CN112209727A - Ceramic coating for heating surface of power plant boiler and preparation method thereof - Google Patents

Ceramic coating for heating surface of power plant boiler and preparation method thereof Download PDF

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Publication number
CN112209727A
CN112209727A CN202010907733.9A CN202010907733A CN112209727A CN 112209727 A CN112209727 A CN 112209727A CN 202010907733 A CN202010907733 A CN 202010907733A CN 112209727 A CN112209727 A CN 112209727A
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coating
ceramic
ceramic coating
melting
days
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胡东润
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Zhuhai Hongde Surface Technology Co ltd
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Zhuhai Hongde Surface Technology Co ltd
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    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/66Monolithic refractories or refractory mortars, including those whether or not containing clay
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/24Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing alkyl, ammonium or metal silicates; containing silica sols
    • C04B28/26Silicates of the alkali metals
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/9607Thermal properties, e.g. thermal expansion coefficient

Abstract

The invention belongs to the technical field of coatings, and discloses a ceramic coating for a heating surface of a power plant boiler and a preparation method thereof. The ceramic coating mainly comprises sodium silicate, low-melting-point glass powder, ceramic whiskers, zirconia, zirconium phosphate, rare earth and a coagulant. The coating can be naturally converted into a ceramic phase at about 400 ℃ without high-temperature sintering, and the ceramic rate reaches over 75 percent; the coating formed after spraying is stable, corrosion-resistant and wear-resistant, and the wear resistance is more than 5 times of that of 20# steel; when the coating thickness is too large or is heated unevenly, cracks can not occur; the surface of the coating is compact and smooth, and molten soot particles are not easily adhered to a heated surface, so that the coating has good anti-sticking and anti-coking properties; the coating has better heat conductivity and is not easy to generate the phenomenon of slag fusion and bonding. The preparation method is simple and has low requirements on equipment.

Description

Ceramic coating for heating surface of power plant boiler and preparation method thereof
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to a ceramic coating for a heating surface of a power plant boiler and a preparation method thereof.
Background
The boiler is an important energy conversion device, a power plant boiler, especially a large coal-fired power plant boiler, a boiler pipe of the boiler comprises a hearth water-cooled wall, a superheater pipe, a coal economizer pipe and the like, the boiler pipe is in a sulfuration corrosion, chlorine corrosion and high-temperature oxidation corrosion environment for a long time due to the fact that the working environment of the boiler pipe is severe, and due to the fact that coal quality is different, a part of coal can generate some colloids after high-temperature combustion, and the colloids are accumulated to a certain degree to form deposits with different thicknesses and attached to the water-cooled wall, so that a thermal protection phenomenon is generated, the heating efficiency of the boiler is influenced, and energy waste is caused. The coking materials can also make the water wall conduct heat unevenly, and high-pressure steam or dry burning phenomenon of the water wall pipe is generated locally in the pipeline, thereby causing pipe explosion.
At present, a compact protective layer is formed mainly by spraying paint to isolate a substrate from contacting with the external environment; meanwhile, the problems of high fuel consumption, low wear resistance, easy coking and the like are solved through the performance of the coating. The ceramic coating is widely applied to power plant boilers due to the performances of oxidation resistance, high-temperature corrosion resistance and the like, but when the ceramic coating is made of a ceramic material, when the coating is too large in thickness and uneven in heating, cracks and other problems are easy to occur on the surface of the coating, and the protective performance of the coating is damaged.
Therefore, it is highly desirable to provide a ceramic coating for a heating surface of a power plant boiler, which has corrosion resistance and wear resistance, and after spraying, the surface of the coating is not easy to crack.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the ceramic coating for the heating surface of the power plant boiler has the performances of corrosion resistance and wear resistance, and cracks are not easy to appear on the surface of the coating after spraying.
A ceramic coating is mainly composed of sodium silicate, low-melting-point glass powder, ceramic whiskers, zirconia, zirconium phosphate, rare earth and a coagulant; the melting point of the low-melting-point glass powder is 300-420 ℃.
Preferably, the ceramic coating mainly comprises the following components in parts by weight:
further preferably, the ceramic coating mainly comprises the following components in parts by weight:
preferably, the modulus of the sodium silicate is less than or equal to 3.5.
Preferably, the ceramic whisker is at least three of alumina, silicon carbide, aluminum nitride and silicon nitride; further preferably, the ceramic whisker is alumina, silicon carbide, aluminum nitride and silicon nitride; more preferably, the mass ratio of the aluminum oxide, the silicon carbide, the aluminum nitride and the silicon nitride is (3-5): (1-2): (1-2): (0.5-1). When selecting alumina, silicon carbide, aluminum nitride and silicon nitride whisker, the mass ratio is (3-5): (1-2): (1-2): (0.5-1), a three-dimensional structure with uniform distribution and stability is more easily formed.
Preferably, the diameter of the ceramic whisker is 0.05-6 μm, and the length of the ceramic whisker is 50-200 μm. The crystal whisker with larger length-diameter ratio is easier to form a network structure when forming a ceramic phase, and when the diameter of the ceramic crystal whisker is 0.05-6 mu m and the length of the ceramic crystal whisker is 50-200 mu m, the performance of the prepared ceramic phase is better.
Preferably, the melting point of the low-melting-point glass powder is 350-400 ℃. And the low-melting-point glass powder is adopted to promote the coating to be naturally converted into a ceramic phase at low temperature.
Preferably, the particle size of the low-melting glass powder is 5-10 μm.
Preferably, the particle size of the zirconia is 10 to 45 μm.
Preferably, the rare earth is selected from at least three of lanthanum (La), cerium (Ce), gadolinium (Gd), and terbium (Tb); more preferably, the rare earth is lanthanum (La), cerium (Ce), gadolinium (Gd), terbium (Tb); the mass ratio of lanthanum (La), cerium (Ce), gadolinium (Gd) and terbium (Tb) is (1-2): (1-2): (1-2): (1-2).
Preferably, the accelerator is sodium fluorosilicate.
A preparation method of a ceramic coating comprises the following steps:
(1) weighing low-melting-point glass powder, ceramic whiskers, zirconia, zirconium phosphate and rare earth according to a formula, drying and mixing to obtain mixed powder.
(2) And (2) adding sodium silicate into the mixed powder prepared in the step (1), and mixing to obtain the ceramic coating.
The powders are dried before mixing to make the mixing more complete, and the dried powder can reduce the influence of moisture.
Sodium water glass is used as a ceramic precursor liquid and an adhesive to fuse the mixed powder.
Specifically, the preparation method of the ceramic coating comprises the following steps:
(1) weighing low-melting-point glass powder, ceramic whiskers, zirconia, zirconium phosphate and rare earth according to a formula, putting the mixture into a drying furnace, drying the mixture for 2 hours at the temperature of 200 ℃, and then mixing to obtain mixed powder.
(2) And (2) adding sodium silicate into the mixed powder prepared in the step (1), and uniformly mixing to obtain the ceramic coating.
Compared with the prior art, the invention has the following beneficial effects:
(1) ceramic whiskers, zirconia and zirconium phosphate are used as basic frameworks of the ceramic coating, high-temperature sintering is not needed, the ceramic whiskers can be naturally converted into a ceramic phase at about 400 ℃, and the ceramic rate reaches over 75%; the ceramic whisker and the zirconia form a reinforced 3D network structure, and the zirconium phosphate is distributed in the 3D network structure through a stable layered structure, so that the instability of the ceramic whisker and the zirconia possibly caused by uneven distribution is compensated, a coating formed after spraying is stable, corrosion-resistant and wear-resistant, and the wear resistance is more than 5 times of that of 20# steel; when the coating thickness is too large or is heated unevenly, cracks can not occur; and the surface of the coating is compact and smooth, the fused soot particles are not easy to adhere to the heated surface, and the coating has good anti-sticking and anti-coking properties.
(2) The coating prepared by the coating has good thermal conductivity and high thermal conductivity, can well keep the temperature balance of the surface of the pipe wall, and cannot generate the phenomenon of slag fusion and bonding.
(3) The preparation method of the ceramic coating is simple and has low requirements on equipment.
Drawings
FIG. 1 is a surface condition diagram of a furnace tube in example 1 after one year use;
FIG. 2 is a surface condition diagram of a furnace tube after one year of use without spraying ceramic paint.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples are given for illustration. It should be noted that the following examples are not intended to limit the scope of the claimed invention.
The starting materials, reagents or apparatuses used in the following examples are conventionally commercially available or can be obtained by conventionally known methods, unless otherwise specified.
Example 1
(1) Weighing low-melting-point glass powder, ceramic whiskers, zirconia, zirconium phosphate and rare earth according to a formula, putting the mixture into a drying furnace, drying the mixture for 2 hours at the temperature of 200 ℃, and then mixing to obtain mixed powder.
(2) And adding sodium silicate into the mixed powder, and uniformly mixing to obtain the ceramic coating.
The surface of the boiler pipe wall is polished and cleaned, and then the prepared ceramic coating is uniformly sprayed on the metal surface by an atomizing spray gun, wherein the spraying pressure is 0.8MPa, and the thickness of the coating is 30-120 mu m. After the spraying is finished, the coating is naturally dried for 10 hours, and after the furnace is started, the coating is cured along with the temperature rise of the furnace, so that the coating does not crack.
Then, when the boiler is continuously used for 180 days, 270 days and 365 days, the appearance of the furnace tube is observed, as can be seen from figure 1, the furnace tube is still bright as new after being used for one year, and the surface is seriously corroded without being sprayed with the ceramic coating, as can be seen from figure 2; in order to detect the corrosion resistance of the metal tube, the surface of the furnace tube is polished by using a grinding wheel until the metal surface is exposed, the wall thickness of the tube is measured by uniformly taking 20 measuring points, and the average value is taken, so that the result shows that the furnace tube is only thinned by 0.05nm after 180 days, is only thinned by 0.1nm after 270 days and is only thinned by 0.15nm after 365 days.
Example 2
(1) Weighing low-melting-point glass powder, ceramic whiskers, zirconia, zirconium phosphate and rare earth according to a formula, putting the mixture into a drying furnace, drying the mixture for 2 hours at the temperature of 200 ℃, and then mixing to obtain mixed powder.
(2) And (2) adding sodium silicate into the mixed powder prepared in the step (1), and uniformly mixing to obtain the ceramic coating.
The surface of the boiler pipe wall is polished and cleaned, and then the prepared ceramic coating is uniformly sprayed on the metal surface by an atomizing spray gun, wherein the spraying pressure is 0.8MPa, and the thickness of the coating is 30-120 mu m. After the spraying is finished, the coating is naturally dried for 10 hours, and after the furnace is started, the coating is cured along with the temperature rise of the furnace, so that the coating does not crack.
Then, when the boiler is continuously used for 180 days, 270 days and 365 days, the appearance of the furnace tube is observed, and the furnace tube is still bright as new after being used for one year; in order to detect the corrosion resistance of the metal tube, the surface of the furnace tube is polished by using a grinding wheel until the metal surface is exposed, the wall thickness of the tube is measured by uniformly taking 20 measuring points, and the average value is taken, so that the result shows that the furnace tube is only thinned by 0.08nm after 180 days, is only thinned by 0.15nm after 270 days and is only thinned by 0.2nm after 365 days.
Example 3
(1) Weighing low-melting-point glass powder, ceramic whiskers, zirconia, zirconium phosphate and rare earth according to a formula, putting the mixture into a drying furnace, drying the mixture for 2 hours at the temperature of 200 ℃, and then mixing to obtain mixed powder.
(2) And (2) adding sodium silicate into the mixed powder prepared in the step (1), and uniformly mixing to obtain the ceramic coating.
The surface of the boiler pipe wall is polished and cleaned, and then the prepared ceramic coating is uniformly sprayed on the metal surface by an atomizing spray gun, wherein the spraying pressure is 0.8MPa, and the thickness of the coating is 30-120 mu m. After the spraying is finished, the coating is naturally dried for 10 hours, and after the furnace is started, the coating is cured along with the temperature rise of the furnace, so that the coating does not crack.
Then, when the boiler is continuously used for 180 days, 270 days and 365 days, the appearance of the furnace tube is observed, and the furnace tube is still bright as new after being used for one year; in order to detect the corrosion resistance of the metal tube, the surface of the furnace tube is polished by using a grinding wheel until the metal surface is exposed, the wall thickness of the tube is measured by uniformly taking 20 measuring points, and the average value is taken, so that the result shows that the furnace tube is only thinned by 0.1nm after 180 days, is only thinned by 0.15nm after 270 days and is only thinned by 0.2nm after 365 days.
Example 4
(1) Weighing low-melting-point glass powder, ceramic whiskers, zirconia, zirconium phosphate and rare earth according to a formula, putting the mixture into a drying furnace, drying the mixture for 2 hours at the temperature of 200 ℃, and then mixing to obtain mixed powder.
(2) And (2) adding sodium silicate into the mixed powder prepared in the step (1), and uniformly mixing to obtain the ceramic coating.
The surface of the boiler pipe wall is polished and cleaned, and then the prepared ceramic coating is uniformly sprayed on the metal surface by an atomizing spray gun, wherein the spraying pressure is 0.8MPa, and the thickness of the coating is 30-120 mu m. After the spraying is finished, the coating is naturally dried for 10 hours, and after the furnace is started, the coating is cured along with the temperature rise of the furnace, so that the coating does not crack.
Then, when the boiler is continuously used for 180 days, 270 days and 365 days, the appearance of the furnace tube is observed, and the furnace tube is still bright as new after being used for one year; in order to detect the corrosion resistance of the metal tube, the surface of the furnace tube is polished by using a grinding wheel until the metal surface is exposed, the wall thickness of the tube is measured by uniformly taking 20 measuring points, and the average value is taken, so that the result shows that the furnace tube is only thinned by 0.05nm after 180 days, is only thinned by 0.1nm after 270 days and is only thinned by 0.15nm after 365 days.
Example 5
(1) Weighing low-melting-point glass powder, ceramic whiskers, zirconia, zirconium phosphate and rare earth according to a formula, putting the mixture into a drying furnace, drying the mixture for 2 hours at the temperature of 200 ℃, and then mixing to obtain mixed powder.
(2) And (2) adding sodium silicate into the mixed powder prepared in the step (1), and uniformly mixing to obtain the ceramic coating.
The surface of the boiler pipe wall is polished and cleaned, and then the prepared ceramic coating is uniformly sprayed on the metal surface by an atomizing spray gun, wherein the spraying pressure is 0.8MPa, and the thickness of the coating is 30-120 mu m. After the spraying is finished, the coating is naturally dried for 10 hours, and after the furnace is started, the coating is cured along with the temperature rise of the furnace, so that the coating does not crack.
Then, when the boiler is continuously used for 180 days, 270 days and 365 days, the appearance of the furnace tube is observed, and the furnace tube is still bright as new after being used for one year; in order to detect the corrosion resistance of the metal tube, the surface of the furnace tube is polished by using a grinding wheel until the metal surface is exposed, the wall thickness of the tube is measured by uniformly taking 20 measuring points, and the average value is taken, so that the result shows that the furnace tube is only thinned by 0.1nm after 180 days, is only thinned by 0.15nm after 270 days and is only thinned by 0.25nm after 365 days.
Comparative example 1
(1) Weighing low-melting-point glass powder, ceramic whiskers, zirconia and rare earth according to a formula, putting the mixture into a drying furnace, drying the mixture for 2 hours at 200 ℃, and then mixing to obtain mixed powder.
(2) And adding sodium silicate into the mixed powder, and uniformly mixing to obtain the ceramic coating.
The surface of the boiler pipe wall is polished and cleaned, and then the prepared ceramic coating is uniformly sprayed on the metal surface by an atomizing spray gun, wherein the spraying pressure is 0.8MPa, and the thickness of the coating is 30-120 mu m. After the spraying is finished, the coating is naturally dried for 10 hours, and after the furnace is started, the coating is cured along with the temperature rise of the furnace, and the coating has cracks.
Then, when the boiler is continuously used for 180 days, 270 days and 365 days, the appearance of the furnace tube is observed, and the furnace tube is still bright as new after being used for one year; in order to detect the corrosion resistance of the metal tube, the surface of the furnace tube is polished by using a grinding wheel until the metal surface is exposed, the wall thickness of the tube is measured by uniformly taking 20 measuring points, and the average value is taken, so that the result shows that the furnace tube is thinned by 0.55nm after 180 days, 0.75nm after 270 days and 1.15nm after 365 days.
Comparative example 2
(1) Weighing low-melting-point glass powder, ceramic whiskers, zirconia and zirconium phosphate according to a formula, putting the mixture into a drying furnace, drying the mixture for 2 hours at 200 ℃, and then mixing to obtain mixed powder.
(2) And adding sodium silicate into the mixed powder, and uniformly mixing to obtain the ceramic coating.
The surface of the boiler pipe wall is polished and cleaned, and then the prepared ceramic coating is uniformly sprayed on the metal surface by an atomizing spray gun, wherein the spraying pressure is 0.8MPa, and the thickness of the coating is 30-120 mu m. After the spraying is finished, the coating is naturally dried for 10 hours, and after the furnace is started, the coating is cured along with the temperature rise of the furnace, so that slight cracks appear on the coating.
Then, when the boiler is continuously used for 180 days, 270 days and 365 days, the appearance of the furnace tube is observed, and the furnace tube is still bright as new after being used for one year; in order to detect the corrosion resistance of the metal tube, the surface of the furnace tube is polished by using a grinding wheel until the metal surface is exposed, the thickness of the tube wall is measured by uniformly taking 20 measuring points, and the average value is taken, so that the result shows that the furnace tube is thinned by 0.45nm after 180 days, 0.65nm after 270 days and 1.25nm after 365 days.

Claims (10)

1. A ceramic coating is characterized by mainly comprising sodium silicate, low-melting-point glass powder, ceramic whiskers, zirconia, zirconium phosphate, rare earth and a coagulant; the melting point of the low-melting-point glass powder is 300-420 ℃.
2. The ceramic coating of claim 1, consisting essentially of, in parts by weight:
3. the ceramic coating of claim 1 or 2, wherein the ceramic whiskers are at least three of alumina, silicon carbide, aluminum nitride, and silicon nitride.
4. The ceramic coating of claim 3, wherein the ceramic whiskers are aluminum oxide, silicon carbide, aluminum nitride, and silicon nitride.
5. The ceramic coating according to claim 4, wherein the mass ratio of the aluminum oxide, the silicon carbide, the aluminum nitride and the silicon nitride is (3-5): (1-2): (1-2): (0.5-1).
6. The ceramic coating according to claim 1 or 2, wherein the ceramic whiskers have a diameter of 0.05-6 μ ι η and a length of 50-200 μ ι η.
7. The ceramic paint as claimed in claim 1 or 2, wherein the low-melting-point glass frit has a melting point of 350-400 ℃.
8. Ceramic paint according to claim 1 or 2, characterized in that the zirconia has a particle size of 10-45 μm.
9. Ceramic coating according to claim 1 or 2, characterized in that the rare earth is selected from at least three of lanthanum, cerium, gadolinium, terbium; preferably, the rare earth is lanthanum, cerium, gadolinium or terbium; more preferably, the mass ratio of lanthanum, cerium, gadolinium and terbium is (1-2): (1-2): (1-2): (1-2).
10. The preparation method of the ceramic coating is characterized by comprising the following steps:
(1) weighing the low-melting-point glass powder, the ceramic whisker, the zirconia, the zirconium phosphate and the rare earth according to the formula, drying and mixing to obtain mixed powder;
(2) and (2) adding sodium silicate into the mixed powder prepared in the step (1), and mixing to obtain the ceramic coating of any one of claims 1-9.
CN202010907733.9A 2020-09-02 2020-09-02 Ceramic coating for heating surface of power plant boiler and preparation method thereof Pending CN112209727A (en)

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