CN115521644A - Degradable oxynitride coating and preparation method and application thereof - Google Patents
Degradable oxynitride coating and preparation method and application thereof Download PDFInfo
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B37/00—Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/465—Coatings containing composite materials
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
- F27D1/00—Casings; Linings; Walls; Roofs
- F27D1/0003—Linings or walls
- F27D1/0006—Linings or walls formed from bricks or layers with a particular composition or specific characteristics
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The invention discloses a degradable oxynitride coating and a preparation method and application thereof, belonging to the technical field of kiln materials and comprising the following steps: uniformly spraying the degradable oxynitride coating on the surface of the refractory fiber to obtain refractory fiber cotton; spraying the refractory fiber cotton and the cementing agent into a refractory fiber furnace lining at one time by a fiber spraying machine; spraying a layer of degradable oxynitride coating on the surface of the formed refractory fiber furnace lining again. The invention changes the traditional refractory brick into refractory fiber (the shape is like cotton) in the kiln lining, and sprays a layer of degradable oxynitride coating on the fiber surface and the surface of the formed kiln lining, the coating has fine particle size, the fiber is exposed in the kiln and has extremely large spreading area, the coating is attached to the fiber surface, the contact surface with the smoke is enlarged, and the smoke flows in the kiln, so that the undegraded smoke continuously moves to the fiber surface, and the catalytic degradation effect on NOx compounds in the smoke is improved to the maximum extent.
Description
Technical Field
The invention belongs to the technical field of kiln materials, and particularly relates to a degradable oxynitride coating and a preparation method and application thereof.
Background
The nitrogen oxide as a primary pollutant can cause harm to human health, and can stimulate eyes, nose, throat and lungs of people to cause respiratory diseases; the secondary pollution can generate photochemical smog, acid rain, greenhouse effect and ozone layer cavity effect. For ceramic kilns, the formation of nitrogen oxides is unavoidable during combustion.
At the source, the way of reducing nitrogen oxide includes three aspects: 1. the kiln furniture coated with the catalytic degradation coating contacts flue gas in a large area, so that the degradation efficiency is improved; 2. the flame temperature of the burner is reduced, and the generation of nitrogen oxides is reduced; 3. the structure of the kiln is optimized, the smoke flow line is changed, the contact chance of smoke and degradation materials is increased, and the contact time is prolonged.
The first method is continuously studied by people in the professional field due to its low cost and easy implementation. The coating is generally prepared by degrading NOx compounds by using rare earth materials, and has the advantages of no secondary pollution, no consumption of reducing agents, good economy, simple process and the like. However, the kiln furniture for catalyzing and degrading the coating has the following defects: 1. the binding force between the active substance and the kiln furniture is difficult to meet the requirement, thereby influencing the catalytic degradation effect; 2. the contact area and the contact time of the active substances and the flue gas in the kiln are limited, and the catalytic degradation function is difficult to fully exert; 3. it is difficult for the active material to satisfy both the requirements of high catalytic oxidation-reduction activity and thermal stability. Therefore, the development of the kiln lining capable of overcoming the defects has very important significance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art in the kiln liner and the preparation method thereof, and provides a degradable oxynitride coating and a preparation method and application thereof.
The invention changes the traditional refractory brick into refractory fiber (the shape is like cotton) in the kiln lining, and sprays a layer of degradable oxynitride coating on the fiber surface and the molded lining surface, the coating has fine granularity, the fiber is exposed in the kiln and has extremely large spreading area, the coating is attached on the fiber surface, namely the spreading area of the coating is extremely large, the contact surface with the smoke is enlarged, and the smoke flows in the kiln, so that undegraded smoke continuously moves to the fiber surface, the degradable oxynitride coating and the smoke not only have larger contact area but also have longer contact time, and the catalytic degradation effect on NOx compounds in the smoke is improved to the maximum extent.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of a degradable oxynitride coating comprises the following steps:
s1, dissolving citric acid monohydrate and ammonium metatungstate in deionized water to form a mixed solution, adding cerium nitrate into the mixed solution under uniform stirring at 300r/min, continuously stirring and dissolving, adding metatitanic acid, continuously stirring for 1h after adding, performing suction filtration, drying the solid in a forced air drying oven at 100 ℃ for 10h, and calcining for 2h at 600 ℃ to obtain a composite rare earth material; the dosage ratio of citric acid monohydrate, ammonium metatungstate, deionized water, cerium nitrate and metatitanic acid is (10g);
CeO 2 having a catalytic redox effect on NOx compounds, WO 3 Because of its strong solid acidity, it is often used as active component, the self-made composite rare earth material of the present invention uses TiO 2 As carrier, with CeO 2 And WO 3 As active component, the prepared composite catalystThe agent has rich surface acidity and oxidation-reduction performance, not only has stronger catalytic removal activity to NOx, but also has excellent thermal stability and sulfur poisoning resistance;
s2, dissolving a silane coupling agent KH550 in an ethanol aqueous solution (volume fraction of 50%) to prepare a coupling agent solution with the mass fraction of 18%, mixing the composite rare earth material with the coupling agent solution according to the solid-to-liquid ratio of 1g;
the composite rare earth material is treated by a silane coupling agent KH550, and-NH is introduced on the surface 2 Laying reaction sites for subsequent reactions;
s3, dissolving p-hydroxyphenylacetic acid in hot water (at the temperature of 70-80 ℃) to form a modified liquid with the mass fraction of 15%, adding the pre-modified composite rare earth material into the modified liquid according to the solid-to-liquid ratio of 1g to 10mL, and stirring at the temperature of 70-80 ℃ for 60min to obtain the modified composite rare earth material;
-COOH and-NH 2 Has higher reaction activity, and under stirring, the-COOH on the p-hydroxyphenylacetic acid molecule and the-NH on the pre-modified composite rare earth material 2 Reaction, grafting on the surface of material, introducing
A chain group;
s4, adding alkylphenol ethoxylates into a three-neck flask, adding sodium hydroxide under the stirring condition of 45 ℃, continuously stirring for 2 hours, adding acetone, adding chloroacetic acid under the uniform stirring condition, reacting for 4 hours, finishing the reaction, heating to 58 ℃ to evaporate acetone, pickling with a dilute hydrochloric acid solution (mass fraction is 10%), separating an organic phase, collecting the organic phase, and washing with distilled water to obtain a dispersing agent; the dosage ratio of alkylphenol polyoxyethylene ether, sodium hydroxide, acetone and chloroacetic acid is 189g;
alkalizing-OH on alkylphenol ethoxylates and-COOH on chloroacetic acid by NaOH to respectively form-ONa and-COONa, carrying out nucleophilic substitution reaction on the-ONa and the-COONa, and finally acidifying by HCl to obtain the dispersing agent, wherein the structural formula of the dispersing agent is shown as follows:
the obtained dispersing agent contains-COOH, polyoxyethylene groups and benzene rings, the ability of hydrogen bonds formed by the-COOH and hetero atoms such as N, O on the modified composite rare earth material is strong, and the polyoxyethylene groups can increase the molecular polarity of the dispersing agent, so that the molecular polarity of the dispersing agent and the polar composite rare earth material are enhanced to be adsorbed through the dipole effect; in addition, benzene rings in the dispersing agent and benzene rings grafted on the surface of the modified composite rare earth material can further enhance the adsorption effect between the dispersing agent and the composite material through conjugated pi bonds, and finally, the self-made dispersing agent has extremely high dispersing performance on the composite rare earth material due to the steric hindrance effect of alkyl chains; the uniformly dispersed composite rare earth material can be more uniformly adsorbed on the surface of the fiber, and in addition, the modified and dispersant-adsorbed composite rare earth material can generate hydrogen bonds, polar adsorption and other effects with the surface of the refractory fiber, so that the modified and dispersant-adsorbed composite rare earth material is more firmly adsorbed on the refractory fiber, and more uniform and stable catalytic degradation effect is exerted;
and S5, mixing and stirring the modified composite rare earth material, a dispersing agent and water, performing ultrasonic treatment for 30min, and grinding for 1h to obtain the degradable oxynitride coating.
Furthermore, the dosage mass ratio of the modified composite rare earth material to the dispersant to the water is 100.
The application of the degradable oxynitride coating in the kiln lining comprises a refractory fiber layer and a degradable oxynitride coating sprayed on the surface of the refractory fiber layer, and the preparation method of the kiln lining comprises the following steps:
firstly, uniformly spraying a degradable oxynitride coating on the surface of a refractory fiber, and forming a thin catalytic material layer on the surface of the refractory fiber after drying to obtain refractory fiber cotton;
the spraying amount of the degradable oxynitride coating is 5-6% of the mass of the refractory fiber;
secondly, spraying the refractory fiber cotton and the cementing agent into a refractory fiber furnace lining at one time by a fiber spraying machine;
the loose refractory cellucotton forms a three-dimensional network structure in the spraying process, so that the directional shrinkage crack generated by a fiber product at high temperature is avoided, and the sprayed furnace lining has no construction gap;
thirdly, spraying a layer of degradable oxynitride coating on the surface of the formed refractory fiber furnace lining again, and drying to form a coating layer;
in the third step, the spraying amount of the degradable oxynitride coating is 3-4 times that in the first step.
Furthermore, the cementing agent used by the fiber spraying furnace lining is a high-temperature resistant adhesive XZ-T002, has strong bonding force at normal temperature and high temperature, does not shrink after being cured, has good fluidity, dispersibility and solidification time, and has good construction performance.
Further, the refractory fiber is prepared by the steps of:
mixing kyanite and silica to prepare a mixture, heating the mixture to form a stable high-temperature melt, blowing a melt flow by utilizing compressed air with certain pressure to realize drawing and forming fibers, and collecting the fibers to obtain refractory fibers;
the granularity of the silica is less than 0.15mm, and the adding amount of the silica is 6 percent of the mass of the kyanite; the silica has the functions of improving the high-temperature viscosity of the melt and improving the fiber forming performance of the melt;
decomposition of kyanite at high temperature to yield mullite and SiO 2 Meanwhile, along with obvious volume expansion, the expansion effect is often utilized to offset the shrinkage of some matrix materials or the sintering shrinkage of the product, so that the product has the advantages of good high-temperature volume stability, thermal shock resistance and the like, and the high-temperature service performance of the product is further improved; the kyanite is prepared into the refractory fiber which is used as a furnace lining material, so that the kyanite has excellent high-temperature resistance and has obvious superiority in reducing the thickness of a furnace lining and reducing the heat dissipation loss of a furnace.
The invention has the beneficial effects that:
according to the invention, the degradable oxynitride coating with uniform texture is obtained by modifying the composite rare earth material, mixing the modified composite rare earth material with the self-made dispersant and grinding, and active ingredients in the catalytic coating can generate hydrogen bonds, polar adsorption and other effects with the surface of the refractory fiber, so that the catalytic coating is more firmly adsorbed on the refractory fiber and plays a more uniform and stable catalytic degradation effect;
the invention changes the traditional refractory brick into refractory fiber (the shape is like cotton) in the kiln lining, and sprays a layer of degradable oxynitride coating on the fiber surface and the molded lining surface, the coating has fine granularity, the fiber is exposed in the kiln and has extremely large spreading area, the coating is attached on the fiber surface, namely the spreading area of the coating is extremely large, the contact surface with the smoke is enlarged, and the smoke flows in the kiln, so that undegraded smoke continuously moves to the fiber surface, the degradable oxynitride coating and the smoke not only have larger contact area but also have longer contact time, and the catalytic degradation effect on NOx compounds in the smoke is improved to the maximum extent.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Preparing refractory fiber:
1kg of kyanite and 60g of silica (the granularity is less than 0.15 mm) are mixed to prepare a mixture, the mixture is heated to form a stable high-temperature melt, the melt flow is blown by compressed air with certain pressure to realize drawing fiber forming, and the fiber is collected to obtain the refractory fiber.
Example 2
Preparing a degradable oxynitride coating:
s1, dissolving 100g of citric acid monohydrate and 100g of ammonium metatungstate in 4L of deionized water to form a mixed solution, adding 76g of cerium nitrate into the mixed solution under uniform stirring at 300r/min, continuously stirring and dissolving, adding 585g of metatitanic acid, continuously stirring for 1h after adding, performing suction filtration, drying the solid in a forced air drying oven at 100 ℃ for 10h, and calcining at 600 ℃ for 2h to obtain a composite rare earth material;
s2, dissolving a silane coupling agent KH550 in an ethanol aqueous solution (volume fraction of 50%) to prepare a coupling agent solution with the mass fraction of 18%, mixing 100g of the composite rare earth material with 2L of the coupling agent solution, raising the temperature to 75 ℃, stirring for 70min, filtering, and drying in a vacuum oven for 3-4h to obtain a pre-modified composite rare earth material;
s3, dissolving p-hydroxyphenylacetic acid in hot water (at the temperature of 70 ℃) to form 15% modified liquid, adding 100g of pre-modified composite rare earth material into 1L of modified liquid, and stirring at the temperature of 70 ℃ for 60min to obtain a modified composite rare earth material;
s4, adding 1mol of alkylphenol polyoxyethylene into a three-neck flask, adding 120g of sodium hydroxide under the stirring condition of 45 ℃, continuously stirring for 2h, adding 348mL of acetone, adding 189g of chloroacetic acid under the uniform stirring condition, reacting for 4h, finishing the reaction, heating to 58 ℃ to evaporate acetone, then pickling with a dilute hydrochloric acid solution (mass fraction of 10%), separating an organic phase, collecting the organic phase, and then washing with distilled water to obtain a dispersing agent;
and S5, mixing and stirring 100g of the modified composite rare earth material, 0.39g of the dispersing agent and 35g of water, performing ultrasonic treatment for 30min, and grinding for 1h to obtain the degradable oxynitride coating.
Example 3
Preparing a degradable oxynitride coating:
s1, dissolving 100g of citric acid monohydrate and 100g of ammonium metatungstate in 4L of deionized water to form a mixed solution, adding 76g of cerium nitrate into the mixed solution under uniform stirring at 300r/min, continuously stirring and dissolving, adding 585g of metatitanic acid, continuously stirring for 1h after adding, performing suction filtration, drying the solid in a forced air drying oven at 100 ℃ for 10h, and calcining at 600 ℃ for 2h to obtain a composite rare earth material;
s2, dissolving a silane coupling agent KH550 in an ethanol aqueous solution (volume fraction is 50%) to prepare a coupling agent solution with the mass fraction of 18%, mixing 100g of the composite rare earth material with 2L of the coupling agent solution, raising the temperature to 75 ℃, stirring for 70min, filtering, and drying in a vacuum oven for 3-4h to obtain a pre-modified composite rare earth material;
s3, dissolving p-hydroxyphenylacetic acid in hot water (at the temperature of 80 ℃) to form 15% modified liquid, adding 100g of pre-modified composite rare earth material into 1L of modified liquid, and stirring at the temperature of 80 ℃ for 60min to obtain a modified composite rare earth material;
s4, adding 1mol of alkylphenol polyoxyethylene into a three-neck flask, adding 120g of sodium hydroxide under the stirring condition of 45 ℃, continuously stirring for 2h, adding 348mL of acetone, adding 189g of chloroacetic acid under the uniform stirring condition, reacting for 4h, finishing the reaction, heating to 58 ℃ to evaporate acetone, then pickling with a dilute hydrochloric acid solution (mass fraction of 10%), separating an organic phase, collecting the organic phase, and then washing with distilled water to obtain a dispersing agent;
and S5, mixing and stirring 100g of the modified composite rare earth material, 0.42g of the dispersing agent and 40g of water, performing ultrasonic treatment for 30min, and grinding for 1h to obtain the degradable oxynitride coating.
Example 4
Preparing a kiln lining:
firstly, 50g of the degradable oxynitride coating prepared in the embodiment 2 is uniformly sprayed on the surface of 1kg of the refractory fiber prepared in the embodiment 1, and after drying, a thin catalytic material layer is formed on the surface of the refractory fiber to obtain refractory fiber cotton;
secondly, spraying the refractory fiber cotton and 180g of high-temperature-resistant adhesive XZ-T002 into a refractory fiber furnace lining at one time by a fiber spraying machine;
and thirdly, spraying 150g of degradable oxynitride coating on the surface of the formed refractory fiber furnace lining again, and drying to form a coating layer to obtain the kiln lining.
Example 5
Preparing the kiln lining:
step one, 55g of the degradable oxynitride coating prepared in the embodiment 3 is uniformly sprayed on the surface of 1kg of the refractory fiber prepared in the embodiment 1, and after drying, a thin catalytic material layer is formed on the surface of the refractory fiber to obtain refractory fiber cotton;
secondly, spraying the refractory fiber cotton and 190g of high-temperature-resistant adhesive XZ-T002 into a refractory fiber furnace lining at one time by a fiber spraying machine;
and thirdly, spraying 200g of degradable oxynitride coating on the surface of the formed refractory fiber furnace lining again, and drying to form a coating layer to obtain the kiln lining.
Example 6
Preparing a kiln lining:
step one, 60g of the degradable oxynitride coating prepared in the embodiment 3 is uniformly sprayed on the surface of 1kg of the refractory fiber prepared in the embodiment 1, and after drying, a thin catalytic material layer is formed on the surface of the refractory fiber to obtain refractory fiber cotton;
secondly, spraying the refractory fiber cotton and 200g of high-temperature-resistant adhesive XZ-T002 into a refractory fiber furnace lining at one time by a fiber spraying machine;
and thirdly, spraying 240g of degradable oxynitride coating on the surface of the formed refractory fiber furnace lining again, and drying to form a coating layer to obtain the kiln lining.
The kiln linings of examples 4 to 6 were applied to ceramic kilns, and the content of NOx in the discharged flue gas was measured to be 110 to 120mg/m 3 The content of NOx in the smoke discharged from the lining of the original brick furnace in the using process is 230mg/m 3 The ultralow emission standard of the ceramic kiln is<＝150g/m 3 The application of the kiln lining can increase the contact time and the contact area of the composite rare earth material and the flue gas, thereby effectively improving the degradation effect of the composite rare earth material on nitrogen oxides in the flue gas and realizing the great reduction of NOx emission.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (10)
1. A preparation method of a degradable oxynitride coating is characterized by comprising the following steps:
s1, dissolving citric acid monohydrate and ammonium metatungstate in deionized water to form a mixed solution, adding cerium nitrate into the mixed solution under uniform stirring at 300r/min, continuously stirring and dissolving, adding metatitanic acid, continuously stirring for 1h after adding, performing suction filtration, drying the solid in a forced air drying oven at 100 ℃ for 10h, and calcining for 2h at 600 ℃ to obtain a composite rare earth material;
s2, dissolving a silane coupling agent KH550 in an ethanol aqueous solution to prepare a coupling agent solution with the mass fraction of 18%, mixing the composite rare earth material with the coupling agent solution according to the solid-to-liquid ratio of 1g;
s3, dissolving p-hydroxyphenylacetic acid in hot water to form a modified liquid with the mass fraction of 15%, adding the pre-modified composite rare earth material into the modified liquid according to the solid-liquid ratio of 1g to 10mL, and stirring at 70-80 ℃ for 60min to obtain a modified composite rare earth material;
s4, adding alkylphenol ethoxylates into a three-neck flask, adding sodium hydroxide under the stirring condition of 45 ℃, continuously stirring for 2 hours, adding acetone, adding chloroacetic acid under the uniform stirring condition, reacting for 4 hours, finishing the reaction, heating to 58 ℃ to evaporate acetone, pickling with a dilute hydrochloric acid solution, separating an organic phase, collecting the organic phase, and washing with distilled water to obtain a dispersing agent;
and S5, mixing and stirring the modified composite rare earth material, a dispersing agent and water, and then carrying out ultrasonic treatment for 30min and grinding for 1h to obtain the degradable oxynitride coating.
2. The method for preparing a degradable oxynitride coating according to claim 1, wherein the dosage ratio of citric acid monohydrate, ammonium metatungstate, deionized water, cerium nitrate and metatitanic acid in step S1 is 10g.
3. The method for preparing the degradable oxynitride coating according to claim 1, wherein the ratio of the dosage of alkylphenol ethoxylates, sodium hydroxide, acetone and chloroacetic acid in the step S4 is 1120g.
4. The method for preparing the degradable oxynitride coating according to claim 1, wherein the dosage mass ratio of the modified composite rare earth material, the dispersant and the water in the step S5 is 100-0.39-0.42.
5. A degradable oxynitride coating prepared by the method of any one of claims 1 to 4.
6. The application of the degradable oxynitride coating of claim 5 in a kiln liner, comprising the following steps:
firstly, uniformly spraying a degradable oxynitride coating on the surface of a refractory fiber, and forming a thin catalytic material layer on the surface of the refractory fiber after drying to obtain refractory fiber cotton;
secondly, spraying the refractory fiber cotton and the cementing agent into a refractory fiber furnace lining at one time by a fiber spraying machine;
and thirdly, spraying a layer of degradable oxynitride coating on the surface of the formed refractory fiber furnace lining again, and drying to form a coating layer to obtain the kiln lining.
7. The application of the degradable oxynitride coating of claim 6 wherein the amount of the degradable oxynitride coating sprayed in the first step is 5-6% of the mass of the refractory fiber.
8. The use of a degradable oxynitride coating of claim 7 wherein the amount of the degradable oxynitride coating applied in the third step is 3 to 4 times that of the first step.
9. The use of a degradable oxynitride coating according to claim 6 wherein the refractory fiber is prepared by the steps of:
mixing kyanite and silica to prepare a mixture, heating the mixture to form a stable high-temperature melt, blowing a melt flow by utilizing compressed air with certain pressure to realize drawing fiber forming, and collecting fibers to obtain the refractory fibers.
10. Use of a degradable oxynitride coating according to claim 9 wherein the silica has a particle size of less than 0.15mm and is added in an amount of 6% by mass of kyanite.
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