Stress corrosion resistant material based on oil slurry steam generator tube plate and preparation method of stress corrosion resistant material

Abstract

The invention discloses a stress corrosion resistant material based on an oil slurry steam generator tube plate and a preparation method of the stress corrosion resistant material, and belongs to the technical field of stress corrosion resistant material preparation. The preparation method of the stress corrosion resistant material based on the oil slurry steam generator tube plate comprises the following steps: step 1, adding deionized water into a water-based polytetrafluoroethylene resin dispersion liquid, stirring and mixing, then sequentially adding a composite high-temperature stabilizer and a stress corrosion resistant agent, continuously mixing, then adding a surfactant and a coupling agent, and stirring to obtain a mixed solution; performing dispersion treatment to obtain a composite coating; 2, the surface of the Q345R steel plate is cleaned with ethyl alcohol, then sand blasting treatment, cleaning and preheating are conducted, and a pretreated steel plate is obtained; and step 3, loading the composite coating into a spray gun charging bucket, spraying, curing, sintering and cooling to obtain the stress corrosion resistant material based on the oil slurry steam generator tube plate. The material prepared by the method has excellent stress corrosion resistance and high-temperature-resistant stability.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of stress corrosion resistant material preparation, and particularly relates to a stress corrosion resistant material based on a slurry steam generator tube plate and a preparation method thereof. BACKGROUND

[0002] In the field of petroleum refining, the slurry steam generator is a key equipment of the catalytic cracking device. The tube plate of the slurry steam generator long-term bears the combined action of high-temperature slurry, water vapor and corrosive medium. The insufficient stress corrosion resistance has become a core problem restricting the safe and stable operation of the equipment. The traditional tube plate material is mainly carbon steel or low alloy steel. The microstructure of the traditional tube plate material is prone to phase transition under a high-temperature environment, which leads to the weakening of the grain boundary. The active corrosion medium such as sulfide, chloride and naphthenic acid contained in the slurry will be preferentially adsorbed at the grain boundary defects to form a local corrosion cell. During the operation of the equipment, the residual stress and thermal stress generated by the rigid fixed structure of the tube plate are superimposed, and the synergistic effect with the corrosion medium is generated, which can easily induce stress corrosion cracking. This cracking often expands along the grain boundary, which is difficult to be found by conventional detection in the early stage. However, when the crack expands to the critical size, it will cause sudden leakage, resulting in unplanned shutdown of the device and even safety accidents.

[0003] Patent CN117781763A discloses a composite aluminum strip material for preparing a heat exchanger tube plate and a preparation method thereof. The composite aluminum strip material comprises an aluminum strip, a heat-conducting material and a corrosion-resistant material. The heat-conducting material comprises polycarbonate, polyimide and silicon carbide whiskers, and the mass ratio of each component is 1:1:2. The corrosion-resistant material comprises polytetrafluoroethylene, polyperfluoroethyl propylene and liquid crystal polymer, and the mass ratio of each component is 2:1:2. The heat-conducting material and the corrosion-resistant material are formed on one side or both sides of the aluminum strip. The composite aluminum strip material for preparing a heat exchanger tube plate can solve the problem that the heat-conducting performance and corrosion resistance of the aluminum strip cannot reach a good state in the prior art, and can enhance the heat-conducting performance and corrosion resistance of the aluminum strip and improve the service life of the tube plate in the heat exchanger. However, in the method, the corrosion-resistant material is composed of polytetrafluoroethylene, polyperfluoroethyl propylene and liquid crystal polymer in a specific proportion. However, the materials are simply mixed, and a highly synergistic and tightly combined corrosion-resistant protection system cannot be formed. In actual complex working conditions, the combination strength between different materials is not enough, and small gaps are formed when the materials are eroded by corrosive media for a long time, which provides a channel for the penetration of corrosive media. Therefore, it is necessary to further optimize the corrosion-resistant material system and the composite process. SUMMARY

[0004] The application aims to provide a stress corrosion resistant material based on a slurry steam generator tube plate and a preparation method thereof, which can solve the technical problem of poor stress corrosion resistance and heat stability of the tube plate material in the prior art.

[0005] In order to achieve the above object, the present invention adopts the following technical solutions: The present invention provides a method for preparing a stress corrosion resistant material based on a slurry steam generator tube sheet, comprising the following steps: Step 1: Add deionized water to the water-based polytetrafluoroethylene resin dispersion, stir and mix, then add the composite high-temperature stabilizer and the stress corrosion inhibitor in sequence, continue to mix, then add the surfactant and the coupling agent, stir and disperse, and obtain a composite coating; Step 2: Clean the surface of the Q345R steel plate with ethanol, then perform sandblasting, cleaning, and preheating to obtain a pretreated steel plate; Step 3: Load the composite coating into a spray gun tank, spray, solidify, sinter, and cool to obtain a stress corrosion resistant material based on an oil slurry steam generator tube sheet.

[0006] Preferably, the preparation method of the composite high-temperature stabilizer comprises the following steps: Q1: Under nitrogen atmosphere, 3,5-dibromo-2-methylthiophene and anhydrous tetrahydrofuran were added to a container and stirred. An n-hexane solution containing n-butyl lithium was added and the mixture was stirred for reaction. Trimethylsilyl chloride was then added and the reaction was continued at room temperature. After the reaction was completed, distilled water was added to quench the reaction, and the organic phases were extracted, combined, washed, dried, filtered, rotary evaporated, and purified to obtain intermediate 1. Q2: Under a nitrogen atmosphere, intermediate 1 and anhydrous tetrahydrofuran are added to a container, stirred, and a n-hexane solution containing n-butyl lithium is added and stirred to react to obtain a mixed solution. At the same time, perfluorocyclopentene is added to anhydrous tetrahydrofuran, stirred and mixed, and then added to the mixed solution to react. The reaction is continued at room temperature, and methanol is added to quench the reaction. Distilled water is then added, extracted, and the organic phases are combined, washed, dried, filtered, rotary evaporated, purified, and recrystallized to obtain intermediate 2. Intermediate 2, anhydrous tetrahydrofuran, and N-bromosuccinimide are stirred and reacted at room temperature in the dark, acetone is added to quench the reaction, rotary dried, dissolved, washed, dried, filtered, rotary dried, and recrystallized to obtain intermediate 3. Q3: Add intermediate 3 and pyridine-4-boric acid to a container containing tetrahydrofuran and sodium carbonate aqueous solution, introduce argon after magnetic stirring, then add tetrakis(triphenylphosphine)palladium, heat and reflux to react. After the reaction is completed, evaporate under reduced pressure, extract, combine the organic phases, wash, dry, filter under reduced pressure, spin dry, and purify to obtain a composite high-temperature stabilizer.

[0007] In the above process, the synthetic reaction formula of the composite high temperature stabilizer is as follows:

[0008] The mass spectrometry analysis results of intermediate 1 are: m / z: 249.97 (100.0%), 247.97 (98.8%), 250.97 (14.8%), 248.97 (14.4%), 251.96 (7.7%), 249.96 (4.5%); the mass spectrometry analysis results of intermediate 2 are: m / z: 512.09 (100.0%), 513.10 (23.0%), 514.09 (18.8%), 513.09 (11.8%), 515.09 (5.2%), 514.10 (2.6%); the mass spectrometry analysis results of intermediate 3 are: m / z: 525.83 (100.0%), 527.83 (55.5%), 523.83 (49.1%), 526.84 (15.6%), 528.83 (9.8%), 524.84 (8.0%), 529.83 (4.5%), 526.83 (2.3%), 527.84 (1.2%); the mass spectrometry analysis results of the composite high-temperature stabilizer are: m / z: 522.07 (100.0%), 523.07 (28.8%), 524.06 (9.1%), 524.07 (4.1%), 525.07 (2.5%).

[0009] As preferred, in the Q1, the use amount ratio of 3,5-dibromo-2-methylthiophene, anhydrous tetrahydrofuran, n-butyllithium, n-hexane and trimethylchlorosilane is (30-45) g:(300-500) mL:(8.12-8.42) g:(50.2-52.8) mL:(15.88-17.26) mL, stirring and cooling to-78℃, the stirring reaction temperature is-78℃, the time is 20-30 min, and the continuous reaction time is 10-12 h.

[0010] As preferred, in the Q2, the use amount ratio of intermediate 1, n-butyllithium, n-hexane and perfluorocyclopentene is (20.08-24.12) g:(5.82-6.04) g:(32-43) mL:(5.34-6.48) mL, stirring and cooling to-78℃, the stirring reaction temperature is-78℃, the time is 50-60 min, the reaction temperature is-78℃, the time is 2-4 h, and the continuous reaction time at room temperature is 10-12 h; the use amount ratio of intermediate 2, anhydrous tetrahydrofuran and N-bromosuccinimide is (13.88-14.16) mL:(220-280) mL:(10.12-10.81) g, the stirring reaction time is 14-18 h.

[0011] Preferably, in Q3, the usage ratio of intermediate 3, pyridine-4-boric acid, tetrahydrofuran, sodium carbonate aqueous solution and tetrakis(triphenylphosphine)palladium is (10-18.88) g: (5.14-6.78) g: (100-180) mL: (150-220) mL: (0.147-0.322) g, the mass fraction of sodium carbonate aqueous solution is 20 wt%, the heating reflux temperature is 70-80 ° C, and the time is 10-12 h.

[0012] Preferably, the method for preparing the stress corrosion inhibitor comprises the following steps:

[0013] S1: adding thiosemicarbazide and potassium carbonate to ethanol, stirring and mixing, adding ethanol dissolved with carbon disulfide, heating and reflux reaction, after the reaction is completed, rotary evaporation, adding distilled water, stirring, acidifying, filtering, washing, and obtaining product a; adding 4-(trifluoromethoxy)benzoic acid, HATU, N,N-dimethylformamide and N,N-diisopropylethylamine to a container, stirring and mixing, adding product a, stirring and reacting at room temperature, after the reaction is completed, adding to distilled water, suction filtration, washing, filtering, and drying to obtain product b; S2: 5-trifluoromethylindole and N,N-dimethylformamide are added to a container, followed by sodium hydride, stirring, and then adding epibromopropane. The mixture is heated under reflux for reaction. After the reaction is completed, the mixture is cooled, distilled water is added, extraction is performed, washing, drying, and rotary evaporation to obtain product c. S3: Add product c, N,N-dimethylformamide and potassium carbonate to a container, stir, then add product b, heat and reflux to react. After the reaction is completed, cool, add distilled water, extract, wash, dry, filter, rotary evaporate, and purify to obtain an anti-stress corrosion agent.

[0014] In the above process, the synthetic reaction formula of the stress corrosion inhibitor is as follows:

[0015] The results of mass spectrometry analysis of product a were: m / z: 132.98 (100.0%), 134.97 (9.1%), 133.98 (3.8%), 133.97 (1.1%); the results of mass spectrometry analysis of product b were: m / z: 320.99 (100.0%), 321.99 (11.0%), 322.98 (9.1%), 321.98 (2.7%), 322.99 (1.3%), 323.98 (1.2%); the results of mass spectrometry analysis of product c were: m / z: 241.07 (100.0%), 242.07 (13.3%), 243.08 (1.0%); the results of mass spectrometry analysis of the stress corrosion inhibitor were: m / z: 562.06 (100.0%), 563.06 (25.7%), 564.05 (9.1%), 564.06(4.1%), 565.06 (2.4%), 563.05 (1.5%).

[0016] Preferably, in S1, the amount ratio of thiosemicarbazide, potassium carbonate and carbon disulfide is (0.628-0.742) g: (1.623-1.667) g: (0.101-0.112) g, the mixture is stirred for 10-20 min, and the reaction temperature is heated to reflux at 40-50°C for 4-6 h; the amount ratio of 4-(trifluoromethoxy)benzoic acid, HATU, N,N-dimethylformamide, N,N-diisopropylethylamine and product a is (0.517-0.605) g: (1.012-1.042) g: (15-20) mL: (0.562-0.604) g: (0.312-0.357) g, the mixing time is 20-30 min, and the reaction time is 10-12 h under stirring at room temperature.

[0017] Preferably, in S2, the amount ratio of 5-trifluoromethylindole, N,N-dimethylformamide, sodium hydride and epibromopropane is (0.261-0.311) g: (10-18) mL: (0.09-0.13) g: (0.608-0.647) g, and epibromopropane is added after stirring for 10-20 min. The reaction is heated under reflux at a temperature of 40-50°C for 10-12 h. In S3, the amount ratio of product c, N,N-dimethylformamide, potassium carbonate and product b is (0.388-0.446) g: (18-22) mL: (0.688-0.742) g: (0.688-0.748) g, the stirring time is 20-25 min, and the heating under reflux reaction temperature is 75-80°C for 10-12 h.

[0018] As preferred, the water-based polytetrafluoroethylene resin dispersion liquid, deionized water, composite high-temperature stabilizer, stress corrosion inhibitor, surfactant and coupling agent in step one are used in a ratio of (70-85) g: (20-40) mL: (10-15) g: (8-14) g: (2.4-4.3) g: (1.1-1.5) g.

[0019] As preferred, the stress corrosion resistant material based on the oil slurry steam generator tube plate is prepared by the above preparation method.

[0020] In summary, due to the adoption of the above technical solutions, the present application has the following advantages: 1. The composite high-temperature stabilizer and stress corrosion inhibitor prepared by the present application can be applied to the stress corrosion resistant material based on the oil slurry steam generator tube plate, which can effectively improve the high-temperature stability and stress corrosion cracking resistance of the material.

[0021] 2. The composite high-temperature stabilizer prepared by the present application can be applied to the stress corrosion resistant material based on the oil slurry steam generator tube plate, which can effectively improve the high-temperature stability and stress corrosion cracking resistance of the material. The perfluorocyclopentene fragment contained in the composite high-temperature stabilizer has an excellent stable structure, high carbon-fluorine bond energy, short bond length and strong intramolecular cohesion, so that the stabilizer itself will not degrade and fail in the high-temperature and high-pressure steam environment of the oil slurry steam generator, and can continue to play a role for a long time to prevent high-temperature oxidation and creep of the material matrix. The perfluoro fragment contained in the composite high-temperature stabilizer has strong "hydrophobic and oleophobic" properties, which can effectively repel water molecules and corrosive ions and prevent them from reaching the metal surface, cutting off the electrochemical corrosion path. The pyridine group contained in the composite high-temperature stabilizer is an excellent organic corrosion inhibitor, and the nitrogen atom lone pair electrons can strongly adsorb on the metal surface to form a dense monomolecular protective film, isolate the corrosion medium and improve the hydrogen evolution overpotential of the metal surface, significantly inhibit the anodic dissolution and hydrogen-induced cracking.

[0022] 3. The present invention applies the prepared anti-stress corrosion agent to the anti-stress corrosion material based on the tube sheet of the slurry steam generator, which can effectively improve its protective performance. The thiadiazole and indole groups contained in the anti-stress corrosion agent are rich in sulfur and nitrogen heteroatoms, which can provide lone pairs of electrons, form strong coordination bonds with the empty d orbitals of the tube sheet metal, and chemically adsorb on the metal surface to form a dense and strong monomolecular protective film, which effectively isolates the metal matrix from the corrosive medium, significantly inhibits the anodic metal dissolution reaction, and prevents the initiation of corrosion pits. The introduced trifluoromethyl and trifluoromethoxy groups can form a super-hydrophobic barrier on the substrate surface, effectively repelling high-temperature water vapor, condensed water and organic polar substances in the slurry, preventing them from contacting the substrate surface, inhibiting electrochemical corrosion, and also improving its chemical and thermal stability, making it difficult to be oxidized or decomposed in a high-temperature environment. At the same time, the dense adsorption film directly inhibits the anodic process. The sulfur and nitrogen-containing heterocyclic compounds can poison the hydrogen evolution reaction, increase the hydrogen evolution overpotential, reduce the generation and penetration of hydrogen atoms, and prevent hydrogen-induced cracking. DETAILED DESCRIPTION

[0023] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0024] Example 1: This example discloses a method for preparing a composite high-temperature stabilizer, comprising the following steps: Q1: Under nitrogen atmosphere, 37.5 g of 3,5-dibromo-2-methylthiophene and 400 mL of anhydrous tetrahydrofuran were added to a container, stirred and cooled to -78°C, 51.5 mL of an n-hexane solution containing 8.27 g of n-butyl lithium was added, and the mixture was stirred at -78°C for 20 min. Subsequently, 16.54 mL of trimethylsilyl chloride was added, and the reaction was continued at room temperature for 12 h. After the reaction was completed, distilled water was added to quench the reaction, and the organic phases were extracted, combined, washed, dried, filtered, rotary evaporated, and purified to obtain intermediate 1; Q2: Under nitrogen, 22.11 g of intermediate 1 and 300 mL of anhydrous tetrahydrofuran were added to a container, stirred and cooled to -78°C, 37.5 mL of n-hexane solution containing 5.93 g of n-butyl lithium was added, and the mixture was stirred and reacted at -78°C for 50 min to obtain a mixed solution. At the same time, 5.92 mL of perfluorocyclopentene was added to 80 mL of anhydrous tetrahydrofuran, stirred and mixed, and then added to the mixed solution. The mixture was reacted at -78°C for 2 h, and then at room temperature for 12 h. Methanol was added to quench the reaction, and distilled water was added, extracted, and the organic phases were combined, washed, dried, filtered, rotary evaporated, purified, and recrystallized to obtain intermediate 2. 13.98 mL of intermediate 2, 250 mL of anhydrous tetrahydrofuran, and 10.41 g of N-bromosuccinimide were stirred and reacted at room temperature in the dark for 16 h. Acetone was added to quench the reaction, rotary dried, dissolved, washed, dried, filtered, rotary dried, and recrystallized to obtain intermediate 3. Q3: 14.44 g of intermediate 3 and 5.91 g of pyridine-4-boric acid were added to a container containing 140 mL of tetrahydrofuran and 185 mL of a 20 wt% sodium carbonate aqueous solution. After magnetic stirring, argon was introduced, and then 0.235 g of tetrakis(triphenylphosphine)palladium was added. The mixture was heated under reflux at 75 ° C for 12 h. After the reaction was completed, vacuum rotary evaporation was performed, extraction was performed, the organic phases were combined, washed, dried, filtered under reduced pressure, spin-dried, and purified to obtain a composite high-temperature stabilizer.

[0025] This embodiment discloses a method for preparing an anti-stress corrosion agent, comprising the following steps: S1: 0.685 g of thiosemicarbazide and 1.645 g of potassium carbonate were added to 15 mL of ethanol, stirred for 15 min, and then 0.106 g of carbon disulfide dissolved in 8 mL of ethanol was added. The mixture was heated under reflux at 45°C for 6 h. After the reaction was completed, the mixture was rotary evaporated, distilled water was added, stirred, acidified, filtered, and washed to obtain product a; 0.562 g of 4-(trifluoromethoxy)benzoic acid, 1.027 g of HATU, 17.5 mL of N,N-dimethylformamide, and 0.583 g of N,N-diisopropylethylamine were added to a container, mixed and stirred for 20 min, and then 0.335 g of product a was added. The mixture was stirred at room temperature for 10 h. After the reaction was completed, the mixture was added to distilled water, filtered, washed, filtered, and dried to obtain product b; S2: 0.281 g of 5-trifluoromethylindole and 14 mL of N,N-dimethylformamide were added to a container, followed by 0.11 g of sodium hydride. After stirring for 10 min, 0.628 g of epibromopropane was added. The mixture was heated under reflux at 45°C for 12 h. After the reaction, the mixture was cooled, distilled water was added, and the mixture was extracted, washed, dried, and rotary evaporated to obtain product c. S3: Add 0.412 g of product c, 20 mL of N,N-dimethylformamide and 0.715 g of potassium carbonate to a container, stir, then add 0.718 g of product b, heat under reflux at 75°C for 12 h. After the reaction is completed, cool, add distilled water, extract, wash, dry, filter, rotary evaporate, and purify to obtain an anti-stress corrosion agent.

[0026] This embodiment discloses a method for preparing a stress corrosion resistant material based on a slurry steam generator tube sheet, comprising the following steps: Step 1: Add 30 mL of deionized water to 77.5 g of water-based polytetrafluoroethylene resin dispersion, stir and mix, then add 12.5 g of composite high-temperature stabilizer and 11 g of anti-stress corrosion agent in sequence, continue mixing, then add 5.3 g of surfactant and 1.3 g of silane coupling agent KH-550, stir at 1500 rpm for 1 hour, and disperse for 30 minutes to obtain a composite coating; Step 2: Clean the surface of the Q345R steel plate with ethanol, then perform sandblasting, clean it, and preheat it at 100°C for 10 minutes to obtain a pretreated steel plate; Step 3: Load the composite coating into a spray gun tank, spray, solidify, sinter, and cool to obtain a stress corrosion resistant material based on an oil slurry steam generator tube sheet.

[0027] Example 2: This example discloses a method for preparing a composite high-temperature stabilizer, comprising the following steps: Q1: Under nitrogen, 30 g of 3,5-dibromo-2-methylthiophene and 300 mL of anhydrous tetrahydrofuran were added to a container, stirred and cooled to -78°C, 50.2 mL of an n-hexane solution containing 8.12 g of n-butyl lithium was added, and the mixture was stirred at -78°C for 20 min. Subsequently, 15.88 mL of trimethylsilyl chloride was added, and the reaction was continued at room temperature for 12 h. After the reaction was completed, distilled water was added to quench the reaction, and the organic phases were extracted, combined, washed, dried, filtered, rotary evaporated, and purified to obtain intermediate 1. Q2: Under nitrogen, 20.08 g of intermediate 1 and 300 mL of anhydrous tetrahydrofuran were added to a container, stirred and cooled to -78 ° C, 32 mL of n-hexane solution containing 5.82 g of n-butyl lithium was added, and the mixture was stirred at -78 ° C for 50 min to obtain a mixed solution. At the same time, 5.34 mL of perfluorocyclopentene was added to 80 mL of anhydrous tetrahydrofuran, stirred and mixed, and then added to the mixed solution. The mixture was reacted at -78 ° C for 2 h, and the reaction was continued at room temperature for 12 h. Methanol was added to quench the reaction, and distilled water was added, extracted, and the organic phases were combined, washed, dried, filtered, rotary evaporated, purified, and recrystallized to obtain intermediate 2; 13.88 mL of intermediate 2, 220 mL of anhydrous tetrahydrofuran and 10.12 g of N-bromosuccinimide were stirred and reacted at room temperature in the dark for 16 h, acetone was added to quench the reaction, rotary dried, dissolved, washed, dried, filtered, rotary dried, and recrystallized to obtain intermediate 3; Q3: 10 g of intermediate 3 and 5.14 g of pyridine-4-boric acid were added to a container containing 100 mL of tetrahydrofuran and 150 mL of a 20 wt% sodium carbonate aqueous solution. After magnetic stirring, argon was introduced, and then 0.147 g of tetrakis(triphenylphosphine)palladium was added. The mixture was heated under reflux at 75 ° C for 12 h. After the reaction was completed, vacuum rotary evaporation was performed, extraction was performed, the organic phases were combined, washed, dried, filtered under reduced pressure, spin-dried, and purified to obtain a composite high-temperature stabilizer.

[0028] This embodiment discloses a method for preparing an anti-stress corrosion agent, comprising the following steps: S1: 0.628 g of thiosemicarbazide and 1.623 g of potassium carbonate were added to 15 mL of ethanol, stirred for 15 min, and then 0.101 g of carbon disulfide dissolved in 8 mL of ethanol was added. The mixture was heated under reflux at 45°C for 6 h. After the reaction was completed, the mixture was rotary evaporated, distilled water was added, stirred, acidified, filtered, and washed to obtain product a; 0.517 g of 4-(trifluoromethoxy)benzoic acid, 1.012 g of HATU, 15 mL of N,N-dimethylformamide, and 0.562 g of N,N-diisopropylethylamine were added to a container, mixed and stirred for 20 min, and then 0.312 g of product a was added. The mixture was stirred at room temperature for 10 h. After the reaction was completed, the mixture was added to distilled water, filtered, washed, filtered, and dried to obtain product b; S2: 0.261 g of 5-trifluoromethylindole and 18 mL of N,N-dimethylformamide were added to a container, followed by 0.13 g of sodium hydride. After stirring for 10 min, 0.608 g of epibromopropane was added. The mixture was heated under reflux at 45°C for 12 h. After the reaction, the mixture was cooled, distilled water was added, and the mixture was extracted, washed, dried, and rotary evaporated to obtain product c. S3: Add 0.388 g of product c, 18 mL of N,N-dimethylformamide and 0.688 g of potassium carbonate to a container, stir, then add 0.688 g of product b, heat under reflux at 75°C for 12 h. After the reaction is completed, cool, add distilled water, extract, wash, dry, filter, rotary evaporate, and purify to obtain an anti-stress corrosion agent.

[0029] This embodiment discloses a method for preparing a stress corrosion resistant material based on a slurry steam generator tube sheet, comprising the following steps: Step 1: Add 20 mL of deionized water to 70 g of water-based polytetrafluoroethylene resin dispersion, stir and mix, then add 15 g of composite high-temperature stabilizer and 8 g of anti-stress corrosion agent in sequence, continue mixing, then add 2.4 g of surfactant and 1.1 g of silane coupling agent KH-550, stir at 1500 rpm for 1 hour, and disperse for 30 minutes to obtain a composite coating; Step 2: Clean the surface of the Q345R steel plate with ethanol, then perform sandblasting, clean it, and preheat it at 100°C for 10 minutes to obtain a pretreated steel plate; Step 3: Load the composite coating into a spray gun tank, spray, solidify, sinter, and cool to obtain a stress corrosion resistant material based on an oil slurry steam generator tube sheet.

[0030] Example 3: This example discloses a method for preparing a composite high-temperature stabilizer, comprising the following steps: Q1: Under nitrogen atmosphere, 45 g of 3,5-dibromo-2-methylthiophene and 500 mL of anhydrous tetrahydrofuran were added to a container, stirred and cooled to -78°C, 52.8 mL of a n-hexane solution containing 8.42 g of n-butyl lithium was added, and the mixture was stirred at -78°C for 20 min. Subsequently, 17.26 mL of trimethylsilyl chloride was added, and the reaction was continued at room temperature for 12 h. After the reaction was completed, distilled water was added to quench the reaction, and the organic phases were extracted, combined, washed, dried, filtered, rotary evaporated, and purified to obtain intermediate 1; Q2: Under nitrogen, 24.12 g of intermediate 1 and 300 mL of anhydrous tetrahydrofuran were added to a container, stirred and cooled to -78 ° C, 43 mL of n-hexane solution containing 6.04 g of n-butyl lithium was added, and the mixture was stirred and reacted at -78 ° C for 50 min to obtain a mixed solution. At the same time, 6.48 mL of perfluorocyclopentene was added to 80 mL of anhydrous tetrahydrofuran, stirred and mixed, and then added to the mixed solution. The mixture was reacted at -78 ° C for 2 h, and the reaction was continued at room temperature for 12 h. Methanol was added to quench the reaction, and distilled water was added, extracted, and the organic phases were combined, washed, dried, filtered, rotary evaporated, purified, and recrystallized to obtain intermediate 2; 14.16 mL of intermediate 2, 280 mL of anhydrous tetrahydrofuran and 10.81 g of N-bromosuccinimide were stirred and reacted at room temperature in the dark for 16 h, acetone was added to quench the reaction, rotary dried, dissolved, washed, dried, filtered, rotary dried, and recrystallized to obtain intermediate 3; Q3: 18.88 g of intermediate 3 and 6.78 g of pyridine-4-boric acid were added to a container containing 180 mL of tetrahydrofuran and 220 mL of a 20 wt% sodium carbonate aqueous solution. After magnetic stirring, argon was introduced, and then 0.322 g of tetrakis(triphenylphosphine)palladium was added. The mixture was heated under reflux at 75 ° C for 12 h. After the reaction was completed, vacuum rotary evaporation was performed, extraction was performed, the organic phases were combined, washed, dried, filtered under reduced pressure, spin-dried, and purified to obtain a composite high-temperature stabilizer.

[0031] This embodiment discloses a method for preparing an anti-stress corrosion agent, comprising the following steps: S1: 0.742 g of thiosemicarbazide and 1.667 g of potassium carbonate were added to 15 mL of ethanol, stirred for 15 min, and then 0.112 g of carbon disulfide dissolved in 8 mL of ethanol was added. The mixture was heated under reflux at 45°C for 6 h. After the reaction was completed, the mixture was rotary evaporated, distilled water was added, stirred, acidified, filtered, and washed to obtain product a; 0.605 g of 4-(trifluoromethoxy)benzoic acid, 1.042 g of HATU, 20 mL of N,N-dimethylformamide, and 0.604 g of N,N-diisopropylethylamine were added to a container, mixed and stirred for 20 min, and then 0.357 g of product a was added. The mixture was stirred at room temperature for 10 h. After the reaction was completed, the mixture was added to distilled water, filtered, washed, filtered, and dried to obtain product b; S2: 0.311 g of 5-trifluoromethylindole and 10 mL of N,N-dimethylformamide were added to a container, followed by 0.09 g of sodium hydride. After stirring for 10 min, 0.647 g of epibromopropane was added. The mixture was heated under reflux at 45°C for 12 h. After the reaction, the mixture was cooled, distilled water was added, and the mixture was extracted, washed, dried, and rotary evaporated to obtain product c. S3: 0.446g of product c, 19mL of N,N-dimethylformamide and 0.742g of potassium carbonate were added into a container, after stirring, 0.748g of product b was added, heated to reflux at 75℃ for 12h, after the reaction was completed, cooled, added with distilled water, extracted, washed, dried, filtered, rotary evaporated, purified to obtain a stress corrosion resistant agent.

[0032] The embodiment discloses a preparation method of a stress corrosion resistant material based on a slurry steam generator tube plate, comprising the following steps: Step one: 40mL of deionized water was added into 85g of water-based polytetrafluoroethylene resin dispersion liquid, stirred and mixed, then 10g of composite high-temperature stabilizer and 14g of stress corrosion resistant agent were added in sequence, continued to be mixed, then 4.3g of surfactant and 1.5g of silane coupling agent KH-550 were added, stirred at 1500rpm for 1h, and dispersed for 30min to obtain a composite coating; Step two: the surface of the Q345R steel plate was cleaned with ethanol, then sandblasting treatment was performed, cleaned, and preheated at 100℃ for 10min to obtain a pretreated steel plate; Step three: the composite coating was loaded into a spray gun tank, sprayed, cured, sintered, and cooled to obtain a stress corrosion resistant material based on a slurry steam generator tube plate.

[0033] Embodiment 4: The embodiment discloses a preparation method of a composite high-temperature stabilizer, comprising the following steps: Q1: 32g of 3,5-dibromo-2-methylthiophene and 350mL of anhydrous tetrahydrofuran were added into a container under a nitrogen environment, stirred and cooled to-78℃, then 50.8mL of n-hexane solution containing 8.17g of n-butyllithium was added, stirred at-78℃ for 20min, then 16.21mL of trimethylchlorosilane was added, and the reaction was continued at room temperature for 12h, after the reaction was completed, distilled water was added to quench the reaction, extracted, combined organic phase, washed, dried, filtered, rotary evaporated, purified to obtain intermediate 1; Q2: Under nitrogen, 21.18 g of intermediate 1 and 300 mL of anhydrous tetrahydrofuran were added to a container, stirred and cooled to -78 ° C, 35 mL of n-hexane solution containing 5.87 g of n-butyl lithium was added, and the mixture was stirred at -78 ° C for 50 min to obtain a mixed solution. At the same time, 5.63 mL of perfluorocyclopentene was added to 80 mL of anhydrous tetrahydrofuran, stirred and mixed, and then added to the mixed solution. The mixture was reacted at -78 ° C for 2 h, and the reaction was continued at room temperature for 12 h. Methanol was added to quench the reaction, and distilled water was added, extracted, and the organic phases were combined, washed, dried, filtered, rotary evaporated, purified, and recrystallized to obtain intermediate 2; 14.08 mL of intermediate 2, 230 mL of anhydrous tetrahydrofuran and 10.27 g of N-bromosuccinimide were stirred and reacted at room temperature in the dark for 16 h, acetone was added to quench the reaction, rotary dried, dissolved, washed, dried, filtered, rotary dried, and recrystallized to obtain intermediate 3; Q3: 12.22 g of intermediate 3 and 5.52 g of pyridine-4-boric acid were added to a container containing 120 mL of tetrahydrofuran and 170 mL of a 20 wt% sodium carbonate aqueous solution. After magnetic stirring, argon was introduced, and then 0.188 g of tetrakis(triphenylphosphine)palladium was added. The mixture was heated under reflux at 75 ° C for 12 h. After the reaction was completed, vacuum rotary evaporation was performed, extraction was performed, the organic phases were combined, washed, dried, filtered under reduced pressure, spin-dried, and purified to obtain a composite high-temperature stabilizer.

[0034] This embodiment discloses a method for preparing an anti-stress corrosion agent, comprising the following steps: S1: 0.657 g of thiosemicarbazide and 1.637 g of potassium carbonate were added to 15 mL of ethanol, stirred for 15 min, and then 0.103 g of carbon disulfide dissolved in 8 mL of ethanol was added. The mixture was heated under reflux at 45°C for 6 h. After the reaction was completed, the mixture was rotary evaporated, distilled water was added, stirred, acidified, filtered, and washed to obtain product a; 0.538 g of 4-(trifluoromethoxy)benzoic acid, 1.018 g of HATU, 16 mL of N,N-dimethylformamide, and 0.572 g of N,N-diisopropylethylamine were added to a container, mixed and stirred for 20 min, and then 0.328 g of product a was added. The mixture was stirred at room temperature for 10 h. After the reaction was completed, the mixture was added to distilled water, filtered, washed, filtered, and dried to obtain product b; S2: 0.276 g of 5-trifluoromethylindole and 12 mL of N,N-dimethylformamide were added to a container, followed by 0.1 g of sodium hydride. After stirring for 10 min, 0.618 g of epibromopropane was added. The mixture was heated under reflux at 45°C for 12 h. After the reaction, the mixture was cooled, distilled water was added, and the mixture was extracted, washed, dried, and rotary evaporated to obtain product c. S3: Add 0.399 g of product c, 21 mL of N,N-dimethylformamide and 0.698 g of potassium carbonate to a container, stir, then add 0.738 g of product b, heat under reflux at 75°C for 12 h. After the reaction is completed, cool, add distilled water, extract, wash, dry, filter, rotary evaporate, and purify to obtain an anti-stress corrosion agent.

[0035] This embodiment discloses a method for preparing a stress corrosion resistant material based on a slurry steam generator tube sheet, comprising the following steps: Step 1: Add 25 mL of deionized water to 75 g of water-based polytetrafluoroethylene resin dispersion, stir and mix, then add 11 g of composite high-temperature stabilizer and 10 g of stress corrosion inhibitor in sequence, continue mixing, then add 2.8 g of surfactant and 1.2 g of silane coupling agent KH-550, stir at 1500 rpm for 1 hour, and disperse for 30 minutes to obtain a composite coating; Step 2: Clean the surface of the Q345R steel plate with ethanol, then perform sandblasting, clean it, and preheat it at 100°C for 10 minutes to obtain a pretreated steel plate; Step 3: Load the composite coating into a spray gun tank, spray, solidify, sinter, and cool to obtain a stress corrosion resistant material based on an oil slurry steam generator tube sheet.

[0036] Comparative Example 1: Compared with Example 1, in Comparative Example 1, during the preparation of the stress corrosion resistant material based on the slurry steam generator tube sheet, no composite high-temperature stabilizer was added, and other conditions remained unchanged.

[0037] Comparative Example 2: Compared with Example 1, in Comparative Example 2, during the preparation of the stress corrosion resistant material based on the slurry steam generator tube sheet, no stress corrosion resistant agent was added, and other conditions remained unchanged.

[0038] Performance testing: The stress corrosion resistant materials based on the slurry steam generator tube sheet prepared according to Examples 1-4 and Comparative Examples 1-2 were subjected to performance tests. The high temperature performance of the samples was tested at 400° C. according to GB / T 228.2-2015. The stress corrosion cracking resistance of the samples was tested according to GB / T 4157-2017. The test results are shown in Table 1: Table 1

[0039] As can be seen from the test results in Table 1, by using the method of Examples 1-4, the stress corrosion resistant material based on the oil slurry steam generator tube plate prepared has excellent high temperature stability and stress corrosion resistance. As can be seen from the comparison between Comparative Example 1 and Examples 1-4, adding the composite high temperature stabilizer can effectively improve the high temperature stability and stress corrosion resistance of the sample; as can be seen from the comparison between Comparative Example 2 and Examples 1-4, adding the stress corrosion inhibitor can effectively improve the high temperature stability and stress corrosion resistance of the sample.

[0040] The above description is merely preferred embodiments of the present application. The protection scope of the present application is not limited to this, and any person skilled in the art can make equivalent replacements or changes to the technical scheme and the inventive concept of the present application within the technical scope disclosed by the present application, which should be covered by the protection scope of the present application.

[0041] The preferred embodiments of the present application disclosed above are only used to help explain the present application. The preferred embodiments do not describe all the details and do not limit the present application to the specific embodiments. Obviously, many modifications and changes can be made according to the content of the present application. The present application selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present application, so that those skilled in the art can well understand and use the present application. The present application is limited by the claims and their entire scope and equivalents.

Claims

1. A method for preparing a stress corrosion resistant material for a slurry steam generator tube sheet, characterized in that: The following steps are involved: Step 1: Add deionized water to the water-based polytetrafluoroethylene resin dispersion, stir and mix, then add the composite high-temperature stabilizer and the stress corrosion inhibitor in sequence, continue to mix, then add the surfactant and the coupling agent, stir and disperse, and obtain a composite coating; Step 2: Clean the surface of the Q345R steel plate with ethanol, then perform sandblasting, cleaning, and preheating to obtain a pretreated steel plate; Step 3: Load the composite coating into a spray gun tank, spray, solidify, sinter, and cool to obtain a stress corrosion resistant material based on an oil slurry steam generator tube sheet.

2. The method for preparing the stress corrosion resistant material based on the slurry steam generator tube sheet according to claim 1, characterized in that: The preparation method of the composite high-temperature stabilizer, The following steps are involved: Q1: Under nitrogen atmosphere, 3,5-dibromo-2-methylthiophene and anhydrous tetrahydrofuran were added to a container and stirred. An n-hexane solution containing n-butyl lithium was added and the mixture was stirred for reaction. Trimethylsilyl chloride was then added and the reaction was continued at room temperature. After the reaction was completed, distilled water was added to quench the reaction, and the organic phases were extracted, combined, washed, dried, filtered, rotary evaporated, and purified to obtain intermediate 1. Q2: Under a nitrogen atmosphere, intermediate 1 and anhydrous tetrahydrofuran are added to a container, stirred, and an n-hexane solution containing n-butyl lithium is added, stirred and reacted to obtain a mixed solution. At the same time, perfluorocyclopentene is added to anhydrous tetrahydrofuran, stirred and mixed, and then added to the mixed solution, reacted, and continued to react at room temperature. Methanol is added to quench the reaction, and distilled water is added, extracted, and the organic phases are combined, washed, dried, filtered, rotary evaporated, purified, and recrystallized to obtain intermediate 2; Intermediate 2, anhydrous tetrahydrofuran and N-bromosuccinimide were stirred and reacted at room temperature in the dark, and acetone was added to quench the reaction, and the mixture was spin-dried, dissolved, washed, dried, filtered, spin-dried, and recrystallized to obtain intermediate 3; Q3: Add intermediate 3 and pyridine-4-boric acid to a container containing tetrahydrofuran and sodium carbonate aqueous solution, introduce argon after magnetic stirring, then add tetrakis(triphenylphosphine)palladium, heat and reflux to react. After the reaction is completed, evaporate under reduced pressure, extract, combine the organic phases, wash, dry, filter under reduced pressure, spin dry, and purify to obtain a composite high-temperature stabilizer.

3. The method for preparing the stress corrosion resistant material based on the slurry steam generator tube sheet according to claim 2, characterized in that: In Q1, the usage ratio of 3,5-dibromo-2-methylthiophene, anhydrous tetrahydrofuran, n-butyl lithium, n-hexane and trimethylsilyl chloride is (30-45) g: (300-500) mL: (8.12-8.42) g: (50.2-52.8) mL: (15.88-17.26) mL.

4. The method for preparing the stress corrosion resistant material based on the slurry steam generator tube sheet according to claim 2, characterized in that: In Q2, the usage ratio of intermediate 1, n-butyl lithium, n-hexane and perfluorocyclopentene is (20.08-24.12) g: (5.82-6.04) g: (32-43) mL: (5.34-6.48) mL; the usage ratio of intermediate 2, anhydrous tetrahydrofuran and N-bromosuccinimide is (13.88-14.16) mL: (220-280) mL: (10.12-10.81) g.

5. The method for preparing the stress corrosion resistant material based on the slurry steam generator tube sheet according to claim 2, characterized in that: In Q3, the usage ratio of intermediate 3, pyridine-4-boric acid, tetrahydrofuran, sodium carbonate aqueous solution and tetrakis(triphenylphosphine)palladium is (10-18.88) g: (5.14-6.78) g: (100-180) mL: (150-220) mL: (0.147-0.322) g.

6. The method for preparing the stress corrosion resistant material based on the slurry steam generator tube sheet according to claim 1, characterized in that: The preparation method of the stress corrosion inhibitor comprises the following steps: S1: adding thiosemicarbazide and potassium carbonate to ethanol, stirring and mixing, adding ethanol dissolved with carbon disulfide, heating and reflux reaction, after the reaction is completed, rotary evaporation, adding distilled water, stirring, acidifying, filtering, washing, and obtaining product a; adding 4-(trifluoromethoxy)benzoic acid, HATU, N,N-dimethylformamide and N,N-diisopropylethylamine to a container, stirring and mixing, adding product a, stirring and reacting at room temperature, after the reaction is completed, adding to distilled water, suction filtration, washing, filtering, and drying to obtain product b; S2: 5-trifluoromethylindole and N,N-dimethylformamide are added to a container, followed by sodium hydride, stirring, and then adding epibromopropane. The mixture is heated under reflux for reaction. After the reaction is completed, the mixture is cooled, distilled water is added, extraction is performed, washing, drying, and rotary evaporation to obtain product c. S3: Add product c, N,N-dimethylformamide and potassium carbonate to a container, stir, then add product b, heat and reflux to react. After the reaction is completed, cool, add distilled water, extract, wash, dry, filter, rotary evaporate, and purify to obtain an anti-stress corrosion agent.

7. The method for preparing the stress corrosion resistant material based on the slurry steam generator tube sheet according to claim 6, characterized in that: In S1, the usage ratio of thiosemicarbazide, potassium carbonate and carbon disulfide is (0.628-0.742) g: (1.623-1.667) g: (0.101-0.112) g; the usage ratio of 4-(trifluoromethoxy)benzoic acid, HATU, N,N-dimethylformamide, N,N-diisopropylethylamine and product a is (0.517-0.605) g: (1.012-1.042) g: (15-20) mL: (0.562-0.604) g: (0.312-0.357) g.

8. The method for preparing the stress corrosion resistant material based on the slurry steam generator tube sheet according to claim 6, characterized in that: In S2, the usage ratio of 5-trifluoromethylindole, N,N-dimethylformamide, sodium hydride and epibromopropane is (0.261-0.311) g: (10-18) mL: (0.09-0.13) g: (0.608-0.647) g; in S3, the usage ratio of product c, N,N-dimethylformamide, potassium carbonate and product b is (0.388-0.446) g: (18-22) mL: (0.688-0.742) g: (0.688-0.748) g.

9. The method for preparing the stress corrosion resistant material based on the slurry steam generator tube sheet according to claim 1, characterized in that: In the step 1, the usage ratio of the water-based polytetrafluoroethylene resin dispersion, deionized water, composite high-temperature stabilizer, anti-stress corrosion agent, surfactant and coupling agent is (70-85) g: (20-40) mL: (10-15) g: (8-14) g: (2.4-4.3) g: (1.1-1.5) g.

10. Anti-stress corrosion material based on slurry steam generator tube sheet, characterized in that: The preparation method is described in any one of claims 1 to 9.

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