CN118374796B - Corrosion-resistant coating for inner wall of pipeline - Google Patents
Corrosion-resistant coating for inner wall of pipeline Download PDFInfo
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- CN118374796B CN118374796B CN202410834813.4A CN202410834813A CN118374796B CN 118374796 B CN118374796 B CN 118374796B CN 202410834813 A CN202410834813 A CN 202410834813A CN 118374796 B CN118374796 B CN 118374796B
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/48—Coating with alloys
- C23C18/50—Coating with alloys with alloys based on iron, cobalt or nickel
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
- C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
- C22C19/057—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being less 10%
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1603—Process or apparatus coating on selected surface areas
- C23C18/1614—Process or apparatus coating on selected surface areas plating on one side
- C23C18/1616—Process or apparatus coating on selected surface areas plating on one side interior or inner surface
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1689—After-treatment
- C23C18/1692—Heat-treatment
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
- C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
- C23C18/1837—Multistep pretreatment
- C23C18/1844—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
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Abstract
The invention provides a corrosion-resistant coating for the inner wall of a pipeline, which belongs to the technical field of coatings, wherein a coating with the thickness of 1-1.5mm is coated on the inner wall of the pipeline by utilizing mixed powder through cold spraying and high-temperature heating technology, and the mixed powder comprises 10-15% of multi-element metal powder, 10-20% of ceramic particles with a first size and 65-80% of ceramic particles with a second size in percentage by mass; the components of the multi-element metal powder are as follows by mass fraction: 6-8% of Cr, 1-2% of Mo, 1-2% of W, 1-2% of Nb, 1-2% of Si, 10-12% of Cu, 1-3% of B, 2-4% of Ti, less than 0.5% of Fe, less than 0.005% of C and the balance of Ni; the first size ceramic particles are core-shell structure powder with the particle size of 20-50 mu m; the second size ceramic particles are core-shell structure powder with the particle size of 200-500 nm. The coating disclosed by the invention can be well combined with the inner wall of a pipeline, and has good sulfur corrosion resistance, naphthenic acid corrosion resistance and flushing resistance, so that the corrosion resistance and flushing resistance of the pipeline are improved.
Description
Technical Field
The invention relates to the technical field of coatings, in particular to a corrosion-resistant coating for the inner wall of a pipeline.
Background
In the prior art, in order to solve the corrosion problem, some measures are taken, but some problems exist, and the specific steps are as follows:
In the first measure, corrosion inhibitors such as imidazole corrosion inhibitors and phosphorus corrosion inhibitors are used in pipelines, and the corrosion inhibitors solve the problems of corrosion of hydrogen sulfide, naphthenic acid and the like to a certain extent. However, these materials must be used in an aqueous environment, have great water solubility, and in a coating layer, a permeable film is easily formed, and cannot be used as a coating material;
Secondly, organic polymer coatings such as resin coatings are coated on the inner wall and the outer wall of the pipeline, and the resin with excellent acid resistance is phenolic epoxy resin in terms of acid resistance, but on one hand, the phenolic epoxy resin has the defect of brittle paint film, is easy to peel off under the working condition of repeated flushing, and is difficult to meet the actual requirement; on the other hand, when the organic polymer coating is used in a pipeline with complex environment, the defects of low use strength, poor binding force, low hardness, poor wear resistance, short service life and the like exist;
And thirdly, coating a metal coating on the inner wall of the pipeline, wherein the corrosion-resistant coating commonly used at present is NiCr alloy, and when the alloy is used as the coating, a layer of high-density sulfide corrosion-resistant Cr 2O3 oxide film is easily formed on the surface of the alloy in a high-temperature environment, so that the corrosion-resistant effect is realized. The NiCr coating has good corrosion resistance under low-sulfur low-acid corrosion strips, but the corrosion resistance is obviously reduced along with the increase of the concentration of sulfur, naphthenic acid and other components in crude oil, pits, flaking and other conditions are easy to occur, and the corrosion resistance effect is difficult to ensure after long-term use;
and fourthly, coating a ceramic coating on the inner wall of the pipeline, wherein the ceramic coating has excellent corrosion resistance, but the single ceramic coating has larger difference between the thermal expansion coefficients of the pipeline and the carbon steel material, and is easy to peel.
Therefore, there is a need to develop a coating for the inner wall of a pipeline with high bonding strength with a substrate and excellent corrosion resistance, so as to solve the problems that the existing coating and the substrate are easy to peel off and have poor corrosion resistance.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides the corrosion-resistant coating for the inner wall of the pipeline, which can be well combined with the inner wall of the pipeline, has good sulfur corrosion resistance, naphthenic acid corrosion resistance and flushing resistance, and can further improve the corrosion resistance and flushing resistance of the pipeline.
In order to achieve the above purpose, the invention adopts the following specific scheme:
The corrosion-resistant coating for the inner wall of the pipeline is prepared by coating a coating with the thickness of 1-1.5mm on the inner wall of the pipeline by using mixed powder through cold spraying and high-temperature heating technology, wherein the mixed powder comprises 10-15% of multi-element metal powder, 10-20% of ceramic particles with a first size and 65-80% of ceramic particles with a second size in percentage by mass; wherein the particle size of the multi-element metal powder is 50-200nm, and the multi-element metal powder comprises the following components in percentage by mass: 6-8% of Cr, 1-2% of Mo, 1-2% of W, 1-2% of Nb, 1-2% of Si, 10-12% of Cu, 1-3% of B, 2-4% of Ti, less than 0.5% of Fe, less than 0.005% of C and the balance of Ni;
The first-size ceramic particles are core-shell structure powder with the particle size of 20-50 mu m, wherein in the core-shell structure powder, a shell is a nickel layer, a core adopts first ceramic powder, and the first ceramic powder is mixed powder obtained by taking BN, zrO 2 and Si 3N4 as raw materials and performing high-temperature sintering, water quenching and crushing;
The second-size ceramic particles are core-shell structure powder with the particle size of 200-500nm, in the core-shell structure powder, the shell is a nickel layer, the inner core adopts the second ceramic powder, and the second ceramic powder is mixed powder obtained by taking aluminum oxide, chromium boride, kyanite and zinc oxide whiskers as raw materials through high-temperature sintering, water quenching and crushing.
Further, the preparation method of the first-size particle ceramic and the second-size particle ceramic comprises the following steps:
weighing raw materials for the inner core, crushing the raw materials for the inner core for the first time, sintering the crushed particles at high temperature, performing water quenching to prepare ceramic, and crushing the ceramic for the second time to prepare ceramic powder with target particle size;
step (2), cleaning the ceramic powder in methanol, dilute NaOH solution and dilute HCl solution sequentially, applying ultrasonic waves in the cleaning process to effectively remove pollutants on the surface of the ceramic powder, and cleaning the ceramic powder by deionized water;
Step (3), adding the cleaned ceramic powder into a roughening solution for roughening, wherein the components of the roughening solution are HF 60-80mL/L, HNO 390-100mL/L、NH4 F3-5 g/L, cleaning the roughened ceramic powder with deionized water, and performing sensitization activation treatment in a sensitization solution containing SnCl 2 -20g/L, absolute ethyl alcohol 50-60mL/L and an activation solution containing PdCl 2 0.8-1.0g/L, HCl-20 mL/L;
Step (4), cleaning the sensitized and activated ceramic powder with deionized water, adding the cleaned ceramic powder into a plating solution with the loading capacity of 2-50 g/L, and plating under the conditions of ultrasonic oscillation and water bath constant temperature, wherein the temperature of the plating solution is kept at 80-90 ℃, and the plating time is 5-200min;
And (5) after the reaction is finished, centrifugally separating out solid particles, washing with deionized water, drying under a vacuum condition after washing is finished, wherein the drying temperature is 70-80 ℃, and drying treatment is carried out to obtain the ceramic particles with the core-shell structure.
Further, in the step (1), when the ceramic particles with the first size are prepared, the sintering temperature is 1800-1900 ℃, and the temperature is kept for 0.5-1.5h; the particle size of the first ceramic powder is 18-48 mu m;
when preparing the ceramic particles with the second size, the sintering temperature is 2000-2200 ℃, and the temperature is kept for 1-1.5h; the particle size of the second ceramic powder is 180-490nm.
Further, in the step (4), the preparation method of the plating solution comprises the following steps: based on each liter of deionized water, 30-400g/L of nickel sulfate, 30-50ml/L of N 2H4﹒H2 O, 20-40g/L of boric acid, 30-40g/L of ethylenediamine tetraacetic acid, 40-60g/L of sodium hydroxide and 2-8mg/L of polyvinylpyrrolidone are added, and the pH value of the solution is controlled to be 8-11.
Further, in the step (4), plating time is 100-200min when preparing the ceramic particles with the first size; the plating time is 5-10min when preparing the ceramic particles with the second size.
Further, the technological parameters of cold spraying are as follows: the working gas is compressed air, the air pressure is 0.08-0.1MPa, the spraying speed is 60-80mL/min, the spraying distance is 190-210mm, and the spraying angle is 80-90 degrees.
Further, during high-temperature heating, the temperature is firstly increased to 700-900 ℃ at a heating rate of 5 ℃/min, then the temperature is kept for 1-3 hours, and then the temperature is increased to 1300-1400 ℃ at a heating rate of 10 ℃/min, and the temperature is kept for 0.5-1 hour.
Further, after heating at high temperature, the whole pipeline including the coating is subjected to heat treatment by adopting surface flame heat spraying treatment, wherein the outer flame temperature of the surface flame heat spraying treatment is 300-600 ℃, the moving speed is 0.1-10 m/min, and the surface flame heat spraying treatment time is 1-5 h.
The effect of each component in the multi-component metal powder is explained below.
In a Ni-Cr system, ni and Cr form a nickel-chromium solid solution, so that the solid solution strengthening effect is achieved, and the strength and hardness of the coating are improved; b and Ni and Cr in the alloy form various hard phase compounds, such as Ni 3B、Ni2B、Cr2 B, and the like, which play a role in dispersion strengthening in the coating, and can further improve the hardness of the coating. The main functions of Mo and Nb are to prevent the corrosion of high Wen Jingjian caused by Cr deficiency at the grain boundary in the coating, and meanwhile, the content of Mo and Nb is lower, so that segregation of Mo and Nb can be avoided when the coating material is solidified; the addition of Cu can improve the corrosion resistance of the coating by improving the density of the passivation film. Ti and Ni can generate Ni-Ti intermetallic compound in the high-temperature heating process, and the intergranular corrosion resistance of the alloy is improved. The W element can improve the hardness of the coating and ensure that the coating has good pitting corrosion resistance and crevice corrosion resistance. Si takes oxygen away by separation vaporization during alloy preparation, and protects important metal elements. The main function of defining the C content is to prevent carbide formation with Cr during solidification of the coating material and to avoid high Wen Jingjian corrosion at grain boundaries in the coating due to chromium depletion.
The beneficial effects are that:
1) The mixed powder for preparing the coating comprises the multi-element metal powder, the ceramic particles with the first size and the ceramic particles with the second size, and the performance of the coating is regulated and controlled by optimizing the powder components and regulating the proportion. Specifically, the multi-element metal powder can reduce the difference of thermal expansion coefficients between the coating and the matrix while improving the corrosion resistance of the coating, and the first-size ceramic particles and the second-size ceramic particles both adopt core-shell structures of the nickel powder coated ceramic particles, so that the corrosion resistance and the flushing resistance of the coating can be further improved while ensuring the bonding force of the ceramic particles and the multi-element metal powder. The invention can make the multi-element metal powder, the first-size ceramic particles and the second-size ceramic particles play a synergistic effect by limiting the dosage ratio of substances, combines the advantages of metal and ceramic, prepares the coating with the advantages of metal strength and toughness, ceramic wear resistance, corrosion resistance and the like, and can optimize the performance and improve the surface quality of the inner wall of the pipeline.
2) The first-size ceramic particles and the second-size ceramic particles in the invention are of approximate spherical or approximate elliptic core-shell structures, and the ceramic particles are taken as cores, and the outer surfaces of the ceramic particles are coated with nickel, so that the ceramic material has high hardness and toughness of the metal material. On one hand, the existence of the metal shell remarkably improves the wettability among ceramic powder particles, the Ni shell plays a role of a binder, the binding force among particles can be improved, the porosity is further reduced, and the defect of poor binding force caused by directly adding the ceramic particles is avoided; on the other hand, the first-size ceramic particles adopt micron-sized and nano-sized multi-element metal powder, and the second-size ceramic particles with submicron-sized can further reduce the porosity through particle grading, so that the compactness of the coating is improved; on the other hand, the ceramic particles have pinning effect on the grain boundary, effectively inhibit migration of the grain boundary at high temperature, refine grains and improve the mechanical property of the coating.
3) The first-size ceramic particles have larger particle sizes, have better flushing resistance than the second-size ceramic particles with small particle sizes, and have supporting and protecting effects on the coating. In the second-size ceramic particles, the inner core adopts mixed powder obtained by taking aluminum oxide, chromium boride, kyanite and zinc oxide whisker as raw materials through high-temperature sintering, water quenching and crushing. The introduction of the high-hardness alumina can improve the hardness of the coating, so that the flushing resistance of the coating is improved. The kyanite can be decomposed into mullite and quartz phases, and the mullite phase formed can continuously react with alumina in the material to generate mullite, so that the material has high strength and excellent flushing resistance. The zinc oxide whisker can improve the bonding strength of the coating. Chromium boride can improve the washout and corrosion resistance of the coating.
4) The ceramic powder is subjected to chemical nickel plating, and the thickness of the shell is controlled by reasonably controlling the nickel plating time, so that the ceramic particles with high stability of the required size are finally obtained. The ceramic powder obtained by crushing the ceramic is used as the inner core of the ceramic particles, and the ceramic powder is sintered at high temperature, so that the ceramic powder has the advantages of low melting temperature, difficult agglomeration, low porosity of the later reaction, and the like, and the coating can be obtained without setting higher sintering temperature during the preparation of the later coating, so that the efficiency of site construction is greatly improved.
5) The invention prepares the coating by means of cold spraying and high-temperature heating, the core-shell structure of the ceramic particles with the first size and the ceramic particles with the second size can be reserved in the coating by the low-temperature characteristic of cold spraying, and the powder is sprayed on the inner wall of the pipeline by a spraying technology. And after cold spraying, high-temperature heating is performed, so that alloy elements and ceramic elements are diffused again in the formed sub-layer, and the ceramic phases are distributed uniformly in the whole coating, so that the overall corrosion resistance and the scouring resistance are effectively improved. The coating prepared by the method not only meets the corrosion requirements of medium environments such as high-temperature hydrogen sulfide, naphthenic acid and the like, but also can greatly improve the bonding strength (not lower than 300 MPa) between the coating and a substrate and eliminate the porosity (generally less than 0.2%) of the coating.
6) After the high-temperature heating is carried out to obtain the coating, the pipeline and the whole coating are subjected to heat treatment, so that the bonding strength of the coating can be further enhanced by enhancing the bonding force among particles, the higher stress existing in the process of preparing the coating is released, and the bonding strength of the coating and the pipeline can be improved.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below in connection with specific embodiments, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to fall within the scope of the invention.
The invention discloses a corrosion-resistant coating for the inner wall of a pipeline, which is formed by coating the inner wall of the pipeline with a coating thickness of 1-1.5mm by using mixed powder through cold spraying and high-temperature heating technology. The mixed powder comprises 10-15% of multi-element metal powder, 10-20% of first-size ceramic particles and 65-80% of second-size ceramic particles by mass fraction. The mixed powder provided by the invention contains low-content multi-element metal powder, low-content first-size ceramic particles and high-content second-size ceramic particles, not only can be effectively combined with the inner wall of a pipeline, but also can balance the difference of thermal expansion coefficients between the inner wall of the pipeline and a coating layer, so that cracks are prevented from occurring during the preparation of the coating layer, and meanwhile, the mixed powder contains high-content ceramic particles, so that the corrosion resistance and the flushing resistance of the coating layer can be further improved.
The particle size of the multi-element metal powder is 50-200nm, and the multi-element metal powder comprises the following components in percentage by mass: 6-8% of Cr, 1-2% of Mo, 1-2% of W, 1-2% of Nb, 1-2% of Si, 10-12% of Cu, 1-3% of B, 2-4% of Ti, less than 0.5% of Fe, less than 0.005% of C and the balance of Ni. The first-size ceramic particles are core-shell structure powder with the particle size of 20-50 mu m, wherein in the core-shell structure powder, the shell is a nickel layer, the inner core adopts first ceramic powder, and the first ceramic powder is mixed powder obtained by taking BN, zrO 2 and Si 3N4 as raw materials and performing high-temperature sintering, water quenching and crushing. The second-size ceramic particles are core-shell structure powder with the particle size of 200-500nm, in the core-shell structure powder, the shell is a nickel layer, the inner core adopts the second ceramic powder, and the second ceramic powder is mixed powder obtained by taking aluminum oxide, chromium boride, kyanite and zinc oxide whiskers as raw materials through high-temperature sintering, water quenching and crushing.
The first-size ceramic particles and the second-size ceramic particles are prepared by adopting an electroless plating method.
The method for preparing the corrosion-resistant coating on the inner wall of the pipeline by using the mixed powder is described in detail below.
Firstly, weighing multi-element metal powder, ceramic particles of a first size and ceramic particles of a second size according to mass percentage, and preparing mixed powder; before spraying, placing the mixed powder into a vacuum drying oven, and preserving the temperature for 1-2h at 70-80 ℃;
step two, cleaning, drying and sand blasting pretreatment are carried out on the surface of the inner wall of the pipeline;
Thirdly, placing the pipeline on a pipe frame, and spraying by adopting set cold spraying process parameters, wherein the cold spraying process parameters are as follows: the working gas is compressed air; the air pressure is 0.08-0.1MPa; the spraying speed is 60-80mL/min; the spraying distance is 190-210mm; the spraying angle is 80-90 degrees, and the coating with the overall thickness of 0.15-1.5mm is obtained after repeated cyclic spraying;
And fourthly, heating the pipeline at high temperature by adopting flame heating, spray gun heating or circular coil induction heating, and clamping the spray gun or the coil on a tool or carrying out handheld movement. Specifically, heating to 700-900 ℃ at a heating rate of 5 ℃/min, preserving heat for 1-3h, then heating to 1300-1400 ℃ at a heating rate of 10 ℃/min, and preserving heat for 0.5-1h; the sectional heating can make the erosion resistance and corrosion resistance of the coating more stable;
And fifthly, carrying out heat treatment on the whole pipeline, wherein the heat treatment adopts surface flame heat spraying treatment, the outer flame temperature of the surface flame heat spraying treatment is 300-600 ℃, the moving speed is 0.1-10 m/min, and the surface flame heat spraying treatment time is 1-5 h, so that the final corrosion-resistant coating is obtained.
Compared with the traditional method adopting sintering and heat treatment in a furnace, the method adopts cold spraying and mobile high-temperature heating modes in the whole process, is more convenient for site construction, and improves the convenience of site construction.
The technical scheme of the invention is further described below by combining two parts with specific embodiments. The raw materials used in the examples of the present invention, unless otherwise specified, were all available commercially.
The first section illustrates an embodiment of preparing first size ceramic particles and second size ceramic particles.
Example A-1
The preparation method of the first-size particle ceramic comprises the following steps:
Weighing BN, zrO 2 and Si 3N4 (the mass ratio is 1:1:1), crushing for one time, sintering the crushed particles at a high temperature of 1800 ℃ for 1.5 hours, performing water quenching to prepare ceramic, and crushing for the second time to prepare 18 mu m first ceramic powder (hereinafter referred to as powder);
step (2), cleaning the powder in methanol, dilute NaOH solution and dilute HCl solution in sequence, applying ultrasonic waves in the cleaning process to effectively remove the surface pollution of the powder, and then cleaning the powder by deionized water;
Step (3), adding the cleaned powder into a roughening solution for roughening, wherein the components of the roughening solution are HF 60mL/L, HNO 390mL/L、NH4 F3 g/L, cleaning the roughened powder with deionized water, and performing sensitization activation treatment in a sensitization solution containing SnCl 2 g/L, absolute ethyl alcohol 50mL/L and an activation solution containing PdCl 2 0.8g/L, HCl mL/L;
Step (4), washing the sensitized and activated powder with deionized water, adding the powder into a plating solution, wherein the loading capacity is 2g/L, and plating under the conditions of ultrasonic oscillation and water bath constant temperature, wherein the plating solution temperature is kept at 80 ℃, and the plating time is 100min;
And (5) after the reaction is finished, centrifugally separating out solid particles, washing with deionized water, drying under a vacuum condition after washing is finished, wherein the drying temperature is 70 ℃, and obtaining the ceramic particles with the core-shell structure and the particle size of 20 mu m after drying treatment.
The preparation method of the plating solution comprises the following steps: based on each liter of deionized water, 400g/L nickel sulfate, 30ml/L N 2H4﹒H2 O, 20g/L boric acid, 30g/L ethylenediamine tetraacetic acid, 40g/L sodium hydroxide and 2mg/L polyvinylpyrrolidone are added, and the pH of the solution is controlled to be 8.
Example A-2
Example a-2 differs from example a-1 only in that: in the step (1), sintering is carried out at a high temperature of 1900 ℃ for 0.5h; secondary crushing to obtain first ceramic powder with the diameter of 45 mu mm; in the step (4), the plating time is 200min; in the step (5), the particle diameter of the first ceramic particles is 50. Mu.m.
Example A-3
The preparation method of the second-size particle ceramic comprises the following steps:
Step (1), weighing aluminum oxide, chromium boride, kyanite and zinc oxide whisker (the mass ratio is 3:1:1:0.2), crushing for the first time, sintering the crushed particles at a high temperature of 2000 ℃ for 1h, quenching with water to prepare ceramic, and crushing for the second time to prepare 180nm second ceramic powder (hereinafter referred to as powder);
step (2), cleaning the powder in methanol, dilute NaOH solution and dilute HCl solution in sequence, applying ultrasonic waves in the cleaning process to effectively remove the surface pollution of the powder, and then cleaning the powder by deionized water;
Step (3), adding the cleaned powder into a roughening solution for roughening, wherein the components of the roughening solution are HF 80mL/L, HNO 3100mL/L、NH4 F5 g/L, cleaning the roughened powder with deionized water, and performing sensitization activation treatment in a sensitization solution containing SnCl 2 g/L, absolute ethyl alcohol 60mL/L and an activation solution containing PdCl 2 g/L, HCl20 mL/L;
Step (4), washing the sensitized and activated powder with deionized water, adding the powder into a plating solution, wherein the loading capacity is 50g/L, and plating under the conditions of ultrasonic oscillation and water bath constant temperature, wherein the plating solution temperature is kept at 90 ℃, and the plating time is 5min;
And (5) after the reaction is finished, centrifugally separating out solid particles, washing with deionized water, drying under vacuum condition after washing is finished, wherein the drying temperature is 80 ℃, and obtaining the second-size ceramic particles with core-shell structure and particle size of 200nm after drying treatment.
The preparation method of the plating solution comprises the following steps: based on each liter of deionized water, 30g/L of nickel sulfate, 50ml/L of N 2H4﹒H2 O, 40g/L of boric acid, 40g/L of ethylenediamine tetraacetic acid, 60g/L of sodium hydroxide and 8mg/L of polyvinylpyrrolidone are added, and the pH value of the solution is controlled to be 11.
Examples A to 4
Example a-4 differs from example a-3 only in that: in the step (1), sintering is carried out at a high temperature of 2200 ℃ for 1.5 hours; secondary crushing to obtain 490nm second ceramic powder; in the step (4), the plating time is 10min; in step (5), the second ceramic particles have a particle size of 500nm.
The second part is a specific example concerning the coating. The water wall tube adopted in the embodiment of the invention is made of high carbon steel.
Example B-1 (refinery pressure reducing overhead atmospheric leg piping, 8 m long DN500 pipe)
The corrosion-resistant coating for the inner wall of the pipeline has the thickness of 1.5mm, and the preparation method mainly comprises the following steps:
Step one, mixing powder comprises 15% of multi-element metal powder, 20% of first-size ceramic particles and 65% of second-size ceramic particles in percentage by mass; the particle size of the multi-element metal powder is 50nm, and the multi-element metal powder comprises the following components in percentage by mass: cr 6%, mo 1%, W1%, nb 1%, si 1%, cu 10%, B1%, ti 2%, fe < 0.5%, C < 0.005%, ni as the rest; the ceramic particles prepared in the embodiment A-1 are selected as the ceramic particles of the first size, and the ceramic particles prepared in the embodiment A-3 are selected as the ceramic particles of the second size;
step two, cleaning, drying and sand blasting pretreatment are carried out on the surface of the substrate to be coated;
Step three, spraying the mixed powder on the inner wall of the pipeline in a cold spraying mode; the technological parameters of the cold spraying are as follows: the working gas is compressed air; the air pressure is 0.09MPa; the spraying speed is 70mL/min; the spraying distance is 200mm; the spraying angle is 85 degrees;
Heating the coating at a high temperature, firstly heating to 800 ℃ at a heating rate of 5 ℃/min, preserving heat for 2 hours, then heating to 1350 ℃ at a heating rate of 10 ℃/min, and preserving heat for 0.8 hours;
And fifthly, carrying out heat treatment on the whole pipeline, wherein the heat treatment adopts surface flame heat spraying treatment, the outer flame temperature of the surface flame heat spraying treatment is 500 ℃, the moving speed is 5m/min, and the time of the surface flame heat spraying treatment is 3h, so that the corrosion-resistant coating is obtained.
Example B-2 (refinery pressure reducing overhead atmospheric leg piping, 8 m long DN500 pipe)
The corrosion-resistant coating for the inner wall of the pipeline has the thickness of 1.5mm, and the preparation method mainly comprises the following steps:
the method comprises the following steps of firstly, mixing powder comprising 12% of multi-element metal powder, 15% of first-size ceramic particles and 73% of second-size ceramic particles in percentage by mass; the particle size of the multi-element metal powder is 200nm, and the multi-element metal powder comprises the following components in percentage by mass: cr 8%, mo 2%, W2%, nb 2%, si 2%, cu 12%, B3%, ti 4%, fe < 0.5%, C < 0.005%, ni as the rest; the ceramic particles prepared in the embodiment A-2 are selected as the ceramic particles of the first size, and the ceramic particles prepared in the embodiment A-4 are selected as the ceramic particles of the second size;
step two, cleaning, drying and sand blasting pretreatment are carried out on the surface of the substrate to be coated;
Step three, spraying the mixed powder on the inner wall of the pipeline in a cold spraying mode; the technological parameters of the cold spraying are as follows: the working gas is compressed air; the air pressure is 0.1MPa; the spraying speed is 80mL/min; the spraying distance is 210mm; the spraying angle is 90 degrees;
Heating the coating at a high temperature, firstly heating to 900 ℃ at a heating rate of 5 ℃/min, preserving heat for 1h, and then heating to 1400 ℃ at a heating rate of 10 ℃/min, preserving heat for 1h;
And fifthly, carrying out heat treatment on the whole pipeline, wherein the heat treatment adopts surface flame thermal spraying treatment, the outer flame temperature of the surface flame thermal spraying treatment is 600 ℃, the moving speed is 10m/min, and the time of the surface flame thermal spraying treatment is 5h, so that the corrosion-resistant coating is obtained.
Example B-3 (refinery pressure reducing overhead atmospheric leg piping, 8 m long DN500 pipe)
The corrosion-resistant coating for the inner wall of the pipeline has the thickness of 1.3mm, and the preparation method mainly comprises the following steps:
The method comprises the following steps that firstly, mixed powder comprises 10% of multi-element metal powder, 10% of first-size ceramic particles and 80% of second-size ceramic particles in percentage by mass; the particle size of the multi-element metal powder is 100nm, and the multi-element metal powder comprises the following components in percentage by mass: cr 7%, mo 1.5%, W1.5%, nb 1.5%, si 1.5%, cu 11%, B2%, ti 3%, fe < 0.5%, C < 0.005%, ni as the rest; the ceramic particles prepared in the embodiment A-2 are selected as the ceramic particles of the first size, and the ceramic particles prepared in the embodiment A-3 are selected as the ceramic particles of the second size;
step two, cleaning, drying and sand blasting pretreatment are carried out on the surface of the substrate to be coated;
step three, spraying the bottom layer powder, the transition layer powder and the surface layer powder on the inner wall of the pipeline in sequence by adopting a cold spraying mode; the technological parameters of the cold spraying are as follows: the working gas is compressed air; the air pressure is 0.08MPa; the spraying speed is 60mL/min; the spraying distance is 190mm; the spraying angle is 80 degrees;
heating the coating at a high temperature, firstly heating to 700 ℃ at a heating rate of 5 ℃/min, preserving heat for 3 hours, then heating to 1300 ℃ at a heating rate of 10 ℃/min, and preserving heat for 0.5 hours;
And fifthly, carrying out heat treatment on the whole pipeline, wherein the heat treatment adopts surface flame thermal spraying treatment, the outer flame temperature of the surface flame thermal spraying treatment is 300 ℃, the moving speed is 0.1m/min, and the time of the surface flame thermal spraying treatment is 1h, so that the corrosion-resistant coating is obtained.
Comparative example 1
The only difference from example B-1 is that only nickel-chromium powder (chromium 8% and the balance nickel) was used in step one.
The coatings prepared in examples B-1 to B-3 and comparative example 1 were subjected to performance tests by: the hardness detection is to detect the hardness of the surface of the coating by adopting a hardness meter; the combination strength detection is carried out by adopting a synchronous test block drawing test; the porosity is measured by a porosity tester; the corrosion weight gain is to put the pipeline with the coating under the conditions of high sulfur and high naphthenic acid (the volume fraction is 5 per mill naphthenic acid and1 per mill H 2 S), the detection temperature is 60 ℃, the detection time is 30 days, and the quality of the pipeline before and after corrosion is compared. The flushing weight reduction is to flush the pipeline with the coating under 10mL/min of crude oil for one month, the inclination angle is about 25 degrees, and the peristaltic pump is used as the power of the crude oil. The results are shown in Table 1.
TABLE 1 coating Performance test results prepared in examples B1-B3 and comparative example 1
As can be seen from Table 1, the hardness, bonding strength, corrosion resistance and abrasion resistance of the coating of the present application are all superior to those of the conventional nickel-chromium metal coating of the prior art. Moreover, after the coating is used for one year on the inner wall of the oil refining pipeline, the phenomena of cracking, peeling and the like do not occur, and the corrosion resistance and scouring resistance effect are good.
The above description is only of the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. All equivalent changes or modifications made according to the essence of the present invention should be included in the scope of the present invention.
Claims (8)
1. The corrosion-resistant coating for the inner wall of the pipeline is characterized in that a coating with the thickness of 1-1.5mm is coated on the inner wall of the pipeline by utilizing mixed powder through cold spraying and high-temperature heating technology, and the mixed powder comprises 10-15% of multi-element metal powder, 10-20% of ceramic particles with a first size and 65-80% of ceramic particles with a second size in percentage by mass; wherein the particle size of the multi-element metal powder is 50-200nm, and the multi-element metal powder comprises the following components in percentage by mass: 6-8% of Cr, 1-2% of Mo, 1-2% of W, 1-2% of Nb, 1-2% of Si, 10-12% of Cu, 1-3% of B, 2-4% of Ti, less than 0.5% of Fe, less than 0.005% of C and the balance of Ni;
The first-size ceramic particles are core-shell structure powder with the particle size of 20-50 mu m, wherein in the core-shell structure powder, a shell is a nickel layer, a core adopts first ceramic powder, and the first ceramic powder is mixed powder obtained by taking BN, zrO 2 and Si 3N4 as raw materials and performing high-temperature sintering, water quenching and crushing;
The second-size ceramic particles are core-shell structure powder with the particle size of 200-500nm, in the core-shell structure powder, the shell is a nickel layer, the inner core adopts the second ceramic powder, and the second ceramic powder is mixed powder obtained by taking aluminum oxide, chromium boride, kyanite and zinc oxide whiskers as raw materials through high-temperature sintering, water quenching and crushing.
2. The corrosion resistant coating for an interior wall of a pipe according to claim 1, wherein the first size particulate ceramic and the second size particulate ceramic are prepared by:
weighing raw materials for the inner core, crushing the raw materials for the inner core for the first time, sintering the crushed particles at high temperature, performing water quenching to prepare ceramic, and crushing the ceramic for the second time to prepare ceramic powder with target particle size;
step (2), cleaning the ceramic powder in methanol, dilute NaOH solution and dilute HCl solution sequentially, applying ultrasonic waves in the cleaning process to effectively remove pollutants on the surface of the ceramic powder, and cleaning the ceramic powder by deionized water;
Step (3), adding the cleaned ceramic powder into a roughening solution for roughening, wherein the components of the roughening solution are HF 60-80mL/L, HNO 3 90-100mL/L、NH4 F3-5 g/L, cleaning the roughened ceramic powder with deionized water, and performing sensitization activation treatment in a sensitization solution containing SnCl 2 -20g/L, absolute ethyl alcohol 50-60mL/L and an activation solution containing PdCl 2 0.8-1.0g/L, HCl-20 mL/L;
step (4), cleaning the sensitized and activated ceramic powder with deionized water, adding the cleaned ceramic powder into a plating solution, and plating under the conditions of ultrasonic oscillation and water bath constant temperature, wherein the temperature of the plating solution is kept at 80-90 ℃ and the plating time is 5-200min;
And (5) after the reaction is finished, centrifugally separating out solid particles, washing with deionized water, drying under a vacuum condition after washing is finished, wherein the drying temperature is 70-80 ℃, and drying treatment is carried out to obtain the ceramic particles with the core-shell structure.
3. The corrosion resistant coating for an inner wall of a pipe according to claim 2, wherein in the step (1), when the ceramic particles of the first size are prepared, the sintering temperature is 1800-1900 ℃, and the temperature is kept for 0.5-1.5 hours; the particle size of the first ceramic powder is 18-48 mu m;
when preparing the ceramic particles with the second size, the sintering temperature is 2000-2200 ℃, and the temperature is kept for 1-1.5h; the particle size of the second ceramic powder is 180-490nm.
4. The corrosion-resistant coating for the inner wall of a pipeline according to claim 2, wherein in the step (4), the preparation method of the plating solution is as follows: based on each liter of deionized water, 30-400g/L of nickel sulfate, 30-50ml/L of N 2H4﹒H2 O, 20-40g/L of boric acid, 30-40g/L of ethylenediamine tetraacetic acid, 40-60g/L of sodium hydroxide and 2-8mg/L of polyvinylpyrrolidone are added, and the pH value of the solution is controlled to be 8-11.
5. The corrosion resistant coating for an inner wall of a pipe according to claim 2, wherein in step (4), the plating time for preparing the ceramic particles of the first size is 100 to 200 minutes; the plating time is 5-10min when preparing the ceramic particles with the second size.
6. The corrosion-resistant coating for an inner wall of a pipe according to claim 1, wherein the process parameters of the cold spray are: the working gas is compressed air, the air pressure is 0.08-0.1MPa, the spraying speed is 60-80mL/min, the spraying distance is 190-210mm, and the spraying angle is 80-90 degrees.
7. The corrosion-resistant coating for the inner wall of a pipeline according to claim 1, wherein when the pipeline is heated at a high temperature, the temperature is raised to 700-900 ℃ at a temperature raising rate of 5 ℃/min for 1-3 hours, and then the temperature is raised to 1300-1400 ℃ at a temperature raising rate of 10 ℃/min for 0.5-1 hour.
8. The corrosion-resistant coating for the inner wall of a pipeline according to claim 1, wherein after heating at a high temperature, the whole pipeline including the coating is subjected to heat treatment by adopting surface flame heat spraying treatment, the outer flame temperature of the surface flame heat spraying treatment is 300-600 ℃, the moving speed is 0.1-10 m/min, and the surface flame heat spraying treatment time is 1-5 h.
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