800 r / min for 25 minutes. After being fully blended, the pipeline anticorrosion material was obtained.

[0040] A pipeline anti-corrosion construction process comprises the following steps: sandblasting the pipeline surface to remove rust at a sandblasting pressure of 0.8 MPa and a pipeline surface roughness of 80 μm, then cleaning the pipeline surface with gasoline to remove oil; mixing the above-mentioned anti-corrosion materials evenly and then brushing them on the pipeline surface to a coating thickness of 100±5 μm; and finally, leaving the coated pipeline to stand at room temperature for 48 hours to allow it to cure naturally.

[0041] The rest are all referred to Example 1.

[0042] Example 4 Compared with Example 1, this embodiment does not load the corrosion inhibitor benzotriazole, and the rest is referred to Example 1, specifically as follows: A method for preparing a pipeline anti-corrosion material, specifically comprising: adding 48 parts by weight of a modified alkyd resin, 10 parts by weight of Co-MOFs powder, 2 parts by weight of Zn-Al-NO3 powder, 6 parts by weight of zinc oxide, 1 part by weight of manganese cyclohexane and 42 parts by weight of isopropyl alcohol into a reactor, stirring at a speed of 2200 r / min for 20 minutes, and obtaining the pipeline anti-corrosion material after sufficient fusion; the preparation method of the modified alkyd resin, Co-MOFs powder and Zn-Al-NO3 powder refers to Example 1.

[0043] Example 5 Compared with Example 1, this example does not add Co-MOFs powder. The rest is similar to Example 1, specifically as follows: A method for preparing a pipeline anticorrosion material comprises: adding 48 parts by weight of a modified alkyd resin, 12 parts by weight of benzotriazole-loaded hydrotalcite, 6 parts by weight of zinc oxide, 1 part by weight of manganese naphthenate, and 42 parts by weight of isopropyl alcohol to a reactor; stirring at a speed of 2200 r / min for 20 minutes; and obtaining the pipeline anticorrosion material after thorough blending. The preparation methods of the modified alkyd resin and the benzotriazole-loaded hydrotalcite are as described in Example 1.

[0044] Example 6 Compared with Example 1, this embodiment does not perform boron modification during the preparation of the silicone resin. The rest is similar to Example 1, as follows: A method for preparing a pipeline anticorrosion material, comprising: adding 48 parts by weight of a modified alkyd resin, 12 parts by weight of a benzotriazole-loaded hydrotalcite@Co-MOFs composite, 6 parts by weight of zinc oxide, 1 part by weight of manganese naphthenate, and 42 parts by weight of isopropyl alcohol to a reactor; stirring at 2200 r / min for 20 minutes; and obtaining the pipeline anticorrosion material after sufficient fusion; wherein the preparation method of the benzotriazole-loaded hydrotalcite@Co-MOFs composite is similar to that of Example 1; The preparation process of modified alkyd resin is as follows: S1, adding 35 parts by weight of phenyltriethoxysilane, 32 parts by weight of methyltriethoxysilane and 18 parts by weight of dimethyldiethoxysilane to a reactor, raising the temperature to 75° C., adding 6 parts by weight of 4M hydrochloric acid thereto while stirring, continuing the reaction for 6 hours after the addition is completed, and distilling under reduced pressure to obtain a silicone resin after the reaction is completed; S2. Add 22 parts by weight of silicone resin, 65 parts by weight of alkyd resin, 15 parts by weight of propylene glycol methyl ether acetate and 3 parts by weight of tetrabutyl titanate into the reactor, mix well and then raise the temperature to 110° C. for dehydration for 1.5 hours. After the dehydration is completed, raise the temperature to 120° C. and perform reduced pressure distillation for 20-40 minutes to obtain a modified alkyd resin.

[0045] Example 7 Compared with Example 1, this embodiment does not add boron-containing silicone resin during the preparation of the pipeline anti-corrosion coating. The rest is referred to Example 1, as follows: A method for preparing a pipeline anticorrosion material comprises: adding 48 parts by weight of an alkyd resin, 12 parts by weight of a benzotriazole-loaded hydrotalcite@Co-MOFs composite, 6 parts by weight of zinc oxide, 1 part by weight of manganese naphthenate, and 42 parts by weight of isopropyl alcohol to a reactor; stirring at a speed of 2200 r / min for 20 minutes; and obtaining the pipeline anticorrosion material after sufficient fusion; wherein the preparation method of the benzotriazole-loaded hydrotalcite@Co-MOFs composite is as described in Example 1.

[0046] Example 8 Compared with Example 4, this embodiment does not add Co-MOFs powder, and the rest refers to Example 4, specifically as follows: A method for preparing a pipeline anti-corrosion material, specifically: adding 48 parts by weight of modified alkyd resin, 12 parts by weight of Zn-Al-NO3 powder, 6 parts by weight of zinc oxide, 1 part by weight of manganese cyclohexane and 42 parts by weight of isopropanol into a reactor, stirring at a speed of 2200r / min for 20 minutes, and obtaining the pipeline anti-corrosion material after sufficient fusion; wherein the preparation method of the modified alkyd resin and Zn-Al-NO3 powder refers to Example 4.

[0047] Comparative Example 1 A method for preparing a pipeline anticorrosion material comprises the following steps: adding 48 parts by weight of a modified alkyd resin, 6 parts by weight of zinc oxide, 1 part by weight of manganese naphthenate, and 42 parts by weight of isopropyl alcohol into a reactor, stirring at a speed of 2200 r / min for 20 minutes, and obtaining the pipeline anticorrosion material after the mixture is fully blended.

[0048] The preparation process of modified alkyd resin is as follows: S1, adding 35 parts by weight of phenyltriethoxysilane, 32 parts by weight of methyltriethoxysilane and 18 parts by weight of dimethyldiethoxysilane to a reactor, raising the temperature to 75° C., adding 6 parts by weight of 4M hydrochloric acid thereto while stirring, continuing the reaction for 6 hours after the addition is completed, and distilling under reduced pressure to obtain a silicone resin after the reaction is completed; S2. Add 22 parts by weight of silicone resin, 65 parts by weight of alkyd resin, 15 parts by weight of propylene glycol methyl ether acetate and 3 parts by weight of tetrabutyl titanate into the reactor, mix well and then raise the temperature to 110° C. for dehydration for 1.5 hours. After the dehydration is completed, raise the temperature to 120° C. and perform reduced pressure distillation for 20-40 minutes to obtain a modified alkyd resin.

[0049] Comparative Example 2 A method for preparing a pipeline anticorrosion material comprises the following steps: adding 48 parts by weight of alkyd resin, 6 parts by weight of zinc oxide, 1 part by weight of manganese naphthenate, and 42 parts by weight of isopropyl alcohol into a reactor, stirring at a speed of 2200 r / min for 20 minutes, and obtaining the pipeline anticorrosion material after the mixture is fully blended.

[0050] Related tests The pipeline anticorrosion materials prepared in Examples 1 to 8 and Comparative Examples 1 to 2 were subjected to coating adhesion testing, hardness testing, high temperature resistance testing, salt spray resistance testing, alkali resistance testing, and acid resistance testing, respectively. The coating adhesion testing method was based on GB / T5210-2006, and the substrate for the coating adhesion testing was steel. The hardness testing method was based on GB / T6739-2006; the high temperature resistance testing method was based on GB1735-2009; the salt spray resistance testing method was based on GB / T1771-91; the alkali resistance testing method was based on GB / T9274-88 (10% NaOH); and the acid resistance testing method was based on GB / T9274-88 (10% H2SO4). The test results are shown in Table 1.

[0051] Table 1 Performance test results It can be seen from the test data in Table 1 that the anti-corrosion material prepared by the present invention has excellent corrosion resistance and high temperature resistance, and the coating hardness and adhesion effects are good.

[0052] It should be noted that, in this document, relational terms such as first and second, etc., are used only to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual relationship or order between these entities or operations. Moreover, the terms "comprises," "comprising," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that includes a list of elements includes not only those elements but also other elements not explicitly listed, or elements inherent to such process, method, article, or apparatus.

[0053] Although the embodiments of the present application have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and variations may be made to these embodiments without departing from the principles and spirit of the present application, and the scope of the present application is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a pipeline anticorrosive material, characterized in that: The steps include: S100, using raw materials including zinc nitrate, aluminum nitrate, sodium nitrate, and benzotriazole to prepare benzotriazole-loaded hydrotalcite by an ion exchange method; S200, preparing Co-MOFs powder using raw materials including cobalt nitrate hexahydrate and trimesic acid, and then compounding it with benzotriazole-loaded hydrotalcite to obtain a benzotriazole-loaded hydrotalcite@Co-MOFs composite; S300, using raw materials including phenyltriethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, and boric acid to obtain a boron-containing silicone resin, and then mixing it with raw materials including alkyd resin, propylene glycol methyl ether acetate, and tetrabutyl titanate to obtain a modified alkyd resin; S400, the anti-corrosion material is obtained by mixing raw materials including a modified alkyd resin, a benzotriazole-loaded hydrotalcite@Co-MOFs composite, zinc oxide, a drying agent and a solvent.

2. The method for preparing a pipeline anticorrosive material according to claim 1, characterized in that: Step S100 specifically includes: S110, under an inert atmosphere, dissolving zinc nitrate and aluminum nitrate in deionized water and adding the solution to a sodium nitrate solution to obtain a mixed solution, adding an alkaline solution to the mixed solution, controlling the pH of the system to maintain at 9.0-10.0, and after the addition, crystallizing in a water bath at 70-80° C. for 20-28 hours, then washing by centrifugation and drying to obtain a Zn-Al-NO3 powder; S120, dissolving benzotriazole in deionized water, adding sodium hydroxide and stirring until completely dissolved to obtain a benzotriazole anion solution; S130, dispersing Zn-Al-NO3 powder in deionized water to obtain a suspension, adding benzotriazole anion solution thereto, stirring at 25-35°C for 20-28 hours, and after completion of the reaction, centrifuging, washing, and drying to obtain benzotriazole-loaded hydrotalcite.

3. The method for preparing a pipeline anticorrosive material according to claim 1, characterized in that: Step S200 specifically includes: S210, adding cobalt nitrate hexahydrate to N,N-dimethylformamide, stirring until completely dissolved, then adding trimesic acid thereto, stirring for 1-2 hours, and then placing the mixture in a reactor at 200-240° C. for 4-6 hours. After the reaction, cooling to room temperature, washing, and drying to obtain Co-MOFs powder; S220. Add Co-MOFs powder to deionized water, add benzotriazole-loaded hydrotalcite after ultrasonic dispersion, continue ultrasonication to mix evenly, then raise the temperature to 30-60°C and stir for 4-8 hours, centrifugally wash, and dry to obtain a benzotriazole-loaded hydrotalcite@Co-MOFs composite.

4. The method for preparing a pipeline anticorrosive material according to claim 3, characterized in that: In step S210, the mass ratio of cobalt nitrate hexahydrate to trimesic acid is 1.5-3:

1.

5. The method for preparing a pipeline anticorrosive material according to claim 1, characterized in that: Step S300 specifically includes: S310, adding phenyltriethoxysilane, methyltriethoxysilane and dimethyldiethoxysilane to a reactor, raising the temperature to 70-80° C., adding hydrochloric acid thereto while stirring, continuing the reaction for 2-4 hours after the addition is completed, then adding an anhydrous ethanol solution of boric acid thereto, reacting for 4-6 hours, and after the reaction is completed, distilling under reduced pressure to obtain a boron-containing silicone resin; S320, adding boron-containing silicone resin, alkyd resin, propylene glycol methyl ether acetate and tetrabutyl titanate into a reactor, raising the temperature to 100-120° C. and dehydrating for 1-2 hours. After the dehydration is completed, raising the temperature to 115-135° C., and performing reduced pressure distillation for 20-40 minutes after the reaction is completed to obtain a modified alkyd resin.

6. The method for preparing a pipeline anticorrosive material according to claim 5, characterized in that: In step S310, the mass ratio of phenyltriethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane and boric acid is 30-40:20-35:15-25:5-15.

7. The method for preparing a pipeline anticorrosive material according to claim 5, characterized in that: In step S320, the mass ratio of the boron-containing silicone resin, the alkyd resin, the propylene glycol methyl ether acetate, and the tetrabutyl titanate is 10-25:50-70:10-20:1-5.

8. The method for preparing a pipeline anticorrosive material according to claim 1, characterized in that: In step S400 , the mass ratio of the modified alkyd resin, the benzotriazole-loaded hydrotalcite@Co-MOFs composite, the zinc oxide, the drying agent, and the solvent is 45-50:10-12:5-8:1-2:33-36.

9. A pipeline anticorrosion material, characterized in that: The pipeline anticorrosion material is prepared by the preparation method of any one of claims 1 to 7.

10. A pipeline anti-corrosion construction process, characterized in that: The construction process steps are: remove rust and oil from the pipeline surface, then apply the pipeline anti-corrosion material on the treated pipeline surface, and let the coated pipeline stand at room temperature for 24-48 hours to allow it to cure naturally.

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